Progress in Colloid and Polymer Science . Volume 117 .

2001
Springer
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Progress in Colloid and Polymer Science
Editors: F. Kremer, Leipzig and G. Lagaly, Kiel

Volume 117 200 1

Adsorption
and Nanostructures

Volume Editor:
Imre Dtkany

Springer
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The Third International Conference of the Kolloid-Gesellschaft (Germany) was held in Budapest at September 25-
28, 2000 and was jointly organized together with the Colloid Committee of the Hungarian Academy of Sciences.

"Adsorption and Nanostructures - from Theory to Application"

The Hungarian Academy of Sciences was founded 175 years ago by Count Istvhn Sztchenyi. Since this time, the
Academy was the center of sciences in Hungary. The scientific cooperation between Hungary and Germany goes back
to 1925 when Aladar von Buzagh joined the group of Wolfgang Ostwald in Leipzig and the group of Herbert
Freundlich in Berlin. In 1935 he established the first laboratory of colloid chemistry in Hungary at the University of
Budapest. Buzagh became a member of the Kolloid-Gesellschaft and enjoyed many friendly relationships with
German colloid scientists. Since this time a strong cooperation between Hungarian and German scientists survived all
political troubles and hard times.
The subject of this cooperation is related to two fundamental topics of colloid science: adsorption and
nanostructured materials. The lectures and posters in this conference were, therefore, related to dispersions,
nanoparticles, nanocomposites, adsorption processes, microemulsions, and environmental aspects.
In discussing adsorption phenomena in Budapest, two scientists have to be remembered: Gtza Schay and Lajos
Gyorgy Nagy. Professor Schay was born in 1900 and died at the age of 91. Professor Nagy passed away in 1999. The
important contribution of both scientists to colloid science was acknowledged during the conference.

G . Lagaly
 Lagaly G: Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Adsorption at solid/liquid interfaces

Ulbig P, Seippel J: Development of a group contribution method for liquid-phase
adsorption onto activated carbons . . . . . . . . . . . . . . . . . . . . .

Laszlb K: Adsorption from aqueous phenol and 2,3,4-trichlorophenol solutions

on nanoporous carbon prepared from poly(ethy1ene terephthalate) . .

Mizukami M, Kurihara K: Alcohol cluster formation on silica surfaces in cyclohexane . .

Tombacz E, Szekeres M: Effects of impurity and solid-phase dissolution on surface charge

titration of aluminium oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Horanyi G, Job P: Radiotracer study of the specific adsorption of anions on oxides

Kovaeevit D, c o p A, Bradetic A, Interfacial equilibria at a goethite aqueous interface in the presence

Kallay N, Pohlmeier A, of amino acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Narres H-D, Lewandowski H:

Ruffmann B, Zimehl R: Liquid sorption and stability of polystyrene latices . . . . . . . . . . .

Zimehl R, Hannig M: Adsorption onto tooth enamel the - biological interface and its
modification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Lengyel Z, Foldinyi R: Adsorption of chloroacetanilide herbicides on Hungarian soils . . . . .

Paszli I, Laszlo K: Stagnation phenomenon of solid/fluid interfaces . . . . . . . . . . . . . . . .

Mielke M, Zimehl R: Measures to determine the hydrophobicity of colloidal polymers .

Farkas A, Dekany I: Interlamellar

. .
adsorption of organic pollutants on hydrophobic
vermiculite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Dabrowski A, Biilow M, Adsorption against pollution: current state and perspectives . . . . . . .

Podkocielny P:

Textor T, Bahners T, Schollmeyer E: Organically modified ceramics for coating textile materials . . . . . . . .

Nanostructured materials
Esumi K, Torigoe K: Preparation and characterization of noble metal nanoparticles using
dendrimers as protective colloids . . . . . . . . . . . . . . . . . . . . . . . . . . .

Mogyorbsi K, Nemeth J, Dekany I, Preparation, characterization, and photocatalytic properties

Fendler JH: of layered-silicate-supported TiOz and ZnO nanoparticles . . . . . . . .

Papp S, Dekany I: Growth of nearly monodisperse palladium nanoparticles

on disaggregated kaolinite lamellae . . . . . . . . . . . . . . . . . . . . . . . . . .

Landfester K: Quantitative considerations for the formulation of miniemulsions . .

Vekas L, Bica D, Potencz I, Concentration and composition dependence of rheological

Gheorghe D, BZl5u 0 , Raga M: and magnetorheological properties of some magnetic fluids
Tiarks F, Willert M, Landfester K, The controlled generation of nanosized structures in miniemulsions . 110
Antonietti M:

Hartl W, Beck C: The glass transition and propagating transverse phonons in colloidal
systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

Nagy NM, Konya J, Beszeda M, Lead accumulation on montmorillonite . . . . . . . . . . . . . . . . . . . . . . 117

Beszeda I, Kalman E, Keresztes Z,
Papp K:

Pozsgay A, Papp L, Frater T, Polypropylene /montmorillonite nanocomposites prepared by the

Pukanszky B: delamination of the filler . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120

Beck C, Hart1 W: Fullerenes as new colloidal model systems . . . . . . . . . . . . . . . . . . . . 126

Socoliuc V, Bica D: Experimental investigation of magnetic-induced phase-separation

kinetics in aqueous ferrofluids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131

Surfactants, polymers
Varga I, Gilanyi T,Meszaros R: Characterisation of ionic surfactant aggregates by means of activity
measurements of a trace probe electrolyte . . . . . . . . . . . . . . . . . . . . . 136

Gilanyi T, Meszaros R, Varga I: Determination of binding isotherms of ionic surfactants in

polymergels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141

Csiszar A, Bota A, Novak C, Changes in the thermotropic and the structural behaviour
Klumpp E, Subklew G: of 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine/water liposomes
effected by 2,4-dichlorphenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

Marton A, Miyazaki Y: Correlation between equilibrium and N M R spectroscopic data in

the study of the selectivity of cross-linked ionic polymers . . . . . . . . . 153

Halasz L, Nemeth Z, Structural and viscoelastic properties of lamellar systems formed

Horanyi JPT, B6ta A: from concentrated nonionic surfactant solutions . . . . . . . . . . . . . . . . 159

Kiss E, Lam CNC, Duc TM, Surface characterization of polylactide/polyglycolide coplymers . . . . 167
Vargha-Butler EI:

Kilian H-G, Koepf M,Vettegren V: Model of reversible aggregation: universal features of fluctuating
ensembles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172

Pawlowski D, Tieke B: Change of structure and phase behaviour during homo- and
copolymerisation of (2-methacryloyloxyethyl)dodecyldimethylammonium
bromide in a hexagonal lyotropic mesophase . . . . . . . . . . . . . . . . . . 182

Borbas R, Kiss E, Nagy M: Elastic properties of protein gels obtained by three-phase

partitioning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189

KolariC 8,Forster S, Interactions between polyelectrolyte brushes in free-standing liquid

von Klitzing R: films: Influence of ionic strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195

Colfen H, Qi L: The mechanism of the morphogenesis of CaC03 in the presence of

poly(ethy1ene glycol)-b -poly(methyl methacrylic acid) . . . . . . . . . . . . 200
VIII

Dispersions
Benna M, Kbir-Ariguib N, Card-house microstructure of purified sodium montmorillonite
Clinard C, Bergaya F: gels evidenced by filtration properties at different pH . . . . . . . . . . . . 204

Horvath 0, Hegyi J: Light-induced reduction of heavy-metal ions on titanium dioxide

dispersions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 1

Fetter G, Horhnyi T, Bota A: In situ structural investigations of the Synperonic(A7) - water system
undershear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
Progr Colloid Polym Sci (2001) 117: 1±4
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

Peter Ulbig Development of a group contribution method

Johannes Seippel
for liquid-phase adsorption onto activated
carbons

Abstract The description of liquid- parameters were ®tted to experi-

P. Ulbig á J. Seippel phase adsorption equilibria onto mental data. By using these param-
University of Dortmund, activated carbons was investigated eters predictions of liquid-phase
Department of Chemical Engineering,
Institute for Thermodynamics, in terms of group contributions. The adsorption equilibria of di€erent
Emil-Figge-Strasse 70, adsorbate±solid solution theory was systems, especially with other
44221 Dortmund, Germany used in order to introduce the active activated carbons, are possible.
P. Ulbig (&) sites of the adsorbent as a compo-
Physikalisch-Technische Bundesanstalt, nent in a multicomponent mixture
Section 3.14, Bundesallee 100, with the liquids. The active sites and Key words Liquid-phase
38116 Braunschweig, Germany the liquids are subdivided into adsorption á Group contribution á
e-mail: [email protected]
Tel.: +49-531-5923142 functional groups and the corre- Activated carbon á Surface-excess
Fax: +49-531-5923205 sponding group contribution isotherms

Introduction to be used and how it is possible to introduce these

properties into the thermodynamic model arise.
Nowadays, the use of computational methods in order to
calculate whole separation processes is common practice
in chemical engineering. Group contribution methods Theory
are often applied in this context in order to calculate, for
example, the vapour±liquid equilibrium of multicompo- The thermodynamic framework of the ASST is given in
nent mixtures for distillation processes. The adsorption Ref. [2]. It is based on the equality of the chemical
from the liquid phase is seldom used for a separation potential for a component, li, in every phase. The
process, owing to the fact that experimental data for the adsorbed liquid phase is taken together with the active
given mixture are often not available or no computa- sites of the adsorbent in order to obtain a so-called
tional method exists. Therefore, the question is whether reference phase. The chemical potential for a liquid
the group contribution principle in combination with a component i has, therefore, to be equal in the bulk (index
corresponding solution theory can be used in order to b) and in the reference phase (index *):
describe liquid-phase adsorption equilibria. The main
advantage of this principle is the possibility of carrying lbi ˆ li : 1†
out predictions for adsorption equilibria onto di€erent This leads to the formulation of the phase equilibrium:
activated carbons. The surface-excess isotherms of !
binary liquid systems onto zeolites were successfully b b   U U0i
described [1] by the use of the so-called adsorbate±solid xi ci ˆ xi ci exp ; 2†
RT Csm;i
solution theory (ASST) [2] in combination with the
modi®ed UNIFAC equation [3]. Activated carbons are where xi denotes the molar fraction of this component, ci
much more heterogeneous than zeolites and therefore the the activity coecient, F the free enthalpy of immersion
questions of which properties of activated carbons have of the mixture, F0i the free enthalpy of a pure liquid
2

Table 1 Characterisation of the

activated carbons used Activated carbon (from) CWS (Lurgi) ROTH (Roth) L3S (Elf) CPL (Elf)
Raw material Hard coal Peat Pine wood Pine wood
Activation procedure Steam Steam Steam, acid Phosphoric acid
washed
Brunauer±Emmett±Teller 500 750 1,150 1,700
surface area (m2g)1)
PH 9±10 9±10 4 4±7
Acid solubility (%) 12.0 5.5 0.5 2.0
Total pore volume 0.297 0.441 0.659 1.122
(N2 isotherm) (cm3g)1)
Acidic surface groups
(mmolg)1):
Carboxylic 0.000 0.000 0.005 0.430
Lactonic 0.000 0.000 0.105 0.115
Phenolic 0.290 0.400 0.200 0.425
Basic surface groups 2.100 1.180 0.395 0.170

under the same conditions as the mixture, R the molar (A_COOH), the lactonic group (A_OCO), and the
gas constant, T the temperature, and Csm,i the saturation phenolic group (A_OH). These groups can also be
capacity of the pure liquid onto the activated carbon. determined by stepwise Boehm titrations. The number
This equation is similar to the often-used equation of each group on the surface is calculated by an
describing the phase equilibrium between a bulk liquid algorithm which takes into account the number of C
mixture and the adsorbed surface phase [3, 4]. atoms per gram of adsorbent (calculated from the BET
For the calculations of the activity coecient of a number and the average area per C atom), and from the
liquid component in the bulk phase cbi the modi®ed results of the Boehm titrations, which give the number of
UNIFAC equation was taken [5]. For the introduction of basic and acidic groups per gram of adsorbent. From
the active sites as a component a molar mass has to be that, the corresponding parts for ``one'' group (a ``unit
de®ned: cell''). is calculated (Table 2). For the investigations
 C atom NA experimental data of four commercially available acti-
A
Mactivated carbon ˆ : 3† vated carbons were used [6, 7].
BET For every kind of group the relative van der Waals
The calculation consists of the average area of a carbon volumes (RvdW) and surfaces (QvdW) have to be known.
atom A  C atom within a graphitic structure, the Avogadro This is necessary owing to the fact that the group
constant, NA, and the Brunauer±Emmett±Teller (BET) interactions in the modi®ed UNIFAC model are weighed
number (Table 1) of the activated carbon.
The group classi®cation for the active sites was
subdivided into three main groups:the nonpolar group,
the basic group, and the acidic group. The nonpolar
group contains only a C atom of a graphitic structure
(N_gC). The basic group contains one group (B_O),
which covers all types of basic oxides on the surfaces and
which can be determined by Boehm titrations altogether.
The basic group is subdivided into the carboxylic group

Fig. 2 Correlation of n-hexane (1)±2,2,4-trimethylpentane (2) onto

Fig. 1 The interaction matrix of the chosen test system ROTH
 3

Table 2 Number of di€erent groups (active sites) found on the

activated carbons

Activated Carboxylic Lactonic Phenolic Basic Nonpolar

carbon group, group, group, group, group,
A_COOH A_OCO A_OH B_O N_gC
CWS 0.000 0.000 0.008 0.062 0.930
ROTH 0.000 0.000 0.008 0.024 0.968
L3S 0.000 0.000 0.003 0.005 0.990
CPL 0.004 0.001 0.004 0.002 0.989

Table 3 Relative van der Waals properties of the active sites

Group Relative volume, RvdW Relative surface, QvdW

N_gC 0.3652 0.120
B_O 0.7536 0.526
A_COOH 1.7647 1.396
A_OCO 2.6094 1.392
A_OH 0.7688 0.570
Fig. 4 Correlation of n-hexane (1)±2,2,4-trimethylpentane (2) onto
CPL
Table 4 Enthalpies of wetting and the factors for the saturation
capacities

Activated Wetting Wetting enthalpy Ratio of Chosen

carbon enthalpy of 2,2,4- enthalpies ratio
of n-octane trimethylpentane of wetting
(J/g) (J/g)
CWS 56.7 40.0 0.705 0.705
ROTH 100.1 71.1 0.710 0.710
L3S 128.0 117.1 0.915 0.915
CPL 147.8 136.3 0.922 0.975

Fig. 5 Prediction of n-hexane (1)±2,2,4-trimethylpentane (2) onto

CWS

One of the most important parameters is the satura-

tion capacity, Csm,i, which describes the total amount of
pure liquid within the pore system in¯uenced by the
solid. This quantity usually cannot be measured and
therefore assumptions have to be made. A ®rst assump-
tion was taken for the maximum of the saturation
capacity, Cs,max
m,i, the whole amount of liquid with its
Fig. 3 Correlation of n-hexane (1)±2,2,4-trimethylpentane (2) onto density, qi, at 298.15 K which can be placed inside the
L3S pore system Vpore:
Cs;max
m;i ˆ qi Vpore : 4†
by the volume and surface fractions. The values were
calculated from the atom diameters and the bond lengths In wide pores only a part of the liquid is in¯uenced by the
(Table 3). solid and therefore the saturation capacity was treated as
4

parameter which can be ®tted [6]. Values of 60±75% of of the test system onto three activated carbons. With the
the maximum amount were obtained; therefore all ®tted parameters the surface-excess isotherm of the test
saturation capacities were calculated as system was predicted for the CWS activated carbon. As
can be seen from Fig. 5 a good prediction was possible
Csm;i ˆ 0:7Cs;max
m;i : 5†
and it has to be emphasised that this prediction was
The values obtained were decreased additionally if a obtained by only introducing the properties of this
branched molecule had to be adsorbed. In the case of carbon into the model.
2,2,4-trimethylpentane enthalpies of wetting, DwH, were The results show that this theoretical framework can
known from previous investigations [8, 9]. The ratios of be used in order to correlate and predict the surface-
the enthalpies of wetting of 2,2,4-trimethylpentane to excess isotherms for a whole class of adsorbents, in this
n-octane were taken as a factor in order to decrease the investigation activated carbons; however, the carbon-
accessible pore volume (Table 4) and therefore the and molecule-dependent parameters, especially the sat-
saturation capacity corresponding to uration capacities of the pure liquids, have to be known
with only a small uncertainty. Nevertheless predictions
Dw Hbranched
Csm;i ˆ 0:7Cs;max
m;i : 6† for a completely di€erent activated carbon were carried
Dw Hlinear out with success for the ®rst time. Additional investiga-
tions have to be carried out in the future in order to ®nd
an algorithm for calculating the saturation capacities of
Results pure liquids as a function of the pore size distribution of
the activated carbon.
For the investigations alkane±cycloalkane mixtures onto
the four carbons were considered. For the ®tting
procedure of the UNIFAC model parameters (interac- Conclusion
tion energies) only the data of three carbons were used
(ROTH, L3S, CPL). The surface-excess isotherms for The simultaneous correlation of surface-excess isotherms
CWS were predicted by making use of the ®tted onto di€erent activated carbons was performed by using
parameters. As an example, the surface-excess isotherms the ASST, the modi®ed UNIFAC model, and measured
of the n-hexane (1)±2,2,4-trimethylpentane (2) system at and calculated properties of the activated carbons. By
298.15 K on all four carbons were chosen [6, 7]. The using this whole framework, a prediction for a com-
corresponding interaction matrix of the functional main pletely di€erent activated carbon was carried out suc-
groups can be seen in Fig. 1. cessfully. The limitations of the whole theory were
The interactions between the localised active sites apparent: the saturation capacities of the pure liquids
were set to zero; therefore only seven main group on the di€erent activated carbons calculated from
interactions exist. For the modi®ed UNIFAC method enthalpies of wetting of branched and linear molecules
only two interaction parameters per main group were seem to be good choice, but are not as precise as is
®tted (Duij, Duji). Altogether 14 interaction energies were necessary. However, the physical background of the
®tted. The results can be seen in Figs. 2, 3, 4, and 5. With adsorption from solution onto activated carbons was
the original value of 0.922 obtained from the enthalpies introduced into a complex thermodynamic framework
of wetting for 2,2,4-trimethylpentane onto the CPL and tested successfully.
carbon the results were not sucient. By increasing this
value up to 0.975 good results were obtained for the Acknowledgement The authors thank the German Research Foun-
simultaneous correlation of the surface-excess isotherms dation (Deutsche Forschungsgemeinschaft) for ®nancial support.

References

1. Berti C, Ulbig P, Schulz S (2000) Ad- 4. Schay G (1969) Surf Colloid Sci 2:155± 7. Seippel J, Ulbig P, Schulz S (2000)
sorption 6:79±92 211 J Chem Eng Data 45:780±783
2. Berti C, Ulbig P, Burdorf A, Schulz S 5. Weidlich U, Gmehling J (1987) Ind Eng 8. Ulbig P, Surya-Lukito, Schulz S, Seippel
(1999) Langmuir 15:6035 Chem Res 26:2274 J (1998) J Therm Anal 54:333±342
3. Everett DH (1965) Trans Faraday Soc 6. Seippel J, Ulbig P, Klueppel M, Berti C, 9. Ulbig P, Friese T, Schulz S, Seippel
61:2478±2495 Schulz S (1999) Chem Tech 51:129±133 J (1998) Thermochim Acta 310:217±222
Progr Colloid Polym Sci (2001) 117: 5±12
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

Krisztina LaÂszlo Adsorption from aqueous phenol

and 2,3,4-trichlorophenol solutions
on nanoporous carbon prepared
from poly(ethylene terephthalate)

Abstract Highly microporous acids used. In the case of phenol, a

poly(ethylene terephthalate) based competitive adsorption takes place,
activated carbon exhibits a Bru- as the interactions are weak in the
nauer±Emmett±Teller surface area three media investigated (pH 3, un-
of 1170 m2/g and a total pore vol- bu€ered and pH 11). The triple
ume of 0.625 cm3/g. It contains chlorine substitution in 2,3,4-tri-
mesopores in a sucient proportion chlorophenol signi®cantly enhances
of 42% of the total pore volume, the surface interactions. Owing to
which promotes the di€usion avail- the smaller pKa value of trichloro-
ability of the micropore region. The phenol in an unbu€ered medium,
surface possesses an amphoteric na- ionic interaction occurs as has been
ture owing to the oxygen function- concluded from the outstandingly
alities present; however, the majority high value of the adsorption equi-
of the groups are basic. The ad- librium constant. At pH 11 the ad-
sorption properties from aqueous sorption of the phenols is hindered
solution of weak acids, such as by electrostatic repulsion.
K. LaÂszloÂ
Department of Physical Chemistry, phenol and 2,3,4-trichlorophenol,
Budapest University of Technology depend both on the pH of the
and Economics, 1521 Budapest, solutions and on the pKa of the Key words Activated carbon á
Hungary phenols, as the pH in¯uences both X-ray photoelectron spectroscopy á
e-mail: [email protected]
Tel.: +36-1-4631893 the surface chemistry of the carbon Amphoteric surface á Functional
Fax: +36-1-4633767 and the dissociation of the weak groups á pH e€ect

Introduction as neither the surface area nor the pore structure was
sucient to explain many of the properties of the
Nanostructured materials can be manufactured either by carbons. Their surface chemistry is governed by the
building the system atom by atom or molecule by presence of heteroatoms such as hydrogen, oxygen,
molecule or by dispersing a continuous matrix. One nitrogen, phosphorus, etc., originating from the organic
example is tailoring nanosized cavities into a solid phase. precursor and the method of carbon preparation,
Thus, activated carbon might be considered as nano- activation or further treatments [1±5]. The most frequent
structured material known and applied since ancient heteroatom in the carbon matrices is oxygen, which is
times. generally bonded along the edges of the turbostratic
Activated carbons, owing to their versatility, are the graphite crystallites. Oxygen may be present in various
most frequently applied adsorbents of gases, vapors and forms, such as carboxyls, carbonyls, phenols, lactones,
liquids. Activated carbons of desired surface area and aldehydes, ketones, quinones, hydroquinones, anhy-
pore structure are now commercially available. It was in drides or ethereal structures [1, 4, 6±8]. Carbonyl,
the late 1980s when the previously neglected importance carboxyl, phenolic hydroxyl and lactonic groups are
of carbon surface chemistry was ®rst analyzed in depth, acidic, while pyrene, chromene and quinone are basic
6

[1, 2, 9±14]. These groups and the delocalized electrons of [24], the micropore volume derived from the t-method [25] and the
the graphitic structure determine the apparent acid/base pore size distribution calculated from the desorption branch of the
isotherm, according to Barrett el al. [26], were used to characterize
character of the activated carbon surface [4]. Thus, the the pore structure.
nature and distribution of surface functionalities is
fundamental in activated-carbon-based water-treatment
processes [15±18]. Adsorption from completely miscible binary mixtures
Several workers have exploited the potential of Benzene±methanol binary liquid mixtures were used in order to
activated carbons for studying the adsorption behaviour characterize the chemical heterogeneity of the carbon surfaces.
of phenols and other organic compounds [19, 20]. The Isotherms were obtained by a batchwise method in the whole
removal of phenol by activated carbon was ®rst reported composition range, at ambient temperature. Dry methanol and
by Honig [21]. Phenol and its derivatives are antropo- benzene of high-performance liquid chromatography grade
(Merck) were used. The solid/liquid ratio applied was 1:5. The
genic pollutants, existing widely in industrial e‚uents 6-h contact time was established from preliminary experiments.
such as those from oil re®neries and the coal tar, plastics, The concentrations were derived from the refractive index [27].
paint, pharmaceutical and steel industries. Since they are Excess isotherms (n1r(n) versus x1 functions) were computed from
highly toxic and, in general, not easily biodegradable, the primary experimental data, as


methods of treatment are continuously being developed. r n†
n1  n0 x1;0 x1 ; 1†
Of all the methods, adsorption appears to provide the
best prospect for overall treatment, especially in the where n1r(n) is the speci®c surface-excess amount (millimoles per
gram) of benzene in the interfacial layer, n0 is the speci®c amount of
lower concentration range. For phenol is one of the most the initial bulk liquid phase (millimoles per gram) and x1,0 and x1
frequent contaminants of industrial wastewaters, one of are the initial and the equilibrium molar fractions of benzene,
the important features of the activated carbons used in respectively, in the bulk phase. The intersection of the function with
wastewater treatment is their capability to adsorb phenol the abscissa (in the case of isotherms of S shape), the so-called
adsorption azeotropic composition, x1,a, can be used as a measure
[11, 16]. Besides being carcinogenic, in the chlorinating of the hydrophobic/hydrophilic character of the surface.
process, which is applied very often as a complementary
puri®cation step in wastewater treatment, it reacts with
the chlorine and produces carcinogenic mono- and X-ray photoelectron spectroscopy
polychlorinated compounds [14, 17, 22]. In our experi-
The surface chemical composition of the samples was determined
ments, the latter was represented by 2,3,4-trichlorophe- by X-ray photoelectron spectroscopy (XPS) using an XR3E2 (VG
nol. Microtech) twin-anode X-ray source and a Clam2 hemispherical
The objective of this work is to demonstrate the electron energy analyzer. The base pressure of the analysis chamber
in¯uence of pH on the surface chemistry and thus the was 5 ´ 10)9 mbar. The Mg Ka radiation used (1253.6 eV) was
nonmonochromatized. Wide-scan spectra in the 1000±0 eV bind-
adsorption mechanism and capacity of a highly micro- ing-energy range were recorded with a pass energy of 50 eV for all
porous activated carbon derived from poly(ethylene samples. High-resolution spectra of the O 1s and C 1s signals were
terephthalate) (PET). recorded in 0.05 eV steps with a pass energy of 20 eV. After the
linear base line had been subtracted, curve-®tting was performed
assuming a Gaussian peak shape.
Experimental
pH
Precursors and sample preparation
One gram of carbon sample was shaken with 35 ml bidistilled water
Granulated PET (Qualon) was obtained from Mitsubishi (Singa- in a sealed glass bottle for 72 h, at ambient temperature, to reach
pore). The polymer was carbonized at 750 °C for 30 min in a steel equilibrium. At the end of this period the pH of the aqueous phase
reactor ¯ushed with nitrogen gas (50 dm3/h). After cooling to room was detected using an Orion 720 A (Inovata, Broma, Sweden) pH
temperature, the pyrolyzed material was ground and sieved. meter. Each determination was performed in triplicate, as well as
Particles in the range 0.8±2.0 mm were activated at 900 °C, up to that of the bidistilled water blank [17].
a burno€ of 50% in a ¯ow of steam. Details have been published
recently [23]. This carbon was studied without further treatment.
Boehm titration

Characterization of the activated carbon The oxygenated surface groups were determined according to
Boehm's method [7, 28±30]. One gram of carbon sample was
Nitrogen adsorption immersed in 35 ml 0.05 M HCl, NaHCO3, Na2CO3 and NaOH
solutions, respectively. The vials were sealed and shaken for 72 h at
The surface area and the pore size distribution were determined ambient temperature. The ®ltrates were titrated with NaOH and
from nitrogen adsorption/desorption isotherms measured at 77 K HCl depending on the original titrant. The number of basic sites
using an AUTOSORB (Quantachrome, Syosset, N.Y., USA) was calculated from the amount of HCl that reacted with the
computer-controlled surface analyzer. The sample was outgassed carbon. The various free acidic groups were derived using the
at 300 °C in a vacuum (p<3 ´ 10)4 mbar). The apparent surface assumption that NaOH neutralizes carboxyl, lactone and phenolic
area was derived according to the Brunauer±Emmett±Teller (BET) groups, Na2CO3 neutralizes carboxyl and lactone and NaHCO3
model. The total pore volume, also called the Gurvitsch volume neutralizes only carboxyl groups, respectively.
 7

Sorption from dilute aqueous solutions of phenols A BET surface area of 1,170 m2/g and an average pore
radius of 1.07 nm were derived from the nitrogen
Solutions of phenol (Merck, 99.5%) and 2,3,4-trichlorophenol adsorption isotherm. According to the pore size distri-
(Fluka, 98%) were prepared using bidistilled water or the
appropriate bu€er solutions (Titrisol pH 3 and Titrisol pH 11, bution (Fig. 1a) it contains both micropores and mes-
Merck). The carbon (0.05 g) was shaken with 5±60 ml phenol opores; however, 0.425 cm3/g of the 0.625 cm3/g total
(5 mmol/l) or 2,3,4-trichlorophenol (2 mmol/l) solutions for 24 h pore volume is microporous (Fig. 1b). The high surface
and 7 days, respectively, in sealed vials at ambient temperature. area and the pore structure designate this carbon for
The contact times needed to reach equilibrium were concluded
from preliminary kinetic measurements [31]. Initial and equilibrium
application in aqueous adsorption processes. It contains
concentrations were determined by detecting the UV absorption of mesopores in a sucient proportion of 42% of the total
phenol (265 nm) and 2,3,4-trichlorophenol (k ˆ 290 nm) using a pore volume, which promotes the di€usion availability of
UVIKON 930 UV±vis spectrophotometer (Kontron, Zurich, the micropore region.
Switzerland). The amount of phenol adsorbed by 1 g activated
carbon (na, millimoles per gram) was calculated according to the
following equation: Chemistry of the surface
V c0 ce †
na ˆ ; 2†
1000m Elemental composition and surface heterogeneity
where V is the volume of the liquid phase, m is the mass of the The bulk and surface compositions, obtained from
activated carbon and c0 and ce are the initial and equilibrium elemental analysis and XPS, respectively, are compared
concentrations of the liquid phase, respectively. The curves were in Table 2. The discrepancy of the surface and bulk
evaluated according to the linear Langmuir ®t:
regions is obvious from the deviation of the O/C
ce 1 ce
ˆ ‡ ; 3† proportions determined by the two methods, as the
na Knm nm information obtained from the XPS analysis character-
where na is the phenol or 2,3,4-trichlorophenol adsorbed by 1 g izes only the upper few nm layer of the sample.
carbon, ce is the equilibrium concentration in the aqueous phase,
nm is the monolayer capacity and K is the adsorption equilibrium
constant. However, it should be noted that the surface homoge-
neity, which is one of the basic conditions applied in the Langmuir
model, is hardly ful®lled in the case of these systems.
Selected physicochemical properties of the phenols are collected
in Table 1. The electron-withdrawing e€ect of the chlorine atoms
reduces the electron density of the aromatic ring, which is re¯ected
in the lower pKa value as well. The surface occupied by a single
adsorbate molecule was applied to characterize the coverage of the
carbon surface.

Results

Characterization of the carbon

Surface area and pore structure

The carbon obtained from the PET by the two-step

physical activation applied exhibits high microporosity.
Table 1 Selected properties of phenol and 2,3,4-trichlorophenol

Molecular pKaa Solubility Cross-sectional Ref.

weight (g/l)a area
(nm2/molecule)
Phenol 94.11 9.89 82 0.42 [41]
0.30 [19]
0.522 [16]
0.437 [42]
0.437 [20]
0.43 [43]
2,3,4-Tri- 197.45 7.59 0.4 0.72 [41]
chloro-
phenol Fig. 1 a Di€erential pore size distribution derived from the desorp-
0.631±0.649 [43] tion branch of the nitrogen adsorption/desorption isothem of the
poly(ethylene terephthalate) (PET) carbon, 77 K; b t-plot derived
a
At ambient temperature from the same isotherm
8

Table 2 Elemental composition in atomic percent zigzag sites at the edges of the basal planes. The presence
of hydrophilic centers, such as carboxylic or phenolic
C H O O/C
groups, renders the surface polar, enhancing the inter-
Bulk 90.7 4.6 4.7 0.052 action with the polar methanol; however, interaction
Surface 95.7 ± 4.3 0.045 between the benzene and some of the oxygen-containing
functional groups may take place as well [2, 35]. These
surface functional groups were determined by the XPS
The carbon displays an excess isotherm of type IV method (Fig. 3).
according to the Schay±Nagy classi®cation (Fig. 2) [32]. Five peaks, i.e. ®ve di€erent carbon bonds, were
The S shape means that the surface contains both identi®ed in the C 1s range, and two di€erent oxygen
hydrophilic and hydrophobic surface locations and, thus, bonds in the O 1s range. The results of the deconvolution
the preferentially adsorbing component (nir(n)>0) de- and ®tting processes are collected in Tables 3 and 4.
pends on the bulk concentration. The nonpolar benzene
adsorbs preferentially below x1,a ˆ 0.85, while in the Acid/base properties
0.85<x1<1 range the adsorption of the polar methanol
is preferred. Thus, the surface exhibits amphoteric The pH of the aqueous slurry of the carbon was 6.2 (the
character, as it contains both hydrophobic and hydro- pH of the bidistilled water blank was measured to be 5.5),
philic surface sites. The adsorption of benzene is i.e. this carbon can be classi®ed as of type H because it
attributed mainly to the interaction between p electrons
in the benzene ring and the condensed aromatic rings on
the carbon surface [33] referred to as basic structural
units [34]. The adsorption of methanol is preferred on
hydrophilic functional groups as well as armchair and

Fig. 3 a X-ray photoelectron spectroscopy (XPS) C 1s spectrum of

the PET carbon. I: C±C, C±H; II: C±O; III: C ˆ O, O±C±O; IV:
O ˆ C±O; V: shakeup satellite peaks owing to p-p* transitions in
Fig. 2 Adsorption-excess isotherms on PET carbon from benzene aromatic rings. b XPS O 1s spectrum of the PET carbon. I: C ˆ O; II:
(1)±methanol (2) binary liquid mixture C±O
 9

Table 3 Distribution of carbon structures (atomic percent) from Adsorption of the phenols
the X-ray photoelectron spectroscopy (XPS) C 1s spectrum [8, 44]

Peak Binding energy Carbon Atomic % The saturation capacities of the PET carbon from
(eV) structure unbu€ered phenol and 2,3,4-trichlorophenol solutions
were found to be 2.58 and 3.16 mmol/g, respectively, i.e.
I 284.0 C±C, C±H 60.0
II 285.2 C±O 18.1 signi®cantly more adsorbed from the larger molecule. A
III 286.7 C=O, O±C±O 8.1 nearly complete monolayer coverage, as can be deduced
IV 288.6 O=C±O 5.3 from the molecular areas, was achieved only in the case
V 290.3 Shakeup 4.2 of trichlorophenol [6]. In order to understand this
satellite peaks anomalous behavior, the pH dependence of the adsorp-
owing to p±p*
transitions in
tion process was studied, as both the nature of the
aromatic rings phenols and the chemistry of the surface sites are a€ected
by pH. Solutions bu€ered to pH 3 and pH 11 were used
as all the functional groups of the carbon surface are
protonated below pH 3 and are deprotonated at pH 11
Table 4 Distribution of oxygen structures (atomic percent) from (Fig. 4).
the XPS O 1s spectrum [8, 44]
The Langmuir parameters derived from the linearized
Peak Binding energy Oxygen structure Atomic % isotherms (Figs. 5, 6, Table 6) con®rm the expectations
(eV) that the adsorption capacity and mechanism are in¯u-
I 531.3 C=O 1.2 enced by the pH.
II 533.1 C±O 3.1 The sequence of the monolayer capacities is unbuf-
fered>pH 3>pH 11, and pH 3  unbu€ered>pH 11 in
the case of phenol and trichlorophenol, respectively. It is
exhibited a pH value higher than that of the blank [17]. in accordance with former observations that in the pH
The acid/base properties of the functional groups range 9±12 the increasing pH results in a decreasing
detected by XPS were determined by Boehm titration adsorption capacity [36, 37]. In the case of phenol, the
(Table 5). values of the K parameter derived from the Langmuir ®t
In accordance with the pH shift experienced in the are practically similar in the bu€ered solutions, but K
carbon suspension, 81.6% of the functional groups are exhibits a higher value when the system is not bu€ered.
basic. No carboxylic groups were detected within the The sequence of the K values from the trichlorophenol
experimental error of the Boehm titration [30]. The acidic isotherms is unbu€ered  pH 11  pH 3. The numerical
character rises from the phenolic (81.1%) and lactonic values are 1 or 2 orders of magnitude higher than in
(8.1%) groups. This is consistent with the ratio of the phenolic systems. The enhanced interaction in the case of
deconvoluted peaks of the C 1s spectrum, whereas, from the trichlorophenol adsorbate is due to the electron-
among the carbon atoms related to oxygen (peaks II, III withdrawing phenomenon of the three chlorine substit-
and IV), the ratio of peak II derived from carbons in uents.
phenolic, alcoholic or ethereal groups is 57% (Table 3). By comparing the number of functional groups per
Similarly, in the O 1s spectrum, the ratio of the single 100 nm2 from the titration and the number of adsorbed
C±O bonds is dominant (72%) (Table 4). The origin of
the basic character can be partly traced back to the
delocalized electrons of the graphitic structure. The C 1s
spectrum also suggests that most of the surface carbon
atoms are present in graphitic form.

Table 5 Results of Boehm titration of poly(ethylene terephthalate)

(PET) carbon

Functional group Concentration (lmol/g) Group/

100 nm2a
Carboxylic Below the detection limit ±
Lactonic 17.7 0.91
Phenolic OH 76.0 3.85
Total acidic groups 93.7 4.76
Total basic groups 416.8 21
Total functional groups 510.5 26
a NA
Calculated as 100  concentration  aS;BET , applying the corre- Fig. 4 Charge development on activated carbon surface in aqueous
sponding unit conversions; NA is the Avogadro number solution [45]
10

Fig. 5 Linearized adsorption isotherms (ambient temperature) from Fig. 6 Linearized adsorption isotherms (ambient temperature) from
aqueous phenol solutions of various pH. The symbols represent aqueous 2,3,4-trichlorophenol solutions of various pH. The symbols
measured values, the solid lines represent the ®t by the Langmuir represent measured values, the solid lines represent the ®t by the
equation Langmuir equation

phenols per 100 nm2 listed in Tables 5 and 6 respectively, and the basic surface oxygens does not play a signi®cant
it is clear that the adsorption does not takes place only on role in this case, as the concentration of the surface
the titrated functionalities, as the number of the adsorbed oxygen atoms is relatively low.
molecules signi®cantly exceeds that of the oxygen- At pH 3, both the surface functional groups and the
containing surface sites. The highest surface population phenolic compounds are in nonionic form, that is, the
was developed from the unbu€ered and acidic trichloro- surface groups are either neutral or positively charged.
phenol solutions and the lowest when the media were The interaction between the carbon surface and the
basic. phenolic compounds is weak and can be attributed to the
The fundamental interactions between the carbon dispersion e€ect (Fig. 7a).
surface and phenols are a) dispersion e€ect between the This weak interaction in the case of the phenol results
aromatic ring and the p electrons of the graphitic in the coadsorption of water molecules, yielding a
structure and b) electrostatic attraction and repulsion if reduced surface concentration in comparison with tri-
ions are present [16±19, 38±40]. The interaction between chlorophenol. For the stronger interaction, trichlorophe-
the water molecules and the surface sites cannot be nol may complete a more or less complete monolayer. It
excluded as well, and their competitive adsorption results cannot be excluded that some of the molecules interact
in the depletion of the amount adsorbed [16]. Electron via hydrogen bonds formed between the protonated
donor±acceptor interaction between the aromatic ring surface functional groups along the edge of graphitic

Table 6 Adsorption parameters of aqueous phenol and 2,3,4-trichlorophenol solutions on PET carbon

Phenol 2,3,4-Trichlorophenol

pH 3 Unbu€ered pH 11 pH 3 Unbu€ered pH 11
a
a 0.2244 0.0873 0.3367 0.0132 0.0007 0.0226
ba 0.4684 0.3881 0.7574 0.3124 0.3167 0.5120
R 0.9936 0.9977 0.9938 0.9941 0.9952 0.9949
nm (mmol/g) 2.14 2.58 1.32 3.20 3.16 1.95
K [(mmol/l))1] 2.09 4.45 2.25 23.67 479.85 22.66
Adsorbed molecule/100 (nm2)b 108 130 67 161 159 99
Surface area occupied by one 0.93 0.77 1.50 0.62 0.63 1.01
adsorbed molecule, (nm2)c
a
y = a+bx, where a = 1/Knm and b = 1/nm, according to Eq. (3)
b NA
Calculated as 100  nm  aS;BET , applying the corresponding unit conversions
c aS;BET
Calculated as nm NA , applying the corresponding unit conversions
 11

the trichlorophenolate anions and the positively charged

surface sites (Fig. 7c) is re¯ected by the outstanding K
value of the Langmuir ®t. The surface coverage in this
case is similar to that developing at pH 3, indicating also
dispersion force driven adsorption within the graphene
layers.

Conclusion

The microporous carbon produced from PET shows

amphoteric surface nature, owing to the presence of
oxygen-containing groups. 81.6% of the surface sites can
be titrated by HCl, i.e., the majority of the functional
groups exhibit basic character. The acidity derives from
lactonic and phenolic oxygens. The adsorption mecha-
nism fundamentally depends on the pH of the solution
applied, as the phenols are weak acids and the surface is
amphoteric, with acid/base character.
Fig. 7 Schematic representation of the adsorption of phenols on a The relatively low K values and the high surface area
carbon surface a by the dispersion e€ect, b when electrostatic available for a single phenol molecule compared to the
repulsion takes place and c when electrostatic attraction is possible. theoretical cross-sectional area lead to the conclusion
(Water molecules are not shown.) that in the three media applied phenol adsorbs mainly by
dispersion interaction and, therefore, competitive ad-
layers and the phenolic OH groups, which may reduce sorption of the solvent molecules may take place as well.
the availability of the graphitic region. The introduction of the three chlorine substituents
At pH 11 the phenols dissociate, forming phenolate results in a signi®cantly di€erent electron structure in the
anions, while the surface functional groups are either case of 2,3,4-trichlorophenol and the dispersion interac-
neutral or negatively charged. The electrostatic repulsion tion becomes stronger than in the case of phenol: this is
between the alike charges lowers the adsorption capac- re¯ected in the higher K values. In unbu€ered medium
ities in the case of both phenols (Fig. 7b). The deprot- the lower pKa value of the trichlorophenol results in a
onated acidic groups along the graphitic layers repel the signi®cant number of trichlorophenolate anions in
deprotonated phenolate ions, hindering the access of the comparison with the simple phenol. This leads to ionic
phenolate ions into the space between the graphite sheets. attraction between the trichlorophenolate ions and the
Dispersion interaction may occur when the penetration positively charged surface sites. The ionic interaction is
of the phenol molecules into the graphitic region is not shown by the remarkably high K value. A practically
blocked. The competitive adsorption of water molecules complete monolayer is formed at pH 3 and from
occurs as well: the surface area related to a single unbu€ered solution as well.
adsorbed unit shows the highest value (i.e., the lowest At pH 11 the electrostatic repulsion existing between
coverage) at pH 11 in the case of both phenols. the negative surface sites and the phenolate or 2,3,4-
When the adsorption takes place in unbu€ered trichlorophenolate ions reduces the adsorption capacities.
solutions (pH about 6.5), the carbon surface contains
both protonated and deprotonated sites. Owing to the Acknowledgements This research was supported by the OTKA
Fund (Hungary) nos. T 017019 and T 025581. The authors wish to
di€erent pKa values of the two adsorbate species, express their appreciation to Katalin Josepovits for the XPS
trichlorophenol produces a signi®cantly higher number spectra. The technical support of Emese FuÈloÈp and GyoÈrgy
of ions than phenol. The ionic attraction acting between Bosznai and AndraÂs Szucs is gratefully acknowledged.

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Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

Masashi Mizukami Alcohol cluster formation on silica surfaces

Kazue Kurihara
in cyclohexane

Abstract Adsorption of ethanol centration range of 0.1±0.5 mol%,

onto silica surfaces from ethanol± where the attractions were especially
cyclohexane binary liquids was long-ranged and practically no
investigated by a combination of ethanol cluster formed in the bulk
colloidal probe atomic force micro- solutions. The spectra also indicated
scopy and Fourier transform IR that the cluster formation involved
spectroscopy using the attenuated hydrogen-bonding interactions
total re¯ection (ATR) mode. An between surface silanol groups and
unusually long range attraction was ethanol hydroxyl groups in addition
found between the silica surfaces in to those between ethanol molecules.
the presence of ethanol in the con- We account for the observed long-
centration range of 0.1±1.4 mol%. range attraction by the bridging of
At 0.1 mol% ethanol, the attraction opposed adsorption layers of etha-
appeared at a distance of 35  3 nm nol on the silica surfaces.
M. Mizukami á K. Kurihara (&) and turned into a repulsive force
Institute for Chemical Reaction Science, below 3.5  1.5 nm upon compre- Key words Adsorption from binary
Tohoku University, Katahira 2-1-1, ssion. The ATR spectra demon- liquid á Alcohol cluster á Silica
Aoba-ku, Sendai 980-8577, Japan strated that ethanol adsorbed on the surface á Surface force á Fourier
e-mail: [email protected]
Tel.: +81-22-2175673 surfaces formed hydrogen-bonded transform IR±attenuated total
Fax: 81-22-2175673 clusters even in a low ethanol con- re¯ection

Introduction and Fourier transform IR spectroscopy in attenuated

total re¯ection (FTIR±ATR) mode to shed light on the
Adsorption from solutions onto solid surfaces is a key in preferential (selective) adsorption of alcohol (methanol,
colloid and surface science. It plays important roles in ethanol and propanol) onto silica surfaces from their
many industrial processes, such as colloidal stabilization binary mixtures with cyclohexane.
and catalysis. Elegant application of adsorption in Surface forces measurement is a unique tool for surface
advanced materials has been demonstrated recently in characterization [3]. It can directly monitor the distance
the formation of self-assembling monolayers and multi- dependence of surface forces, which re¯ect distance-
layers on various substrates [1, 2]. However, only a limited dependent changes of surface properties from the surface
number of researches have been devoted to the study of to the bulk [4]. Such information is dicult to obtain by
adsorption in binary liquids. Adsorption isotherms and other techniques. One of the simplest examples is the case
colloidal stability measurements have been the main tools of the electric double layer force. The repulsion observed
for these studies, which limit our understanding of the between charged surfaces follows the counterion distri-
phenomena to the macroscopic level. The molecular level bution in the vicinity of surfaces and is called the electric
of characterization is necessary to elucidate and further double layer force (repulsion) [3]. It is easy to extend this
utilize the phenomenon in the future technology. We idea to other surface properties, such as adsorption.
employed a combination of surface force measurement Indeed, our studies have revealed the formation of alcohol
14

clusters extending for about 10 nm on silica surfaces and a in the same manner as for the force measurements. The glass
long-range attraction associated with this phenomenon spheres (typically 1.0 g) dispersed in ethanol±cyclohexane mixtures
(10 ml) precipitated after they were equilibrated for about 24 h at
[5, 6]. Among the alcohols studied, we report results 20  0.5 °C. The composition of the supernatant was determined
obtained for ethanol adsorption on silica surfaces. Here, using a di€erential refractometer (Otsuka Electronics, DRM-1021).
we use silica as a general word to call the substrates, glass The adsorption layer thickness (t) was estimated by assuming that
(for colloidal probe atomic force microscopy, AFM) and only ethanol is present in the adsorption layer using the speci®c
adsorption amount [9, 10].
oxidized silicon (for FTIR±ATR), chosen on the basis of IR spectra were recorded using a PerkinElmer FTIR 2000
the experimental requirement. system using a triglycine sulfate detector. For the ATR mode, the
ATR attachment from Grasby Specac was used. A homemade
stainless steel ATR ¯ow cell was used and was sealed with a Te¯on
Experimental O-ring. Transmission IR spectra were obtained using a CaF2 cell
(Nihon Bunko) with a path length of 25 lm. An ATR prism made
of silicon crystal (Nihon PASTEC, 60 ´ 16 ´ 4 mm trapezoid) was
Cyclohexane and ethanol were dried with sodium and magnesium, used as a solid adsorbent surface. It is known that on the silicon
respectively, and distilled immediately prior to use. surface, the oxide layer gradually grows up to 3±5 nm thickness
The interaction force (F) between a glass sphere and a glass plate when the surface is exposed to air at room temperature [11], thus
was measured as a function of the surface distance (D) in exhibiting similar properties as those of glass. In order to clean the
cyclohexane±ethanol mixtures using AFM (Seiko II, SPI3700- oxide surface, the silicon crystal was immersed in a mixture of
SPA300) [7]. Colloidal glass spheres (Polyscience) and glass plates sulfuric acid and hydrogen peroxide (4:1, v/v) and thoroughly
(Matsunami, micro cover glass) were washed in a mixture of rinsed with pure water. The crystal was then treated with water
sulfuric acid and hydrogen peroxide (4: 1, v/v) and thoroughly vapor plasma for 20 min immediately prior to each experiment to
rinsed with pure water. The colloidal glass sphere (4±5-lm radius) ensure the formation of silanol groups on the silicon oxide surface
was then attached to the top of a cantilever (Olympus, RC-800PS- [8]. It was kept in pure cyclohexane until assembled into the ATR
1) with epoxy resin (Shell, Epikote1004). The spheres and the plates cell.
were treated with water vapor plasma (Samco, BP-1) for 3 min. just
prior to each experiment in order to ensure the existence of silanol
groups on the glass surface [8]. The forces obtained were
normalized by the radius (R) of the sphere using the Derjaguin Results and discussion
approximation [1], F/R ˆ 2pGf. Here, Gf is the interaction free
energy per unit area between two ¯at surfaces. R was measured
using an optical microscope. Typical force pro®les measured between glass surfaces in
The adsorption-excess isotherm was measured using adsorbent ethanol±cyclohexane mixtures are shown in Fig. 1. In
glass spheres which were washed and water-vapor-plasma treated pure cyclohexane, the observed force agreed well with the

Fig. 1 Pro®les of interaction

forces between glass surfaces
upon compression in ethanol±
cyclohexane mixtures. The
dashed line and the solid line
represent the van der Waals
force calculated using the non-
retarded Hamaker constants of
3 ´ 10)21 J for glass/cyclohex-
ane/glass and 6 ´ 10)21 J for
glass/ethanol/glass, respectively
[3]
 15

conventional van der Waals attraction calculated with appears, 18  2 nm, is close to the apparent layer
the nonretarded Hamaker constant for glass/cyclohex- thickness of the adsorbed ethanol, 13  1 nm. This
ane/glass, 3.1 ´ 10)21 J. At an ethanol concentration of supports our interpretation that the attraction is caused
0.1 mol%, the interaction changed remarkably: the long- by contact of opposed ethanol adsorption layers. Half
range attraction appeared at a distance of 35 nm, showed the attraction range is constant up to about 0.4 mol%
a maximum around 10 nm, and turned into repulsion at ethanol and decreases with increasing ethanol concen-
distances shorter than 5 nm. The pull-o€ force of the tration, while the apparent adsorption layer thickness
contacting surfaces was 140  19 mN/m, which was remains constant for all the concentration ranges stud-
much higher than that in pure cyclohexane, 10  7 mN/ ied. The discrepancy between the two quantities indicates
m. Similar force pro®les were obtained at ethanol a change in the structure of the ethanol adsorption layer
concentrations up to 0.4 mol%. A further increase in at concentrations higher than about 0.4 mol%, which we
the concentration decreased the long-range attraction. At will discuss later.
an ethanol concentration of 1.4 mol%, the interaction The structures of the adsorbed ethanol were studied
was identical to that in pure cyclohexane. The range using FTIR±ATR spectroscopy. They turned out to be
where the long-range attraction extended changed par- hydrogen-bonded clusters as described later. The spectra
allel to the value of the pull-o€ force at various ethanol obtained were examined by referring to well-established,
concentrations, indicating that both forces are associated general spectral characteristics of hydrogen-bonded
with the same phenomenon, most likely the adsorption of alcohols in the fundamental OH stretching region
ethanol. It is natural to ascribe the short-range repulsion because ethanol is known to form hydrogen-bonded
to the steric force of structured ethanol molecules dimers and polymers (clusters) in nonpolar liquids [11].
adjacent to the glass surfaces which is similar to the We also examined hydrogen-bonded ethanol cluster
hydration force [3]. formation in bulk ethanol±cyclohexane mixtures using
In order to understand the condition better, we transmission IR spectroscopy.
determined the adsorption isotherm by measuring the FTIR±ATR spectra of ethanol adsorbed onto silica
concentration changes in the alcohol upon adsorption surfaces in cyclohexane at various ethanol concentra-
onto glass particles using a di€erential refractometer. tions (0.0±2.0 mol%) are presented in Fig. 3. At
Plots of the range of the attraction versus the ethanol 0.1 mol% ethanol, a narrow negative band at
concentration are shown in Fig. 2 together with the 3,680 cm)1, a weak absorption at 3,640 cm)1 (free
apparent adsorpion layer thickness estimated from the OH), and a broad strong absorption (3,600±
adsorption isotherm assuming that only ethanol is 3,000 cm)1) with shoulders at 3,530 cm)1 (cyclic dimer
present in the adsorption layer [9]. For 0.1 mol%
ethanol, half the distance where the long-range attraction

Fig. 3 Fourier transform IR±attenuated total re¯ection FTIR-AIR

Fig. 2 A plot of half the attraction range between glass surfaces and spectra of ethanol on an oxidized silicon surface in ethanol±
that of the apparent adsorption layer thickness of ethanol on glass cyclohexane binary liquids at various ethanol concentrations of 0.0±
surfaces in ethanol±cyclohexane binary liquids 2.0 mol%
16

or donor end OH), 3,450 and 3,180 cm)1 were observed.

The isolated silanol group is known to exhibit an
absorption band at 3,675±3,690 cm)1 in a nonpolar
liquid, for example, CCl4 [12]. Therefore, the negative
absorption at 3,680 cm)1 should correspond to the
decrease in the isolated silanol groups. On the other
hand, the positive shoulder at 3,450 cm)1 indicated the
appearance of the silanol groups hydrogen bonded with
the adsorbed ethanol, because the absorption band shifts
to a lower wavenumber (3,425±3,440 cm)1) when the
silanol groups hydrogen bond with esters [12]. The strong
broad band at 3,600±3,000 cm)1 (the polymer OH)
demonstrated the hydrogen-bonded polymer cluster
formation of ethanol adsorbed on the silicon oxide
surface even at 0.1 mol% ethanol where no polymer
peak appeared in the spectrum of the bulk solution at
0.1 mol% ethanol. With increasing ethanol concentra-
tion, the intensity of the polymer OH peak (3,330 cm)1)
increased.
At higher ethanol concentrations, the ATR spectra Fig. 4 Plots of integrated peak intensities of polymer OH as a
should contain a contribution from the bulk species, function of the ethanol concentration. The ®lled circles represent the
because of the long penetration depth of the evanescent values obtained from transmission spectra (ATS), while the ®lled
wave, 250 nm. To distinguish the bulk contribution, the squares represent those from ATR (AATR)
integrated peak intensities of polymer OH peaks of
transmission (ATS) and ATR (AATR) spectra are plotted clearly indicated that the ethanol cluster formed locally
as a function of the ethanol concentration in Fig. 4. The on the surface at ethanol concentrations lower than
former followed cluster formation in the bulk liquid, about 0.5 mol%, where practically only a negligible
whilst the latter contains contributions of clusters both number of clusters existed in the bulk. In the adsorption
on the surface and in the bulk. A sharp increase is seen in layer, ethanol formed polymer clusters through hydrogen
AATR even at 0.1 mol% ethanol, but there is no bonding of surface silanol groups and ethanol as well as
signi®cant increase in ATS at ethanol concentrations those between ethanol molecules. A plausible structure of
lower than 0.5 mol%. A comparison of ATS and AATR the ethanol adsorption layer is presented in Fig. 5.

Fig. 5 Plausible structures of

the adsorption layer composed
of ethanol cluster
 17

The contact of adsorbed ethanol layers should bring silica surfaces in cyclohexane, which probably brought
about the long-range attraction observed between glass about the long-range attraction between silica surfaces.
surfaces in ethanol±cyclohexane mixtures. The attraction A similar long-range attraction associated with cluster
starts to decrease at about 0.5 mol% ethanol, where formation has been found for mixtures of other alcohols
ethanol starts to form clusters in the bulk phase. It is (methanol and propanol) and carboxylic acid with
conceivable that the cluster formation in the bulk cyclohexane and is under active investigation in our
in¯uences the structure of the adsorbed alcohol cluster laboratory. Such knowledge should be important for
layer, thus modulating the attraction. We think that the understanding surface treatment processes performed in
decrease in the attraction is due to the exchange of solvent mixtures and for designing new materials with the
alcohol molecules between the surface and the bulk use of molecular assemblies at solid±liquid interfaces. To
clusters (Fig. 5). show an example of utilizing these novel molecular
assemblies, we have prepared polymer thin ®lms by in
situ polymerization of acrylic acid preferentially ad-
Conclusion sorbed on glass surfaces [14].

This study, to the best of our knowledge, is the ®rst Acknowledgements This work was supported in part by a grant
from the Ministry of Education, Science, Culture and Sports,
attempt at employing the modern technique to under- Japan (11167204). K.K. is grateful to the Canon Foundation for a
stand the liquid adsorption at the molecular level. We visiting professorship to Hungary which provided her with the
found that ethanol formed hydrogen-bonded clusters on opportunity for writing this article.

References

1. Adamson AW, Gast AP (1997) Phys- 6. Mizukami M, Kurihara K (2000) 11. Sze SM (1985) Semiconductor devic-
ical chemistry of surfaces, 6th edn. Chem Lett 248 es:Physics and technology. Wiley, New
Wiley, New York 7. Ducker WA, Sendan TJ, Pashley RM York
2. Decher G (1997) Science 277:1232 (1992) Langmuir 8:1831 12. Liddel U, Becker ED (1957) Spectro-
3. Israelachivili JN (1992) Intermolecular 8. Okusa H, Kurihara K, Kunitake T chim Acta 10:70
and surface forces, 2nd edn. Academic, (1994) Langmuir 10:3577 13. Cross SNW, Rochester CH (1979)
London 9. DeÂkaÂny I, SzaÂnto F, Nagy LG (1978) J Chem Soc Faraday Trans 75:2865
4. Kurihara K (2001) In: Roso€ M (ed) Prog Colloid Polym Sci 65:125 14. Kurihara K, Mizukami M, Nakasone
Nano-surface chemistry. Dekker, New 10. DeÂkaÂny I, TuÂri L, TombaÂcz E, Fendler S, Miyahara T (2001) Trans MRS-J
York, pp 1±16 JH (1995) Langmuir 11:2285 26:(in press)
5. Mizukami M, Kurihara K (1999)
Chem Lett 1005
Progr Colloid Polym Sci (2001) 117: 18±26
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

E. TombaÂcz Effects of impurity and solid-phase

M. Szekeres
dissolution on surface charge titration
of aluminium oxide

Abstract Potentiometic and calori- solid phase and the simultaneous

metric acid±base titration of alu- equilibria of mononucleous alumin-
minium oxide C (Degussa) was ium-species formation have to be
performed. This pyrogenic alumina inserted into an appropriate model.
contains chlorine impurity (about Calorimetric data can be assigned to
1 ´ 10)4 mol/g). Its hydrolysis re- chemical reactions in the absence of
sults in inde®nite numbers of H+ impurities and dissolution and if the
and Cl) ions in aqueous suspension, initial state of titration is ®xed to the
which disturb the surface charge reference state of oxide suspensions.
titration. The chlorine impurity The partial molar enthalpy of the
could be removed by heat treatment surface protonation process de-
of alumina powder at 1000 °C. The creases in absolute value from )34
®tting of the titration data for heat- to )28 kJ/mol and that of deproto-
treated alumina in indi€erent elec- nation process increases from 33 to
trolyte (KNO3) solutions between 41 kJ/mol with increasing ionic
pH5 and pH9 is good enough strength. The standard enthalpy of
assuming only surface charging re- the surface protolysis reaction on
actions and any kind of surface alumina is 34.6 ‹ 0.6 kJ/mol.
complexation model. Outside these
material-speci®c limits the dissolu-
E. TombaÂcz (&) á M. Szekeres tion of the amphoteric solid plays Key words Oxides á Surface charg-
University of Szeged,
Department of Colloid Chemistry, the governing role, especially below ing á Surface complexation model á
6720 Szeged, Aradi Vt. 1. Hungary pH4.5. A partial dissolution of the Potentiometry á Calorimetry

Introduction Potentiometric acid±base titration, frequently called

surface charge titration of oxides, is the most often used
Aluminium oxides are of great practical importance and method; unfortunately, the interpretation of experimen-
are frequently used as adsorbents in aqueous electrolyte tal data has been extended beyond the limitation of this
solutions. The acid±base properties of amphoteric alu- method in some cases. All the information from poten-
minium oxides have been studied by many authors with tiometric titration on the composition of the interfacial
various techniques for many years. The popular theories layer is indirect and is considerably a€ected by the
for the surface chemistry of hydrous oxides based on the assumptions applied during the data evaluation, since
data mainly from acid±base titration and electrophoresis only the change in the activity of H+ ions in bulk
measurements appear to be inadequate when results solution is obtained directly from the experiments. The
from other types of investigations are considered [1]. e€ect of a trace amount of impurity and of additional
Titration calorimetry is a useful and adequate technique acid±base reactions, however, is often neglected and the
to measure the heat changes accompanying the processes whole H+/OH) consumption is taken for the surface
during acid±base titration. charge formation alone. In addition, the calculation of
 19

the surface charge density involves the speci®c surface The study of the dissolution kinetics of aluminium oxide
area of the solid, obtained usually from nitrogen [8] shows that the dissolution rate considerably depends
adsorption measurement, which may not be relevant to on the pH of the aqueous solution. In some work the
the available surface area in aqueous media; therefore, possibility of alumina dissolution is excluded with
the calculation of charge potential functions from reference to chemical equilibrium calculations [6] or it
titration data without verifying the reality of the source is not mentioned at all [9±11]. The ®tting of experimental
data is questionable. surface charging curves led to more and more compli-
It is well known that di€erent crystalline forms of cated theoretical approaches with increasing numbers of
aluminium oxides/hydroxides result from di€erent pro- layers for charge-compensating ions in the surface
cesses and di€erent raw materials. The products always complexation models (di€use double-layer model, tri-
contain more or less impurity. Pyrogenic alumina ple-layer model, TLM, and four-layer model [10, 11]) and
obtained from hydrolysis of aluminium chloride in a with the introduction of surface site heterogeneity
¯ame, such as the product of Degussa (type C), for parameters. The heterogeneity of the proton binding
example, contains chlorine impurity. Chlorine is bound sites at the oxide/solution interface has been studied
to the active surface sites and in¯uences their number and theoretically [12±14] and both theoretically and experi-
acid)base properties in a vacuum [2]. In aqueous mentally [6, 9±11, 15, 16].
suspension the hydrolysis of bound chlorine results in Interfacial acid±base reactions in aqueous oxide
acidic species. As a consequence, the pH of dense suspensions can be characterized by direct calorimetric
suspensions is much lower (e.g. pH 5±5.5) than the pH measurements. In the interpretation of the data, howev-
of the point of zero charge (PZC) [3] for pure alumina er, one meets the problem of distinguishing between the
suspensions. Heat treatment at high temperature is an di€erent contributions [17]. In simple cases, such as
e€ective tool to remove chlorine contamination [2]. The surface charging owing to the adsorption of potential-
usual cleaning procedure, i.e. exhaustive washing with determining ions, calorimetric experiments may be
pure water, however, is ine€ective in this particular case, designed in an appropriate way and the data may be
since chloride ions are involved in surface reactions and interpreted [17]. An additional problem is how to
can suppress the surface hydroxylation of alumina [4]. account for the incorporated electrostatic e€ect. The
Dissolution of aluminium oxide in both acidic and enthalpy of the surface charging reaction (DHr) can be
alkaline solutions and its dependence of the crystal separated into a ``chemical'' (i.e. the standard DHr0 ) and
structure is well known [5]. Below pH 4 and above an electrostatic (DHelec) contribution [18]:
pH10, the dissolution of this amphoteric solid becomes
perceptible; therefore, the interfacial charging is often DHr ˆ DHr0 ‡ DHelec : 1†
studied within these pHs [6, 7]. A schematic representa- The electrostatic contribution is given by a Gibbs±
tion of charge formation on the aluminium oxide surface, Helmholtz relationship [1]:
the dissolution of amphoteric solid and some of the
aqueous aluminium species formed is shown in Fig. 1. DHelec ˆ F DzT ow0 =oT †p ‡ F Dzw0 ; 2†
where F is the Faraday constant, Dz is the change in
charge of the surface owing to the adsorption reaction, T
is the temperature; (@w0/@T )p is the temperature coe-
cient of the surface potential (w0) at constant pressure
and FDzw0 is the electrostatic contribution to the Gibbs
energy (DGelec). The electrostatic enthalpy contribution
can be larger or smaller than the electrostatic free energy,
depending on the sign of the coecient (@w0/@T )p.
The surface protolysis enthalpy [1], i.e. the di€erence
between the standard enthalpies of protonation
SOH ‡ H‡ ! SOH‡
2;
0
DHpr 3†
and deprotonation
SOH ! SO ‡ H‡ ; 0
DHdepr 4†
of surface groups [18], can be determined from the
temperature dependence of the PZC of the amphoteric
Fig. 1 A schematic representation of interfacial acid±base processes oxides. The plot pHPZC versus 1/T is a linear function
taking place spontaneously in aqueous suspensions of aluminium and the standard enthalpy of the surface protolysis
oxide with changing pH of the equilibrium solution phase process,
20

SOH‡ ‡
DH 0 ˆ DHdepr
0 0 is less than 0.5%. The pH of the aqueous suspension is 5±5.5. Data
2 ! SO ‡ 2H ; DHpr ; 5†
were taken from the brochure of Degussa [30]. In order to eliminate
chlorine contamination, a powder sample was heated for 6 h at
calculated from the slope is 14.6 kJ/mol for TiO2 [17] and 1,000 °C. Only the freshly puri®ed alumina powder was measured
33.2 kJ/mol for hematite [19]. in the calorimetric experiments. Millipore water was used and all
It has been proved [17, 18] that the electrostatic the chemicals were analytical reagent grade products of Merck.
contribution to the enthalpy can be neglected in a
smartly designed, so-called ``symmetric'' experiment, Methods
0
where the di€erence in the standard enthalpies (DHch ˆ
0 0 Potentiometric titration
DHdepr DHpr ) can be obtained from direct calorimetric
measurements. The published values, 14.7 kJ/mol for
TiO2 [18] and 33.3 kJ/mol for hematite [19], agree well The pH-dependent surface charge state was determined from acid±
base titration under CO2-free conditions using di€erent back-
with that from the temperature dependence of pHPZC. ground electrolytes (KCl, KNO3) to maintain the constant ionic
Confusing experimental data and theoretical consid- strength over the region 0.005±0.5 M. Before titration, the solid
erations are presented in some cases. Some metal oxide± samples were equilibrated with the electrolyte solution for 1 h, with
aqueous solution systems have been investigated [1, 20± gentle stirring under a continuous stream of puri®ed, wet nitrogen.
Equilibrium titration was performed by means of a self-developed
22] by titration calorimetry; however, the di€erent titration system (GIMET1) with 665 Dosimat (Metrohm) burettes,
enthalpy values for the interfacial processes scatter nitrogen bubbling, a magnetic stirrer and a high-performance
widely. An essential feature is that the enthalpies of the potentiometer. The whole system (millivolt measurement, stirring,
surface charging processes should exhibit an ionic bubbling, amount and frequency of titrant) was controlled by an
IBM PS/1 computer using AUTOTITR software. A Radelkis OP-
strength dependence; however, there are published 0808P (Hungary) combination pH electrode was calibrated for
results [1, 20, 21] showing that the electrolyte concentra- three bu€er solutions to check the Nernstian response. The
tion practically has no in¯uence on the enthalpies hydrogen ion activity versus concentration relationship was
observed. Although it is unquestionable that the proton determined from reference solution titration so that the electrode
adsorption is an exothermic process and that the proton output could be converted directly to the hydrogen ion concentra-
tion instead of activity. The net proton surface excess amount (Dq,
desorption is endothermic, data are given [21] for surface moles per gram) has been de®ned as the di€erence of the H+ and
deprotonation due to the adsorption of hydroxyl ions )
OH surface-excess amounts (nrH‡ , nrOH ) related to the unit mass of
with an exothermic heat e€ect. The situation is even for solid (Dq ˆ nrH‡ nrOH ). The surface-excess amount de®ned for
the theoretical analysis of ion adsorption at oxide± adsorption [31] can be determined directly from the initial (c0i ,
moles per litre) and equilibrium (cei , moles per litre) concentration
electrolyte interfaces [23±25], since it is not determined of solute nri ˆ c0i cei †V/m, where V is the volume (litres) of the
whether exothermic or endothermic processes are in- liquid phase and m is the mass of adsorbent) for adsorption from
volved. dilute solution.
A thermodynamic analysis for the ionization process
on the surface of insoluble solids with ®xed dissociable Determination of dissolved aluminium species
groups has recently been published [26]. It is stated that
the partial molar enthalpy of surface group protonation, Several alumina suspensions with the same composition as that in
DHp, is physically well de®ned and accessible via the acid±base titration were prepared between pH3 and pH10.
Samples from the equilibrium liquid phase at each pH were taken
calorimetry. after standing for 1 day by means of centrifugation at 13,000 rpm
Di€erent aluminium oxides have been investigated in for 2 h. The aluminium content of the supernatant liquids was
our laboratory [27±29] by potentiometric acid±base measured by the inductively coupled plasma (ICP) method. A
titration using a variety of electrolytes containing K+, Jobin Yvon 24 sequential ICP±atomic emission spectrometer was
Na+, NO3 or Cl) ions. The purpose of this study is to used under the following conditions: the frequency of the radio-
frequency generator was 40.68 MHz; the power of the radio-
show some results from potentiometric and calorimetric frequency generator was 0.8 kW; the ¯ow rates of the plasma, the
acid±base titration of a pyrogenic sample (aluminium aerosol carrier and the sheath gas (argon) were 12, 0.37 and 0.2 l/
oxide C, Degussa) with special attention to the e€ect of min, respectively; the ¯ow rate of nebulization (Babington) was 1.4
impurities and dissolution of alumina on the data ml/min; the wavelength (Al) was 237.324 nm.
evaluation.
Titration calorimetry

An isothermal microcalorimeter (Thermometric thermal activity

Experimental monitor TAM 2277) was used at 25 °C. Alumina powder (1 g) was
dispersed in 10 ml electrolyte solution (0.01, 0.1 and 1 M KNO3)
Materials and purged with argon to eliminate dissolved CO2 impurity. The
suspensions were titrated separately with the portions of standard
Aluminium oxide C (highly dispersed commercial products of acid or base solutions under a CO2-free argon atmosphere. In
Degussa) was investigated. This ®ne powder is produced by ¯ame parallel, blank titrations were performed in the absence of the
hydrolysis of AlCl3 and is characterized by a nonporous d-Al2O3 alumina at the same concentrations of indi€erent electrolyte
structure, a high speci®c surface area (100 ‹ 15 m2/g) and a small KNO3. The heat ¯ow across the titration cell of the TAM was
particle size (13 nm). The density is 3.2 g/cm3 and the HCl content continuously recorded. The accuracy of the measured reaction
 21

heats was tested by measuring the standard heat of reaction almost independent (pH between 8.2 and 8.4) of the ionic
between tris(hydroxymethyl)aminomethane [(HO)CH2)3)C)NH2] strength, while in the suspensions of the original sample,
and HCl (DH=)55 ‹ 1 kJ/mol).
The measured heat (Qmeas) is the overall heat ¯ow of the it signi®cantly increases from pH 6.1 to 7.5 with
simultaneous chemical reactions and the mixing processes in the increasing KCl concentration. Bonded chlorine atoms
calorimeter cell: hydrolyse in aqueous media releasing acidic species into
X the bulk liquid phase and so the pH of the suspension is
Qmeas ˆ Qri ‡ Qmix ˆ DHri Dni ‡ Qmix ; 6†
i acidic. The pH of the unpuri®ed alumina suspensions has
to increase with the KCl addition, since the increasing
where DHri is the enthalpy change of reaction i, Dni is the change of
the extent of reaction i and Qmix is the mixing heat of the titrant concentration of chloride ions in the equilibrium liquid
portion. Reactions with added acid (DHa), reactions with added phase hinders the propagation of AlCl3 hydrolysis.
base (DHb) and the water formation (neutralization) reaction (DHn)
can be distinguished. The heat of mixing was determined in blank AlCl3 ‡ 3H2 O ! Al(OH)3 ‡ 3H‡ ‡ 3Cl 7†
experiments. Uncontrolled acid±base reactions with signi®cant heat
e€ects were eliminated. The common intersection point (CIP) [32] of curves
measured at di€erent ionic strengths, assigned as the
point of zero salt e€ect (PZSE) by Sposito [33, 34] shifts
Results and discussion up after removal of AlCl3 contamination, showing the
absence of base-consuming hydrolysis product (H+).
Potentiometric titration The pH of the PZSE for the original sample is about 9.2
and it slightly shifts down (pHPZSE8.6) for the puri®ed
The aluminium oxide C (d-Al2O3) contains chlorine sample. It has to be stated that a simple additive
contamination originating from the production proce- correction of base-consuming impurities cannot be the
dure (¯ame hydrolysis of AlCl3). The experimental net correct way of experimental data evaluation.
proton consumption versus pH functions of the original Since the position of pHPZSE for the heat-treated
and puri®ed alumina samples are obviously di€erent as alumina sample dispersed in KCl solution (Fig. 2) is
shown in Fig. 2. The most conspicuous feature is that the indicative of a weak speci®c anion adsorption [35], it was
pH of the suspensions from heat-treated alumina is also titrated in an indi€erent electrolyte (KNO3). The pH
dependence of the net proton consumption for d-Al2O3
heat treated at 1000 °C, dispersed in KNO3 solutions at
room temperature, is demonstrated in Fig. 3. The data
calculated can be identi®ed with the net proton
surface excess amount (Dq ˆ nrH‡ nrOH ), which would
be proportional
to the surface charge density
[r0 ˆ F nrH‡ nrOH =aS where aS is the speci®c surface
area] of aluminium oxide, since this solid can develop
charges only conditionally [17, 27, 36, 37] and electrolyte
KNO3 is indi€erent [27].
The forward and backward curves in Fig. 3 are
reversible within the experimental error of this method
down to pH5. Below pH 4.5, however, the backward
curves show a sharp increase in proton consumption with
decreasing pH and gradually become independent of
ionic strength. A similar feature of the curves was
explained [15] as the protonation of the most acidic triply
coordinated groups of type III on the alumina surface
neglecting the dissolution of the solid phase, although
beyond the roughly de®ned limits of the pH values the
dissolution of amphoteric aluminium oxides becomes
perceptible [38, 39].

Fig. 2 Experimental net proton consumption curves for original and Evaluation of titration results
puri®ed (treated at 1,000 °C) d-Al2O3, dispersed in KCl solutions at
room temperature. The points were calculated from the data of a
forward equilibrium titration with 0.1 M KOH solution. The initial
The evaluation of the experimental data from acid±base
suspension were prepared with (puri®ed samples) and without titration of amphoteric solid material demands cautious
(original samples) adding a given amount of 0.1 M HCl solution work. Other acid- or base-consuming reactions (e.g.
22

The measured data of the forward titration in

indi€erent electrolyte (KNO3) solutions might be well
®tted by choosing any surface complexation model. In
the presence of KCl electrolyte only the choice of the
TLM option led to an acceptable level of the optimiza-
tion process by FITEQL [45], presumably because of
speci®c adsorption of Cl± ions. The calculated intrinsic
equilibrium constants for charge- and ion-pair-forma-
tion reactions occurring on the surface hydroxyl groups
of alumina in di€erent electrolyte solutions are summa-
rized in Table 1. The pK values obtained in our previous
work [27] and this study lie within the values for di€erent
Al2O3 reported in the literature [7, 9, 16, 37]. The data in
Table 1 clearly show that there is more than 1 order of
magnitude di€erence between the logK values of the
protonation and deprotonation reactions on surface site
(SOH) depending on the evaluation methods.
The ®tting of the backward titration data was
impossible when only the surface charge formation
processes were postulated as H+/OH) consuming reac-
tions in alumina suspensions; therefore we assumed a
partial dissolution of alumina particles during the long
period of equilibrium titration. A component identi®ed
as a solid compound Al(OH)3(s) and its solubility
product [Al(OH)3(s)=Al3++3OH)] as well as the
formation of di€erent mononuclear aluminium species
were inserted in the stoichiometry matrix of FITEQL
[45]. The following reactions and logK values [45] were
assumed:
Fig. 3 Experimental net proton consumption curves for puri®ed
d-Al2O3 (treated at 1,000 °C for 6 h) dispersed in KNO3 solutions at
room temperature. The points were calculated from the data of a logK
forward (open symbols) and a backward (closed symbols) equilibrium
titration with 0.1 M KOH and 0.1 M HNO3 solutions, respectively
3+
Al + * Al(OH)
H2 O ) 2+
+ H+
)4.99
Al3+ + 2H2O )* Al(OH)2 + 2H+ )9.30
Al3+ + 3H2O )* Al(OH)3 + 3H+ )15.00
dissolution of solid at lower or higher pHs) can take Al3+ + 4H2O )* Al(OH)4 + 4H+ )23.00
place in parallel with the surface charging processes,
which cannot be separated experimentally. Problems in
modelling the surface charging of oxides have been We assumed that the surface charging is reversible,
discussed in several articles [17, 40, 41]. The pH- and i.e. the processes are the same in both directions of
ionic-strength-dependent surface charge formation pro- titration. The CCM parameters (total concentration of
cess can be described by various model approximations, SOH site, capacitance of oxide±electrolyte interface)
the most widely accepted models are the site-binding calculated from the data of the forward titration were
electrostatic models [7, 9±11, 27, 42, 43]. The surface ®xed in the course of the data ®tting for the backward
charge development can be a€ected by the solubility of titration. The single ®tting parameter was the total
the solid [44], which is not incorporated in the models. amount of dissolved Al(OH)3(s). The measured points
The experimental data shown in Fig. 3 were evaluated of the backward titration of puri®ed alumina dispersed
using a numerical data-®tting program [45]. In the in KNO3 solutions and the calculated curves are
optimization procedure of FITEQL the experimental compared in Fig. 4. The calculated curves (thick lines
data and the corresponding theoretical values calculated in Fig. 4) assuming both surface charging and dissolu-
from a multicomponent chemical equilibrium model tion of alumina coincide well with the measured data.
incorporating interfacial charging equilibria are com- The calculated curves (thin lines in Fig. 4) related only
pared. The parameters of the model are adjusted to to the H+/OH) consumption of interfacial protonation/
minimize the di€erence between the measured and deprotonation reactions resulting in surface charging
calculated data. The choice of di€erent surface complex- are also plotted. It can be seen that the net proton
ation [constant-capacitance model (CCM), di€use-layer consumption from the dissolution of amphoteric solid
model (DLM), Stern and TLM] models is optional. becomes signi®cant where the calculated curves start to
 23

Table 1 Intrinsic equilibrium

constants for charge- and ion- Electrolyte, KNO3 Average
pair-formation reactions occur- 0.005 M 0.05 M 0.5 M
ring on the surface hydroxyl
groups of aluminium oxide C Graphic extrapolation [27]
‡
(Degussa) in electrolyte solu- LogKint
al SOH2 † 5.8 ‹ 0.2
tions LogKint
a2 SO † )10.2 ‹ 0.2
Point of zero charge 8.0 ‹ 0.1
FITEQL [45] optimization Constant-capacitance model
‡
LogKint
a1 SOH2 ) 6.56 7.04 7.61 7.07 ‹ 0.51
int )
LogKa2 (SO ) )9.39 )9.13 )8.79 )9.10 ‹ 0.31
Point of zero charge 7.97 8.09 8.20 8.09 ‹ 0.12
Di€use-layer model
‡
LogKint
a1 (SOH2 ) 6.95 7.47 7.63 7.35 ‹ 0.30
int )
LogKa2 (SO ) )9.00 )8.71 )8.77 )8.82 ‹ 0.18
Point of zero charge 7.98 8.09 8.20 8.09 ‹ 0.11
Triple-layer model
LogKint
a1 (SOH‡2 ) ®xed 6.8
LogKint
a2 (SO)) ®xed )9.2
LogKint
aA SOH‡2A † 8.77 8.35 8.26 8.46 ‹ 0.31
LogKint
ak (SO)K+) )7.15 )7.85 )8.15 )7.72 ‹ 0.57
Electrolyte, KCl, triple-layer model
‡
LogKint
aA (SOH2 A ) 8.95 8.49 8.06 8.50 ‹ 0.45
) +
LogKint
aK (SO K ) )7.35 )8.25 )8.81 )8.13 ‹ 0.78

diverge from each other, i.e. below pH5 and above

pH9.5. On the basis of the experimental curves
showing a sharp increase in the net proton consumption
values at pH 4 (Fig. 3), the assumption of alumina
dissolution at low pHs seems to be evident.
It is a remarkable result of our model calculation that
there is a probable interference of dissolution under
alkaline conditions during surface charge titration above
pH9.5, where alkaline dissolution of alumina starts to
contribute to the measured OH) consumption. The
calculated curves also coincide well with the measured
points above pH9.5, if the dissolution of alumina is
inserted into the chemical model of the data-®tting
procedure.
To verify the assumption of alumina dissolution, we
measured the total aluminium concentration in equilib-
rium supernatants separated from alumina suspensions
with di€erent pHs between pH 4 and pH10 by means
of the ICP method. The measured values together with
the calculated distribution of the dissolved aluminium
species from the FITEQL output ®les and their total
amounts are plotted as a function of pH in Fig. 5. The
measured values coincide very well, especially in the
alkaline region, with the calculated total amount of Fig. 4 Experimental points of net proton consumption from back-
dissolved aluiminum species. ward titration with 0.1 M HNO3 for puri®ed d-Al2O3 (treated at
1000 °C for 6 h) dispersed in KNO3 solutions at room temperature.
The continuous thick lines are numerically ®tted (FITEQL) using a
Calorimetric titration combined surface complexation and chemical dissolution model: the
constant capacitance model (C ˆ 1.2F/m2) for surface charging,
partial dissolution of solid alumina and formation of mononuclear
The measurements were performed under delicate exper- aluminium species with logK values from the literature [45]. The
imental conditions. Freshly puri®ed aluminium oxide continuous thin lines show that part of the net proton consumption
samples were measured in the presence of only indi€erent which belongs to the surface charge formation
24

The reaction in Eq. (7) is the surface protonation

process, while the OH) association reaction in Eq. (8)
di€ers from the surface deprotonation reaction
SOH ! SAO ‡ H‡ 9†
since Eq. (8) involves water formation
H‡ ‡ OH ! H2 O; DH 0 ˆ 56:5 kJ=mol 10†
Therefore, if we wish to identify the reaction heat of
the negative charge formation on the oxide surface, i.e. of
the surface deprotonation reaction (Eq. 9), the reaction
heat of the formation of a given amount of water in each
step must be subtracted from the measured heat e€ects of
titration with base solution (the OH) association reac-
tion, Eq. 8).
The cumulative heats of the surface protonation and
deprotonation reactions during titration, measured di-
rectly or calculated with the correction for water forma-
tion, are plotted against the calculated amount of the
surface charges formed in the reactions in Eqs. (7) and (9).
This presentation of experimental data shows a satisfac-
tory linear relationship for both the acidic and alkaline
sides of the titration. This linearity means that the molar
Fig. 5 Comparison between the calculated distribution of dissolved enthalpy changes of the surface charging processes
aluminium species from FITEQL output ®les (same as shown in
Fig. 4) and the experimental values measured by means of the (DHdepr and DHpr) are independent of the surface charge
inductively coupled plasma method density within experimental accuracy. Therefore, the
slope of the cumulative heat of surface charging versus
electrolyte and within a region of pH where the extent of the charged sites' amount functions would be identi®ed
alumina dissolution is negligible. The measured data with the partial molar enthalpies of the surface protona-
were corrected by mixing and neutralization heats. The tion and deprotonation reactions (DHpr and DHdepr). The
ionic strength dependence of the surface charging calculated values are given in Table 2.
processes was evaluated. While the partial molar enthalpy data for the
The extent of the surface protonation and deproto- surface protonation and deprotonation reactions (sec-
nation reactions due to the amount of reactant added ond and third columns of Table 2) show a systematic
was calculated in each step of the titration. The titration change with increasing concentration of indi€erent
with acid and base solutions was simulated. The material electrolyte, the di€erence between them results in a
balance for the conditions in the calorimetric titration molar enthalpy which is practically independent of
was calculated by MINTEQA2 [46] assuming the ionic strength. Applying the basic thermochemistry
following H+ and OH) association reactions rule, subtracting one reaction (Eq. 7) from another
(Eq. 9), we get
SAOH ‡ H‡ ! SAOH‡
2; log K1int ˆ 6:8 ; 7† SOH‡ ‡
2 ! SO ‡ 2H ; DHdepr DHpr 11†
SAOH ‡ OH ! SAO ‡ H2 O; log K2int ˆ 9:2 8† or written for one proton
1=2‡
and using the CCM. SOH2 ! SOH1=2 ‡ H‡ ; DHdepr DHpr †=2 12†

Table 2 Partial molar enthalpy

values of surface charging pro- Partial molar enthalpies of surface charging process (kJ/mol)
cess in indi€erent electrolyte 1=2‡
solutions for aluminium oxide Surface SOH ‡ H‡ ! SOH‡
2 SOH ! SO ‡ H‡ SOH2 ! SOH1=2 ‡ H‡
at 25 °C reaction Exothermic Endothermic Endothermic

cKNO3 ,(M) DHpr DHdepr (DHdepr)DHpr)/2

0.01 )34.16 33.61 33.88
0.1 )31.11 39.19 35.15
1 )28.28 41.34 34.81
Average 34.6 ‹ 0.6
 25

and the enthalpy change of the resulting reaction can be example, an acidic impurity shifts the CIP to the negative
calculated. region of the surface charge density. In the presence of
It can be stated that the calculated, ionic-strength- additional acid±base consuming reactions the calculation
independent enthalpy value of 34.6 ‹ 0.6 kJ/mol is the of charge potential functions is meaningless. The good-
same standard reaction enthalpy for surface charging of ness of the ®t between the experimental points and the
1=2‡
alumina (SOH2 ! SOH1=2 ‡ H‡ ) in a thermody- calculated curves does not prove the reality of the
namic sense as that given for titania (14.6 kJ/mol) and theoretical model, the assumed structure of the surface
hematite (33.2 kJ/mol) from the temperature dependence layer and the presumed interfacial reactions. The as-
of the PZC and from calorimetric measurements per- sumed chemical model has to be supported by indepen-
formed under a ``symmetric'' condition [18, 19]. These dent measurements (e.g. spectroscopy, analysis of the
results can be hardly compared with the uncertain data bulk phase) to prove its reality.
published for alumina in the literature [20] apart from the On the basis of the calorimetric titration of alumina, it
sign and the magnitude of the proton adsorption enthal- can be stated that the reference state of aqueous oxide
pies. The proton adsorption enthalpy value of )42 kJ/mol suspensions, the PZC, is a correct initial state of the
is comparable with our data between )34 and )28 kJ/mol calorimetric titration, where the electrostatic contribu-
given in the second column of Table 2, which, in general, tion can be neglected. The partial molar enthalpies of the
are between )20 and )50 kJ/mol for metal oxides [20]. surface ionization processes (SAOH ‡ H‡ ! SAOH‡ 2;
It has to be emphasized that the evaluation of the DHpr and SAOH ! SAO ‡ H‡ ; DHdepr ) and the stan-
titration calorimetric measurements results in valuable dard reaction enthalpy for surface charging
1=2‡
thermodynamic quantities only if the experiments are (SOH2 ! SOH1=2 ‡ H‡ ; DHch 0
) can be determined.
performed carefully, with controlled systems without any Calorimetric titration at any single concentration of
side reactions from impurities and dissolution, since only indi€erent electrolyte is sucient to determine the
0
these can give us a chance to assign the measured heats to standard reaction enthalpy (DHch ). The de®nite ionic
the corresponding reactions. strength dependence of the partial molar enthalpy
changes of the surface charging processes (DHdepr,I and
DHpr,I) was determined; it is a small, uniform endother-
Conclusions mic e€ect of increasing salt concentration for both sides
of surface charging.
The results of the potentiometric acid±base titration of
aluminium oxide suspensions allow us to conclude that Acknowledgements Calorimetric measurements were performed at
the e€ect of a trace amount of impurity and dissolution the Department of Applied Physical Chemistry, Research Center
JuÈlich, Germany. Dissolved aluminium was determined by ICP at the
of solid cannot be separated experimentally and the net Department of Inorganic and Analytical Chemistry, University of
H+/OH) consumption is considerably a€ected in their Szeged. The authors are grateful for the measurements. This work
presence. The position of the CIP may refer to them, for was supported by grants OTKA T034755 and FKFP 0587/1999.

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Progr Colloid Polym Sci (2001) 117: 27±31
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

G. HoraÂnyi Radiotracer study of the speci®c adsorption

P. JooÂ
of anions on oxides

35
Abstract The possibility of the ex- S-labeled sulfate ions as indicator
tension of the radiotracer technique species.
G. HoraÂnyi (&) to the study of speci®c adsorption of
Institute of Chemistry, anions on oxides is discussed. It is
Chemical Research Center,
Hungarian Academy of Sciences, shown that the indirect version of
P.O. Box 17, 1525 Budapest, Hungary the so-called ``thin foil'' method
e-mail: [email protected] could be a useful tool for the clari-
Tel.: +36-1-2670820
Fax: +36-1-2663899 ®cation of adsorption behavior of
certain species. The main tendencies
P. Joo characterizing the adsorption of Key words Speci®c adsorption á
Department of Colloid Chemistry,
University of Debrecen, P.O. Box 31, phosphate species on hematite and Anions á Hematite á c-Al2O3 á
4010 Debrecen, Hungary c-Al2O3 are demonstrated using Radiotracer technique

Introduction concerning the adsorption phenomena occurring at

oxide surfaces.
The in situ study of the speci®c adsorption on electrodes As to the role of the labeled species in the radiotracer
using the radiotracer technique is a well-known method study of adsorption phenomena, two di€erent versions of
in electrochemistry that furnished in the second half of the method may be distinguished. The ®rst one, reported
the past century important information on the state of in our previous communications [11±14], is the direct
the double layer formed at the metal/solution interface. method. In this case the species to be studied is labeled
Several review articles published during the last two and the radiation measured gives direct information on
decades have given a survey on both the technical the adsorption of this species. However, this method
achievements and the phenomena studied in this ®eld cannot be used in several cases owing to the technical
[1±10]. On the other hand, although the radiotracer restrictions connected with the very nature of the
technique found its application in colloid chemistry the radiotracer method (limitations in the available concen-
methods used are far from being able to follow in situ the tration range; there is no possibility of distinguishing
adsorption phenomena and to study the e€ect of various between the adsorption of the labeled compound studied
parameters on the adsorption without disturbing the and that of a product formed from it; the number of
original experimental conditions. commercial easily available labeled compounds is re-
In our previous communications [11±14] it was stricted).
demonstrated that some of the radiotracer methods Considering all these problems the use of the so-called
elaborated for the investigation of electrosorption phe- indirect radiotracer methods was suggested. Instead of
nomena occurring at electrodes can be used for the study labeling the species to be studied another adequately
of adsorption phenomena at oxide surfaces. chosen labeled species (indicator species) is added to the
In the present article an attempt is made to show system and the adsorption of this component is followed
that a version of the so-called ``thin foil'' method, the by the usual radiotracer measuring technique. Evidently,
indirect method, could furnish important information the sorption of the indicator species should be in relation
28

to that of the species to be studied. The nature of this link A commercial hematite powder (Reanal, analytical grade)
could be di€erent in di€erent systems. For instance, in characterized by its X-ray di€raction pattern was used (ATOMKI/
Siemens horizontal h±2h X-ray di€ractometer with Cu Ka
some cases the competitive adsorption with the labeled radiation).
species, while in other cases induced adsorption of the The speci®c surface area of the oxide powder, 0.15 ‹ 0.05 m2/g,
labeled species may furnish information about the was estimated from the particle size distribution according to the
adsorption behavior of a given molecule. The principle microscopic method based on the measurements with a BuÈrker
chamber.
of the study in the former case can be demonstrated by In the case of thin oxide layers, the radiation intensity
Scheme 1. measured should be proportional to the amount of the powder
sprinkled on the bottom of the measuring cell. With increasing
thickness the radiation intensity tends to a limiting value as a
consequence of the self-adsorption of the soft b radiation of 35S
in the layer. In the case of powders with relatively low speci®c
surface area (as in the present case of hematite) it is preferable
to carry out the experiments at this limiting value in order to
attain the highest count rates in the system. In contrast to this,
thin layers were considered in the case of Al2O3 (high speci®c
surface area).
The time required for reliable equilibrium measurements varied
between 20 and 100 min, depending on the concentrations and on
the amount of the powder used. The attainment of the equilibrium
In the following, the results obtained from the indirect was controlled by the observation of the response of the system
study of PO43) adsorption on hematite and Al2O3 are following its stirring. As a result of stirring, the oxide particles with
adsorbed labeled species are lifted up from the bottom of the cell
reported. As the adsorption of labeled sulfate ions at and the count rate decreases: the detector does not ``see'' these
hematite and Al2O3 was studied in detail in our previous particles. Following the deposition of the powdered adsorbent the
communications [13, 14] and a reversible adsorption was count rate increases and in the case of equilibrium attains its
found 35S-labeled sulfate ions could be used as an ideal original value.
indicator species.
On the other hand, preliminary results with phosphate
species allow us to assume that the adsorption of these
ions is also reversible; thus, the validity of the principle of Results and discussion
the indirect study characterized by Scheme 1 can be
considered as a basis for the evaluation of the experi- The fundamental relationships for the evaluation
mental results. of experimental data

Denoting by A the phosphate species and by B the

indicator sulfate species and by taking into account that
Experimental according to the results reported in Refs. [13, 14] the
adsorption of sulfate ions can be described by a
The experimental technique and setup for the radiotracer study of Langmuir isotherm in the case of both adsorbents
sorption processes (involving powdered sorbents) are described and
surveyed in Refs. [11±14]. studied the following equations can be used:
The principle of the method used in the present study is the b A cA
measurement of radiation intensity originating from adsorbed hA ˆ ; 1†
species on a powdered oxide layer sprinkled on a thin plastic foil 1 ‡ bA cA ‡ bB cB
that serves simultaneously as the window for the radiation
measurement. The measurements were carried out at ambient b B cB
temperature in an Ar atmosphere, bubbling Ar in the solution hB ˆ : 2†
phase and letting it through the gap between the bottom of the
1 ‡ bA cA ‡ bB cB
measuring cell and the detector. Labeled H2SO4 was used Transformation of Eq. (2) leads to the expression
(Amershem, speci®c activity: 200 MBqmmol)1) for the preparation
of the solutions. 1 1 bA c A
The concentration of the labeled species was several orders ˆ1‡ ‡ : 3†
hB bB cB bB cB
of magnitude lower than that of the supporting electrolyte
(0.5 moldm)3 NaClO4) in order to get information concerning At a ®xed concentration of the indicator species (B)
the speci®c interaction of the former species with the oxide surface. and taking into account that hB is proportional to the
Thus, the nonspeci®c electrostatic forces and the formation of a
double layer could not play a signi®cant role in the sorption process radiation intensity measured (I)
of the sulfate species. hB ˆ qI ; 4†
A commercial neutral Al2O3 powder was used (Merck, Art
1077, particle size: 0.063±0.200 mm). The speci®c surface area of where q is a proportionality factor, we obtain
the oxide powder, determined by the N2±Brunauer±Emmett±Teller
method, was 156 ‹ 9 m2/g, while by the methylene blue adsorp-
1
ˆ D ‡ FcA : 5†
tion method 17 ‹ 3 m2/g was obtained. I
 29

From Eqs. (1) and (2) labeled species present in very low concentrations in the
hA bA cA solution phase (in comparison with that of the support-
ˆ
6† ing electrolyte).
hB bB cB Our approach was based on the classical double layer
theory in accordance with the well-known de®nition:
and ``speci®c adsorption of ions is their adsorption by non-
electrostatic forces''. It was clearly demonstrated that
hA ˆ F 0 IcA : 7†
owing to the presence of the great excess of supporting
electrolyte the measurable adsorption values found with
The problem of speci®c adsorption.
respect to the labeled species cannot be ascribed to
It was emphasized in our previous communications
electrostatic forces.
[13, 14] that one of the main and characteristic advan-
In the case of the indirect measuring technique the
tages of the radiotracer technique is that this method,
same statement refers to the nonlabeled species to be
using a great excess of supporting electrolyte, furnishes
studied if its concentration remains 1±2 orders of
direct information on the speci®c adsorption of the
magnitude lower that that of the supporting electrolyte.

Fig. 1 The e€ect of H3PO4 concentration on the radiation intensity

measured in the case of c-Al2O3 (1 mg/cm2 referred to the geometric
surface area) in the presence of 0.5 moldm)3 NaClO4, pH 2.5. The Fig. 3 The experimental data in Fig. 1 expressed as count-rate versus
concentration of labeled H2SO4 was 2 ´ 10)4 moldm)3 logc

Fig. 2 The e€ect of H3PO4 concentration on the radiation intensity Fig. 4 The experimental data presented in Fig. 1 in a representation
measured in the case of hematite (20 mg/cm2). Other data as in Fig. 1 corresponding to Eq. (5)
30

Fig. 5 The experimental data presented in Fig. 2 in a representation

corresponding to Eq. (5) Fig. 7 The adsorption isotherm at phosphate species on hematite
calculated by Eq. (7) (coverage in arbitrary units)

With respect to Eq. (5), by plotting the 1/I values

against the concentration of phosphate species linear
relationships are obtained as shown by Figs. 4 and 5 (the
regressions are 0.9995 and 0.998, respectively). The
existence of this linear relationship con®rms the initial
assumption of the applicability of the Langmuir isotherm
for the speci®c adsorption of both anions.
The shape of the adsorption isotherm of the phos-
phate species can be obtained for both adsorbents using
Eq. (7). The results are shown in Figs. 6 and 7. Only the
shape of the curves in terms of arbitrary coverage values
can be given at the present stage of the studies;
nevertheless, the results obtained clearly demonstrate
that the main tendencies of phosphate adsorption can be
followed easily by the indirect radiotracer technique.
Fig. 6 The adsorption isotherm at phosphate species on Al2O3 Further results of the quantitative analysis of the results
calculated by Eq. (7) (coverage in arbitrary units)
will be the subject of a further study.

On the basis of the approach outlined earlier

0.5 moldm)3 NaClO4 supporting electrolyte was used
to shift the pH of the solution to pH 2.5 by addition of Conclusions
HClO4. The concentration of the indicator species,
labeled H2SO4, was 2 ´ 10)4 moldm)3. pH 2.5 was The results obtained con®rm that the indirect version of
chosen in order to attain the limiting value of the the thin foil method can be applied for the in situ study of
sulfate adsorption determined by the complete proto- adsorption of anions (and presumably of other species as
nation of the surface in both cases (Fe2O3 and Al2O3) well) on oxide surfaces.
[13, 14]. Labeled sulfate can be used as indicator species for
The direct e€ect of the addition of phosphate on the Al2O3 and Fe2O3. The results obtained with H3PO4 show
radiation intensity measured in the case of c-Al2O3 and that the adsorbabilities of sulfate and phosphate ions are
hematite is shown in Figs. 1 and 2, respectively. In the of the same order of magnitude as in commensurable
case of hematite (Fig. 2) it may be seen that the addition concentrations the adsorption competition between the
of H3PO4 to the solution phase in very low concentra- two species is remarkable.
tions, c < 1 ´ 10)4 moldm)3, does not exert in¯uence on
Acknowledgements Financial support from the Hungarian Scien-
the sulfate adsorption. This phenomenon can be well ti®c Research Fund and the Ministry of Environmental Protection
demonstrated for Al2O3 as well by plotting the radiation is acknowledged (OTKA grants T 023056, T 031703, OKTKP
intensity values against logc (Fig. 3). grant 021856-01/2000).
 31

References Modern aspects of electrochemistry, vol 12. The Royal Society of Chemis-
vol 21. Plenum, New York, pp 65±119 try, Cambridge, pp 254±301
5. Zelenay P, Wieckowski A (1991) In: 10. HoraÂnyi G (1999) In:Wieckowski A
1. Balashova NA, Kazarinov VN (1969) Abruna HD (ed) Electrochemical in- (ed) Interfacial electrochemistry, Theo-
In: Bard AJ (ed) Electroanalytical terfaces: modern techniques for in situ ry, experiment, and applications.
chemistry, vol 3. Dekker, New York, surface characterization, VCH, New Dekker, New York, pp 477±491
pp 135±197 York, pp 479±527 11. Joo P, HoraÂnyi G (2000) J Colloid
2. HoraÂnyi G (1980) Electrochim Acta 6. Krauskopf EK (1992) In: Lipkowski J, Interface Sci 223:308
25:45 Ross PN (eds) Adsorption of molecules 12. HoraÂnyi G, Joo P (2000) Russ
3. Kazarinov VE, Andreev VN (1984) In: at metal electrodes. VCH, New York, J Electrochem 36:1189
Yeager E, Bockris JO'M, Conway BE pp 119±169 13. HoraÂnyi G, Joo P (2000) J Colloid
(eds) Comprehensive treatise on elec- 7. HoraÂnyi G (1989) B Electrochem 5:235 Interface Sci 227:206
trochemistry, vol 9. Plenum, New 8. HoraÂnyi G (1995) Rev Anal Chem 14:1 14. HoraÂnyi G, Joo P (2000) J Colloid
York, pp 393±443 9. HoraÂnyi G (1996) In: Spivey JJ (ed) Interface Sci 231:373
4. Wieckowski A (1990) In: Bockris Catalysis. Specialist periodical report,
JO'M, Conway BE, White RE (eds)
Progr Colloid Polym Sci (2001) 117: 32±36
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

D. KovacÏevic Interfacial equilibria at a goethite aqueous

A. CÏop
A. Bradetic interface in the presence of amino acids
N. Kallay
A. Pohlmeier
H.-D. Narres
H. Lewandowski

Abstract Adsorption of o-, m- and acids, suggesting adsorption of nega-

p-aminobenzoic acid on goethite was tively charged species ()1). This con-
investigated by means of adsorption clusion was con®rmed by calculations
and electrokinetic measurements and based on the SCM. The equilibrium
D. KovacÏevic á A. CÏop á A. Bradetic was interpreted on the basis of the constant for exchange of Cl) ions
N. Kallay (&) surface complexation model (SCM). with amino acid ions ()1) were de-
Laboratory of Physical Chemistry, All three acids examined showed termined as logKA/L ˆ 2.62 ‹ 0.13
Faculty of Science, University of Zagreb,
MarulicÂev trg 19, P.O. Box 163, similar behavior, with adsorption for o-aminobenzoic acid, logKA/L ˆ
10001 Zagreb, Croatia maximum at pH 4.5, while the 2.37 ‹ 0.11 for m-aminobenzoic
e-mail: [email protected] adsorption anity decreased in the acid and logKA/L ˆ 2.85 ‹ 0.14 for
Tel.: +385-1-4895502 order p-, o-, m-aminobenzoic acid. p-aminobenzoic acid.
Fax: +385-1-4829958
Electrokinetic measurements indi-
A. Pohlmeier á H.-D. Narres cated that isoelectric points of goeth-
H. Lewandowski ite with adsorbed amino acids were Key words Adsorption á Electroki-
Institute for Applied Physical Chemistry,
Research Centre JuÈlich, 52425 JuÈlich, shifted to lower pH values with re- netics á Goethite á Aminobenzoic
Germany spect to goethite in absence of amino acid

Introduction species, as well as zwitterionic species, in the bulk of

the solution should be taken into account. Better
In the last decades, with the development of ecological understanding of adsorption of amino acids would be
conscience, the importance of understanding processes in one of the crucial steps towards the solution of a more
natural systems is permanently growing. The binding of complex problem, which is the adsorption of proteins.
di€erent pollutants on soil particles is, in laboratory
conditions, examined through model systems, for exam-
ple, speci®c adsorption of heavy metals, organic acids or
amino acids on metal oxides. The simultaneous inter- Theory
pretation of adsorption and electrokinetic data at the
metal oxide aqueous interface, based on the surface The interpretation of surface equilibria based on the
complexation model (SCM) [1], was introduced. This SCM [1] takes into account interaction of ions from the
approach was successfully applied to lead ions/goethite bulk of the solution with active surface groups. The
[2], cadmium ions/goethite [3], salicylic acid/hematite [4, classical 2-pK model [7] assumes protonation (p) and
5] and salicylic acid/titania [6] systems. In the study deprotonation (d) of amphoteric MOH groups, resulting
presented the adsorption of a more complex system, i.e. in positive and negative surface groups
adsorption of amino acids (o-, m- and p-aminobenzoic) MOH ‡ H‡ ! MOH‡
2
on metal oxide (goethite), is examined. In the interpre-

C MOH‡
tation, the e€ect of amino acid dissociation, i.e. the Kp ˆ exp /0 F =RT † 2
; 1†
presence of negatively and positively charged ionic a H‡ †C MOH†
 33

MOH ! MO ‡ H‡ rs ˆ rd ˆ r0 ‡ rb ˆ F ‰C MOH‡
2† C MO †Š: 8†
‡
a H †C MO † The potential drop between the 0 and the b planes
Kd ˆ exp /0 F =RT † ; 2†
C MOH† depends on the constant capacitance (C1) of the Helm-
holtz layer,
where Kp and Kd are the corresponding equilibrium
r0
constants, G denotes surface concentration, while F, R / 0 /b ˆ ; 9†
and T have their usual meaning. Both positively C1
(MOH2+) and negatively (MO)) charged surface species while the potential drop in the region between the b and
are exposed to the same electrostatic potential, denoted the d planes depends on the capacitance of the second
as /0. capacitor (C2)
Counterion association, i.e. the binding of ions of the rb
opposite charge (counterions) can be described as / b /d ˆ : 10†
C2
MOH‡ ‡
2 ‡ A ! MOH2
A The surface charge density in the di€use layer (rd) is,


C MOH‡2
A according to the Gouy±Chapman theory, related to the
KA ˆ exp /b F =RT †
; 3† /d potential as
a A †C MOH‡ 2
p / F
MO ‡ C‡ ! MO
C‡ rd ˆ 8RT eIc sinh d ; 11†
2RT
C MO
C‡ † where Ic is the ionic strength and e is the medium
KC ˆ exp /b F =RT † ; 4† permittivity (e ˆ e0er).
a C‡ †C MO †
The relationship between the potential at the onset of
where A) and C+ denote anions and cations, and KA and the di€use layer (/d) and the f-potential at a distance s
KC are respective equilibrium constants. The state of the from the onset of the di€use layer is given by the Gouy±
associated counterions is a€ected by electrostatic poten- Chapman theory
tial, /b.  
The total surface concentration of the active surface exp sj† ‡ tanh F f=4RT †
/d ˆ 2RTF 1 ln ; 12†
sites in the interfacial layer (Ctot) is the sum of all exp sj† tanh F f=4RT †
contributions: with j being the Debye±HuÈckel reciprocal length,
r
Ctot ˆ C MOH† ‡ C MOH‡
2† ‡ C MO † 2FIc
‡ C MO C † ‡ C MOH‡
‡ jˆ : 13†
2A † : 5† eRT
For a metal oxide aqueous interface several versions The zero-charge conditions at the surface of a metal
of the electrical interfacial layer are described in the oxide are characterized by two values: the point of zero
literature and all of them may be considered as simpli- charge (PZC), corresponding to the pH value at which
®cations of a general model [8]. That general model r0 ˆ 0, and the isoelectric point (IEP), characterized by
includes four equipotential planes: a 0 plane, in which f ˆ 0.
surface charge groups formed by interactions with
potential-determining ions are located, a b plane, in
which centers of associated counterions are located, a d Speci®c adsorption
plane, which is the onset of the di€use layer (character-
ized by a /d potential), and the electrokinetic slipping or The previous considerations deal with metal oxides in
shear plane, e, characterized by a f-potential and aqueous solutions of ``indi€erent'' electrolytes. Potential-
separated by a distance, s, from the d plane. determining ions (H+ and OH) in the case of metal
The surface charge densities in the 0 plane (r0) and in oxides) are responsible for the formation of surface
the b plane (rb) are given by charge, while counterions do not chemically react with
surface groups, but become associated with oppositely
r0 ˆ F ‰C MOH‡ ‡
2 † ‡ C MOH2 A † C MO † charged surface groups owing to electrostatic (Coulom-
‡
C MO C †Š ; 6† bic) interactions. However, several molecules and ionic
groups may be bound ``chemically'' to the surface. Such
rb ˆ F ‰C MO C‡ † C MOH‡ processes are commonly called speci®c adsorption.
2 A †Š : 7†
Speci®c adsorption in¯uences signi®cantly the surface
The surface charge density in the di€use layer (rd) is equilibria and should not be neglected in the interpreta-
equal in magnitude, but di€erent in sign, to the net tion. In the case of adsorption of an organic acid or an
charge bound to the surface (rs) amino acid several possibilities regarding the species that
34

actually adsorb exist, which is due to the acid dissocia-

tion in the bulk of the solution. Additionally, one has to
take into account protonation and deprotonation of the
surface, i.e. the types of surface sites (positive, negative,
neutral) which participate in the speci®c adsorption.

Experimental

All the chemicals (o-, m-, p-aminobenzoic acid, HCl, NaOH, NaCl)
used in this study were of analytical purity grade. The goethite was
prepared by precipitation from Fe(NO3)3 and NaOH according to
the procedure described by Cornell and Schwertmann [9]. The
speci®c surface area, as determined by the Brunauer±Emmett±
Teller method, is 69 m2 g)1. The PZC obtained by titration at
di€erent ionic strengths is at pH 8.5, which coincides with the IEP
of goethite in the absence of amino acid, as determined electroki-
netically.
Adsorption experiments were performed at 20 °C. Suspensions
of di€erent pH (2<pH<9), containing a constant mass concen-
tration of goethite (2.6 g cm)3) and a constant initial concentration
of amino acid (c ˆ 1 ´ 10)3 mol dm)3) were prepared. HCl and
NaOH were used to adjust the pH. The samples were shaken for Fig. 1 Adsorption of o-, m- and p-aminobenzoic acid at the goethite
16 h. Goethite was separated by centrifugation, and the concen- interface. Dependency of the surface concentration of adsorbed amino
tration of amino acid in the supernatant was determined spectro- acid species on pH at 20 °C and Ic ˆ 1 ´ 10)2 mol dm)3. The initial
photometrically. The absorbance was measured in a basic medium concentration of amino acid was 1 ´ 10)3 mol dm)3 and the mass
at 310, 300 and 265 nm, which are characteristic bands of o-, m- concentration of goethite was 2.6 g cm)3
and p-aminobenzoic acid, respectively.
Electrokinetic measurements, performed at 20 °C, were carried
out with an Otsuka ELS-800 electrophoretic light scattering
instrument. In these experiments the mass concentration of goethite
was kept suciently low, while the bulk concentration of amino
acid, pH and ionic strength were the same as in the adsorption
experiments.

Results and discussion

The e€ect of pH on the adsorption of o-, m- and p-

aminobenzoic acid on goethite is presented in Fig. 1. The
adsorption behavior of all three amino acids is similar,
with the maximum at pH » 4.5, with the adsorption
anity decreasing in the order p-, o-, m-aminobenzoic
acid.
The e€ect of pH on the electrokinetic potential of
goethite particles after adsorption of o-, m- and p-
aminobenzoic acid in comparison to the electrokinetic
potential of goethite particles in the absence of amino
acid is presented in Fig. 2. The shift of the IEP of goethite
with adsorbed amino acid to lower pH values, with
respect to the IEP of goethite in the absence of amino Fig. 2 Adsorption of o-, m- and p-aminobenzoic acid at the goethite
acid, con®rms the assumption that the adsorption of interface. Dependency of the f-potential of goethite particles after
adsorption of amino acids and goethite in the absence of amino acids
negatively charged ionic species takes place. (pure goethite) on pH at 20 °C and Ic ˆ 1 ´ 10)2 mol dm)3. The mass
Additional con®rmation of the assumed reaction can concentration of goethite was kept suciently low
be obtained from the comparison of the adsorption and
electrokinetic data with the so-called ``speciation dia-
gram'' describing fractions of species in the bulk of the In the pH region 2<pH<5 the adsorption isotherm
solution as a function of pH. The ``speciation diagram'' (Fig. 1) follows the fraction of negatively charged
of o-aminobenzoic acid is shown in Fig. 3. m- and p- aminobenzoic acid species (L)) in the bulk of the
aminobenzoic acid show similar behavior. solution, indicating that these species are adsorbed. In
 35

where KA/L is the corresponding thermodynamic equi-

librium constant for the exchange reaction. In the model
used in this study no potential drop between the b and d
planes is assumed, C2®¥, so /0¹/b ˆ /d¹f.
The interpretation of the data, performed according
to the SCM, was based on the following procedure:

s G:C: C MOH‡2
L†

f ! /d ! r s ˆ rd † ƒƒƒƒƒƒ! r0 F C MOH‡
2
A ;
17†

a C1
pH !/0 !r0 : 18†
The ®rst step Eq. (17) in the interpretation is the
calculation of /d from the measured f-potential (Eq. 12)
assuming di€erent values of the electrokinetic slipping
plane separation, s, from 5 to 20 AÊ. No signi®cant e€ect
of the choice of s value on the ®nal results was found. The
value of s ˆ 15 AÊ was used in further calculations
because it was found to be representative for the metal
oxide aqueous interface [10±13]. The surface charge
Fig. 3 ``Speciation diagram'' demonstrating the change in fractions of density, rs ( ˆ )rd), was calculated from the /d potential
di€erent ionic species of o-aminobenzoic acid with pH in the bulk of via Eq. (11). In the next step of the interpretation one
the solution calculates r0±F C(MOH2+áA)) from rs and C(MOH+ 2 á
L)) using Eq. (15).
the pH region pH>5 the adsorption of L) species is In a parallel procedure (Eq. 18) the value of r0 was
suppressed owing to the reduction of the positive calculated as follows. The surface potential, /0, was
potential at the surface. Accordingly, the adsorption of obtained on the basis of the Nernstian approximation as
amino acids may be described as
RT ln 10
 MOH‡ ‡
2 ‡ L ! MOH2
L /0  a pHPZC pH† : 19†

F
C MOH‡2
L
KL ˆ exp F /b =RT † ‡

; 14†
The correction factor, a, was taken to be 0.8, which is
C MOH2 a L †
the representative value for the metal oxide aqueous
where KL is the thermodynamic equilibrium constant for interface [7, 14] and the PZC is at pH 8.5. From the
speci®c adsorption of L) species. Speci®cally adsorbed calculated /0 and /b ( ˆ /d) (Eq. 12) and the assumed
L) species are assumed to be located in the b plane and capacitance C1 the surface charge density in the 0 plane,
are exposed to the /b potential. In the positive region the r0, can be obtained via Eq. (9). For the capacitance C1,
)2
association of cations could be neglected. The net surface di€erent values between 0.5 and 1 F m were assumed
charge density is equal to [15±17]. The proper value of C1 corresponds to the


 minimum in the standard deviation of the resulting
rs ˆ r0 ‡rb ˆ r0 F C MOH‡ 2
A ‡C MOH‡ 2
L : logK
A/L value. These two procedures (Eqs. 17, 18) lead
15† to the determination of C(MOH2+áA)) (Eq. 15). Conse-
quently, the thermodynamic equilibrium constant for
In the case of higher ionic strength most of the
+ exchange, KA/L, was calculated by Eq. (16). The
MOH2 groups are associated with counterions so the
constants are determined as logKA/L ˆ 2.62 ‹ 0.13
exchange of anions and L) ions needs to be considered,
for o-aminobenzoic acid, logKA/L ˆ 2.37 ‹ 0.11 for
so
m-aminobenzoic acid and logKA/L ˆ 2.85 ‹ 0.14 for
 MOH‡ 2
A ‡ L ! MOH ‡
2
L ‡ A p-aminobenzoic acid for capacitance C1 of 0.65, 0.55
‡

and 0.95 F m)2, respectively. Among the acids exam-
C MOH2
L a A †
KA=L ˆ
; 16† ined, p-aminobenzoic acid has the largest exchange
C MOH‡ 2
A a L † constant and, therefore, the highest adsorption anity.
36

References

1. Yates DE, Levine S, Healy TW (1974) 7. Lyklema J (1995) Fundamentals of 14. Kallay N, Sprycha R, Tomic M, ZÏalac
J Chem Soc Faraday Trans I 70:1807 interface and colloid science. Academ- S, Torbic Z (1990) Croat Chem Acta
2. Kovacevic D, Pohlmeier A, OÈzbas G, ic, London 63:467
Narres H-D, Schwuger MJ, Kallay N 8. Kallay N, KovacÏevic D, CÏop A (1999) 15. Blesa MA, Kallay N (1988) Adv Col-
(2000) Colloids Surf 166:225 In: Kallay N (ed) Interfacial dynamics. loid Interface Sci 28:111
3. KovacÏevic D, Pohlmeier A, OÈzbas G, Dekker, New York, pp 249±271 16. Lumsdon DG, Evans LJ (1994)
Narres H-D, Kallay N (1999) Prog 9. Cornell RM, Schwertmann U (1996) J Colloid Interface Sci 164:119
Colloid Polym Sci 112:183 The iron oxides. VCH, Weinheim 17. Nilsson N, Persson P, LoÈvgren L,
4. KovacÏevic D, Kallay N, Antol I, 10. Healy TW, White LR (1978) Adv SjoÈberg S (1996) Geochem Cosmochem
Pohlmeier A, Lewandovski H, Narres Colloid Interface Sci 9:303 Acta 60:4385
H-D (1998) Colloids Surf 140:261 11. Sprycha R, Matijevic E (1989) Lang-
5. KovacÏevic D, Kobal I, Kallay N (1998) muir 5:479
Croat Chem Acta 71:1139 12. Harding H, Healy TW (1985) J Colloid
6. Kallay N, CÏop A, KovacÏevic D, Po- Interface Sci 107:382
hlmeier A (1998) Prog Colloid Polym 13. Chow RS, Takamura K (1988) J Col-
Sci 109:221 loid Interface Sci 125:226
Progr Colloid Polym Sci (2001) 117: 37±41
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

B. Ru€mann Liquid sorption and stability of polystyrene

R. Zimehl
latices

Abstract The surface structure of to determine the mole fraction of the

the colloidal polymer particles and adsorbed layer. The di€erent surface
the liquid structure in the dispersion structure of the particles leads to
medium strongly a€ect the stability di€erent stability behaviour of the
of a latex dispersion. Two kinds of dispersions. The critical coagulation
polystyrene latices, stabilised by concentrations (ck) for barium
sulfonate groups, were synthesised perchlorate in 1-propanol/water
by emulsion polymerisation. The mixtures were obtained by test-tube
reactions were started by a redox experiments. At low 1-propanol
starter of potassium peroxodisulfate concentrations the stability of the
and sodium bisul®te. Type 1 latices type 3 latices increases, exhibits a
have a smooth surface and were maximum stability at about x1 » 0.1
prepared from styrene. The type 3 and decreases upon further addition
latices were prepared by a two-step of 1-propanol. The decreased ck
mechanism. In the ®rst step, seed values for type 3 latices in water-rich
particles were prepared. In the sec- mixtures are explained by swelling of
ond step, the seed particles were the hairy surface. Imbedding 1-pro-
grown by further polymerisation of panol/water clusters between the
styrene and sodium styrene sulfo- oligomers causes swelling of the out-
nate. By this method oligomers of er sphere of the particles. Formerly
styrene and sodium styrene sulfonate not dissociated surface groups in the
accumulate in the outer spheres of oligomer region are able to dissoci-
the particles; thus a hairy surface is ate. This leads to a vaster double
formed. The stability of the disper- layer and thus higher ck values. By
sions and the selective liquid sorption further addition of 1-propanol,
were investigated for both kinds of counterions are pushed back to the
R. Zimehl latices: selective liquid sorption from surface and the stability decreases.
Institut fuÈr anorganische Chemie der
UniversitaÈt Kiel, 24098 Kiel, Germany 1-propanol(1)/water(2) mixtures on
the colloidal polymer particles with Key words Adsorption á
B. Ru€mann (&) di€erent surface structure was ob- Coagulation á Liquid structure á
Institut fuÈr Chemie, GKSS Forschungs-
zentrum Geesthacht, 21502 Geesthacht, tained by the reduced surface excess. Polystyrene latices á Surface
Germany The isotherms were analysed in order structure

Introduction corona of macromolecules (i.e. steric stabilisation) or by

charges linked to the particle surface (i.e. electrostatic
The preparation of stable colloidal systems requires a stabilisation) is most prominent. Electrostatic stabilisa-
subtle balance of surface forces of di€erent nature. tion of colloidal particles is very well described by the
Among others, the stabilisation of dispersions by a Derjaguin±Landau±Verwey±Overbeek (DLVO) theory.
38

The model is based on the formation of electrical double

layers at the particle surfaces. Repulsion between ap-
proaching particles is due to the high ion density in the
contact zone of the fully relaxed double layers. Electro-
lyte addition leads to the compression of the double layer
and usually this decreases the stability of the dispersion.
If the electrical double layer is not in equilibrium with
either the particle surface or the bulk electrolyte solution
or both, the distribution of ions can no longer be
described by the dogmatic equations of the DLVO
theory. For example, alcohols as cosolvents of water
decrease the solubility of electrolytes; counterions are
pushed back to the surface and the stability decreases [1,
2]. The stability of di€erent kinds of dispersions com- Fig. 1 Particles of di€erent types of latices: A type 1 latex (smooth
surface); B type 3 latex (hairy surface)
posed from mixtures of water and organic liquids has
been investigated by several authors. None of them
presented coherent formalisms in predicting the proper- layer, xs2 . The critical coagulation concentration, ck, for
ties of colloidal particles in mixed aqueous media of barium perchlorate in 1-propanol/water mixtures is
di€erent composition. reported. The aim of this study is to show the in¯uence
The situation is even more disappointing for colloidal of surface structure on the adsorption behaviour and
systems of technological importance. Especially for ind- thus the stability of polystyrene latices.
ustrial use, dispersions are made up from really complex
systems. Many modi®ers, regulators and cosolvents are
added to optimise the properties of the ®nal dispersion. Experimental
This leads to deviations from the ideal behaviour
The adsorption of 1-propanol (index 1) and water (index 2) was
described by DLVO theory for the stabilisation of studied with di€erent polymer particles.
dispersions. Even the addition of small amounts of
cosolvents (e.g. lower aliphatic alcohol) to an aqueous
Preparation of colloidal particles
dispersion provokes unusual stability behaviour of
latices [3, 4]. Several latices were prepared by emulsion polymerisation in a
In former studies the sorption of 1-propanol from three-necked vessel under a N2 atmosphere without emulsi®er.
water on polymer networks with di€erent surface
structure was investigated [5, 6]. By a di€erent polarity Type 1 latex
of the polymer frame an additional swelling ability was
introduced to the sorbents. Selective liquid sorption for Styrene (35 ml) was suspended in 500 ml water at 40 °C. The
reaction was initiated by a redox starter of potassium peroxodi-
the di€erent polymer networks depended on the polarity sulfate and sodium bisul®te.
as well; however, the in¯uences of the surface structure
and the polarity of the colloidal polymer particles on the Type 3 latices
swelling behaviour in the presence of 1-propanol has not
been reported yet. Up to now, the adsorption behaviour In a ®rst step, seed particles were prepared by emulsion polymeri-
of polystyrene resins and colloidal particles was investi- sation of styrene using sodium styrene sulfonate as comonomer.
gated by microcalorimetric measurements and confor- The reaction was started by potassium peroxodisulfate and sodium
bisul®te. In a second step, the seed particles were grown by further
mational changes in the adsorption layer of type 3 latices polymerisation of styrene and sodium styrene sulfonate initiated by
were noted [7]. Type 1 latices have a smooth surface the same starter. Di€erent styrene/sodium styrene sulfonate ratios
(Fig. 1a), whereas type 3 latices are supposed to have a and temperatures were used [9, 10, 11]. This preparation leads to
hairy surface (Fig. 1b). The di€erent surface structure particles with oligomers consisting of styrene and sodium styrene
sulfonate in the outer sphere of the particles, which resulted in a
leads to di€erent stability behaviour. As the in¯uence of hairy surface [5].
electrolytes on the stability of colloidal particles strongly
depends on the change in the water structure by the ions, Colloidal resin
structural e€ects of the surface of the colloidal particles
have an in¯uence as well [8]. A dispersion of a ground ion-exchange resin (PS/KM/1) was
In this study the selective liquid adsorption on prepared from Amberlyst 15 (Fluka). The macroreticular cation-
colloidal polymer particles with di€erent surface struc- exchange resin has a polystyrene network cross-linked by 30%
divinylbenzene and bears sulfonate groups in the matrix. It was
ture from 1-propanol(1)/water(2) mixtures is investigated ground in a ball mill to form a dispersion with particles of 180±340-
by the reduced surface excess. The excess isotherms are nm diameter. The dispersed particles are assumed to have no
analysed to determine the mole fraction of the adsorbed oligomers on the surface.
 39

All the dispersions were cleaned by centrifugation and redisper- where n0 is the initial number of moles of the binary
sion, dialysis for 4 weeks and were transformed to the proton form liquid, m the amount of solid, x0i the mole fraction before
by ion exchange.
adsorption and xi the mole fraction after adsorption.
Characterisation of colloidal particles The excess isotherms were analysed according to the
Schay±Nagy extrapolation method [13, 14, 16]. The
The mean diameters of the colloidal particles were determined by extrapolated values jns1 j and jns2 j give the composition of
sedimentation in the centrifugal ®eld (Bi-DCP particle sizer, the adsorbed phase within the linear range of x2. The
Brookhaven Instrument Corporation). The surface area was
calculated from the diameter. The surface charge of the particles volume occupied by the sorbed liquid is
was determined in a particle charge detector (PCD 02, MUÈTEK) V s ˆ jns1 jVm;1 ‡ jns2 jVm;2 : 2†
by titration with 0.001 N poly(diallyldimethyl ammonium chlo-
ride). The particles and their surface charges are listed in Table 1. The adsorption capacity of pure component 2 is then
Surface-excess isotherms Vs
ns2;0 ˆ : 3†
Vm;2
Adsorption measurements were performed in well-sealed test tubes
at room temperature. The binary liquid mixture (3 cm3) was added The mole fraction of component 2 in the adsorption
to sediment containing 0.15 g polymer samples. The colloidal layer xs2 is given by
particles were redispersed by ultrasound. The change in the water
concentration in the bulk liquid (x2) was measured by the ns2
di€erential refractive index in a di€erential refractometer of a xs2 ˆ ; 4†
high-performance liquid chromatography system (Waters) after ns1 ‡ ns2
equilibration periods of 48 h and centrifugation. which is suitable for determining xs2 = f(x2), if ns1 and ns2
Critical coagulation concentration have been derived from the adsorption-excess isotherms
by
The ck values were obtained by test-tube experiments [1]. A series of r n† r n†
dispersions containing increasing amounts of barium perchlorate r0 ns2;0 x1 r0 n2 n2 ‡ r0 ns2;0 x2
were prepared by adding 1 ml salt solution to 1 ml dispersion (®nal ns1 ˆ and ns2 ˆ ;
polymer volume fraction: 2 ´ 10)4 ). After shaking, the dispersions
x1 ‡ r 0 x2 x 1 ‡ r 0 x2
were left for 24 h. It was then determined which salt concentration 5†
causes coagulation. When required, additional series were prepared
by increasing the salt concentration in smaller steps. where r¢ ˆ M2/M1 is the ratio of the molar masses of the
two components.
The mole fraction of the adsorbed layer, xs2 , was
Results calculated from the excess isotherms according to
Eq. (4). The equilibrium diagram (Fig. 2) shows the
Composition and volume of the adsorbed phase

The selective liquid sorption on the di€erent polymer

particles was studied by speci®c-excess quantities which
can be directly determined by experiment [12±14]. The
experimental data are expressed as composite isotherms
nir(n) ˆ f(xi), in which the excess amount, nir(n), adsorbed
of one component is plotted as a function of its
equilibrium concentration, xi [15]:
r n† n0 0
ni ˆ x x i † ˆ f xi † mol=g† ; 1†
m i
Table 1 Speci®c surface charge, S0, of the particles and composi-
tion of the adsorption layer in the linear part of the adsorption-
excess isotherm

Dispersion S0 (Cg)1) jns1 j jns2 j jns1 j/jns2 j

(mmolg)1) (mmolg)1)
P(St/NaSS0)R 2.87 0.7 2.8 0.25
P(St/NaSS5)1 11.77 1.4 6.2 0.23
P(St/NaSS3)4 6.43 1.0 3.35 0.29
P(St/NaSS4)1 9.45 1.45 6.5 0.22
NSS/2/2.1 12.76 1.3 5.4 0.24
NSS/3/1.1 315.3 4.3 29 0.15
PS/KM/1 75.73 1.5 18.8 0.08 Fig. 2 Mole fraction of the adsorption layer, xs2 , of the latices as a
function of the bulk composition, x2
40

composition of the adsorbed layer xs2 versus the compo- The ck values of dispersions of particles with a hairy
sition of the bulk phase x2. Water is bound preferentially surface (type 3 latices) do not decrease continuously with
from the 1-propanol/water mixtures at low water mole increasing 1-propanol concentration. Steplike disconti-
fractions for all the particles. At higher water content, 1- nuities are observed in the curves of type 3 latices with
propanol is partitioned preferably towards all the low speci®c surface charge at x2 ˆ 0.9. For the type 3
particles. The curves indicate that the uptake of water latex with the highest surface charge a maximum of ck
in the plateau region does not depend on the nature of values at x2 ˆ 0.9 is found. Here, the compression of the
the particles. In a wide range the composition of the
adsorption layer does not depend on the surface charge
Table 2 Surface charge density, r0, adsorption capacity, ns2,0,and
of the particles (Table 1). volume of the adsorption layer, Vs, for the colloidal particles
The adsorption capacity ns2;0 was calculated according investigated
to Eq. (3). The data were related to the surface area for
comparison of particles with di€erent diameters. For the r0 ns2;0 Vs
(lCcm)2) (mmolm)2) (llm)2)
type 3 latices the adsorption capacity increases with the
surface charge (Fig. 3). This results in an increase in Polymer material latice
the volume of the adsorption layer, Vs (Table 2, Fig. 4). P(St/NaSS0)R 15.29 0.44 7.94
P(St/NaSS5)1 15.29 0.14 2.61
P(St/NaSS3)4 19.16 0.22 4.03
Critical coagulation concentration P(St/NaSS4)1 19.74 0.26 4.72
NSS/2/2.1 33.87 0.29 5.18
NSS/3/1.1 304.14 0.45 8.15
The critical coagulation concentration of the colloidal Dispersion
particles for barium perchlorate in 1-propanol/water PS/KM/1 252.4 0.83 38.15
mixtures was studied. In Fig. 5 the dispersions investi-
gated are arranged according to the speci®c surface
charge of the particles. The ck values are shown as a
function of the bulk concentration x2.
For the dispersions of particles with a smooth surface
(the type 1 latex P(St/NaSS0)R and the milled resin PS/
KM/1) the ck values decrease with increasing mole
fraction of 1-propanol in the liquid mixture (x2 ˆ 1±0.8).
This e€ect is related to the decrease of the dielectric
constant in the bulk mixture. Thus, the solubility of the
electrolytes decreases and the counterions are pushed
back to the surface. This compression of the double layer
leads to a decrease in stability [1, 2].

Fig. 3 Adsorption capacity, ns2;0 , as a function of surface charge of Fig. 4 Volume of the adsorbed phase, Vs, for low and high charged
the colloidal particles type 3 latex particles
 41

Fig. 5 ck values of the dispersions for BaClO4 in1-propanol (x1)/

water(x2) mixtures(left to right: P(St/NaSS0)R, P(St/NaSS3)4, P(St/ Fig. 6 Adsorption of 1-propanol/water clusters and swelling of the
NaSS4)1, P(St/NaSS5)1, NSS/2/2.1, PS/KM/1, NSS/3/1.1 outer sphere of type 3 latices, oligomer region: A in water; B in 1-
propanol/water at x2 » 0.9
double layer due to the presence of 1-propanol is
superimposed by a stabilising e€ect. The di€erent surface structures of the particles lead to
di€erent coagulation behaviour of the dispersions. The
dispersions of particles with a smooth surface (type 1
Conclusions latex, milled resin) show a decrease in stability with
increasing content of 1-propanol owing to the double-
The aim of this study was to demonstrate the in¯uence of layer compression.
surface structure on the stability of dispersions. The For the type 3 latices, swelling of the hairy surface
adsorption from 1-propanol/water mixtures onto colloi- enables the dissociation of charges trapped in the
dal sulfonated polystyrene particles and the stability of oligomer region (Fig. 6). The additional counterions
their dispersions were examined. enhance the stability of the dispersions with low 1-
Two main structural e€ects have to be accounted for, propanol content (x2 ˆ 0.9). As the swelling ability
the ®rst being the structure of the dispersion medium. increases with the adsorption capacity, this stabilising
The composition of the adsorbed phase of all the latices e€ect is more pronounced for particles with higher
presented here is similar to that of 1-propanol/water surface charge.
clusters formed in a wide range of bulk mixture compo- Usually the stability of latex dispersions is decreased
sition (x2 ˆ 0.6±0.9) [17, 18]. by the addition of hydrophobic cosolvents; however,
The second e€ect considers the surface structure of the structural properties of the surface of the particles can
particles. A smooth surface (type 1 latex, milled resin) is cause stabilising e€ects. The analysis of the adsorption-
assumed to have no swelling ability. By introducing excess isotherms contains important new information
oligomers to the particles surface it obtains a gel-like about the properties of colloidal particles, such as the
character and the ability to swell [7]. The swelling ability composition and the volume of the adsorbed layer. This
increases with surface charge density owing to the information is of crucial importance for understanding
increased adsorption capacity (Table 2). the behaviour of the dispersions.

References

1. de Rooy N, de Bruyn PL, Overbeek 7. Ru€mann B, Ammann L, Zimehl R, 13. Everett DH (1965) Trans Faraday Soc
JTG (1980) J Colloid Interface Sci DeÂkaÂny I (1999) Thermochim Acta 61:2478
75:542 337:55 14. Schay G (1976) Pure Appl Chem
2. Matijevic E, Ronayne ME, Kratohvil 8. Zimehl R, Lagaly G (1986) Prog 48:373
JP (1966) J Phys Chem 70:3830 Colloid Polym Sci 72:28 15. Everett DH (1983) In: Ottewill RH,
3. Seebergh JE, Berg CB (1997) Colloids 9. Okubo M, Nakagawa T (1992) Colloid Rochester CH, Smith AL (eds) Ad-
Surf A 121:89 Polym Sci 270:853 sorption from solution. Academic,
4. Galembeck F, Braga M, da Silva 10. Kim JH, Chainey M, El-Asser MS, London, pp 302
MCVM, Cardoso AH (2000) Colloids Vanderho€ JW (1989) J Polym Sci Part 16. Schay G, Nagy LG (1972) J Colloid
Surf A 164:217 A Polym Chem 27:3187 Interface Sci 38:302
5. Zimehl R, VoÂzaÂr A, DeÂkaÂny I (1996) 11. Ru€mann B (1999) Dissertation. Kiel 17. Ebert G, Wendor€ J (1970) Ber Buns-
Thermochim Acta 271:59 12. Everett DH (1964) Trans Faraday Soc enges Phys Chem 74:1071
6. Zimehl R (1998) Thermochim Acta 60:1803 18. Groûmann GH, Ebert KH (1981) Ber
310:207 Bunsenges Phys Chem 85:1026
Progr Colloid Polym Sci (2001) 117: 42±46
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

R. Zimehl Adsorption onto tooth enamel ± the biological

M. Hannig
interface and its modi®cation

Abstract The purpose of this study and the protein layer (salivary pelli-
was to provide further information cle) adsorbed in vivo on dental
on several aspects of bioadhesion at enamel as well. Enamel test pieces
the enamel surface. In the ®rst part were attached to the buccal surfaces
of the article the arti®cial modi®ca- of the upper ®rst molar teeth in two
tion of dental enamel is illuminated. adults using removable intraoral
The interaction of hydroxyapatite, splints. The splints were carried
which is the main constituent of intraorally over periods ranging
tooth enamel, and tooth enamel with from 1 min to1 h. Pellicle structures
di€erent kinds of carboxylic acids could be identi®ed by AFM on
was investigated by Fourier trans- intraorally exposed specimens as
form IR spectrometry, scanning compared to nonexposed enamel
electron microscopy and X-ray surfaces. The surface of the adsorbed
photoelectron spectroscopy (XPS). salivary pellicle was characterised by
The XPS spectra clearly reveal that a dense globular appearance. The
the surface treatment substantially diameter of the globulelike protein
increases the relative intensities of aggregates varied between 100 and
Ca, P and O with respect to the 250 nm. This study indicates that the
R. Zimehl (&)
Institute for Inorganic Chemistry, surface of the polished enamel ref- combination of microscopic and
Christian Albrechts University of Kiel, erence. In the second part of the spectroscopic techniques is a pow-
Olshausenstrasse 40, 24098 Kiel, article the examination of the natu- erful tool for high-resolution exam-
Germany ral modi®cation of dental enamel by ination of enamel and the salivary
M. Hannig atomic force microscopy (AFM) is pellicle surface structure.
Clinic for Operative Dentistry reported. This study was performed
and Periodontology, to evaluate the use of the aforemen- Key words Atomic force microsco-
Christian Albrechts University of Kiel,
Arnold-Heller-Strasse 16, 24105 Kiel, tioned techniques in examining the py á Salivary pellicle á Protein
Germany surface of the native dental enamel adsorption á Enamel

Introduction di€erent microorganisms. The surface of the teeth is

characterised by a crystallised arrangement of mineral
Dental diseases such as caries and periodontitis are components with incorporated and chemisorbed bio-
serious problems for almost any human being all over polymers. The enamel is highly mineralised, about 96%
the world and cause enormous costs for the public by weight consists of tightly packed hydroxyapatite
health care organizations. One reason for the develop- crystallites with only 1% of its weight being organic
ment of dental diseases can be found from the structure molecules and 3% being water; therefore, it is reason-
of the tooth hard substances, namely enamel, and its able to consider dental enamel as a microporous solid
interaction with the oral environment, saliva and with a superior speci®c surface. Thus, the tooth enamel
 43

is prone to microbial attack and can be dissolved and FTIR absorption spectrometer (GENESIS, ATI Mattson Uni-
solubilised by acidic agents. Formation of a microbial com).
Topographical scanning electron microscopic analyses of the
bio®lm (so-called plaque) causes the main dental enamel surfaces were carried out using an analytical scanning
diseases caries and periodontitis. The natural mecha- electron microscope (XL-30, Philips). Cleaned and dried enamel
nism to protect the metastable biological structure of substrates were exposed for 2 min to a solution of benzoic acid (3%
the tooth hard substance is the formation of the so- weight in acetone). After exposure, the enamel was washed with
distilled water and subsequently dried with compressed air. The
called salivary pellicle owing to adsorption of salivary enamel specimen was sputter-coated with gold in an EMITECH
proteins onto the enamel surface. This protective layer sputter coater prior to SEM analysis.
of di€erent salivary biopolymers is formed in vivo on For XPS investigations a native (nonpolished, nonconditioned)
any solid surface exposed to the oral environment; enamel surface, an enamel specimen cleaned with acetone and a
however, even enamel covered by the natural protective conditioned enamel sample (treated with benzoic acid in acetone)
were conducted using an OMICRON system under an ultrahigh
layer is sensitive to acid attack. A preventive approach vacuum of 10)9 mbar, using a MgKa soft X-ray source. Polished,
could be to cover the dental enamel by suitable nonconditioned enamel was used as a reference surface [3]. The
materials serving as an arti®cial protective layer. To peaks of the following elements were analysed: phosphorus,
analyse the mechanism of bonding between the dental calcium, carbon, and oxygen. Owing to charging e€ects the peak
positions were corrected with the energy of the 1s carbon peak at
enamel and the protective layer we performed experi- 284.5 eV as the reference. Background subtraction and area
ments with di€erent chemical conditioning agents. The calculations of the di€erent peaks were carried out with the
chemical adhesion of protective and restorative materi- software supplied.
als to tooth surfaces has been studied with di€erent For AFM investigation several enamel specimens with a surface
area of about 2 ´ 2 mm2 were cut from labial surfaces of freshly
kinds of carboxylic and polyacrylic acid using hydroxy- extracted bovine incisors. The enamel specimens were mounted on
apatite and polished or ground enamel as a model the buccal surfaces of the maxillary ®rst molars in two subjects
system [1±4] and evidence of chemical binding has been using intraoral acrylic appliances (minisplints [1, 6]) and were
reported recently [5]. Binding is achieved by carboxylate exposed to the oral environment by the subjects over periods of 1,
groups penetrating the apatite matrix and displacing 10, 30, and 60 min. After intraoral exposure the specimens were
removed from the oral cavity, rinsed in distilled water and
calcium and phosphate ions. In recent work we have immediately mounted and analysed by AFM (Autoprobe CP
reported the topography of conditioned and untreated operated in contact mode [7]). For reference purposes, enamel
enamel surfaces by scanning electron microscopy (SEM) specimens not exposed in the oral cavity were investigated by
and X-ray photoelectron spectroscopy (XPS) [3]. We AFM.
have demonstrated that the mechanical strength of the
interface between restorative or protective materials and
the tooth hard substance dental enamel could be Results and discussion
improved by cleaning organic debris o€ with di€erent
carboxylic acids. Nevertheless the mechanism of adhe- The interaction of hydroxyapatite, which is the main
sion of restorative and sealing material to the tooth constituent of tooth enamel, with di€erent kinds of
surface is still under discussion. This study was per- carboxylic acid was investigated by extraction techniques
formed to evaluate future developments and possible and FTIR spectroscopy. After treatment with di€erent
ways out of plaque-related dental diseases by conserva- kinds of carboxylic acid the spectra of the hydroxyapatite
tive and restoring strategies. The use of SEM, atomic powder provided evidence of chemical interaction. The
force microscopy (AFM) and Fourier transform IR appearance of IR peaks at about 1,560 cm)1 indicates
(FTIR) spectroscopy in examining the surface of native that at least a part of the carboxylic acid is adsorbed at
and modi®ed dental enamel is discussed. the mineral powder via ionised carboxylic groups. The
large number of washing cycles needed to reduce the
characteristic IR peaks was taken as an indicator for
Materials and methods strong binding eciency of the carboxylic acid (Table 1).
From SEM we could demonstrate that the interaction of
The interaction of hydroxyapatite with benzoic acid in acetone and
poly(acrylic acid) in water was investigated by extraction tech- Table 1 Number of washing cycles needed to reduce the char-
niques and FTIR spectroscopy. Porous hydroxyapatite (Fluka acteristic IR peaks at about 1,560 cm)1 to a constant amplitude.
``high-resolution'', analytical-reagent grade material) was used in The large number of washing cycles for the hydroxyapatite samples
form of a ®ne powder. The carboxylic acids were used as a 3% is indicative of the strong binding eciency of the carboxylic acids
solution in either organic or aqueous media. The mineral powder
(50 mg) and the solution (2 ml) were ground together with an agate Hydroxyapatite Washing Number of washing
mortar and pestle. The slurry was dried and then washed with a sample with liquid cycles to reach constant
large excess of organic solvent or water. Finally the conditioned value of IR peak
hydroxyapatite was recovered from the slurry by centrifugation. A
small amount of the dried powder was mixed with potassium Poly(acrylic acid) in water Water 10
bromide and pressurised to form a suitable tablet. IR spectra of the Benzoic acid in acetone Acetone 5
original and conditioned hydroxyapatite were recorded using a
44

Table 2 X-ray photoelectron spectroscopy results for the interac-

tion of dental enamel with benzoic acid in acetone. The area under
the peaks for Ca, P, C, and O is given with respect to the polished,
nonconditioned enamel used as the reference surface

Sample Relative peak area (%) for

Ca P C O

Native dental enamel )25 )45 80 )4

covered with pellicle
Enamel conditioned 20 )2 9 7
with acetone
Enamel conditioned 63 23 )5 40
with benzoic acid

native state the Ca peak intensity is weaker than that of

the polished surface because of the attenuation e€ects
due to the outermost organic layer. In comparison to the
polished surface, the relative intensity of the phosphorus
peak increases on the BAA-treated surface by about
20%.
To elucidate further the interaction of tooth enamel
with carboxylic and polycarboxylic acids and related
polyelectrolytes (biopolymers) we investigated the to-
pography of the tooth enamel surface by AFM. We
used the contact mode of AFM to follow up the
formation of salivary protein layers on tooth enamel
in vivo. The characteristic surface pattern of a polished
enamel specimen not exposed to the oral environment
is shown in Fig. 2a. Individual enamel crystallites
measuring 30±90 nm in width could be observed by
AFM. The enamel crystallites appeared rounded and
caused a spotted enamel surface pattern. The appear-
ance of the enamel specimens after intraoral exposure
Fig. 1 a Scanning electron microscope picture of the characteristic
topography of the polished part of the enamel surface. b Conditioning for 60 min towards human salivary changed distinctly
with acetone or benzoic acid in acetone did not lead to visible etching, (Fig. 2b). The ®nely patterned surface of the enamel
and the surface topography appeared unchanged. Magni®cation was masked owing to salivary protein adsorption and
´ 2,500. For details of the preparation see Ref. [3] pellicle formation. The pellicle manifested itself in the
AFM pictures as a tightly packed globular surface
enamel with several carboxylic acids in acetone (e.g. layer. The ®nely patterned surface of the enamel is
benzoic acid in acetone, BAA) does not produce etching masked owing to salivary protein adsorption and
patterns, whereas poly(acrylic acid) in water does [8]. The pellicle formation. The adsorbed protein layers reveals
topography of the polished part of the enamel surface is a globular-shaped surface structure that is also depicted
shown in Fig. 1a. Conditioning with acetone or BAA did in the corresponding transmission electron microscopy
not lead to detectable etching and the surface topography (TEM) micrograph of the ultrathin section depicted in
remained unchanged (Fig. 1b), but from XPS investiga- Fig. 3a. From the AFM picture taken so far we could
tions we obtained ampli®ed peaks for Ca, P, and O with make a rough estimate of the coil dimensions of the
respect to the untreated reference surface [3, 8]. A closer protein molecules in the hydrated surface layer. The
look to the XPS spectra clearly reveals that the surface average diameter of the globular-like structures varied
treatment substantially increases the relative intensities between 100 and 250 nm. The AFM results con®rm
of Ca, P, and O with respect to the polished surface previously published SEM and TEM studies showing
(Table 2). The carbon peak area of the acetone-and that the salivary pellicle layer has a globular-like
BAA-treated surfaces decreases. The area of the carbon surface texture [2, 6, 9, 10]. The present AFM
peak is highest on the native surface. Acetone increases investigation provides evidence that the native salivary
the area of the Ca peak by 20%, whereas an enrichment pellicle is mainly composed of globular-shaped protein
of about 60% is achieved by BAA conditioning. In the agglomerates which are not artefacts resulting from
 45

Fig. 3 a TEM picture of an ultrathin section of dental enamel

Fig. 2a, b The characteristic surface pattern of a polished enamel exposed for 60 min to the oral environment. Note the electron dense
specimen as observed by atomic force microscopy (AFM) and pellicle basal layer adsorbed directly upon the enamel surface. The
transmission electron microscopy (TEM). a AFM picture of reference enamel was dissolved owing to ethylenediaminetetraacetate treatment
surface, not exposed to the oral environment. The individual enamel prior to ultrathin sectioning. Magni®cation ´30,000. For details of
crystallites measure approximately 30±90 nm. b AFM picture of preparation see Refs. [1, 6]. b Model for the orientation of biopolymer
enamel sample exposed for 60 min to the oral environment. The ®nely molecules on the surface of enamel crystallites
patterned surface of the enamel is masked owing to salivary protein
adsorption and pellicle formation. The adsorbed protein layers reveals bonding strength between the mineral constituent of
a globular-shaped surface structure that is also depicted in the
corresponding TEM micrograph (cf. Fig. 3a) tooth enamel. A comparable mechanism is presumably
operative for the adhesion and deposition of protein
dehydration and agglomeration of condensed salivary molecules onto the tooth hard substance (cf. Fig. 3a).
proteins. The so-called pellicle formation is the result of salivary
protein adsorption at the tooth±saliva interface [9, 11].
The composition of the surface layer is largely in¯uenced
Summary and conclusion by the structure and polarity of solid substrate (the
enamel) and the hydrated biopolymers involved. Tradi-
On the basis of the results of the foregoing section we tional electron microscopic techniques do not enable
may speculate about the interaction of polycarboxylic analysis of protein layers and adsorbed polyelectrolyte in
acids and related biopolymers with the tooth surface. their native state. Artefacts resulting from sample
After treatment of hydroxyapatite powder with di€erent preparation as well as dehydration of the specimens in
carboxylic acids in acetone and repeated washing cycles the high vacuum of the electron microscope chamber
the FTIR spectra of the hydroxyapatite still provided strongly limit the validity of electron microscopy in
visual means of evidence for adsorbed carboxylic acid studying the initial stages of bio®lm formation on dental
molecules. Perhaps the carboxylic acid coordinates with tissues. AFM allows surface analysis of wet and fully
calcium ions located at the surface of the hydroxyapatite hydrated specimens without prior evaporation or special
particles and adhesion results from the displacement of ®xation procedures and a lateral resolution in the lower-
anions by the carboxylate groups (Fig. 3b). If this nanometre scale. This overview illuminates the useful-
chemisorption model for the interaction between hy- ness of the combination of di€erent techniques such as
droxyapatite and carboxylate groups is correct, the use of SEM, TEM, AFM and FTIR spectrometry in examining
carboxylic acids with di€erent molecular geometry and interactions at the enamel surface in contact with saliva
electron density distribution enables us to tune the or polyelectrolyte.

References

1. Wilson AD, Prosser HJ, Powis DM 4. Fischer-Brandies H, Scherer R, Theus- Lambrechts P, Vanherle G, Wakasa K
(1983) J Dent Res 62:590 ner J, HaÈusler K (1992) Fortschr (2000) J Dent Res 79:709
2. Hannig M (1997) Eur J Oral Sci 105:422 Kieferorthop 53:131 6. Hannig M (1999) Clin Oral Invest 3:88
3. Es-Souni M, Zimehl R, Fischer-Bran- 5. Yoshida Y, Van Meerbeek B, Nakay- 7. Hannig M, Herzog S, Willigeroth SF,
dies H (1999) Colloid Polym Sci ama Y, Snauwaert J, Hellemans L, Zimehl R (2001) Colloid Polym Sci
277:382 279:479
46

8. (a) Zimehl R, Es-Souni M, Fischer- (b) Es-Souni M, Fischer-Brandies H, ence on Colloid and Interface Science,
Brandies H (2000) Adsorption of ben- Zimehl R (2000) The role of tooth Bristol, UK
zoic acid on dental enamel studied by enamel as a biological interface and its 9. Lie T (1975) Arch Oral Biol 20:739
photoelectron spectroscopy, Third In- modi®cation: 2. Electron microscopy 10. Lie T (1977) Scand J Dent Res 85:217
ternational Conference of the Kolloid- on dental enamel modi®ed by benzoic 11. SoÈnju T, RoÈlla G (1973) Caries Res
Gesellschaft e.V., Budapest, Hungary; acid. The 10th International Confer- 7:30
Progr Colloid Polym Sci (2001) 117: 47±50
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

Zs. Lengyel Adsorption of chloroacetanilide herbicides

R. FoÈldeÂnyi
on Hungarian soils

Abstract Acetochlor and propiso- and sandy soil is small. As propiso-

chlor are chloroacetanilide herbi- chlor is more hydrophobic than
cides that are produced in Hungary. acetochlor, and chernozem has the
Their prolonged use in agriculture highest organic content, these results
can result in soil contamination. The support the idea of hydrophobic
study of adsorption on di€erent soil interaction between the compounds
types helps predict the fate of these studied and the soil constituents but it
compounds in the environment. can be explained by the formation of
Static equilibrium experiments were hydrogen bonding as well. The
carried out with Hungarian soils resulting adsorption isotherms con-
having di€erent pH and humus sist of two parts that can be assigned
content (chernozem, brown forest to two di€erent Langmuir-type
and sandy soil) in 0.1 mol/l phos- isotherms. This phenomenon can
phate bu€er (pH 7). The concentra- be explained by two causes: either
tion of chloroacetanilide herbicides by the two phases of the soils (organic
was measured by high-performance and inorganic phases) or by the
liquid chromatography in the aque- interaction of the dissolved material
Zs. Lengyel á R. FoÈldeÂnyi (&)
University of VeszpreÂm, ous phase. The amount of the com- with the ®rst monomolecular layer.
Department of Environmental Engineering pound adsorbed on a unit mass of
and Chemical Technology, 8201 VeszpreÂm, the soils is higher in the case of Key words Adsorption á
P.O. Box 158, Hungary propisochlor than in the case of Chloroacetanilide á Herbicide á
e-mail: [email protected]
Tel.: +36-88-422022 acetochlor. The di€erence between High-performance liquid
Fax: +36-88-425049 the amounts bonded to chernozem chromatography á Soil

Introduction DeÂkaÂny [4] concerning the adsorption of hexadecylpyri-

midinium chloride from aqueous solution onto various
The solid phase of soil consists of two main fractions clay minerals. The structure and the sorption properties
having high speci®c surface area: clay minerals and of modi®ed silicates were studied in aqueous solutions of
organic matter. The latter is supposed to coat the soil primer alcohols [5±7]. The adsorption on n-alkylammo-
particles as an organic ®lm, leading to a hydrophobic nium vermiculites and graphitized silica gel was investi-
surface [1, 2]. gated by microcalorimetry and X-ray di€raction. It was
The soil as an adsorbent can be characterized by pointed out that from propanol±water mixtures the
means of a model system, by the so-called organoclay. formation of alcohol±water clusters on the surfaces plays
Although the surface of the natural clays is hydrophilic, an important role [6]. In the case of phenol, cyclohexanol
the metal ion content can be exchanged with large and n-hexanol (C6-ols) a multilayer was formed from
surfactant cations, resulting in a hydrophobic surface [3]. their diluted binary aqueous solutions on graphitized
Novel investigations were carried out by Patzko and carbon black (GCB) [8].
48

Small adsorbed amounts of aniline and phenol were and disodium hydrogen phosphate were obtained from the Reanal
determined on untreated montmorillonite, but the ad- Chemical Co. Tetrahydrofuran was purchased from Merck and
acetonitrile was from Spektrum 3D. Some properties of the soil
sorption of both organics was signi®cantly enhanced samples used in these studies are listed in Table 1.
after the modi®cation of the clay mineral by cationic
surfactant [9]. Mortland [3] pointed out that organoclays Methods
are very e€ective in sorbing nonionic organic pollutants.
Many pesticides are nonionic organic compounds that Static equilibrium experiments were carried out in 0.1 mol/l
may adsorb on modi®ed clay minerals as well as on the phosphate bu€er (pH 7). Soil samples (7 g) were left to swell in
5 ml distilled water for 24 h at room temperature, then 65 ml
soils owing to their organic matter content leading to herbicide in an appropriate bu€er solution (300, 240, 180, 150, 120,
hydrophobic surfaces. 96, 60, 30 lmol/l) was added. The suspension was shaken for 1 h,
The present work studies the adsorption behavior of then separated by centrifuging. The aqueous phase was ®ltered,
two chloroacetanilide type herbicides (Fig. 1) on soils. then analysed by high-performance liquid chromatography
Acetochlor and propisochlor are produced in Hungary (HPLC). The standard solutions for calibration were the same as
were used in the static equilibrium experiments.
and are used in large amounts in agriculture, leading to
soil and water pollution. The investigations detailed here
are of special importance owing to the frequent occur- HPLC conditions
rence of these nonionic compounds in the environment
Chromatographic separations were made by using a PerkinElmer
[10, 11]. Series 200 HPLC chromatograph equipped with a LiChrospher
100 column ®lled with 5 lm RP-18 packing material (125 mm ´
4 mm) and with a diode array detector, set at 218 nm. Samples,
Experimental injected using a 20-ll Rheodyne loop, were eluted by a mixture of
50% acetonitrile, 30% water and 20% tetrahydrofuran at a ¯ow
rate of 0.7 ml/min.
Materials

Acetochlor (99.3%) and propisochlor (98.2%) standards were

provided by NitrokeÂmia 2000. Potassium dihydrogen phosphate Results and discussion

The adsorption of acetochlor and propisochlor was

studied on three di€erent Hungarian soils. Although gas
chromatography is mostly used for the determination of
chloroacetanilides [12, 13], these analyses were carried
out directly in the aqueous phase by HPLC with excellent
reproducibility.
Concerning the acetochlor, the adsorption isotherms
on the brown forest and sandy soil are very similar.
Under 150 lmol/l equilibrium concentration chernozem
bonded higher amounts of acetochlor than the other two
soils but over this value the isotherm has almost the same
Fig. 1 The structure of the chloroacetanilide type herbicides pro- shape (Fig. 2).
duced in Hungary: a acetochlor, b propisochlor

Table 1 Mineral composition

and structural properties of Characteristics Chernozem Brown Sandy soil
the soil samples studied (BalatonfoÈkajaÂr, forest soil (Dabrony,
Hungary) (TeÂs, Hungary) Hungary)
pH 7.73 6.35 6.27
Percentage of salt 0.08 0 0
Characteristic number de®ned by Arany 49 42 24
Percentage of organic matter 4.10 2.20 1.32
Brunauer±Emmett±Teller surface (m2/g) 21.58 5.89 2.55
Main minerals
Albite (%) 9.8 12.6 15.1
Chlorite (%) 5.3 6.6 2
Mica (%) 4.2 7.8 2.4
Quartz (%) 30.6 48.4 63.9
Smectite (%) 32.4 14.3 8.3
 49

Fig. 4 Comparison of adsorption isotherms of acetochlor (r) and

Fig. 2 Adsorption isotherms of acetochlor on three di€erent soils propisochlor (n) from 0.1 mol/l phosphate bu€er solution (pH 7.0) on
(chernozem r, brown forest soil n, sandy soil m) from 0.1 mol/l chernozem
phophate bu€er solution (pH 7.0)

Fig. 5 Comparison of adsorption isotherms of acetochlor (r) and

propisochlor (n) from 0.1 mol/l phosphate bu€er solution (pH 7.0) on
brown forest soil
Fig. 3 Adsorption isotherms of propisochlor on three di€erent soils
(chernozem r, brown forest soil n, sandy soil m) from 0.1 mol/l
phophate bu€er solution (pH 7.0)
that higher amounts of propisochlor than acetochlor are
always adsorbed by the soil. Considering the shape of the
In the case of propisochlor, a larger di€erence can be isotherms, the results will be almost the same as those
seen (Fig. 3). Adsorbed amounts per unit mass of the soil mentioned for propisochlor alone: the di€erence between
decrease in the order chernozem, brown forest and sandy the two isotherms decreases in the order chernozem,
soil, respectively, but the shape of the isotherms is similar brown forest and sandy soil, respectively. In both cases
having two steps. two steps, which refer to two di€erent Langmuir-type
A comparison is made between the two chloroace- isotherms, are present.
tanilide type herbicides concerning their behaviour on The comparison between the various soils shows that
the same soil in Figs. 4, 5 and 6. It can be emphasized both pesticides investigated are adsorbed by a unit mass
50

adsorbate (chloroacetanilide) concerning the adsorbed

amount by unit mass (chernozem) as well as on the unit
surface (sandy soil). Another possible explanation
could be the hydrogen bonding between the molecules
and the active sites.
The shape of the isotherms can be explained by the
previously mentioned ideas. As the soil consist of two
fractions (inorganic and organic), it has two main
di€erent types of active sites where hydrogen bonding
as well as hydrophobic interaction can be responsible for
the two steps.
If homogenous active sites are supposed to be on the
surface, the hypothesis is in harmony with the working
mechanism of the accepted model for the adsorbent
coated with an organic ®lm [1±3]. In the case of the
adsorption of C6-ols on GCB the formation of multilayer
regimes was proved [8]. The isotherm of n-hexanol on
GCB had a similar shape to those presented earlier for
Fig. 6 Comparison of adsorption isotherms of acetochlor (r) and chloroacetanilides on soils. This agrees with the suppo-
propisochlor (n) from 0.1 mol/l phosphate bu€er solution (pH 7.0) on sition that in the case of the herbicides investigated a
sandy soil monomolecular layer forms (®rst step) and subsequently
the interaction between this layer and the dissolved
of the soil in the order: sandy soil<brown forest molecules results in the second step.
soil<chernozem.
As chernozem has the highest organic material
content it has the largest speci®c surface, and sandy soil Conclusion
has the smallest. From this point of view the unit surface
of sandy soil adsorbs the highest amounts of these Propisochlor adsorbs in higher amounts than acetochlor
chloroacetanilides while chernozem adsorbs the least. on the soils studied. Concerning the unit mass of the
Propisochlor contains larger alkyl group than aceto- soils, chernozem adsorbs the highest amounts of the
chlor (Fig. 1) and this results in more hydrophobic herbicides investigated ± contrarily, concerning the unit
character. speci®c surface, it can be observed in the case of the
If the surface of quartz present in the soils is sandy soil. Hydrophobic interaction and/or hydrogen
supposed to be nonpolar (see neutral siloxanes in bonding could be supposed. The shape of the isotherms is
Ref. [14]), these results may refer to hydrophobic similar and has two steps referring to that described by
interaction between the adsorbent (soil) and the Langmuir but it has to be proved in the future.

References

1. Chiou CT, Peters LJ, Freed VH (1979) 7. DeÂkaÂny I, Farkas A, KiraÂly Z, Klumpp 11. Visi EÂ, Ambrus AÂ, Hargitai EÂ, KaÂroly
Science 206:831 E, Narres HD (1996) Colloids Surf G, Ferenczi M, Solymos E, Berczi B
2. Karichko€ SW, Brown BJ, Scott TA 119:7 (1998) Monitoring the pesticide resi-
(1979) Water Res 13:241 8. KiraÂly Z, DeÂkaÂny I, Klumpp E, Le- dues in surface water in Hungary
3. Mortland MM (1970) Adv Agron 22:75 wandowski H, Narres HD, Schwuger (presentation), ETECI'98, Budapest
4. Patzko AÂ, DeÂkaÂny I (1993) Colloids MJ (1996) Langmuir 12:423 12. Balinova A (1988) J Chromatogr 391
Surf A 71:299 9. Zhang PC, Sparks DL (1993) Soil Sci 13. SeboÈk D (1991) Magy-KeÂm Lapja
5. Regdon I, KiraÂly Z, DeÂkaÂny I, Lagaly Soc Am J 57:340 (in Hungarian) 46:422
G (1994) Colloid Polym Sci 272:1129 10. Kolpin WD, Goolsby AD, Thurman 14. Johnston CT, TombaÂcz E (in press) In:
6. Marosi T, DeÂkaÂny I, Lagaly G (1994) ME (1996) Environ Sci Technol Dixon J, Schulze D (eds) Environmen-
Colloid Polym Sci 272:1136 30:1459 tal soil mineralogy, chapter 2
Progr Colloid Polym Sci (2001) 117: 51±55
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

I. PaÂszli Stagnation phenomenon of solid/¯uid

K. LaÂszloÂ
interfaces

Abstract In this article we focus on the adsorption from liquid mixtures

I. PaÂszli the adsorption of binary nonelectro- and electrokinetic interactions.
Department of Colloid Chemistry, lytes, where we try to ®nd that speci®c
LoÂraÂnt EoÈtvoÈs University, P.O. Box 32, feature of the layer structure which
1518 Budapest, Hungary supports the interpretation of exper-
K. LaÂszlo (&) imental data. Our hypothesis, consis-
Department of Physical Chemistry, tent with thermostatical consid-
Budapest University of Technology erations, is related to the criteria of Key words Adsorption á Excess
and Economics, 1521 Budapest, Hungary
e-mail: [email protected] the incidence of the phases and pro- isotherm á Layer structure á
Tel.: 36-1-4631893; Fax: 36-1-4633767 vides a uniform description for both Captation

Introduction liquid sorbed forms a ``captive'' phase which does not

belong to the bulk liquid. If the surface of the clay
The study of the adsorption from binary nonelectrolytes mineral is hydrophobic enough, the alkyl chains
has led to the conclusion that the interfacial layer cannot assemble the adsorbed molecules in liquid-crystalline
be exchanged completely by varying the concentration of form [7]. All the interactions are independent and the
the ¯uid bulk phase. e€ect is obviously related only to the structural
The unexchangeable adsorbed quantities are more or behavior of the equilibrium phase boundary layer.
less analogous with the Stern layer or the stagnation In this article we focus on the adsorption of binary
layer joining directly to the solid phase in the case of nonelectrolytes, where we try to ®nd that speci®c feature
electrical double layers. This phenomenon signi®cantly of the layer structure which supports the interpretation
in¯uences the properties of the double layer. Its of experimental data. Our hypothesis, consistent with
characteristic feature is the assumed constant compo- thermostatical considerations [8], is related to the criteria
sition [1], which still requires correct interpretation. The of the incidence of the phases and provides a uniform
existence of a linear section appearing occasionally in description for both the adsorption from mixtures and
the adsorption isotherms of binary nonelectrolytes and electrokinetic interactions.
the shift of the apparent adsorption azeotropic com-
position can be associated with a portion of the
interfacial layer with a relatively constant composition. The adsorption experiment and the Ostwald±de Izaguirre
The appearance of the linear section depends on the equation
adsorbent and provides the essential basis of the
Schay±Nagy method developed to derive the speci®c The equilibrium state of binary ¯uids and a solid phase
surface area [2]. Therefore, there is an analogy between can be established in the so-called adsorption experi-
the adsorption interactions in the interfacial layer ment. When contacting the two phases of known
and the low-speed electrokinetic processes, etc. Similar quantity, the state parameters change: the homogeneous
behavior was experienced by DeÂkaÂny and coworkers ¯uid phase separates into bulk and interfacial phases,
[3±6] in swelling clay systems. When the adsorption with an equilibrium composition of x1 and xs1 , respec-
takes place in the interlamellar layer, 10±30% of the tively, which are supposedly di€erent from the starting
52

composition of the ¯uid phase (x01 ). It should be The ®rst expression in Eq. (9) can be taken as an
mentioned that xs1 cannot be measured directly. The instruction of measurement; the other two relations are
sorption accompanies the modi®cation of the homoge- the alternative forms of the Ostwad±de Izaguirre equa-
neous distribution of the ¯uid components, which is tion [9].
governed by the ®elds of the solid and ¯uid phases The partial domains in the equilibrium ¯uid phase can
interacting. If the variation of the ``input'' quantities be distinguished by the xsI and xi quasilocal compositions;
s† fl†
results in a continuous variation of the ``output'' data, thus, N1 ˆ ns xs1 and N1 are the contributions of
s
the sorption is, necessarily, a competitive process. The component 1 from n in the state of equilibrium.
sorption equilibrium can be described by the adsorption According to Eq. (9), the Defay adsorption can be given
isotherm derived, for example, from the mass balance. If as
the quantities of the solid/¯uid system in the experiment s† fl†
are constant, the sorption equilibrium is distinguished nr1 ˆ N1 N1 : 10†
only by the spatial distribution of the components of the This quantity (of positive or negative sign) expresses
¯uid phase. the deviation (in the case of positive sign the excess) of
The total number of moles in the ¯uid phase (n0) is the the quantities of the same component in the interfacial
arithmetic sum of the quantities of the components 1 and and bulk phases, respectively. Using the de®nition given
2: n0 ˆ n01 +n02 . In the equilibrium state these quantities in Eq. (9) the so-called relative or Gibbs adsorption
split into ni and nsi , characteristic of the bulk phase and excess [10] can be given as
the adsorption layer (Guggenheim adsorption), respec-
tively. n ˆ n1+n2 and ns ˆ ns1 +ns2 , where ns is the so- r 1 x1
G n1 x1 † ˆ nr1 x1 † ˆ ns1 x1 † ns2 x1 †
called adsorption capacity. The ratio of the components 1 x1 1 x1
can be expressed by the molar fraction as n1 s
ˆ ns1 n : 11†
n2 2
n0i
x0i ˆ 1† All the Guggenheim, Defay or Gibbs excesses char-
n01 ‡ n02 acterize the same interface in the same state, only their
in the initial state. In the equilibrium scaling is di€erent; however, only the Defay excess can be
calculated from experimental data and that is the reason
ni
xi ˆ 2† for its metrological application.
n1 ‡ n2
in the bulk phase, while the average composition of the
interfacial layer is The mass balances and the experimental isotherms

nsi The isotherms may be derived directly from the measured

xsi ˆ : 3†
ns1 ‡ ns2 data according to the ®rst relation in Eq. (9). Various
isotherms published earlier are collected in Fig. 1
If the system is closed, [11±13]. In these examples the ¯uid phase is always a

benzene(1)±ethanol(2) mixture, only the solid phase is
n ˆ n1 ‡ n2 † ‡ ns1 ‡ ns2 :
0
4†
di€erent.
Therefore, The Ostwald±de Izaguirre equation is incapable of
 describing the isotherms of these systems. That is, when
ns1 ‡ n1
the composition of the interfacial layer formed in the
n0 x01 ˆ n01 ˆ ; 5†
ns1 ‡ ns2 xs1 ‡ n1 ‡ n2 †x1 experiment is identical to that of the bulk phase, the

  excess, in accordance with the instruction of the mea-
n0 x01 x1 ˆ ‰n1 1 x1 † n2 x1 Š ‡ ns1 1 x1 † ns2 x1 ; surement (®rst relation in Eq. 9), disappears:
6† nr1 x1 † ˆ 0 : 12†

1 x1 †n1 x1 n 2 ˆ 0 ; 7† In these cases the ¯uid phase is an azeotropic mixture

of a quasisingle component. In the case of benzene(1)±


ethanol(2) mixtures xaze
1 x1 †n0 x01 x1 n0 1 x01  n0 xs1 x1 : 8† ethanol ˆ 0:24 at 25 °C [14], i.e. at
this speci®c bulk composition the Defay adsorption
The de®nition of the reduced (or Defay) excess can be excess has to disappear in the case of all the systems;
given directly from the mass balance: however, this condition is not ful®lled in any of the
8 0 0
examples, as none of the isotherms exhibit an intersection
< n x1 x1 at this composition. Apparently, nr1 and the average layer
nr1 ˆ 1 x †ns x ns : 9† composition (xs1 ), respectively, are not a single-valued
: s s 1 1
1 2
n x1 x1 function of the bulk composition. This leads to the
 53

Fig. 1 Selected excess

isotherms obtained with
benzene(1)±ethanol(2) binary
liquid mixtures at 303.15 K.
The solid phase is (a) activated
carbon, BPL (Pittsburgh
Activated Carbon) [11],
(b) graphitized carbon black,
Graphon (Cabot) [12], (c)
graphitized carbon black,
Graphon (Cabot) [13], (d) silica
gel, Cab-O-Sil (Cabot) [13], (e)
silica gel, Hi-Sil 215 (PPG
Industries) [13], respectively

contradiction that the Guggenheim adsorption is appar- where N* is a linear function of x1. The net adsorption is
ently not a single-valued function of x1. a more complex function of x1, as all the Guggenheim
quantities depend on x1.
The captation of the particles takes place simulta-
neously with a phase separation in the ¯uid phase. Both
Interpretation of the captation processes imply energy exchange. The resulting state is
de®ned by the relation of the two e€ects. If the process
In order to solve this contradiction, it can be supposed
is in¯uenced by the morphology of the solid phase, the
that the molecules in the interfacial layer are adsorbed by
captation may take place only on special structures and
two di€erent mechanisms. A part [Nis (x1)] of the ad-
may correspond, for example, to a molecular sieve
sorbed amount obeys the sorption law, i.e. it varies with
e€ect.
the x1 composition of the equilibrium bulk phase (net
When the characteristic size or shape of the surface
adsorption), while the other part (Ni ) is constant over the
vacancies (holes, cracks, ends of pores, etc.) allows the
whole concentration range. This latter one, the so-called
access of only one of the adsorptive species, as the access
stagnation or captive layer does not take part in the mass
of the other one is, for example, sterically hindered, the
transfer. It is possible only if the equilibrium interfacial
captivated amount is generally made up of the former
layer consist of two isolated subsystems which are
component. The lowest energy state may be reached
thermodynamically closed with respect to chemical
either by the captation of a single component or by the
interactions. Thus, in the ¯uid phase
formation of a mixed layer. When mixed layers are
nSi x1 † ˆ Ni
S†
x1 † ‡ Ni 13† formed, the larger particle ®lls in the larger sites
(supposing that this is energetically favorable), while
and as the other sites are covered by the smaller particles. If the
energies involved in these interactions are comparable, in
Nir x1 † ˆ 1 x1 †N1s x1 † x1 N2s x1 † 14†
most of the cases the captation of the smaller particles is
the Ostwald±de Izaguirre equation can be written as preferred.
  The gross and net adsorptions are described by similar
nri x1 † ˆ N1r x1 † ‡ 1 x1 †N1 x1 N2 : 15† formulas; therefore, these quantities can be separated
only if the captivated amount can be derived separately.
Therefore, the gross isotherm [(nr1 (x1)] can be given as
The existence of an adsorption azeotropic point is useful
the total of the net adsorption [N1r (x1)] and the excess of
for this purpose: the net adsorption disappears at this
the captivated amount. The latter can be given as

composition, and the captivated amount can be derived
N  ˆ 1 x1 †N1 x1 N2 ˆ N1 x1 N1 ‡ N2 16† post hoc.
54

The gross isotherm degenerates at the azeotropic Guggenheim adsorption, the shape of the gross isotherm
composition (xaze
1 ), and according to Eq. (15), it can be is necessarily linear. Alternatively, the condition of the
expressed as linearity is that the net isotherm is also linear or
8
negligible.


< N1 1 xaze 1
N2 xaze
r aze  aze  aze
1 The gross isotherm is linear in the same composition
n1 x1 ˆ N x1 ˆ N1 1 x1 : 17† range where the linearity conditions established by
:
N2 xaze
1 Everett are valid [15, 16]. ME(x1) de®ned by Everett
The ®rst relation in Eq. (17) applies in the case of the can be derived from (Eq. 15) as
simultaneous captation of both components. If only one x1 x2 1
of the ¯uid components is captivated, the captivated ME x 1 † ˆ ˆ N  ‡N s N2 ‡N2s
: 18†
nr1 1 1
amount can be derived from the intercepts of the nr1 (x1) x1 x2
versus x1 captivated diagram. If N1s and N2s are signi®cantly smaller than the real
The captivated excess calculated from Eq. (17) may be captivated amounts (i.e. the net sorption can be neglected
subtracted from the gross isotherm at each composition. within the gross sorption), but both components are
The di€erence is characteristic only for the equilibrium captivated, then the Everett quantity is
¯uid phase. The net isotherms derived from the gross
isotherms of the di€erent solids characterize only the
x1 x21
ME x1 ; N1 ; N2 ˆ
; 19†
¯uid phase and thus the net isotherms related to the N1 N1 ‡ N2 x1
surface area result is a single curve (Fig. 2).
The similarity of the curves con®rms the previous i.e, a nonlinear function of x1. If only one component is
interpretation, as the net isotherms derived from the captivated, then, with the same conditions,
 
various gross functions coincide, except in the lowest 

1
composition range. An analogous behavior has been M E x1 ; N 1  x1 ; 20†
N1
experienced in the case of other (e.g. methanol±benzene)
 
mixtures. 

1
The shape of the gross isotherm re¯ects a superim- M E x1 ; N 2  x1 : 21†
N2
posed e€ect and can be applied to the empirical estima-
tion of the existence of the constant captivated amounts. Both formulas give a linear plot (only the sign of their
intercept is di€erent), and the captivated amount can be
estimated. Conversely, if the Everett representation is
Some consequences of the captivation linear, practically only one of the components is
captivated, and the consequences are related to the
If the captivated amount within the interfacial layer ± in a captivated amount and not to the net captivated of
given concentration range ± signi®cantly exceeds the marginal importance.

Fig. 2 Net isotherms calculated

from the excess isotherms in
Fig. 1. The solid line is the
average derived from the
individual plot
 55

In the case of a given binary mixture, the gross surface can be calculated. The Schay±Nagy extrapola-
adsorption [nr1 (x1)] disappears at di€erent compositions, tion method is based on this approximation [2]; however,
depending on N*. Thus, the variability of the apparent paradoxically, this process is based not on the net but on
azeotropic composition can be interpreted by the the gross isotherm. The condition is that the captivated
captivation. amount and the amount needed for the monomolecular
The stagnation behavior of the interfacial layer is also coverage should be calculated from each other. In this
manifested in the constant composition of the ``inner way, a surface area equivalent to the one derived from
plate'' of the electrical double layer. The stagnation layer the vapor adsorption by supposing a complete mono-
plays a fundamental role in the interpretation of either layer can be obtained. It should be noted that both
the zeta-potential and electrokinetic e€ects or the methods are problematic for the uncertainty of the cross-
stability of sols. sectional area values. The existence of a stagnation
layer in the case of solid/vapor interaction needs further
study.
Discussion The e€ects studied in this work ± without giving a
further discussion hic et nunc ± can also be evaluated by
The aim of this article is to illustrate that some the local thermostatics based on the phenomenological
experimental results can be interpreted in an unusual theory. The problem is related to the criteria of incidence
manner as well. The hypothesis applied here can also be of the physical quantities [8].
useful in establishing methods for surface area determi-
nation.
Acknowledgements This research was supported by the OTKA
When the cross-sectional area (am) of the captivated Fund (Hungary) no. T 025581. I.P. is thankful to the SzaÂntoÂ
compound is practically equal to that of the value used in Ferenc Foundation for their ®nancial support. The technical help
vapor adsorption, the speci®c surface area of the solid of GyoÈrgy Bosznai is gratefully acknowledged.

References

1. Lyklema J (2000) Electrokinetics: The 6. DeÂkaÂny I (1992) Pure Appl Chem 12. Brown CE, Everett DH, Morgan CJ
dynamics of the stagnant layer (plenary 64:1499 (1975) Trans Faraday Soc 71:883
lecture). In: Abstracts of the 10th 7. DeÂkaÂny I, SzaÂnto F, Weiss A (1989) 13. Matayo DR, Wightman JP (1973)
International Conference on Colloid Colloids Surf 41:107 J Colloid Interface Sci 44:162
and Interface Science, 23±28 July 2000, 8. PaÂszli I (2000) In: Abstracts of adsorp- 14. Ohe S (1989) Vapor±liquid equilibrium
Bristol, UK tion and nanostructures ± from theory data. Elsevier, Amsterdam
2. Schay G, Nagy LG (1961) J Chim Phys to application, 25±28 September 2000, 15. Everett DH (1964) Trans Faraday Soc
149 Budapest, Hungary, pp 149±151 60:1803
3. DeÂkaÂny I, Weiss A (1990) Mag Kem 9. Ostwald W, de Izaguirre R (1922) 16. Klinkenberg A (1959) Rec Trav Chim
Foly 96:206 Kolloid-Z 279 78:83
4. DeÂkaÂny I, Nagy LG (1990) Colloids 10. SzekreÂnyesy T, FoÂti G (1981) Kem
Surf 58:252 Kozl 55:397
5. DeÂkaÂny I, Nagy LG (1991) J Colloid 11. Sircar S, Myers AL (1970) J Phys
Interface Sci 147:119 Chem 74:2828
Progr Colloid Polym Sci (2001) 117: 56±62
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

M. Mielke Measures to determine the hydrophobicity

R. Zimehl
of colloidal polymers

Abstract The role of latex disper- pared to the adsorption of the corre-
sions as well as water-soluble poly- sponding cationic dyes on negatively
mers in industrial and charged particles. We found a red-
pharmaceutical applications (i.e. shift in the absorption maximum of
analytical and drug delivery systems) the anionic dyes after adsorption
is growing fast. An important at- onto the positively charged particles.
tribute of polymer particles is the A blueshift was observed for cationic
high adsorption capacity for organic dyes bound to negatively charged
moieties (e.g. of molecules of bio- particles. We deduce from our mea-
logical origin). It is important that surements that the nature of the
the biologically active molecules re- surface charges present at the parti-
main fully hydrated during the ad- cle±liquid interphase alters the sur-
sorption by the colloidal system; face characteristics of the particles.
therefore, it is essential to have a We suppose that cationic charged
measure for the hydration of both polymer particles are more hydro-
adsorbent particles and adsorptive phobic than particles from the same
M. Mielke (&) á R. Zimehl molecules and to correlate its value matrix with negative surface charges.
Institute of Inorganic Chemistry, with other properties of the poly- In a qualitative model, we illustrate
University of Kiel, Germany meric material. We have estimated the governing role of hydration forc-
Present address: M. Mielke the hydrophobic/hydrophilic bal- es on particle aggregation.
Unilever Research, ance with adsorption isotherms of
45 River Road, polymethine dyes (surface probes). Key words Microgel á Dye
Edgewater, NJ 07020 The adsorption of the anionic dyes is adsorption á Polymer colloids á
e-mail: [email protected]
Tel.: 201-8402840 10 times stronger on positively Water structure á Hydrophobic
Fax: 201-8402180 charged polystyrene particles com- hydration

Introduction measurements, by either the sessile-drop or the inverted-

plate method. For polymer colloids in nonmiscible ¯uids,
There are only a few ways to measure or compare the depending on the hydrophobicity the particles concen-
hydrophobicity of surfaces in disperse systems. Contact- trate in either phase. Over the last few decades, several
angle measurements cannot be applied to the hydrated improvements to the investigation techniques have been
colloidal particle in its original dispersion medium. suggested, but there is virtually no easy method to
Polymer particles need to be dissolved in an organic provide the desired information.
liquid to cast the polymer ®lm for the contact-angle In the last few years, we have focused our intention on
measurements. The properties of the dry polymer ®lm the determination of the so-called surface hydrophobic-
certainly di€er from the properties of a strongly curved ity of colloidal particles and biopolymers [1]. We were
surface; therefore, it is insucient to determine only the searching for simple and e€ective methods to measure
contact angle on macroscopic surfaces with conventional the extent of hydrophobicity of polymer latices and
 57

developed a preferential solvent adsorption method from Preparation of negatively charged poly(methyl methacrylate)
binary liquid mixtures. In this technique, the colloidal
particles can preferentially adsorb either the polar or Sodium dodecyl sulfate (0.45 g) in water (500 ml, double deionized,
Seradest) was stirred at 600 rpm and heated to 80 °C under nitrogen.
nonpolar liquid from the liquid mixture. Careful analysis A 1.3-ml aliquot of a 5.2% ammonium peroxodisulfate solution and
of the adsorption-excess isotherm gave us some useful 1.5 ml of a 7% potassium phosphate solution were added. One
information about the stagnant layer at the surface of the quarter of the monomer mixture as 124.8 ml methyl methacrylate
colloidal particles and the properties of the polymer (Fluka) and 4.7 ml ethylene glycol dimethacrylate (Fluka) was
added. The rest of the monomer mixture was added over 90 min
network as well [14]. from an addition funnel. After the complete addition of the
In a second set of experiments we investigated the monomers over 2h the reaction was stopped and the latex ®ltered.
adsorption of hydrophobic yet soluble organic dyes onto
di€erent polymer latices. The measurements were con- Preparation of poly(methyl methacrylate)
ducted using a UV±vis spectrophotometer. The advan-
tage in measuring in the visible spectrum is that N-Ethyl-N-hexadecyl-N,N-dimethyl ammonium bromide (0.6 g) in
impurities (e.g. surfactants, monomers) released by the water (500 ml, double deionized, Seradest) was stirred at 600 rpm
colloidal particles over time do not disturb the spectrum and heated to 70 °C under nitrogen. ADMBA (0.13 g) and one
quarter of the monomer mixture (125 ml methyl methacrylate and
of the dyes. The shift in the absorption spectra of 5 ml ethylene glycol dimethacrylate) was added. The rest was
precipitated polymer dye conjugate and the shape of the added over 90 min. After 3 h the reaction was stopped and the
adsorption isotherm of the dye provides information latex ®ltered.
about the particles hydrophobicity. The characterization of these particles is consistent with the data
published in Ref. [14] and the references therein.

Experimental Adsorption experiments

Preparation of particles The Rose Bengal method
In general the polymerization was carried out in a 500-ml Rose Bengal (DAB 8, 46, 132±135) is a standard reagent to dye
round-bottomed four-necked ¯ask with stirrer, cooler and nitrogen biological samples. The xanthene dye is adsorbed depending on
purge. how lipophilic the material is. The molecule is dipositively charged
and soluble up to 1 mmol/l. Owing to its hydrophobic nature it is
Preparation of negatively and positively charged polystyrene strongly adsorbed by polymer surfaces.
Standards of Rose Bengal (0.6±0.02 mmol/l) were used to
measure a calibration curve. These standards (6 ml) were mixed
Water (200 ml, double deionized, Seradest) was stirred at 350 rpm with 1 ml PS latex (2.5 and 6% wt/wt), equilibrated for 3 h and
and heated to 90 °C under a nitrogen blanket. After 10 min 25 ml, centrifuged. The concentration of Rose Bengal in the supernatant
for negatively charged polystyrene, PS( ) ), or 12.5 ml, for (cequil) was determined using a UV±vis spectrophotometer (Hitachi
positively charged PS, PS( + ), styrene (stabilized with 12 ppm 2000) and the adsorbed amount, G (millimoles per gram), was
catechol, HuÈls) was added. Potassium persulfate (0.25 g), for calculated.
PS( ) ), or 0.5 g ADMBA, Wako), for PS( + )], in 25 ml water
was added after 5 min. The stirrer was adjusted to 60 rpm. The
warm dispersion was ®ltered through glass wool and after cooling
was ®ltered through a nylon mesh.

Preparation of negatively charged poly(butyl methacrylate)

Water (480 ml, double deionized, Seradest) was stirred at 600 rpm
and heated to 80 °C under nitrogen. Butyl methacrylate (BMA,
260 ml, Fluka), sodium dodecyl sulfate (2 g) and acrylic acid (2 ml)
were added. After 30 min, 2 g potassium peroxodisulfate in 25 ml
water was added. The stirrer was adjusted to 400 rpm. The reaction
was stopped after 4.5 h and the latex was ®ltered.

Preparation of positively charged poly(butyl methacrylate) Adsorption of polymethine dyes

Water (480 ml, double deionized, Seradest) was stirred at 600 rpm The polymethine dyes were prepared by DaÈhne and coworkers
and heated to 65 °C under nitrogen. BMA (130 ml, Fluka), [3±5]. They are available as both cations and anions. For the
N-ethyl-N-hexadecyl-N,N-dimethyl ammonium bromide (1.3 g, measurements, standards of the dyes were prepared and a
Fluka), acrylamide (1 g) and, after 15 min, ADMBA (1.2 g) were calibration curve recorded. A 6-ml aliquot of the standards
added. The temperature was raised to 70 °C and the reaction (4±0.0003 mmol/l) was mixed with 1 ml latex (solids: 2.5±6%),
started. Bluish opalescence was observed. The temperature was equilibrated for 3 h and centrifuged. The concentrations, cequil, in
reduced to 60 °C. After 3 h the reaction was stopped and the latex the supernatant were measured with a UV±vis spectrophotometer
was ®ltered. (Hitachi 2000) and the adsorbed amount, G, was determined by
58

subtraction. The short equilibration times were chosen because the

lithium and potassium salts of C7( ) ) are sensitive towards
hydrolysis. The measurement of the sample had to be performed
quickly after the calibration in order to achieve reproducible data.

Fig. 1 Adsorption isotherms of Rose Bengal onto polystyrene (PS),

poly(butyl methacrylate) (PBMA), and poly(methyl methacrylate)
(PMMA) latices at 20 °C

It is evident from Fig. 2 that the plateau value for

adsorption of Rose Bengal onto the positively charged
polymer is close to the number of surface charges on the
PS particles.
The di€erence in hydrophobicity of PS, BMA and
PMMA becomes apparent while cleaning the dispersions
extensively. BMA and PMMA latices form gels during
cleanup of the colloids by dialysis and turn transparent,
while PS dispersions form no gel under any conditions
and after dialysis stay turbid. The in¯uence of the
Results and discussion cleaning of the Latex particles on their chemical behavior
is discussed in reference [14]. This di€erent character of
Adsorption isotherms of Rose Bengal for several poly- the polymers is clearly revealed by the adsorption
mer latices are presented in Fig. 1. PS and poly butyl isotherms and show that Rose Bengal is suited to
methacrylate (PBMA) latices exhibit a high-anity document big di€erences in hydrophobicity. It recon-
isotherm and for PS there is a very steep initial increase, ®rms that PS is the most hydrophobic of the systems
whereas the initial increase for the poly methyl methac- analyzed. The decay of the adsorption isotherm of PS
rylate (PMMA) latices is really low and the shape of the latices at higher equilibrium concentrations is due to
isotherm is not sophisticated at all. Obviously the Rose aggregate formation of the dyes [2].
Bengal is adsorbed di€erently by the polymers used in In contrast to the less speci®c Rose Bengal we wanted
this study. The plateau value of the adsorption isotherm, to introduce surface probes which are adsorbed highly
Gmax, which determines the relative hydrophobicity scale speci®cally. For that reason we choose di€erent polyme-
strongly depends on the backbone polymer of the latex thine dyes. They were prepared by DaÈhne and cowork-
particles and on the sign of the charged groups incorpo- ers [3±5] and are available as both cationic and anionic
rated in the polymer network (Table 1). The amount forms. The main advantage lies in the fact that the dyes
adsorbed by the PS()) particles is roughly 1.6 times more can be used as an adsorptive counterion for the
than for the PS(+) particles. corresponding latex particle. Thus, the e€ect of repul-
To level out variations in the speci®c surface area of sive forces between negatively charged PS particles and
the di€erent latex samples it is necessary to calculate G in the anionic Rose Bengal is leveled out. Despite the fact
millimoles per square centimeter. The recalculated values that DaÈhne and coworkers [3±5] also prepared C3
for cationic and anionic PS latices are presented in Fig. 2. bodies the dyes used in our study had a C5- and

Table 1 Plateau value, Gmax,

of Rose Bengal with di€erent Latex PS(+) PS()) PBMA(+) PBMA()) PMMA(+) PMMA())
latices
Gmax (mmol/g) 0.072 0.072 0.018 0.012 0.017 0.0037
 59

Table 2 Saturation concentration, Gmax, of C7 and C5 poly-

methine dyes onto polystyrene latices

Latex PS(+), PS(+), PS()), PS()),

C7()) C5()) C7(+) C5(+)

Gmax (mmol/g) 0.83 0.48 0. 14 0.038

Fig. 2 Adsorption of Rose Bengal onto PS latices at 20 °C (G/mmol/

cm2). The double arrows show the surface charge amount, S, of the PS
particles

C7-carbon skeleton. The adsoprtion data obtained with

the C7 and C5 dyes were highly reproducible. The
isotherms obtained from PS latices as adsorbents for C7
and C5 dyes used as counterions are shown in Fig. 3.
The plateau values, Gmax, are very di€erent. Now the Fig. 4 Adsorption of C7 onto PS latices at 20 °C (G/mmol/cm2). The
di€erence between PS(+) and PS()) with C7 and as well double arrows show S of the PS particles
as with C5 becomes apparent. The di€erence in
adsorption is almost 1 order of magnitude. The cationic
PS(+) latex particles are the most hydrophobic and C5
is adsorbed less than C7. The adsorption capacity of
PS()) particles, i.e. the saturation concentration, Gmax,
at the plateau of the adsorption isotherm, is roughly
1.6 times bigger than the capacity of the PS(+) particles
(Table 2).
After recalculation of G to millimoles per square
centimeter, the di€erences between PS()) and PS(+) are
still prominent enough to eliminate the in¯uence of
particle size on G (Figs. 4. 5). The G value of C7()) with
PS(+) is higher by a factor of 16 and the one obtained
with C5(+) is 10 times higher than the particle charge
amount. Fig. 5 Adsorption of C5 onto PS latices at 20 °C (G/mmol/cm2). The
double arrows show S of the PS particles

The PS()) particles adsorb 9 times more of the

cationic dye C7(+) than it has charges. On the other
hand, the plateau value of the adsorption isotherm of
C5(+) with PS()) coincides with the number of surface
charges, S, of the latex particles. The polymethine dyes
seem to be suitable as surface probes and may scan
hydrophobic surfaces in the aqueous phase.
Isotherms obtained from microgels (BMA, PMMA)
as adsorbents and C7 and C5 dyes used as counterions
are shown in Fig. 6. The di€erence in Gmax between
positively and negatively charged latices is a factor of 2
(PMMA) and 4 (PBMA). The adsorbed amounts are low
Fig. 3 Adsorption isotherms of polymethine (C7 and C5) onto PS even for C7 owing to the hydrophilic character of the
latices at 20 °C. PS particles and dye molecules are oppositely charged microgels. This is the reason why no data could be
60

Some results of the spectrophotometric measure-

ments are summarized in Fig. 7. The absorption max-
imum of the anionic polymethine dyes C7 and C5
adsorbed on cationic PS particles is shifted to the red
region of the absorption spectrum. In contrast, the
spectrum of the C7 cation adsorbed to anionic PS
particles shows a blueshift. All the other polymers used
exhibit a blueshift of the absorption maximum of the
dyes. This phenomenon is well known from adsorption
measurements of cationic dyes on clay minerals [6±8]. A
blueshift is expected when dyes with delocalized elec-
trons form dimers in solution. Charge separation
elevates the energy level of the p ) p* transition in the
polymethine molecule [9]. A redshift can only be
Fig. 6 Adsorption of polymethine (C7 and C5) onto PBMA and observed when the polymethine dyes are present in a
PMMA latices at 20 °C
nonpolar medium [5] or after adsorption on a nonpolar
surface [3]. In a nonpolar environment both mesomeric
achieved with C5. The curve of PMMA()) versus C7(+) structures of the polymethine dyes are energetically
(Gmax ˆ 0.018) shows how sensitive the photometric equal and the p ) p* transition is lowered. Only the
method is (cf. Table 3). The sensitivity of the experimen- PS(+) particles are hydrophobic enough to lower the
tal setup is further supported by the high extinction electron potential in the dye molecule.
coecient of the polymethine dyes (Table 4).

Conclusions
Polymethine dyes as surface probes
To summarize our results with dye adsorption measure-
To gain further insight into the adsorption mechanism ments we note that the more hydrophilic microgel latex
and the molecular arrangement in the adsorbed dye particles adsorb less dye compared to their hydrophobic
layers, we prepared latex sediments from the polymer PS counterparts. However, all the positively charged
dispersions by centrifugation. The samples contained samples (PS, PBMA, PMMA) showed a signi®cantly
coagulated latex particles with the dyes adsorbed on their higher absorbed amount of dye than the corresponding
surface. The dye concentration was chosen in a way so negatively charged polymer of the same matrix. The
that the adsorbed amount of dye of one sample
corresponded to the beginning and the amount of
another one to the middle of the plateau region of the
isotherm. After equilibration and centrifugation the
samples were dried for 24 h at 50 °C. The dye±latex
coagulates as well as pure dye samples were ground and
pressed in KBr. The adsorption maxima of the samples
were measured using a UV±vis spectrophotometer (Cary
5, Varian).

Table 3 Saturation concentration, Ggr;max, of C7 and C5 poly-

methine dyes onto microgels

Latex PBMA(+), PBMA()), PMMA(+), PMMA()),

C7()) C7(+) C7()) C7(+)

Gmax 0.074 0.02 0.038 0.018

(mmol/g)

Table 4 Extinction coecient, e, of the polymethine dyes [3]

Polymethine C7(+) C7()) C5(+) C5()) Fig. 7 Shift in absorption maximum of dye/latexcoagulates. Absorp-
tion maximum of pure dye in KBr (dotted line); absorption maximum
e (l/mol ´ cm) 189,000 179,000 117,000 148,000 coagulates at two di€erent dye concentration in the plateau region
(solid lines)
 61

Fig. 9 Coagulates from PS particles and adsorbed polymethine dyes

as counterions

We conclude that with hydrophobic latices, like PS,

the hydrophobic/hydrophilic balance governs the parti-
cle's behavior mainly in the particle±solvent interphase.
The water molecules around the positive surface charges
are similar to the water structure adjacent to a hydro-
phobic surface. Positive charges ®t well into the hydro-
phobic hydration water layer, whereas negative surface
charges behave oppositely. The water molecules are
forced by the negative charge to orient in a reverse
manner, which leads to a more random water structure.
This structure is comparable to the interphase of swollen,
more hydrophilic polymers. When organic molecules are
adsorbed onto positively charged polymer particles, the
systems gain more entropy compared to a system with
negatively charged polymers as adsorbents surrounded
Fig. 8 Simple hydration model of a charged polymer surface. The by an unorganized water structure.
covalently bound charges are surrounded by a water layer. Grey:
water molecules point with hydrogen atoms towards the bulk phase Fritz et al. [13] studied a new class of drug carrier for
(hydrophobic hydration); white: hydrogen atoms of water molecules oligodeoxyribonuclotides. The particles carried positive
point towards the negative charge groups (amidinopropane) and showed high drug load
capacity. It is interesting that the organic adsorptives
were immobilized and were not attack by nuclease P1
di€erence in Gmax between positively and negatively
enzyme in contrast to unadsorbed molecules. These
charged particles is a factor of 6 for PS, 4 for PBMA and
results of Fritz et al. are in good agreement with our
2 for PMMA. Thus we assume that positively and
water structure model (Fig. 8).
negatively charged latex particles are surrounded by a
Owing to the surface morphology of the positively
di€erent particle±solvent interphase (Fig. 8).
charged particles, which are compact and contain less
This simple model is further supported by earlier
water, organic molecules can get closer to the particle
adsorption studies on the adsorption of tetraphenyl-
surface and bind. A redshift is observed. Negatively
phosphonium and tetraphenylborate ions onto PS latices
charged particles carry a more polar and swollen
and ion-exchange beads [2, 10]. When positively charged
interphase. Organic molecules get into poorer contact
adsorbents adsorb negatively charged organic counteri-
with the particle surface. Also less water is set free by
ons, type 2 and type 3 isotherms (no saturation adsorp-
hydrophobic interaction. The polarity of the particle±
tion) are likely to occur. Negatively charged surfaces or
solvent interphase results in a blueshift of the adsorbed
particles with wel-hydrated poly(ethylene glycol) brushes
dye molecules.
and positively charged counterions exhibit type 1 iso-
therms with an adsorption maximum and a decay of the Acknowledgements We are grateful to L. DaÈhne for preparation of
isotherm at higher ion concentrations [11, 12]. the dyes and to G. Lagaly for helpful advice.
62

References

1. Mielke M, Zimehl R (1998) Ber Buns- 7. Yariv S, Ghosh DK, Hepler LG (1991) 11. Hiemenz PC (1977) Principles of col-
enges Phys Chem 102:1698±1704 J Chem Soc Faraday Trans 87:1201± loid and surface chemistry. Dekker,
2. Priewe J (1994) Thesis. University of 1207 New York
Kiel 8. Yariv S (1988) Int J Trop Agric IV:1±19 12. Rouquerol F, Rouquerol J, Sing K
3. DaÈhne L, Biller E (1998) Adv Mater 9. Klessinger M, Michl J (1989) Lichtab- (1999) Adsorption by powders and
10:241±245 sorption und Photochemie organischer porous solids. Academic, London
4. DaÈhne L, Horvath A, Weiser G, Reck Molekuele. VCH, Weinheim 13. Fritz H, Maier M, Bayer E (1997)
G (1996) Adv Mater 8:486±490 10. Mielke M, Lagaly G, Zimehl R (1997) J Colloid Interface Sci 195:272±288
5. DaÈhne L, Reck G (1995) Angew Chem Stability of colloidal polymers: aggre- 14. Mielke M (1999) Thesis. University of
107:735±737 gation of cationic and anionic latex Kiel
6. Grauer Z, Grauer GL, Avnir D, Yariv particles with organic gegenions. Pro-
S (1987) J Chem Soc Faraday Trans ceedings of the 7th Conference on
83:1201±1207 Colloid Chemistry 200±203, Budapest
Progr Colloid Polym Sci (2001) 117: 63±69
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

A. Farkas Interlamellar adsorption of organic

I. DeÂkaÂny
pollutants on hydrophobic vermiculite

Abstract The adsorption isotherms and the structure of the interlamel-

of nitrobenzene, 2-chlorophenol and lar space were evaluated. The free
4-chlorophenol from water on enthalpy of adsorption and the
hydrophobic vermiculite were adsorption capacity were calculated
studied. The excess isotherms were by analyzing the adsorption iso-
obtained by the immersion method. therm on the basis of the Gibbs
A. Farkas á I. DeÂkaÂny (&) The basal spacings of the hydro- equation and by the Everett±Schay
Department of Colloid Chemistry phobic vermiculite organocomplex- method.
and Nanostructured Materials es in the adsorption equilibrium
Research Group of the Hungarian were determined by X-ray di€rac- Key words Adsorption á
Academy of Sciences,
University of Szeged, Aradi v.t.1, tion. By combining these two inde- Hydrophobic clays á Organic
6720 Szeged, Hungary pendent methods, the composition pollutants á X-ray di€raction

Introduction 14]. The concentration of organic molecules in the

interlamellar space enclosed by the silicate lamellae is
The adsorption of organic molecules on soil components calculated from the adsorption-excess isotherm. Know-
± particularly on clay minerals ± and their organophilized ledge of experimentally determined excess isotherms
derivatives has attracted much interest lately [1±6]. Clay also allows the calculation of some of the thermody-
minerals are the most reactive soil components which, namic properties of the adsorption layer at the solid/
owing to their large speci®c surface area and ion- liquid interface. Using the Gibbs equation [15, 16] the
exchange capacity adsorb di€erent organic pollutants free enthalpy of adsorption may be determined and
[7±10]. In the last few years studies became increasingly combined with the excesses to calculate adsorption
focused on solutions of water with organic molecules capacities [6±8], which, in the case of adsorption in
which are very poorly miscible with water, not least dilute solutions, are often impossible to determine from
because of their outstanding environmental signi®cance the Langmuir adsorption isotherm. Changes in inter-
[11±13]: these solutions are excellent models for water lamellar distances owing to the interlamellar adsorption
polluted with toxic aromatic compounds The exact are monitored by X-ray di€raction (XRD) measure-
description of their adsorption on clay minerals is ments. Values of basal spacing determined by XRD
therefore essential for environmental protection. The make possible the calculation of the volume of the
experimental results will open the way for the develop- interlamellar space and ± knowing the amount and
ment of new procedures for the immobilization of volume of alkyl chains and using the excess isotherms ±
pollutants in static and ¯owing systems. also its composition over the entire concentration
The surface polarity of clay minerals is altered by range, Thus, combining the results obtained by two
hydrophobization via treatment with cationic surfac- independent methods yields detailed information on the
tants. As a consequence, they become capable of adsorption equilibrium and the structure of the
adsorbing organic components very e€ectively [9, 10, adsorption layer.
64

Determination of the adsorption capacity r n†

from adsorption isotherms of dilute solutions n1 ˆ n0 x01 x1 †=m ˆ n0 Dx1 =m ; 1†
r n†
Adsorption on a solid/liquid interface is a displacement n1 ˆ ns1 x2 ‡ ns2 x1 ˆ ns1 ns x1 ˆ ns xs1 x1 † ; 2†
process. Consequently the positive adsorption of one 0
where n is the total material amount of the liquid, and x01
component (i.e. the increase in its concentration in the
x1 are the initial and equilibrium molar fraction,
interfacial layer) is accompanied by the negative adsorp-
respectively, of component 1 in the liquid phase, m is
tion of the other. On the basis of the relationships
the mass of the adsorbent, ns ˆ ns1 +ns2 is the material
postulated by the Gibbs model of solid/liquid interfaces,
content of the adsorption layer and xs1 ˆ (1 xs2 ) ˆ ns1 /ns
the reduced excess amount normalized to unit mass of
r n† is the equilibrium molar fraction of component 1 in the
adsorbent (n1 ) and the Ostwald±de Izaguirre equation
adsorption layer. If component 1 is preferentially ad-
derived from the material balance of the components are
sorbed as compared to component 2, the excess, nr(n),
formulated as [15, 16]
approximately equals the material amount, ns1 [17]. In
dilute solutions, in the case of preferential adsorption of
the dissolved material the volume of the dissolved
material in the adsorption layer is approximately
r n†
V1s ˆ ns1 Vm,1  n1 Vm,1 [7, 8]. The adsorption capacity
of pure component 1 is
ns1;0 ˆ ns1 ‡ rns2 ˆ ns xs1 ‡ rns xs2 ; 3†
where r ˆ Vm,2/Vm,1 ˆ ns1;0 /ns2;0 ,
i.e. the ratio of the molar
volumes of the pure components. After the introduction
of the separation factor, S ˆ xs1 x2/xs2 x1, the equation
ns ˆ ns1 ,0(Sx1 + x2)/(Sx1 + rx2) is obtained for the ma-
terial content of the adsorption layer. The value of ns1 ,0
may be determined from the slope and the intersection of
the Everett±Schay linear representation [15, 16], i.e.
 
x1 x2 1 r S r
ˆ ‡ x 1 : 4†
n
r n† ns1;0 S 1 S 1
1
Using the integrated form of the Gibbs equation
describing solid/liquid interfaces [15±17], the free enth-

Fig. 1 a Adsorption-excess isotherms of nitrobenzene from water on

n-octadecylammonium vermiculite (C18 -vermiculite) (r). b Adsorp-
tion-excess isotherms of nitrobenzene from water on sodium Fig. 2 Adsorption-excess isotherm of 2-chlorophenol (d) and
montmorillonite (d) 4-chlorophenol (h) from water on C18-vermiculite
 65

alpy of adsorption may be formulated in the following content of the interfacial layer, ns. The volume per unit
way: cell of the alkyl chains hydrophobizing the silicate layer,
Z x1 r n†  
n1 d ln c1
D21 G ˆ RT 1‡ dx1 : 5†
0 1 x1 †x1 d ln x1
The index 21 indicates that the molecules of
component 2 are exchanged for those of component 1
and c1 is the activity coecient of component 1 in the
bulk phase. In ideal solutions or in solutions considered
to be ideally dilute (like our systems), the value of the
parenthetic term containing the derivative of the
activity coecient is 1. Using the molar free enthalpies
of the components (gsi ), the equation
s s s
D21 G ˆ n1 g1 g2 =r† holds for the entire concentration
range. After combination with Eqs. (2) and (5) and
appropriate rearrangements, the following relationship
is obtained [7]:
D21 G x1
r n†
ˆ D21 g ‡ ns D21 g r n†
: 6†
n1 n1
The linear representation of the equation yields the
molar free enthalpy of adsorption, D21g, and the material

Fig. 3 Everett±Schay representation of the adsorption-excess iso- Fig. 4 a Free enthalpy of adsorption of 2-chlorophenol (d),
therm for 2-chlorophenol/water (d) and 4-chlorophenol/water (h) on 4-chlorophenol (h) and nitrobenzene (n) from aqueous solutions
C18-vermiculite on C18-vermiculite plotted against x1,r. b as a for x1,r < 0.0004

Table 1 Adsorption capacity

from the Everett±Schay Pollutant ns1;0 (mmolg)1) ns (mmolg)1) )D21g (Jmmol)1) Ssep Ssep
representation, the results of (Eq. 4) (Eq. 6) (Eq. 6) (x1 = 0.0002) (x1 = 0.002)
combination of adsorption-
excess and free-energy data and Nitrobenzene 0.72 ± ± 90 ±
the distribution ratio, Ssep 2-Chlorophenol 2.09 1.08 4.89 600 70
4-Chlorophenol 2.12 0.70 5.74 400 70
66

in units of cubic nanometers per (Si,Al)4O10, for n-

alkylammonium vermiculite as adsorbent is
Valk ˆ f0:205‰0:127 nCC ‡ nCN † ‡ 0:28Šgn : 7†
The term in parenthesis expresses the length (in
nanometers) of the alkyl chains attached to the surface
(nCC and nCN are the number of carbon±carbon and
carbon±nitrogen bonds). The cross-sectional area of the
all-trans alkyl chain is taken as 0.205 nm2. The number
of charges per formal unit (surface charge density,
n ˆ 0.76) was obtained from the amount of organic
material determined by thermogravimetric analysis. The
thickness of the silicate layer is 0.94 nm and the surface
area of the formal unit is 0.2475 nm2; thus, the interla-
mellar volume is
 
Vint ˆ 0:2475 dL 0:94† nm3 = Si; Al†4 O10 : 8†
The volume of the ``free'' interlamellar space is the
di€erence Vint)Valk.
Vint Valk ˆ V1s ‡ V2s;b ; 9†

1 ˆ Ualk ‡ Us1 ‡ Us;b

2 ; 10†
where V2s;b
ˆ V2s b
‡ V is the combined volume of the
water molecules present in the adsorption layer and
the so-called bulk liquid ®lling the adsorption space [5].
The latter does not participate in the formation of
the adsorption layer; it is, however, controlled by the
forces of adsorption, like all molecules in the interlamel-
lar space. Owing to preferential adsorption of the

Fig. 6 a Basal spacing of C18-vermiculite in aqueous solution of

2-chlorophenol/water (d), 4-chlorophenol/water (h) and nitroben-
zene/water (n). b Structure of C18-vermiculite with an alkylammo-
nium monolayer with aromatic components. c Structure of C18-
vermiculite with an expanded monolayer with aromatic components

Fig. 5 Combination of adsorption-excess and free-enthalpy data in dissolved material, Vb consists mostly of water, which
2-chlorophenol/water (d) and 4-chlorophenol/water (h) on is the reason why it may be combined with V2s . Division
C18-vermiculite of Eq. (9) by Vint and subsequent rearrangement yield
 67

Table 2 Basal spacings of n-octadecylammonium vermiculite in

water and in di€erent solutions

Experimental
dL (nm)

Dry sample 2.77

Suspended in water 2.91a
Nitrobenzene 3.41
2-Chlorophenol 3.60
In saturated solution of 4-chlorophenol 3.55
a
Calculated for the bilayer of octadecylammonium ions with 55°
chain orientation

Fig. 8 Composition of the interlamellar space of the C18-vermiculite

in 2-chlorophenol/water solution

Adsorption of the pollutants was studied on n-octadecylammo-

nium vermiculite (C18-vermiculite). The original vermiculite sam-
ples (South Africa, cation-exchange capacity of 1.97 mmol/g) was
organophilized by the addition of octadecylammonium chloride (in
a 1.5-fold excess over the cation-exchange capacity) for an ion-
exchange time of 1 month at 65 ‹ 0.5 °C. The organic derivative
was washed, extracted, dried and cut into small pieces (about
1 ´ 1 mm).

Methods
Fig. 7 Free interlamellar volume of C18-vermiculite in 2-chlorophe-
nol/water solution Adsorption-excess isotherms were determined in the static system
(immersion method) at 25 ‹ 0.1 °C, Known volumes (9 cm3) of
the solution were added to 0.03±0.3 g C18-vermiculite. After
Eq. (10) for the volume fractions of the alkyl chain, Falk equilibration the concentration of the supernatant and original
solution was determined using a Zeiss liquid interferometer at
and the components, Usi . Representation of these data as 25 ‹ 0.1 °C.
a function of the entire range of relative concentrations X-ray di€raction measurements were carried out using a Phillips
or the real volume fraction of the bulk phase gives a X-ray di€ractometer (PW 1930 generator, PW 1820 goniometer)
demonstrative view of the interlamellar concentration of with Cu Ka radiation at 2Q ˆ 1±10°. In order to prevent the
evaporation of the liquids, the adsorbent in contact with the
the various components of the system. equilibrium solution was coated by a thin Mylar foil. The basal
spacing (dL) was calculated from the (001) re¯ection using the
Bragg equation.
Experimental
Materials Results and discussion
The dilute solutions studied were saturated solutions of aromatic
pollutants: nitrobenzene, 2-chlorophenol or 4-chlorophenol (com- Adsorption of nitrobenzene from water solution on
ponent 1), distilled water (component 2). A series of dilutions were organophilized octadecylammonium±vermiculite is pos-
made for 10±12 points in the range x1,relative ˆ x1/x1,saturation ˆ 0)1. itive (preferential) with respect to the organic component
Saturated solutions were made at 20 ‹ 0.5 °C by addition of the over the entire composition range. In other words, the
organic compound to distilled water under continuous mechanical
shaking for 2 weeks. The upper, aqueous phase of lower density is
interfacial layer is enriched by the aromatic molecules.
the stock solution and was stored in a dark bottle for protection The isotherm (Fig. 1a) reaches saturation at an excess
r n†
against photodecompostion. around n1 ˆ 0.2 mmol/g. The course of adsorption is
68

signi®cantly a€ected by the surface polarity of the clay The free-enthalpy functions determined according to
mineral, since on surfaces of polar character either the Gibbs' equation (Eq. 5) are plotted against relative
entire adsorption isotherm or its initial segment indicates molar fractions in Fig. 4. The curves for the two
preferential adsorption of water. The example shown in chlorophenols are quite similar at x1,r > 0.1. Owing to
Fig. 1b is again the adsorption of nitrobenzene from an the lower solubility and reduced adsorption, the free
aqueous solution, but on sodium montmorillonite as enthalpy is much less a€ected for the nitrobenzene
r n†
adsorbent. The excess isotherm shows preferential solutions. The representation D21G/n1 based on the
adsorption of water (negative adsorption for nitroben- free-enthalpy curve yields the values of molar free
zene). The reason behind this phenomenon is the enthalpies and ns (Fig. 5, Table 1). The basal spacing
excellent hydratation of Na+ ions and the hydrophilic of C18-vermiculite as a function of the relative molar
character of the surface. fraction of the solutions is shown in Fig. 6a. The excess
The 2- and 4-chlorophenols are preferentially ad- isotherms are in good correlation with the results of the
sorbed on the surface of hydrophobic vermiculite. X-ray di€raction measurements: a signi®cant increase in
Comparison of the adsorption isotherms of di€erent the basal spacing is observed in each system and the
chlorophenols, however, reveals that both 2-chloro- breakpoints of the curve are in accordance with the
phenol and 4-chlorophenol have saturation-type iso- increase in the adsorption excesses. The increase is
therms within the same concentration range (2.0± caused by the intercalation of the aromatic molecules
2.2 mmol/g) (Fig. 2). in the C18-vermiculite. The lamellae, together with the
Adsorption capacities calculated using the Everett± alkyl chains bound to them, move apart while the
Schay linear representation (Eq. 4) are ns1 ,0 ˆ 2.09 mmol/ concentration of the organic component is increasing in
g for 2-chlorophenol and 2.12 and 2.18 mmol/g for the adsorption layer (Fig. 6).
4-chlorophenol (Fig. 3). The adsorption capacity calcu- The basal spacing of C18-vermiculite is 2.91 nm in
lated from the excess isotherm of nitrobenzene is only water, 3.41 nm in nitrobenzene, close to saturation
ns1 ,0 ˆ 0.72 mmol/g because of the very low solubility of concentration, 3.60 nm in the presence of 2-chlorophenol
nitrobenzene in water (Table 1). and 3.55 nm in the presence of 4-chlorophenol (Table 2).
Owing to the ortho position of the chlorine atom in
2-chlorophenol, this molecule is smaller than the 4-chlor-
ophenol molecule with the chlorine atom in the para
position; therefore, the interlamellar space opens some-
what wider in the middle region of the composition
range. As shown in Fig. 6b, the basal spacing calculated
on the basis of Eqs. (7) and (8) is 3.04 nm, supposing a
55° orientation of the alkyl chains [18]. Figure 6c
represents the state when the silicate lamellae have
moved further apart and the alkyl chains overlap only
partially the intercalation of additional aromatic mole-
cules forming a multimolecular adsorption layer.
Representation of the so-called ``free'' interlamellar
space (Vint)Valk, Eq. 9) as a function of the material
excess of the layer (Fig. 7) allows combination of the
results of adsorption and X-ray di€raction measure-
ments as well as comparison with the volumes
Vs ˆ n1,0Vm,1 calculated from the Everett±Schay repre-
sentation. The ®rst molecules are adsorbed mostly on the
external surfaces and in the monomolecular layer and the
interlayer space is only slightly opened (stage I). When
the concentration in the solution is increased, adsorption
is enhanced, the monolayer structure is expanded and
organic molecules therefore gain easy access to the Vs
volume of the adsorption layer in the interlamellar spaces
(stage II in Fig. 7).
The results of calculations regarding the structure of
the interlamellar space (Eqs. 7±10) and the analysis of
Fig. 9 Distribution ratio, Ssep, for 2-chlorophenol/water (d),
diagrams of interlamellar composition reveal the ratios
4-chlorophenol/water (h) and nitrobenzene/water solution on C18- of the various components (alkyl chains, organic
vermiculite component, water) in the accessible space (Fig. 8).
 69

This conception of adsorption layer structure is also with a cationic surfactant. The adsorption-excess
supported by the fact that the volume fraction relative isotherms (obtained by the immersion method) show
to water, F2s;b is larger in the case of 4-chlorophenol the positive adsorption of the organic components over
than of 2-chlorophenol; in other words, the extent of the whole range of composition up to x1,relative ˆ 1. The
interlamellar swelling is larger when 4-chlorophenol results of X-ray di€raction measurements are in good
is adsorbed than in the case of the adsorption of agreement with excess isotherms: whenever a region of
2-chlorophenol. the isotherm indicates an increase in the organic compo-
The enrichment of the organic component may be nent, an increase in basal spacing is also observed. The
characterized by the ratio Ssep ˆ [/S1 /(1)/alk)]//1. This reason for the increase is the in¯ux of aromatic molecules
value is a function of composition (Fig. 9). Ssep very into the interlamellar space. The adsorption capacity and
descriptively gives information on the ratio of the volume the free enthalpy of adsorption were calculated by
of the bulk phase to that occupied by the liquid analyzing the adsorption isotherm on the basis of the
component adsorbed in the surface layer. This ratio Gibbs equation and by the Everett±Schay method. The
reaches a maximum as high as 600±800 at low molar combination of the two independent measurement
fractions of the aromatic component. Of the three techniques yields further information on the adsorption
aromatic compounds, nitrobenzene has the lowest values equilibrium, the structure of the adsorption layer, the
of Ssep (Table 1). The functions characterizing the two orientation of alkyl chains and the intercalation of
chlorophenol isomers have similar courses; the values for organic contaminants. The results are readily utilizable
2-chlorophenol are slightly higher as a consequence of for planning environmental protection systems and
higher adsorption. procedures as well as in the ®eld of water puri®cation
and soil protection.
Conclusion
Acknowledgements The authors give their thanks for ®nancial
support to the National Scienti®c Research Foundation (OTKA)
Nitrobenzene and chlorophenols are e€ectively adsorbed T034430 and to the Ministry of Education FKFP 0402/1999
from aqueous solutions on vermiculite hydrophobized projects.

References

1. Schieder D, Dobias B, Klumpp 6. DeÂkaÂny I, Farkas A, KiraÂly Z, Klumpp 12. LaÂszlo K, BoÂta A, Nagy LG, TakaÂcs M
E, Schwuger MJ (1994) Colloids Surf E, Narres HD (1996) Colloids Surf A (1997) Acta Chim Hung Models Chem
88:103 119:7 134:81
2. Klumpp E, Heitmann H, Lewandowski 7. Regdon I, DeÂkaÂny I, Lagaly G (1998) 13. LaÂszlo K, BoÂta A, Nagy LG (2000)
H, Schwuger MJ (1992) Prog Colloid Colloid Polym Sci 276:511 Carbon 38:1965
Polym Sci 89:181 8. Regdon I, KiraÂly Z, DeÂkaÂny I, Lagaly 14. Stul MS, Uytterhoeven JB, De Bock J,
3. LaÂszlo K, BoÂta A, Nagy LG (1997) G (1998) Prog Colloid Polym Sci Huykens PL (1979) Clays Clay Miner
Carbon 35:593 109:214 27:377
4. LaÂszlo K, BoÂta A, Nagy LG, Subklew 9. DeÂkaÂny I, SzaÂnto F, Weiss A, Lagaly G 15. Schay, G (1976) Pure Appl Chem 48:373
G, Schwuger MJ, (1998) Colloids Surf (1985) Ber Bunsenges Phys Chem 89:62 16. Everett DH (1981) Pure Appl Chem
138:29 10. DeÂkaÂny I, SzaÂnto F, Weiss A, Lagaly 53:2181
5. DeÂkaÂny I, Farkas A, Regdon I, G (1986) Ber Bunsenges Phys Chem 17. KiraÂly Z, DeÂkaÂny I (1988) Colloids
Klumpp E, Narres HD, Schwuger 90:427 Surf 34:1
MJ (1996) Colloid Polym. Sci 11. BoÂta A, LaÂszlo K, Nagy LG, Copitzky 18. Lagaly G, Witter R (1982) Ber Buns-
274:981 T (1997) Langmuir 13:6502 enges Phys Chem 86:74
Progr Colloid Polym Sci (2001) 117: 70±75
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

A. Daz browski Adsorption against pollution: current

M. BuÈlow
P. Podkos cielny state and perspectives

Abstract An overview of modern applications. Current understanding

trends in the application of adsorp- and perspectives pertaining to envi-
A. DaÎbrowski (&) á P. Podkos cielny tion science for protecting the hu- ronmental applications of adsorp-
Faculty of Chemistry, man environment is presented. The tion phenomena are discussed as
M. Curie-Sklodowska University, essential subject comprises funda- well.
20-031 Lublin, Poland mental information on conventional
e-mail: [email protected]
Tel: +48-81-5375605 pollutants, environmental challenges Key words Adsorption á Environ-
Fax: +48-81-5375685 to adsorption, basic types of envi- mental protection á Conventional
M. BuÈlow
ronmentally relevant adsorbents and pollutants á Environmental
BOC Gases, 100 Mountain Ave., information that refers to adsorbent adsorbents á Trends and
Murray Hill, NJ 07974, USA properties with regard to practical perspectives

Introduction Nowadays, the pressure on industry is becoming

increasingly strong in order to decrease emission of
During the few last decades much e€ort has been various pollutants into the environment, and a number of
devoted to the investigation of adsorption phenomena international agreements and protocols related to that
that occur at various ¯uid±solid interfaces. A variety of issue are being enforced. A broad range of methods is
reasons have caused this strong interest both in available to control the removal from process streams
fundamental research in the adsorption area and in and exhausts of both natural and anthropogenic (munic-
practical application of its results (e.g., Refs. [1±3] and ipal, agricultural, commercial) and other pollutants [6].
references therein). One of the most important utilitar- With regard to their cost±performance relation, adsorp-
ian aspects of adsorption technologies emerges in local tion technologies represent the most important tech-
environmental control and global environmental con- niques to overcome a still ongoing degradation of
servation [4]. The term global environmental problem is environmental quality [7]. These techniques play a
used to characterize, in particular, emission of ozone- signi®cant role both in environmental and in human
depleting gases, such as chloro¯uorocarbons (CFCs), health control and in minimizing and/or preventing
volatile organic (chlor-containing) compounds (VOCs) emission of warming and ozone-layer depleting gases.
and the emission of ``greenhouse'' gases (CO2, CH4, Adsorption phenomena are essential for a large range of
N2O, etc.). The term local environmental problem methods for environmental analysis, which is a discrete
comprises ®rst of all, the phenomena of ¯ue gas and sophisticated branch of modern analytical chemistry
recovery (SOx and NOx), solvent vapor fractionation [8]. Adsorption can also be expected to play a signi®cant
and solvent vapor recovery, wastewater treatment and role in dessicant dehumidi®cation technologies [9] and
supply/production of drinking water. Other major life-support systems aboard spacecraft and planetary
environmental issues are related to industrial solid bases. In the latter cases, adsorbents may be used to
aerosols, which stem from incomplete combustion of a process the habitat air and to recover useful substances
major number of fuels. These aerosols are harmful as such as drinking water, etc., from local environments [10].
precursors to (uncontrolled) synthesis of strong toxins, Major applications of adsorption for protecting the
cancerogenes and mutagenes [5]. environment are as follows [2, 3, 11]:
 71

1. Solvent/chemical recovery. A number of primary pollutants can undergo changes

2. Removal of VOCs, CFCs and other hazardous owing to reactions with other pollutants or with some
chemical compounds from air and industrial waste components of the environment. In this way, new
gases. compounds can be formed, which are often of increased
3. Gas separation and puri®cation. toxicity; they are known as secondary pollutants. Both
4. Surface water management and wastewater treat- primary and secondary pollutants occur in all the
ment. environmental media, i.e., atmosphere, hydrosphere
and soil [13].
Progress in research into the fundamentals of adsorp-
Another important problem results from photochem-
tion phenomena achieved during recent years has very
ical smog that occurs as a direct consequence of
much advanced our understanding of adsorption pro-
secondary atmospheric reactions driven by solar energy.
cesses related to environmental protection [12]. A brief
One of the most important of these reactions is the
review of the state of this art is given in this article. In
formation of ozone by molecular and atomic oxygen, the
addition, challenges related to adsorption for the pro-
latter being obtained from splitting O2 or NO2 by UV
tection of the human environment are outlined.
radiation.
About half the incoming solar radiation is absorbed
or re¯ected by clouds or the atmosphere itself. Di€erent
Environmental pollutants components of the atmosphere react selectively with
incoming radiation. For example, visible light is
The term environmental pollutant refers to any cause of absorbed by stratospheric ozone, which provides pro-
physical, chemical or biological disturbance of the tection for the Earth's inhabitants. The substances
ecological equilibrium in the environment. Environmen- which are the most dangerous with regard to strato-
tal pollution results from random, accidental events, spheric ozone are CFCs, the presence of which causes
emission of certain pollutants owing to the activity of ozone-layer depletion. On the other hand, so-called
nature itself or owing to human activities. Natural greenhouse gases (CO2, CH4, N2O, NO2, tropospheric
pollutants stem from activities of nature itself and they O3 and CFCs), i.e., substances that absorb in the
contain certain sediments in air (dust) and surface waters, spectral range where thermal energy radiated from
dissolved minerals (sometimes toxic metals) in ground Earth is at its maximum, represent a major challenge, in
and surface water and trace elements in air from volcanic particular to industrialized societies, to prevent global
activities. warming.
Anthropogenic pollutants are emitted as a result of Some major conventional pollutants are listed in
human activity. Their main types are as follows: Table 1.
industrial, municipal/domestic, and agricultural, institu-
tional and commercial activities. On the other hand, the
anthropogenic pollutants can be divided into point and Current environmental issues of adsorption
nonpoint sources. Nonpoint sources (e.g., roads, streets,
parking lots, farm ®elds, construction sites, etc.) are The subject of the use of modern adsorption technologies
especially dicult to monitor, regulate and treat. Natural is of tremendous environmental, economic and legal
and anthropogenic pollutants emitted from a given importance and it constitutes a serious challenge to all
source are de®ned as primary pollutants. industrialized societies with strong potential for further

Table 1 Major conventional

pollutants. Chloro¯uoro- Species Major sources Average ``half
carbons are compounds such as time'' in
CFCl3, CF2Cl2, and others atmosphere (days)
Volatile organic compounds CO2 Fossil fuel burning, biomass 2,500
comprise methane, benzene,
CO Fossil fuel burning, biomass 75
formaldehyde, vinyl chloride,
CH4 Anthropogenic activities 3,600
phenol, chloroform, tri-
chloroethylene and gasoline Chloro¯uorocarbons Industry, overconsumption of fossil fuel 1±1,000
ingredients. Organic sulfur Volatile organic compounds Anthropogenic activities 1±1,000
includes methyl mercaptane, Volatile organic compound Isoprene, terpenes from plants <1
carbon disulphide, and di- NOx Fossil fuel, burning biomass 4
methyl sulphide, among others. N2O Fertilizers 60,000
Metals comprise As, Cd, Cr, SO2, SO24 Fossil fuels, smelting 1±4
Cu, Se, Ni, Mo, Hg and Pb. H2S, organic sulfur Anthropogenic activities, biogenic 1±900
Suspended particulate materials Metals Leaded gasoline, coal, industrial waste 1±30
comprise soot, dust and ash Suspended particulate materials Anthropogenic activities, ®res, wind erosion 1±1,000
72

Table 2 Current typical environmental tasks related to adsorption Adsorbents and their properties related
science to practical applications
Local environmental problems
The development and application of adsorption should
Issue Task be considered jointly with that of adsorbent technology
Flue gas treatment SOx, NOx and Hg emission removal
Solvent vapor recovery Volatile organic compound recovery as utilized on both laboratory and industrial scales [13,
and solvent fractionation from work places, among them 14]. These adsorbents cover broad ranges of chemical
from ground water; adsorption specimens and geometrical surface structures, which is
methods are needed to prevent re¯ected by the range of their applications in industry
volatile organic compound and their importance for laboratory practice. This
emission into air by increasing
emphasis on development/use
situation is compatible to that, as far as the variety of
of air puri®cation and solvent adsorbents is concerned, which could be found in various
vapor recovery processes. environmental applications [15].
Wastewater treatment Removal of organics, nitrogen and In earlier adsorption processes, the choice of an
phosphorus, i.e., removal/recov- adsorbent to respond to a given challenge was restricted
ery nutrients from wastewater; to various types of activated carbons, silicas and alum-
removal of heavy metal traces
from wastewater inas [16, 17]. Natural zeolites were known as a scienti®c
Drinking water Deterioration of water sources, curiosity and have never been used as adsorbents on an
production advanced treatment industrial scale. The discovery of synthetic zeolites, also
of wastewater, etc. known as (one group of) molecular sieves, has broadened
Desiccant dehumidi®cation Improvement of indoor air quality; immensely the available range of adsorbents and has led
technology removal of air pollutants;
a number of microorganisms are
to an enormous upsurge in the development of adsorp-
removed/killed by desiccants tion processes [18, 21, 22]. Hydrophobic clays also show
owing to coadsorption by excellent (selective) adsorption properties for di€erent
desiccant materials. pollutants; therefore, the adsorption isotherms and the
Global environmental energetic characterization of adsorption on solid inter-
problems faces were investigated [23±27]. New theoretical ap-
Issue Task
Global warming control Emission control of greenhouse proaches to adsorption phenomena and the emergence
gases (CO2, CH4, N2O, NOx); of numerous groups of novel adsorbents have generated
utilization of CH4 new practical applications [2, 3, 30].
Ozone layer depletion Emission control/recovery/replace- The main types of adsorbents of practical environ-
ment of chloro¯uorocarbons mental importance are presented in Table 3.
as ozone-depleting gases used in
refrigeration systems;
In terms of pore-size engineering, a choice can be
chloro¯uorocarbon-free made from a wide class of nanoporous materials. These
refrigeration systems as adsorbents have pore diameters in the range from several
alternative solutions to vapor- tenths of a nanometer to about 50 nm and they are of
compression heat-chill pumps, di€erent basic pore geometry and chemical nature.
which use valuable electric energy Owing to their excellent adsorption, catalytic and
and polluting refrigerants
(chloro¯uorocarbons) that cause thermal properties [19], many nanoporous adsorbents
ozone depletion and the are very popular in science, ¯uid puri®cation and
greenhouse e€ect separation process technology as well as in environmen-
Defense applications Removal of contaminants used tal protection.
by military, which comprised The principal properties that relate to adsorbent
extremely toxic chemicals;
in contrast to solvent vapor
applications are as follows [7, 10, 13]:
recovery processes, defense 1. Adsorption characteristics.
systems have to purify air only, 2. Regeneration capability.
but both applications are related
to the environment with 3. Physical characteristics (particle geometry, density,
successful use of adsorption hardness, shaping ability, ash content, etc.).
technology
Each of these properties can be important with regard to
whether or not adsorption is considered to be a viable
process option.
intense development. The major important environmen- Adsorption characteristics are those with a direct
tal tasks related to adsorption techniques are summa- e€ect on the cost±performance relation for the product in
rized in Table 2. a given mode of application. They comprise:
 73

Table 3 Basic types of

adsorbents used for environ- Carbon adsorbents Mineral adsorbents Other adsorbents
mental purposes [12] Active carbons Silica gels Synthetic polymers
Activated carbon ®bers Activated alumina Metallorganic microporous
and mesoporous materials
Carbon molecular sieves Oxides of metals Composite adsorbents:
(complex mineral carbons,
X±elutrilithe; X = Zn, Ca)
Mesocarbon microbeads Hydroxides of metals Mixed sorbents
Carbonaceous nanomaterials Zeolites
Clay minerals
Pillared clays
Porous clay heterostructures
Inorganic nanomaterials

1. Adsorption energy and its distribution. 1. Thermal (suitable for granular activated carbon,
2. Adsorption capacity. shaped zeolites, etc.).
3. Porosity and/or speci®c surface area for a given 2. Steam regeneration (for granular activated carbon,
porosity type. polymeric adsorbents).
4. Material to extract. 3. Acid or base regeneration (activated carbon, poly-
5. Resistance to the pH value of ¯uid to be treated. meric adsorbents).
4. Solvent regeneration (polymeric adsorbents).
In general, the use of solid adsorbents in science and
5. Biological regeneration (e.g., carbon regeneration by
technology requires their manifold characterization [12].
biological oxidation).
For achieving this goal, a spectrum of various modern
physicochemical analytical techniques provide useful For cyclic gas and most liquid-phase adsorption
and very speci®c information. In particular, these processes (gas separation, solvent recovery, drying of
techniques comprise X-ray di€raction, X-ray spectros- gases and liquids, recovery of chemicals from industrial
copy, small-angle X-ray spectroscopy, solid-state NMR, and vent gases) the following adsorbent regeneration
atomic emission spectroscopy, Raman spectroscopy, methods are in use [21]:
temperature-programmed desorption, etc. In addition,
1. Temperature swing adsorption (TSA) ± bed regener-
the utilization of classical adsorption/desorption mea-
ation by raising the temperature.
surements is unavoidable to collect information on the
2. Pressure swing adsorption (PSA) ± bed regeneration
adsorption behavior of a solid with regard to a
by alternate reduction of the total pressure in the
pollutant [20].
adsorber beds at constant temperature.
3. Inert purge stripping ± removal of adsorbate without
changing the temperature or the pressure; the void in
Con®guration of adsorption systems and regeneration
the bed is ®lled with an inert gas upon complete
of adsorbents
regeneration.
The con®guration of an adsorption system is de®ned PSA/TSA and related technologies, such as vacuum
in accordance with the basic unit operation, by which swing adsorption (VSA), pressure VSA (PVSA) and
a ¯uid (gas or liquid) is contacted with a solid rapid PSA (RPSA), are executed in many sophistical
adsorbent. There are only three main con®guration variants that have helped to improve separation ecien-
categories [11], viz., bath, ®xed bed and moving bed, cy and to decrease energy consumption. PSA/TSA and
each of which can be operated with particular regard related adsorption processes can be considered as being
to the ¯ow of ¯uid and solid, i.e., co- or counter- very ecient and relevant toward environmental appli-
currently. cations [28, 29].
Irrespective of the con®guration of the adsorption Apart from PSA/TSA and related technologies, the
systems, a suitable regeneration mode is desired. The following important adsorption-based methods are
economical success of adsorption processes depends on utilized for treating issues of environmental pollution
the regenerability of the adsorbent. The regeneration [12, 31]: membrane processes, ion-exchange methods,
mode corresponds, in general, with the types of ¯uid and process-scale chromatographic techniques, hybrid
solid adsorbent used. methods (e.g., adsorption catalysis, adsorption-mem-
For liquid±solid adsorption systems, the following brane separation, coagulation, sedimentation and
regeneration techniques can be utilized [7, 13]: ®ltration).
74

Environmental analysis selectively from the bulk sample matrix; they can be
preconcentrated, cleaned up, separated into individual
Environmental analysis represents a discrete and sophis- substances and analyzed by gas and liquid adsorption
ticated branch of analytical chemistry in which a series of chromatography, or by related chromatographic tech-
various analytical techniques are applied. Of these, niques (high-performance liquid chromatography, thin-
adsorption chromatography, adsorption-electrochemical layer chromatography, etc.).
analysis, spectroscopic and spectrophotometric methods Among the adsorption methods that are used for
are of great importance. Environmental analysis is the isolating analytes from liquid matrices and for their
most applied trace analysis method, where pollutants are preconcentration, increasing practical importance has
present in trace and ultratrace quantities. Thus, the been shown for the solid-phase extraction (SPE) tech-
fundamental requirement of environmental analysis is nique. The idea of SPE consists of retention of analytes
for a fast, modern and reliable method in order to detect from a large sample volume on a small bed of adsorbent,
pollutants in very small quantities, quickly and precisely followed by elution of analytes with a small volume of
[8]. Environmental analysis relevant to adsorption sci- solvent. The proper selection of appropriate parameters
ence should be exempli®ed as follows. of adsorbents and solvents is a crucial condition for
successful employment of this method [34].

Electrochemical analysis of adsorbable

surface-active substances Challenges

This type of analysis deals with the formation of The future development of adsorption science represents
electrode double layers as a result of adsorption of many a major challenge to industry and environmental ®elds
chemical compounds of both organic and inorganic because of its low cost, regenerability of most of the
nature, at the solution±electrode interface. This process adsorbents used and potential ability to design and
e€ects the properties of the electrode double layer in a manufacture novel materials which are speci®c to a given
measurable manner, and it forms the basis for an need.
electrochemical analysis of adsorbable surface-active The following comments can be made with regard to
substances that are present in solution. From a historical developments in environmental adsorption.
point of view and ®rst of all, polarographic adsorption 1. New applications of adsorption methods will emerge
analysis, which was introduced by Heyrovsky [32], as new types of adsorbents speci®c to a given need are
should be mentioned. The method of tensammetry developed [30, 35]. Additional advantages will emerge
developed from polarography or the measurement of if novel microporous and mesoporous adsorbents,
the di€erential capacity of the electrode double layer is like MCM-41 materials, metallorganic molecular
closely related to the former and is widely utilized. From sieves, inorganic ceramics or other solids with nanop-
a practical point of view, with respect to recent voltam- orosity, are manufactured cost-e€ectively and if
metry methods, it is necessary to point out procedures certain practical constraints are overcome.
that are based on adsorptive accumulation of the analyte 2. Environmental applications of adsorption phenome-
on the electrode surface: na have to be developed in conjunction with new
± Adsorptive stripping voltammetry. theoretical approaches and molecular simulations of
± Adsorptive stripping potentiometry. industrial and environmental processes [36]; the same
is true for adsorption techniques, in particular, for
The scope of application of these methods ranges those with new classes of adsorbents, catalysts,
from metal trace analysis to that of organic compounds membranes and ion exchangers [37].
and, in general, to environmental, biochemical, pharma- 3. Another ®eld in continuous progress is that of the
ceutical, toxicological and other applications [33]. expansion of new separation and puri®cation tech-
niques for environmental purposes. In this context,
the improvement and further development of chro-
Chromatographic methods proceeded matographic techniques demonstrates huge practical
by sampling and sample preparations importance. A similar challenge also exists for various
types of membrane separation methods that present
Adsorption phenomena are widely applied for sampling very advanced and innovative molecular separation
many ¯uids, such as air, surface water and wastewater units with great potential for applications in all
[8]. Sampling is realized together with enrichment of sectors of environmental protection; a number of
analytes. owing to the inherent strong selectivity of environmental goals can be approached by hybrid
adsorption, pollutants of interest can be removed processes that combine the processes of adsorption,
 75

membrane separation, catalysis, ®ltration, chroma- protection are presented in various monographs and
tography, etc [38]. conference proceedings [2, 3, 14, 16, 21, 40, 41].
4. The prospective demands toward adsorption and The development and utilization of molecular mod-
related ®elds are based on a growing concern for eling to understand fundamentals of adsorption phe-
environmental control, in order to maintain and nomena and to synthesize novel classes of adsorbent
increase the quality of life. Many of the aspects aimed materials is crucial and becomes extremely valuable if
at this concept will require both the uses of novel used in conjunction with experimental techniques. On the
adsorbents, membranes, catalysts and other materials other hand, new theoretical approaches and novel groups
and the development of ecologically friendly, low- of adsorbents stimulate the development of new practical
energy adsorption technologies. In this context, the environmental applications, among other issues.
PSA, PVSA, RPSA, TSA and other puri®cation and It is widely known that well-understood adsorption
separation techniques will prove to be more favorable science has gained a dominating role in modern
in terms of computer simulation and experiment industry with regard to environmental, economic and
research [22, 39]. energy aspects. Doubtlessly, adsorption technologies
have improved rapidly and they were adapted to
contemporary tasks of mankind. Nowadays, only such
Conclusions technologies which provide the possibility of sustainable
development of people and societies are justi®ed. In this
Only a fraction of the environmental roles played by context, adsorption and related domains are held in
adsorption, have been touched upon here. Numerous high esteem as important environmental technologies of
examples of practical applications in environmental this century.

References

1. (1996) Stud Surf Sci Catal 99 17. Mantell CL (1951), Adsorption. 31. BuÈlow M, Lutz W, Suckow M (1999)
2. (1999) Stud Surf Sci Catal A 120 McGraw-Hill, NewYork Stud Surf Sci Catal A 120:301
3. (1999) Stud Surf Sci Catal B 120 18. Breck DW, Eversole WG, Milton RM, 32. Heyrovsky J, Kuta J (1965) Principles
4. Suzuki M (1996) In: LeVan MD (ed) Reed TB, Thomas TL (1956) J Am of polarography. Academic, New York
Fundamentals of adsorption, vol 5. Chem Soc 78:5963 33. Stulik K, Kalvoda R (eds) (1996) Elec-
Kluwer, Boston, p 4 19. Kaneko T (1999) Stud Surf Sci Catal B trochemistry for environmental protec-
5. Pokrovskiy VA, Bogillo VJ, Dabrowski 120:635 tion, UNESCO Venice Oce, Venice
A (1999) Stud Surf Sci Catal B 120:571 20. Jaroniec M (1995) In: Pinnavaia TJ, 34. Raisglid M, Burke S (1999) Stud Surf
6. Bolt BA, Barcicki J, Kozak Z, Pawlow- Thorpe MF (eds) Access in nanoporous Sci Catal B 120:137
ski L (1984) In: Pawlowski L, Verdier materials. Plenum, New York 35. Ruthven DM (2000) Ind Eng Chem Res
AJ, Lacy WJ (eds) Chemistry for pro- 21. Yang RT (1987) Gas separation by 39:2127
tection of the environment. Elsevier, adsorption processes. Butterworth, Bos- 36. Thomas P (1999) Simulation of indus-
Amsterdam, p 5 ton trial processes for control engineers.
7. Thomas WJ, Crittenden B (1998) Ad- 22. LeVan MD (1998) In: Meunier F (ed) Butterworth±Heinemann, Boston
sorption technology and design. Butter- Fundamentals of adsorption, vol 6. 37. BuÈlow M, von Gemmingen U, Izumi J,
worth-Heinemann, Oxford Elsevier, Amsterdam, p 19 Pullumbi P, Sherman J, Coe C, Suzuki
8. Bladek J, Ne€e S (1999) Stud Surf Sci 23. Patzko A, Dekany I (1993) Colloids M, Baron G (1998 ) In: Meunier F (ed)
Catal B 120:3 Surf A 71:299 Fundamentals of adsorption, vol 6
9. Gosh TK, Hines AL (1999) Stud Surf 24. Regdon I, Kiraly Z, Dekany I, Lagaly Elsevier, Amsterdam, p 47
Sci Catal A 120:879 G (1994) Colloid Polym Sci 272:1129 38. (1997) Proceedings of the Topical Con-
10. DallBauman LA, Fin JE (1999) Stud 25. Marosi T, Dekany I, Lagaly G (1994) ference on Separation Science and
Surf Sci Catal B 120:455 Colloid Polym Sci 272:1136 Technology. AIChE Annual Meeting
11. Slejko FL (ed) (1985) Adsorption tech- 26. Kiraly Z, Dekany I, Klumpp E, Le- November1997, Los Angeles, Calif
nology. Dekker, New York wandowski H, Narres HD, Schwuger 39. Ruthven DM, Farooq D, Knaebel KS
12. Dabrowski A (2001) Adv Colloid In- MJ (1996) Langmuir 12:423 (1994) Pressure swing adsorption.
terface Sci 93:4 27. Dekany I, Farkas A, Kiraly Z, Klumpp VCH, New York
13. Ge Y, Murray P, Hendershot WH E, Narres HD (1996) Colloids Surf A 40. Inui T, Anpo M, Izu K, Yanagida S,
(2000) Environ Pollut 107:137 119:7 Yamaguchi T (eds) (1998) Stud Surf Sci
14. Suzuki M (1990) Adsorption engineer- 28. Liu Y, Subramanian D, Ritter JA Catal 114
ing. Elsevier, Amsterdam (1999) Stud Surf Sci Catal B 120:213 41. (2000) Proceedings of the Topical Con-
15. Cohen Y (ed) (1995) AIChE Symp Ser 29. Ritter JA, Liu Y, Subramanian D ference on Energy and the Environ-
91 (1998) Ind Eng Chem Res 37:1970 ment. AIChE Annual Meeting
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Chichester and separation. October 1997, 5:839
Progr Colloid Polym Sci (2001) 117: 76±79
Ó Springer-Verlag 2001 ADSORPTION AT SOLID/LIQUID INTERFACES

T. Textor Organically modi®ed ceramics

T. Bahners
E. Schollmeyer for coating textile materials

Abstract Fabrics made of poly(eth- hydrophilic properties. The glass

ylene terephthalate) (PET) and glass ®bre fabric was ®nished with a
®bres were coated with di€erent composite that improves the wear
T. Textor (&) á T. Bahners
E. Schollmeyer modi®ed inorganic±organic hybrid resistance.
Deutsches Textilforschungszentrum polymers based on 3-glycidyloxpro-
Nord-West e.V., Adlerstrasse 1, pyl trimethoxysilane. In the case of Key words Poly(ethylene terephtha-
47798 Krefeld, Germany PET the focus was to a€ect the late) á Glass ®bre á Organically
e-mail: [email protected]
Tel.: +49-2151-8430 surface speci®c properties especially modi®ed ceramic á Surface energy á
Fax: +49-2151-843143 the hydrophobic, oleophobic and Wear resistance

Introduction amounts of water, under basic or acidic conditions these

alkoxides undergo a hydrolysis reaction and partly
Increasing demands for functional and highly specialized condense to form sols. In a following curing step, the
textiles, for example, technical textiles, can be observed condensation of the hydrolysed silica alkoxides can be
worldwide. Intense research is presently aimed at new completed by simultaneously cross-linking the functional
methods for surface modi®cation in order to establish groups. The sols can be modi®ed by mixing them with
improved or new properties. other metal alkoxides or dispersing nanosized metal
An innovative method for textile ®nishing is the oxides. Therefore the resulting three-dimensional net-
modi®cation of ®bre material with a thin coating of works are build from organic and inorganic domains.
organically modi®ed ceramics that combine the advan- The sols can be applied by common methods, for
tages of organic polymers and ceramics [1±3]. example, dipping, spraying or knife coating, and in
The application of ceramic materials, primarily es- contrast to ceramic processing the curing temperatures
tablished as thin ceramic layers, o€ers far-reaching are very moderate. Depending on the organic modi®ca-
possibilities for permanent surface modi®cation in mod- tion the curing can be carried out with UV radiation as
ern material development. Primarily because of very high well.
processing temperatures but also owing to huge technical
e€ort textile materials have not been accessible to these
technologies so far. A new perspective is o€ered on the Experimental
background of recent work in the sol±gel technique [4, 5].
Organically modi®ed ceramics, which are made by sol± Materials
gel-processing, combine qualities of ceramics and syn-
thetic polymers and have an immense potential for The coating experiments were carried out with a technical polyester
fabric and a glass ®bre fabric. Prior to the treatment, the fabrics
creative modi®cations of surface properties with low were extracted with ethanol and petrol ether.
technical e€ort at moderate temperatures. These mate-
rials are derived from silica alkoxides that are modi®ed
Chemicals
with one organic group. This group consists of, for
example, a hydrocarbon chain with functional epoxy, As organically modi®ed alkoxysilane 3-glycidoxypropyl trimeth-
metacrylic or thiol groups. In the presence of certain oxysilane (GTPMS) (98%, Aldrich) and for catalysing the
 77

cross-linking reaction of the epoxy-groups 1-methylimidazol (pu- sti€ness and a decreasing wrinkle recovery angle (DIN
rity above 97%, Fluka) were used. For hydrophobic coatings the 53890). The degree of these e€ects depends on the
sols were modi®ed with trideca¯uoro-1,1,2,2-tetrahydrooctyltrieth-
oxysilane (ABCR) and hydrophilic modi®cations were carried out modi®cation of the di€erent sols. Scanning electron
by adding a surfactant (Tween80, Fluka). Aluminium oxide microscopy micrographs (Fig. 1) show that the coatings,
(aluminium C, Degussa, particle size 5±20 nm) and bisphenol A which cover the ®bres, are stuck together by the coating
(Fluka) were used to modify the sols for wear-resistant coatings of material at the points of intersection.
glass ®bre fabrics. Water-repellent aluminium-modi®ed glass ®bre
fabrics were made using n-propyl trimethoxysilane (Merck).

Hydrophilic and hydrophobic coatings

Analytical methods

The e€ects on the hydrophobic and hydrophilic properties were By converting the epoxy ring of the GPTMS into a glycol
examined by measuring the contact angles of water with a group the number of hydroxyl groups rises; therefore the
KruÈss G40 measuring system and by the investigation of the drop surface energy of the coating material is increased. The
penetration behaviour of distilled water following the TEGEWA
test [6]. measured contact angle of distilled water for this coating
The oil repellency was analysed following AATCC (118±1972). is 39° and for the unmodi®ed GPTMS the contact angle
The wear resistance was tested using the Martindale abrasive test is about 66°, which is a little lower than contact angle for
(DIN EN ISO 12947). The climatized fabric samples were scrubbed uncoated polyester (76°). Although the surface energy
radially over a de®ned testing fabric. After 5,000 cycles the samples
were investigated visually. for the coated ®bre increases, the drop penetration time
for the coated fabrics rises from 135 s to more than 1 h
and the drop shows only slight spreading. The prepara-
Preparation of the sols

Most of the sols used were based on GPTMS. GPTMS (1 mol) was
prehydrolysed with 1.5 mol water (0.01 M hydrochloric acid) and
stirred for at least 2 h to build the basis sol. The particular sols were
produced by appropriate modi®cations of the GPTMS sol. The
catalyst for the cross-linking reaction of the epoxy group ±
1-methylimidazol ± was added just before the coating process.
For the hydrophilic coatings two routes were followed. One way
is to convert the epoxy group of the GPTMS to a glycol group,
which is carried out by re¯uxing it for 3 h with a certain amount of
diluted sulfuric acid and subsequent removal of the sulfate ion by
ion exchange. Alternatively hydrophilic coatings were yielded by
stirring in a surfactant 5 min before the coating process, followed
by addition of the catalyst. The same procedure can be used for
hydrophobic coatings by stirring in trideca¯uoro-1,1,2,2,-tetrahy-
dro-octyltriethoxysilane. For wear-resistant coatings the GPTMS
sols were modi®ed with 10 wt% Aluminium C. The aluminium
oxide was dispersed in acidic water with an ultrasonic generator.
Bisphenol A in a ratio of 4:1 was additionally dissolved in these
sols. Finally the complete sol was diluted with ethanol to a
concentration of 10 vol%.
To prepare a hydrophobic surface for a wear-resistant surface in
a second coating step an n-propyl trimethoxysilane sol was made by Fig. 1 Scanning electron microscopy micrograph of a polyester fabric
partly hydrolysing 1 mol silane with 1.5 mol hydrochloric acid coated with a 3-glycidoxypropyl trimethoxysilane sol
(0.01 M) for at least 5 h.

Coating process Table 1 Contact angles of distilled water for di€erently coated
polyester surfaces
The coatings were carried out by a padding process with a
laboratory padder. The coated fabrics were tightened on a pin Surface Contact angle
tenter heat setter and dried in an oven for about 1 h. The drying (degrees)
temperature was adjusted to 130 °C.
Polyester 76
Polyester coated with 3-glycidoxypropyl 66
trimethoxysilane sol
Results Polyester coated with 3-glycidoxypropyl 39
trimethoxysilane sol with hydrolysed
General e€ects on the textile properties epoxy function
Polyester coated with tenside-modi®ed »0
The coatings are clear but have a distinct yellow shade. 3-glycidoxypropyl trimethoxysilane sol
Polyester coated with ¯uorine-modi®ed 95
The tensile strength of the coated fabrics is slightly, but 3-glycidoxypropyl trimethoxysilane sol
signi®cantly, increased. The fabrics show increased
78

Fig. 2 A drop of distilled water

on a polyester fabric with a
hydrophobic coating. The left
photograph is taken directly
after the application, the right
photograph 2 h later

tion of a hydrophilic coating by incorporating 5% of a

nonionic surfactant ± in this case Tween 80 ± leads to a
very hydrophilic surface. The contact angle of water is
close to 0° and the coated fabrics soak up water quickly,
the drop penetration time is only 85 s and is even lower
than for the uncoated fabric.
In order to establish very hydrophobic and oleopho-
bic surfaces a sol was prepared from GPTMS and a
highly ¯uorinated trialkoxysilane, trideca¯uoro-1,1,2,2-
tetrahydrooctyl triethoxysilane. By applying this sol,
surfaces can be created with contact angles of up to 95°.
The experiments showed that 1±2% of the highly
¯uorinated silane is necessary to yield such low-energy
surfaces. Higher amounts do not lead to higher contact
angles.
The TEGEWA test shows no water penetration into Fig. 3 Photographs taken after the abrasive test from an unmodi®ed
the fabrics, the drop remains on the material for several (left) and a modi®ed (right) glass ®bre fabric
hours, and even the oil test showed good results. The oil
repellency is ``satisfactory'' (grading 4) compared to the
unmodi®ed fabric, which was unsatisfactory (grading 0). Conclusion
The high water repellency of the hydrophobized fabric is
illustrated in Fig. 2. Coatings based on organically modi®ed ceramics were
intensively investigated in the last years and several
applications are already used commercially. For textile
Wear-resistant coating materials the composites promise far-reaching possibil-
ities for creative surface design, not only with regard to
One of the disadvantages of glass ®bre fabrics is their hydrophilic and hydrophobic e€ects or to improve the
insucient wear resistance; therefore, they must be wear resistance of glass ®bres.
protected for many applications. By coating glass ®bres Additional interesting properties are conceivable by
with aluminium oxide modi®ed sol fabrics can be suitable modi®cations of the coating materials. Examples
prepared that withstand at least 5,000 cycles of a wear are sun-protection properties, self-adapting colorations
resistance test, whereas the unmodi®ed fabric is de- or magnetic features. By adequate coatings trans-dermal-
stroyed completely under these conditions. This is therapy-systems could be created by incorporating drugs
demonstrated impressively by the photographs in Fig. 3. that are set free over an adjustable period and in
Owing to the hydrophilic character of the aluminium adjustable amounts into the amorphous organically
oxide particles the resulting samples have relatively high modi®ed ceramic networks.
surface energies, which is disadvantageous for many
applications, for example, for textile architecture. Good Acknowledgements We thank the Forschungskuratorium Textil
water repellency can be achieved in a second coating step e.V. for funding this research project (AiF nos.10954 N and
12000 N). The project was funded with ®nancial resources of the
with the previously mentioned ¯uorine modi®ed sol or Bundesministerium fuÈr Wirtschaft und Technologie (BMWi) with a
alternatively with prehydrolysed and diluted n-propyl grant from the Arbeitsgemeinschaft industrieller Forschungsverei-
trimethoxysilane. nigungen ``Otto von Guericke'' e.V. (AiF).
 79

References

1. Nass R, Schmidt HJ (1990) J Non-Cryst 4. Knittel D, Textor T, Bahners T, Scholl- 5. Textor T, Bahners T, Schollmeyer E
Solids 121:329±333 meyer E (1998) UMIST Conference: (1999) Melliand Textilber 80:847±848
2. Schmidt HJ (1994) J Non-Cryst Solids Textiles engineered for performance, 6. Anonymous (1987) Melliand Textilber
178:302±312 20±22 April 1998, Manchester, UK, 68:581€
3. Nass R, Arpac E, Glaubitt W, Schmidt H pp 1±13
(1990) J Non-Cryst Solids 121:370±374
Progr Colloid Polym Sci (2001) 117: 80±87
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

K. Esumi Preparation and characterization of noble

K. Torigoe
metal nanoparticles using dendrimers
as protective colloids

Abstract Noble metal nanoparticles dendrimers with surface methyl

such as gold, platinum, and silver ester groups and hydrocarbon
have been prepared by reduction of chains dendrimer-encapsulated
their metal salts in the presence of noble metal nanoparticles are
poly(amidoamine) dendrimers with obtained. Thus, the size of the
various surface functional groups. noble metal nanoparticles and the
K. Esumi (&) á K. Torigoe In aqueous solutions of dendrimers morphology of noble metal±dendri-
Department of Applied Chemistry with surface amino groups, stable mer composites can be controlled in
and Institute of Colloid
and Interface Science, nanoparticles of gold and platinum aqueous or nonaqueous solutions
Science University of Tokyo, are obtained by adsorbing the sur- by using dendrimers with various
Kagurazaka, Shinjuku-ku, face amino groups of the dendri- surface groups.
Tokyo 162-8601, Japan mers in which the particle size of
Tel.: +81-3-32604272
the gold nanoparticles is consider-
K. Torigoe ably a€ected by the generation of Key words Noble metal
Department of Industrial Chemistry, the dendrimer as well as the den- nanoparticles á Dendrimers á
Faculty of Engineering,
Science University of Tokyo, Kagurazaka, drimer concentration. On the other Reduction á Encapsulation
Shinjuku-ku, Tokyo 162-8601, Japan hand, in nonaqueous solutions of of nanoparticles

Introduction random-coil structures. Dendrimers might provide reac-

tion sites including their interior or periphery. In
The preparation of metal nanoparticles has been studied addition, we can also prepare water-soluble dendrimers
intensively because metal nanoparticles have been ap- or organic-solvent-soluble ones. Accordingly it is expect-
plied in electrooptical devices, electronic devices, imaging ed that nanoparticles prepared in the presence of
materials, catalysis, and so on. Fabrication of nanopar- dendrimers in aqueous or nonaqueous solutions are
ticles becomes one of the important topics in nanotech- a€ected by the generation of dendrimers and show
nology. Accordingly, for that purpose it is very di€erent behavior from those prepared using conven-
important to be able to control the particle size, shape, tional linear polymers. In fact, some groups [6±9] have
and size distribution of metal nanoparticles. In the wet characterized the metal nanoparticles obtained in the
method, various metal nanoparticles have been prepared presence of poly(amidoamine) dendrimers with various
in the presence of polymers or surfactants as a protective surface groups, such as amino, carboxyl or hydroxyl, and
colloid [1]. have shown various applications using such nanosized
Recently, dendrimers having unique structures and materials.
properties have been attracting increasing attention In this article, we describe the physicochemical
[2±5]. Generally, dendrimers of lower generation tend properties of noble metal nanoparticles prepared in
to exist in relatively open forms, while higher generation aqueous solutions or in nonaqueous solutions using
dendrimers take a spherical three-dimensional structure, poly(amidoamine) dendrimers with various surface func-
which is very di€erent from linear polymers adopting tional groups.
 81

Experimental Results and discussion

Materials Preparation of metal nanoparticles
in aqueous solutions
Poly(amidoamine) dendrimers were synthesized, involving exhaus-
tive Michael addition to an ethylenediamine core with methyl
acrylate and exhaustive amidation of the resulting esters with a Gold, platinum, and silver nanoparticles were prepared
large excesses of ethylenediamine [10]. The ester-terminated in aqueous solutions containing dendrimers by reduction
dendrimers were hydrolyzed by addition of NaOH to obtain of the respective metal salts with NaBH4.
dendrimers with surface carboxyl groups. In addition, a hydropho-
bically modi®ed dendrimer was also synthesized [11] from the Transmission electron microscopy (TEM) micro-
reaction of epoxy-1,2-dodecane and poly(amidoamine) dendrimer graphs and the particle size distribution of the gold
with surface amino groups, and is referred as GH(4). The particles are shown in Fig. 1. Here, the concentration of
dendrimers with surface amino groups are referred to as G(3±5) dendrimer means the concentration of the surface
and those with surface carboxyl groups as G(3.5±5.5). The ester-
terminated dendrimers are referred to as GE(1.5±5.5). Metal salts
functional group. One can see that the average particle
were kindly supplied by Tanaka Kikinzoku Kogyo. The water used size of gold using G5 dendrimer is smaller than that using
in this study was puri®ed through a Milli-Q Plus system. The other G3 dendrimer. To obtain the relationship between the
chemicals were of analytical grade. The structures of the dendri- particle size of gold and the generation of the dendrimer,
mers are shown in Scheme 1. the average diameter of the gold particles is plotted
against the ratio of the concentrations of dendrimer to
Au3+ for G3±G5 dendrimers in Fig. 2. The average
diameter decreased rapidly and then gradually with
increasing ratio of the concentration of dendrimer to
Au3+ for G3±G5 dendrimer, where the average diameter
for G3 dendrimer was greater than those for G4 and G5
dendrimers at the same ratio of the concentration of

Methods and measurements

The metal salts and dendrimers were separately dissolved in

deionized water or organic solvents. Then, both solutions were
mixed with deionized water or organic solvents to make the
desired concentrations of the metal salts and dendrimers. The
solutions were stirred vigorously during the addition of excess
reductant.
UV±vis spectra of the solutions before and after the reduction of
the metal salts were measured with a UV spectrophotometer
(Hewlett-Packard 8452A). The average particle sizes of the metals
obtained were determined from several negative ®lms (approxi-
mately 100 particles) taken using a transmission electron micro-
scope (Hitachi H-800). The samples were prepared by mounting a
drop of the solution on carbon-coated Cu grids and allowing the
drop to dry in air.
Fourier transform IR (FT-IR) spectra for dendrimers and metal
particles were obtained by forming a thin transparent KBr pellet
containing the samples.
Hydrogenation of cyclohexene was carried out at 40 °C. The
amount of catalyst used was 0.1 mmol dm)3 in 50 ml ethanol. Fig. 1 Transmission electron microscopy (TEM) and particle size
Before addition of cyclohexene, hydrogen gas was bubbled in the distribution of gold nanoparticles obtained in the presence of
ethanol for 20 min. The hydrogenation from cyclohexene to dendrimer: a [HAuCl4] ˆ 0.2 mmol dm)3, [G3] ˆ 0.4 mmol dm)3,
cyclohexane was determined by gas chromatography from the [NaBH4] ˆ 2 mmol dm)3; b [HAuCl4] ˆ 0.2 mmol dm)3, [G5] ˆ
analysis of the reactant collected from the reaction vessel. 0.4 mmol dm)3, [NaBH4] ˆ 2 mmol dm)3
82

shape of the dendrimers play an important role for the

preparation of gold nanoparticles. A similar trend in the
average particle size of gold with the generation has been
reported for the reduction of Au3+ with UV radiation [6].
To con®rm the interaction between gold nanoparticles
and the dendrimers, FT-IR spectra of G5 dendrimer
alone and gold nanoparticles obtained from dendrimer
solution were measured (Fig. 3). The amide bands at
1,630 and 1,540 cm)1, which are characteristic of the
dendrimer branches, are very similar for both Fig 3,
curves a and b. This may suggest that gold nanoparticles
adsorb on the exterior of the dendrimers.
In the preparation of platinum particles, many
aggregates of platinum colloids were observed below
the ratio of the concentration of G3 to that of Pt4+ of
40:1 and stable platinum colloids could not be obtained.
When the ratio increased, stable platinum nanoparticles
were obtained. As one example, TEM micrographs of
platinum colloids obtained in the presence of G4 and G5
dendrimers and their size distributions are given in
Fig. 4. It is apparent that the size distributions are
relatively small, and the average particle sizes are about
2.4 nm for both systems. In the case of G3 dendrimer, the
Fig. 2 Change in average particle size of gold nanoparticles with ratio average size was about 3.0 nm at the ratio of the
of [dendrimer]/[Au3+]
concentration of dendrimer to that of Pt4+ of 80:1.
Thus, these results indicate that the particle size of plat-
dendrimer to Au3+. Thus, it is found that the dendrimers inum is insensitive to the size and the shape of
operate as a very e€ective protective colloid for the the dendrimers above some ratio of the concentration
preparation of gold particles since only a very small of dendrimer to Pt4+. In addition, the fact that high
amount of the dendrimer is required to obtain nanom- dendrimer concentrations are required for stable plati-
eter-sized gold particles compared to other linear poly- num colloids compared to that for stable gold colloids
mers. In addition, it is suggested that the size and the may suggest that the interaction between platinum

Fig. 3 Fourier transform IR

spectra of G5 dendrimer alone
(a) and G5 dendrimer/gold
nanoparticles (b)
 83

Fig. 5 UV±vis spectra of AgNO3 in the presence of G5.5 dendrimer

after reduction with NaBH4
Fig. 4 TEM and particle size distribution of platinum nanoparticles
obtained in the presence of dendrimer: a [H2PtCl6] ˆ 0.1 mmol dm)3,
[G4] ˆ 8.0 mmol dm)3, [NaBH4] ˆ 1 mmol dm)3; b [H2PtCl6] ˆ silver particles by TEM because the particle size was too
0.1 mmol dm)3, [G5] ˆ 8.0 mmol dm)3, [NaBH4] ˆ 1 mmol dm)3
small to detect under this condition. The absorption
spectra of AgNO3 in the presence of G5.5 after reduction
colloids and the dendrimers is weaker than that between with NaBH4 (Fig. 5) show that a typical plasmon band
gold colloids and the dendrimers. In fact, FT-IR spectra of silver colloids is observed at 380 nm at the ratio of the
of the platinum colloids prepared in the presence of G5 concentration of G5.5 to Ag+ of 1:1 and with an increase
dendrimer show that the absorption band due to the in the ratio another band appears at 450 nm. A similar
interaction between platinum colloids and amino groups absorption band at 440 nm for silver cluster has been
of the dendrimer is very weak. reported when the reduction of Ag+ on polyacrylate in
Since it is expected that Ag+ ions adsorb strongly on aqueous solution is carried out by c irradiation [12].
dendrimers with surface carboxyl groups through elec-
trostatic attractive forces, the reduction of AgNO3 by
addition of NaBH4 in the presence of G3.5, G4.5, or Preparation of metal nanoparticles in nonaqueous
G5.5 dendrimer was carried out. In the absence of the solutions
dendrimers we only obtained very unstable silver parti-
cles, which sedimented rapidly. When Ag+ ions were Two nonaqueous systems have been investigated to
reduced with NaBH4 in the presence of the dendrimers, prepare nanosized gold [13], platinum [14], and silver
the color of the silver colloids changed with increasing particles. One is the reduction of metal salts with
concentration of G5.5; yellow at the ratio of the dimethylamineborane in ethyl acetate in the presence of
concentration of G5.5 to that of Ag+ of 1:1, but turned dendrimers with surface methyl ester groups. The other is
to orange at higher ratios. In the case of G3.5 and G4.5 that metal ions are extracted from aqueous solution to
dendrimers, a similar result was observed as for G5.5 organic solvents containing a hydrophobically modi®ed
dendrimer. It is interesting to note that the time required dendrimer, followed by reduction of metal ions in
for the color change to yellow or orange after addition of organic solvents with dimethylamineborane [15].
NaBH4 increases with increasing concentration of the When HAuCl4 in ethyl acetate was added to dendri-
dendrimers because of the repulsive action of BH4 with mers in ethyl acetate, the formation of a dendrimer±
the negatively charged dendrimers that carry reacting Au3+ complex was observed (Fig. 6). As shown in
Ag+ ions. Such a delay in the reduction of Ag+ ions has Fig. 6a, HAuCl4 in ethyl acetate shows an intense
been observed in the presence of polyacrylate [12]. absorption at 324 nm, which can be assigned to the
Unfortunately, above the ratio of the concentration of ligand-to-metal charge transfer band of AuCl4 . On the
G5.5 to that of Ag+ of 5:1 we could not observe any other hand, GE5.5 dendrimer shows a small absorption
84

of a complex of dendrimers and Au3+ was obtained for

GE1.5 and GE3.5 dendrimers. Au3+ ions in the presence
of dendrimers in ethyl acetate were readily reduced by
adding an excess amount of dimethylamineborane. The
TEM images of Au nanoparticles prepared at various
dendrimer concentrations for a ®xed Au3+ concentra-
tion (0.2 mmol dm)3) are shown in Fig. 7. One can see
that although large particles are produced when the
concentration of GE5.5 dendrimer is low, the particle
size of gold becomes smaller with increasing dendrimer
concentration and above an amide to HAuCl4 concen-
tration ratio of 10 or greater, the mean particle size levels
o€ at 3.5+0.2 nm. Furthermore, it is important to note
that the maximum particle size is in the range 7±8 nm for
an amide to HAuCl4 concentration of 10 or greater. This
size is in good agreement with the hydrodynamic
diameter of GE5.5 dendrimer in ethyl acetate. A similar
result was found for gold nanoparticles obtained with
GE3.5 dendrimer (dH ˆ 4.8). These results strongly
suggest that the gold nanoparticles are encapsulated in
the dendrimer molecules. The FT-IR spectrum for GE5.5
dendrimer containing Au nanoparticles also indicates
that the peak shift of the amide I band and the peak
splitting of the amide II band remain after reduction of
Au3+ to Au, while only a small peak shift is observed for
the stretching band of the surface methyl ester group.
However, since dmax is larger than dH in the case of GE1.5
dendrimer, encapsulation of gold nanoparticles by
GE1.5 dendrimer may not occur.
Platinum nanoparticles were also prepared in ethyl
acetate in the presence of dendrimers with a surface
methyl ester group. Similar to the preparation of gold
nanoparticles, it is important to control the time elapsed
Fig. 6 UV±vis spectra of HAuCl4±dendrimer in ethyl acetate:
a HAuCl4; b GE5.5; c mixture of HAuCl4 and GE5.5 with running
after mixing H2PtCl6 and the dendrimer in ethyl acetate.
time For example, the reduction of PtCl26 ions in the presence
of GE5.5 dendrimer by addition of an excess amount of
maximum at 278 nm, as shown in Fig. 6b. On mixing dimethylamineborane (90 times that of PtCl26 ) after
Au3+ with GE5.5 dendrimer, the absorption spectra are 5 min of elapsed time provides large and small platinum
changed as shown in Fig. 6c. A new band develops at particles, as shown in Fig. 8. It is very interesting to
280 nm at the expense of the 324 nm band and the latter visualize by TEM that small platinum particles are
completely disappears in 15 min of stirring. In addition, encapsulated by GE5.5 dendrimer, while large platinum
an isobestic point is found at 304 nm, indicating that a particles are covered with GE5.5 dendrimer. When the
ligand substitution from AuCl4 to another Au3+ time elapsed increased to 1 day, it was found that
complex occurs through the participation of GE5.5 relatively uniform platinum nanoparticles which are
dendrimer. To con®rm the complex formation of encapsulated by GE5.5 dendrimer were obtained; how-
GE5.5 dendrimer and Au3+, the FT-IR spectra of ever, in the case of GE1.5 dendrimer, platinum nano-
GE5.5 dendrimer were measured in the absence or particles having diameters of 8.8±10.4 nm were obtained;
presence of Au3+. It was found that the bands for the the particle size was greater than the diameter of GE1.5
surface methyl ester group at 1,044, 1,200, 1,438, and dendrimer, indicating that GE1.5 dendrimer is a protec-
1,736 cm)1 do not change by introducing Au3+, while tive colloid rather than an encapsulating agent. Similarly,
the amide I band at 1,647 cm)1 for interior amide groups silver nanoparticles were prepared in ethyl acetate using
undergoes a high-frequency shift to 1,649 cm)1 and the GE5.5 dendrimer.
single peak for the amide II band splits into two peaks on Gold nanoparticles were prepared through the ex-
addition of Au3+. These results suggest that the interior traction of Au3+ from aqueous solution to toluene or
amide groups of GE5.5 dendrimer are responsible for the chloroform containing GH4 dendrimer and reduction by
coordination to Au3+. A similar result for the formation addition of dimethylamineborane. The transfer ratio of
 85

Fig. 8 a TEM image of platinum nanoparticles obtained in the

presence of GE5.5 dendrimer after 5 min elapsed time. b Enlargement
of the particle in a. c Enlargement of the particle in b

Au3+ from aqueous solution to toluene containing GH4

Fig. 7 TEM and size distribution of gold nanoparticles prepared at
various GE5.5 dendrimer concentrations in ethyl acetate: a [amide]/ dendrimer was as follows: 30% at 0.01 g dm)3, 40% at
[Au3+] ˆ 1.5; b [amide]/[Au3+] ˆ 5; c [amide]/[Au3+] ˆ 10; d [amide]/ 0.03 g dm)3, and 42% at 0.05 g dm)3 dendrimer, where
[Au3+] ˆ 15 the initial concentration of Au3+ in aqueous solution
86

was kept constant at 0.2 mmol dm)3. Since Au3+ is not

soluble in toluene at all, Au3+ transferred from the
aqueous to the toluene phase should be incorporated into
GH4 dendrimer. Then, the reduction of Au3+ in the
dendrimer was carried out by addition of dimethylam-
ineborane. The average diameters of the gold nanopar-
ticles obtained was 2.5 nm for 0.01 g dm)3, 3.0 nm for
0.03 g dm)3, and 3.4 nm for 0.05 g dm)3 GH4 dendri-
mer, respectively, the diameters being below the diameter
of G4 dendrimer (4.5 nm). The average Au3+ ion
numbers per dendrimer molecule were calculated to be
about 300±80 from 0.01 to 0.05 g dm)3 GH4 dendrimer
using the transfer ratios and these numbers correspond
to about gold particle of diameter 2.1±1.4 nm, which are
smaller than those obtained by TEM. According to
Balogh and coworkers [16, 17] it has been reported that
noble metal particles consisting of small numbers of
atoms or molecules dispersed within or on the surfaces of
the dendrimers are often amorphous. This may suggest
that the the gold particles formed in the GH4 dendrimer
are composed of many gold clusters. This idea can
explain the gold particle size obtained by TEM observa-
tion. Gold nanoparticles were also obtained in the Fig. 9 Hydrogenation of cyclohexene by platinum nanoparticles
chloroform±Au3+±GH4 dendrimer system; their diame- prepared in the presence of GE dendrimers in ethanol
ters ranged between 3.0 and 4.0 nm.
Polymer-stabilized noble metal particles have been
used as catalysts for the hydrogenation of unsaturated more dense, spheroid topology, which can incorporate
organic compounds. Accordingly, it is interesting to metal ions in the interior of the dendrimers. As a result,
study the catalytic activity of noble metal nanoparticles encapsulated noble metal nanoparticles are obtained in
obtained in the presence of dendrimers. The conversion which the particle size is controlled by the generation of
from cyclohexene to cyclohexane with platinum nano- the dendrimers. In particular, in the case of the
particles prepared in the presence of dendrimers with hydrophobically modi®ed dendrimer±Au3+±toluene or
surface methyl ester groups in ethanol is shown in Fig. 9 dendrimer±Au3+±chloroform systems, relatively mono-
[18]. It is clearly demonstrated that the platinum disperse gold nanoparticles are obtained since Au3+ ions
nanoparticles obtained in the presence of GE1.5 dendri- should be located in the interior of the dendrimer.
mer have much higher catalytic activity than those
obtained in the presence of GE3.5 and GE5.5 dendri-
mers. At the reaction time of 24 h, the conversion was Conclusions
about 86% for GE1.5 dendrimer and 48% for GE3.5
dendrimer and GE5.5 dendrimer, respectively. This result From the results presented here it has been found that
may be derived from a unique structure of the dendrimer when the interaction between metal ions and exterior
so that cyclohexene molecules are less able to penetrate functional groups of dendrimers is strong, for example,
into the interior platinum nanoparticles of the dendrimer HAuCl4 with poly(amidoamine) dendrimer with surface
when the generation of the dendrimer increases. amino groups or Ag+ with poly(amidoamine) dendrimer
It is important to discuss the e€ect of the generation of with surface carboxyl groups, nanoparticles of gold and
the dendrimer for the preparation of noble metal silver are stabilized by adsorption of the dendrimer, while
nanoparticles, in particular, in nonaqueous solutions, metal ions interact strongly with the interior functional
because encapsulated gold or platinum nanoparticles group of dendrimers and encapsulated nanoparticles are
were obtained in ethyl acetate, toluene, or chloroform. In often formed. In addition, an increase of the generation
the early generation of the dendrimers, relatively large as well as of the concentration leads to the formation of
nanoparticles are obtained in which the dendrimers smaller nanoparticles. Thus, dendrimers play a very
adsorb on the nanoparticles and act as protective interesting role for the preparation of nanoparticles and
colloids. This behavior is very similar to that of linear is di€erent from conventional linear polymers. The
polymers because the earlier generation dendrimers have hydrogenation of cyclohexene is considerably a€ected
an open structure or are less compact. On the other hand, by platinum nanoparticles prepared by di€erent gener-
for the later generations, the dendrimers consist of a ation dendrimers.
 87

References

1. Bradley JS (1994) In: Schmid G (ed) 8. (a) Carcia ME, Baker LA, Crooks RM 13. Torigoe K, Suzuki A, Esumi K (in
Clusters and colloids: from theory to (1999) Anal Chem 71:256±258; (b) press)
applications. VCH, Weinheim, pp 459± Zhao M, Crooks RM (1999) Adv 14. Esumi K, Nakamura R, Suzuki A,
544, and references therein Mater 11:217±220; (c) Chechik V, Zhao Torigoe K (2000) Langmuir 16:7842±
2. Tomalia DA, Naylor AM, Goddard M, Crooks RM (1999) J Am Chem Soc 7846
WA III (1990) Angew Chem Int Ed 121:4910±4911; (d) Chechik V, Crooks 15. Esumi K, Hosoya T, Suzuki A, Tori-
Engl 29:138±175 RM (2000) J Am Chem Soc 122:1243± goe K (2000) J Colloid Interface Sci
3. Frechet JM (1994) Science 263:1710± 1244 229:303±306
1715 9. He J-A, Valluzzi R, Yang K, Dolu- 16. Balogh L, Valluzzi R, Laverdure KS,
4. Bosman AW, Janssen HM, Meijer EW khanyan T, Sung C, Samuelson L, Gido SP, Hagnauer GL, Tomalia DA
(1999) Chem Rev 99:1665±1688 Balogh L, Tomalia DA (1999) Chem (1999) J Nanoparticle Res 1:353±368
5. Zeng F, Zimmerman SC (1997) Chem Mater 11:3268±3274 17. Balogh L, Tomalia DA, Hagnauer GL
Rev 97:1681±1712 10. Tomalia DA, Baker H, Dewald J, Hall (2000) Chem Innov 30:19±26
6. Esumi K, Suzuki A, Aihara N, Usui K, M, Kallos G, Martin S, Roeck J, Ryder 18. Esumi K, Satoh K, Suzuki A, Torigoe
Torigoe K (1998) Langmuir 14:3157± J, Smith P (1986) Macromolecules K (2000) J Jpn Soc Colour Mater
3159 19:2466±2468 73:434±437
7. (a) Esumi K, Hosoya T, Suzuki A, 11. Sayed-Sweet Y, Hedstrand DM, Spin-
Torigoe K (2000) Langmuir 16:2978± der R, Tomalia DA (1997) J Mater
2980; (b) Esumi K, Suzuki A, Yamah- Chem 7:1199±1205
ira A, Torigoe K (2000) Langmuir 12. Ershov BG, Henglein A (1998) J Phys
16:2604±2608 Chem B 102:10667±10671
Progr Colloid Polym Sci (2001) 117: 88±93
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

K. MogyoroÂsi Preparation, characterization,

J. NeÂmeth
I. DeÂkaÂny and photocatalytic properties
J. H. Fendler
of layered-silicate-supported TiO2
and ZnO nanoparticles

Abstract TiO2 nanoparticles were space of the clays. The average

prepared in 2-propanol and in water particle diameter of the nanoparti-
K. MogyoroÂsi á J. NeÂmeth from titanium alkoxide, and ZnO cles, determined by TEM, ranged
I. DeÂkaÂny (&) nanoparticles were formed from between 4 and 14 nm. The photo-
Department of Colloid Chemistry, aqueous ZnCl2 either in situ in catalytic activity of TiO2, intercalat-
University of Szeged and Nanostructured
Materials Research Group of the sodium montmorillonite and in syn- ed into montmorillonite, for salicylic
Hungarian Academy of Science, thetic hectorite or, alternatively, acid photooxidation was determined
Aradi v.t. 1, 6720 Szeged, Hungary were incorporated into the silicate to be better than that elicited by
e-mail: [email protected] lamellas. Transmission electron mi- TiO2 alone.
Tel.: +36-62-544210
Fax: +36-62-544042 croscopy (TEM), X-ray di€raction,
and Brunauer±Emmett±Teller mea-
J. H. Fendler surements were used to establish the Key words TiO2 á ZnO
Center for Advanced Materials
Processing, Clarkson University, incorporation of semiconductor nanoparticles á Montmorillonite á
Potsdam, NY 13699-5814, USA nanoparticles into the interlamellar Intercalation á Photooxidation

Introduction Experimental
The preparation and photochemical properties of semi- Materials
conductors has attracted increasing attention from a
wide range of scienti®c interests [1, 2]. Photofunctional TiO2 nanoparticles were prepared using the sol±gel method by the
semiconductors play an important role in the photocat- hydrolysis of titanium(IV) ethoxide (tetraethyl orthotitanate,
Merck, pro anal.) and titanium(IV) isopropoxide (tetraisopropyl
alytic degradation of organic pollutants in water and soil orthotitanate, Fluka Chemika, pract. ) in Milli-Q water (18 MWcm
[3, 4]. In order to control the photocatalytic properties we deionized water, Millipore Co., MilliQ system). For reference
also have to control the size, the dispersity, and the materials we chose P 25 Degussa TiO2. The sodium montmorill-
stability of the nanoparticles. This aim can be achieved onite (Wyoming montmorillonite, USA, 85 mEq/100 g clay cation-
exchange capacity) was used in the 2-propanol (Reanal, a.r.)
by synthesizing the nanoparticles in droplets of micro- medium as a stabilizing agent and support. The basal distance in
emulsions [5], in micellar systems [6], in solid±liquid the air dry state is 1.2 nm. We also used other layered silicates, such
interfacial adsorption layers as nanophase reactors, or in as Optigel SH (SuÈd-Chemie, synthetic hectorite). For the synthesis
the interlayer spacings of clay minerals [7±16]. The of nanosol hydrochloric acid (Reanal, pro anal.) and for the
intention of the present work was the preparation of neutralization of the sols NaOH (Reanal, puriss) were used.
Zinc(II) chloride (Reanal), sodium hydroxide (Reanal) and ZnO
TiO2 and ZnO photocatalysts without any organic (Reanal) were used as received. Sodium montmorillonite was
solvents or surfactants. The synthesis occurred in puri®ed by removing particles that have a diameter greater than
aqueous suspensions of layered silicates (montmorillo- 2 mm by sedimentation for 12 h. Smaller montmorillonite particles
nite and synthetic hectorite). were removed by suction from the coarse settled minerals.
 89

Sedimentation was repeated twice and the sodium montmorillonite (sample: ZnO/M/H/61%) 1% montmorillonite suspension. The
nanoparticles were isolated by centrifugation (15 min at samples were centrifuged, dried, and calcined at 400 °C for 3 h.
5,000 rpm).
The water used in all the preparations was puri®ed by a Milli-Q
system (Millipore), resulting in a resistivity of 18 MWcm. Measurement methods

The formation of the anatase and the thermostability of the clay

Methods carriers were established by thermoanalytical measurements using a
MOM Derivatograph Q-1500 D instrument.
Sample preparation X-ray di€raction (XRD) measurements were performed on solid
samples using a Philips 1800 X-ray di€ractometer (Cu Ka,
TiO2 sol preparation method 1.5418 nm, 40 kV, 35 mA). The basal distances (dL) were calculat-
Titanium dioxide nanoparticles were prepared by the hydrolysis of ed from the ®rst (001) Bragg re¯ections by using the PW 1877
titanium(IV) alkoxides and subsequent heat treatment. In a typical automated powder di€raction software.
preparation 500 ml 5.3 vol% titanium(IV) tetraisopropoxide±2- Surface areas were determined by N2 adsorption (Brunauer±
propanol mixture was added drop by drop to puri®ed 4000 ml Emmett±Teller, BET) experiments using a Gemini 2735 (Microm-
Milli-Q water under vigorous stirring over 45 min to yield a milky eritics) sorptometer at 77 ‹ 0.5 K. Prior to the measurements the
white dispersion. Subsequent to the addition of 27.2 ml concen- samples were pretreated in a vacuum at 393 K for 2 h. The sample
trated hydrochloric acid the dispersion was stirred at 50 °C for vessel was loaded with about 0.1±0.7 g sample. Step-by-step
12 h. During the stirring the dispersion became a transparent (cumulative) measurements were controlled by the Gemini soft-
homogeneous sol. After calcination (at 400 °C for 4 h) the average ware.
particle size was 5.4 nm (standard deviation 1.1 nm) (sample: TiO2/ The surface-potential examinations of the sol particles were
0/S/100%, see sample notation in the Appendix). carried out using a Mutek PCD 02 particle charge detector with Au
electrodes.
Preadsorption of alkoxides Transmission electron microscopy (TEM) images were taken
using a Philips CM-10 electron microscope, using an accelerating
In these experiments we adsorbed titanium(IV) ethoxide and voltage of 100 kV. Powder samples were suspended in ethanol (at a
titanium(IV) isopropoxide onto Wyoming sodium montmorillonite concentration of approximately 0.01%) and the aliquots were
and onto synthetic hectorite. In a typical preparation we dispersed dropped on 2-mm diameter Formvar-coated copper grids. The
1.0 g montmorillonite in 50 ml 2-propanol, then we added a 24 ml particle size distributions were determined by using the UTSSCSA
solution of titanium(IV) isopropoxide in 2-propanol, calkoxide ˆ Image Tool program.
17 v/v%. After 20 min in the adsorption equilibrium 33.5 ml 40 v/ The analysis of the samples after photooxidation was carried
v% water±2-propanol mixture was added drop by drop to the out using a UVIKON 930 UV±vis dual-beam spectrophotometer.
suspension under vigorous stirring at ambient temperature. The The degradation of model pollutants (salicylic acid and surfactants)
system was allowed to stand for 2 h, centrifuged and after this was monitored by UV±vis measurements.
dried at 60±70 °C (sample TiO2/M/P/50%, since the TiO2 content
is approximately 50%). This dispersion was repeated a number of
times with di€erent amounts of alkoxide (0.9±13.3 mmol alkoxide/
g montmorillonite, samples TiO2/M/P/7%, TiO2/M/P/50%) and Results and discussion
with the other silicate support ± at constant alkoxide±water ratio
(1:56 molar ratio).
Nanoparticle growth and incorporation into layer
silicates
Heterocoagulation method
The TiO2 nanosol (pH 1.5, 0.1 wt%) was neutralized with 1 M
NaOH solution to pH 4. We washed and centrifuged the precipitated The calcination of Ti(OH)4 is a multistep polycondensa-
material with Milli-Q water three times. The TiO2 sediment was tion process. By thermogravimetric measurements it was
redispersed into Milli-Q water and later the pH was adjusted at established that the transformation of Ti(OH)4 into TiO2
pH ˆ 4.0 with 0.1 M HCl solution. In this state the sol has positively involved the endothermic loss of water up to 200±250 °C
charged particles which coagulate in a montmorillonite suspension
wherein the platelets are negatively charged. The hydrolysis product, and the subsequent exothermic formation of the anatase
titanium(IV) oxide/hydroxide, was calcined in air at 320 °C for 4 h crystals between 300 and 400 °C. The optimum calcina-
(TiO2/M/P/7%, TiO2/M/P/50%), at 400 °C for 4 h (hydrolyzed tion temperature is between 400±450 °C, i.e., below the
from alkoxide TiO2/0/A/100%, heterocoagulated montmorillonite/ dehydroxylation temperature of the silicates. The for-
TiO2 sample TiO2/M/H/33%), or at 450 °C for 6 h (preadsorption
method, Hec/TiO2 nanocomposite TiO2/Hec/P/50%).
mation of the anatase crystal structures manifested itself
Montmorillonites intercalated by ZnO nanoparticles were in the broadening of the XRD peaks at 2Q ˆ 25.3°, which
prepared by heterocoagulation of previously prepared Zn(OH)2 permitted the assessment of the nanoparticle diameters
sols with negatively charged platelets of the clay mineral. The possible by using the Scherrer equation.
following method was used for the heterocoagulation of ZnO The XRD measurements showed that heterocoagula-
montmorillonite complexes. ZnCl2 (1.5 g) was dissolved in 1.5 ml
distilled water and subsequent to dissolution 4.0 ml aqueous 1.0 M tion method results in an intercalated structure of
NaOH was quickly introduced to produce Zn(OH)2. The crude montmorillonite (Fig. 1). The basal distance ranges from
precipitate was homogenized by stirring and ultrasonication and 2.5 to 5.5 nm in the case of TiO2/montmorillonite
was diluted with distilled water to 1,600 ml and after further nanocomposites. In the case of the ZnO nanoparticles,
ultrasonication was characterized using a particle charge detector.
The surface potential of the sol particles was 429 mV, the pH was Fig. 2 shows the XRD patterns of the nanocomposites
6.7, and the Zn(OH)2 content was 0.2 g in 1,600 ml of the sol. The prepared by heterocoagulation synthesis. Since pillaring
Zn(OH)2 sol was added to 100 (sample: ZnO/M/H/14%) and 10 ml of the montmorillonite by ZnO is incomplete, the peak
90

diameter between the lamellae, but particles are much

larger (10±14 nm) without the support. By the heteroco-
agulation method the average diameter of the TiO2
(anatase) particles is 6.5 nm. The TiO2 particles are
approximately 5.4 nm by the sol method and 7.5 nm by
normal hydrolysis of alkoxide in 2-propanol after
calcination.
The electron micrographs clearly show the presence of
the nanoparticles. These images can also be used for the
construction of particle size distribution functions. A
representative picture and size distribution function of
ZnO nanoparticles can be seen in Figs. 3 and 4.
The reference ZnO (Reanal) has an average particle
diameter of 700 nm. Samples ZnO/M/H/14% and ZnO/
M/H/61% (Figs. 3, 4) were prepared from the same
Fig. 1 Heterocoagulated structure: semiconductor particles on mont- Zn(OH)2 sol by the heterocoagulation method. An
morillonite platelets important di€erence between these composites is that
the amount of the stabilizing montmorillonite is 10 times
due to the basal spacing of the clay lamellae greater in sample ZnO/M/H/14% than in sample ZnO/
(dL ˆ 0.96 nm) appears along with that due to the M/H/61%. The greater amount of stabilizing agent
intercalated ZnO (dL ˆ 5.6±6.9 nm, Table 1). Increasing results in smaller nanoparticles and better monodisper-
the amounts of ZnO diminishes, however, the re¯ection sity as can be seen in the pictures showing the size
due to the montmorillonite basal spacing (in the absence distribution functions. A possible explanation is that the
of any intercalating compounds). increasing number of the negatively charged montmo-
Representative re¯ections of the ZnO wurtzitic struc- rillonite lamellae can better take apart the positively
ture can be seen between 30 and 40°. Sample ZnO/M/H/ charged, aggregated secondary particles of the Zn(OH)2-
14%, which contains 10 times more stabilizing montmo- sol. The TEM images demonstrated the particles to be in
rillonite than sample ZnO/M/H/61%, shows lower and the nanosize range and that their size and dispersity can
broader peaks, indicating the presence of smaller ZnO be controlled by adding di€erent amounts of the
particles (see TEM measurements). stabilizing montmorillonite.
The XRD patterns of ZnO/montmorillonite complex- The data collected in Table 1 show that incorpora-
es also include an intercalation peak which shows the tion of nanoparticles results in a strong e€ect on the
formation of the pillared structure. The exact structural speci®c surface area of sodium montmorillonite. The
parameters can be seen in Table 1. BET speci®c surface areas of samples containing
Using the preadsorption method the TEM images anatase varied between 50 and 270 m2/g as determined
indicated the presence of TiO2 particles of 2±3-nm by N2 adsorption measurement. These data are in the

Fig. 2 X-ray di€raction pat-

terns of calcined (400 °C for
3 h) ZnO montmorillonite
complexes synthesized by the
heterocoagulation method,
ZnO/M/H/14%: 2 mmol ZnO
g montorillonite, ZnO/M/H/
61%: 20 mmol ZnO/g mont-
morillonite. There are interca-
lation peaks in the low-angle
range, and in the 30±40° range
the representative re¯ections of
the wurtzitic ZnO structure
show the di€erent rates of the
crystallinity
 91

Table 1 Structural prpoperties of TiO2 and ZnO layer silicate nanocomposites

Name of the sample Semiconductor content Basal Speci®c surface Mean particle
distance (nm) area (m2/g) diameter (nm)
(wt%) (mmol/g)

Sodium montmorillonite calcined at 300 °C ± ± 0.96 4.9 ±

TiO2 (P 25) 100 ± ± 50.0 22
TiO2/0/S/100% 100 ± ± 105.8 5.4
TiO2/M/P/7% 6.7 0.9 3.9(0.96) 55.0 ±
TiO2/M/P/50% 51.6 13.3 4.0 142.8 5.7
TiO2/Hec/P/50% 51.4 13.2 4.08 267.7 10.3
TiO2/M/H/33% 33 8.3 6.3 130.3 4.3
ZnO (Reanal) 100 ± ± 2.3 700
ZnO/M/H/14% 13.8 2 5.6 31.2 6.3
ZnO/M/H/61% 61.5 20 6.9 42.4 13.4

range 30±40 m2/g after calcination in the case of ZnO rather than that of the bulk materials, and higher
intercalated montmorillonites, while the montmorillo- dispersity ensures a better possibility of using them as
nite support without nanoparticles and reference ZnO catalysts.
show only values under 5 m2/g. This phenomenon As can be observed, on increasing the semiconductor
veri®es the higher degree of dispersity of nanocomplexes content by adding more zinc or tin hydroxide sol, the

Fig. 3 Transmission electron

microscopy (TEM) image of
ZnO/M/H/14% ZnO/montmo-
rillonite nanocomposite and its
size distribution. The ZnO con-
tent is 2 mmol ZnO/g mont-
morillonite. The mean particle
diameter is 6.3 nm

Fig. 4 TEM image of ZnO/M/

H/61% ZnO/montmorillonite
nanocomposite and its size dis-
tribution. The ZnO content is
20 mmol ZnO/g montmorillo-
nite. The mean particle diame-
ter is 13.4 nm
92

Table 2 The photocatalytic

eciency of the catalysts using Name of the Semiconductor Amount Amount of pollutant
a Pyrex reactor (k = 310± sample content (wt%) of pollutant removed (mmol/g
390 nm) or a quartz reactor removed (%) semiconductor)
TiO2 (P 25) 100 83.0 0.125
TiO2/0/S/100% 100 51.8 0.078
TiO2/M/P/50% 51.6 42.1 0.122
TiO2/M/H/33% 33 49.1 0.223
ZnO (Reanal)a 100 88.4 0.133
ZnO/M/H/14%a 13.8 34.3 0.372
ZnO/M/H/61%a 61.5 46.2 0.113
a
k = 250±390 nm

speci®c surface area also increases, indicating the incor- into the sodium montmorillonite we can improve the
poration of the pillaring sols. photodegradation rate of salicylic acid compared to the
reference materials. In the case of ZnO/M/H/14%
nanocomposite the improvment is much greater than
Photocatalytic properties of nanocomposites for the ZnO/M/H/61% nanocomposite because the
semiconductor content of the ZnO/M/H/14% catalyst
The photocatalytic eciency of the synthesized and the is only 13.8%, but still it degrades 34.3% of the
reference materials was tested by the degradation of pollutant, while ZnO/M/H/61% with 61.5% semicon-
salicylic acid in a Pyrex and a quartz UV photoreactor ductor content can oxidize 46.2% of the salicylic acid.
with an inner radiation-type high-pressure mercury arc This can be explained by the fact that the average particle
lamp. The concentration of salicylic acid in the aqueous diameter of ZnO in sample ZnO/M/H/14% is 6.3 nm but
solution was 0.15 mm. The catalysts were employed in in sample ZnO/M/H/61% it is 13.4 nm. The semicon-
suspension form with a concentration of 0.1 wt%. The ductor particles have higher dispersity in the ®rst sample
concentration of the remaining salicylic acid was deter- than that in ZnO/M/H/61%, which results in a better
mined by measuring the absorbance of the solution at adsorption of the organic pollutant on the surface of
296 nm (Fig. 4.). The eciencies of the catalysts, which ZnO nanoparticles, because the geometrical surface area
were calculated after 60 min of irradiation, can be seen in of ZnO in the catalyst increases if the particle diameter
Table 2. decreases.
The P 25 Degussa TiO2 and the TiO2/M/H/33% Controlling the particle size and stability by incorpo-
samples were the best photocatalysts. Although the latter ration into layered silicates has a great e€ect not only on
sample contains 33% semiconductor even so it can the structural parameters (speci®c surface area, basal
degrade 49.1% of the salicylic acid. These values show distance) but also on the photocatalytic properties of the
that by incorporating the semicondutor nanoparticles nanocomposites.

Fig. 5 Photodegradation of
salicylic acid by di€erent cata-
lysts containing anatase
 93

Conclusions
Acknowledgements We thank OTKA (TO25392), FKFP (0402/
1999) and NATO SfP 972652 for support of this work.
TiO2 and ZnO nanoparticles were formed in aqueous
media and were heterocoagulated with sodium montmo-
rillonite suspension to maintain the particle size and the
stability. Independent measurement methods (XRD, Appendix: notation of the samples
TEM, BET experiments) indicated the incorporation of
the nanoparticles into the interlamellar space of mont-
Type of semiconductor TiO2
morillonite. Nanoparticles stabilized by the layered
silicates showed an increased photocatalytic activity for Type of support ZnO
the degradation of salicylic acid model pollutant than Hec (hectorite)
M (montmorillonite)
their unstabilized counterparts. The present inexpensive
0 (no support)
photocatalysts, prepared by an environmentally friendly Preparation method P (preadsorption method)
method, may be very pro®table for industrial applica- H (heterocoagulation method)
tions in a wide range of photocatlytic pollutant destruc- A (alkoxide method)
tions. Semiconductor content of catalyst 0±100%

References

1. Ogawa M, Kuroda K (1995) Chem Rev 8. Kiricsi I, PaÂlinko 13. DeÂkaÂny I, TuÂri L, Vanko Gy, JuhaÂsz
95:399±438 I, Tasi G, Hannus I (1994) Mol Cryst G, VeÂrtes A Burger K (1996) NATO
2. Fujishiro J, Uchida S, Sato T (1999) Int Liq Cryst 244:149±154 Advanced Study Institute Series 18.
J Inorg Mater 1:67±72 9. DeÂkaÂny I, Turi L, TombaÂcz E, Fendler High technology. Kluwer, Dordrecht,
3. Zhuang J, Rhusu CN, Yates JT, Jr. JH (1995) Langmuir 11:2285±2292 pp 555±568
(1999) J.Phys Chem 103:6957±6967 10. DeÂkaÂny I, Fendler JH (1996) In: Peli- 14. DeÂkaÂny I, Nagy L, Turi L, KiraÂly Z,
4. Kormann C, Bahnemann DW, Ho€- zetti E (ed) NATO Advanced Study Kotov NA, Fendler JH (1996) Lang-
mann MR (1988) Environ Sci Technol Institute Series, vol 18, pp 443±455 muir 12:3709±3715
22:798±806 11. DeÂkaÂny I, TuÂri L, Homonnay Z, VeÂrtes 15. DeÂkaÂny I, TuÂri L, SzuÃcs A, KiraÂly Z
5. Song KC, Kim JH (1999) J Colloid A, Burger K (1996) Colloids Surf A (1998) Colloids Surf A 141:405±417
Interface Sci 212:193±196 119:195±203 16. DeÂkaÂny I, TuÂri L, GalbaÂcs G, Fendler
6. Sato H (1996) PhD dissertation. Osaka 12. DeÂkaÂny I (1996) NATO Advanced JH (1999) J Colloid Interface Sci
University, p 34 Study Institute Series 18. High tech- 213:584±591
7. NeÂmeth J, DeÂkaÂny I (2000) Colloid nology. Kluwer, Dordrecht, pp 293±
Polym Sci 278:211±219 322
Progr Colloid Polym Sci (2001) 117: 94±100
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

S. Papp Growth of nearly monodisperse palladium

I. DeÂkaÂny
nanoparticles on disaggregated kaolinite
lamellae

Abstract Palladium nanoparticles Kaolinite samples containing palla-

were prepared by in situ growth dium nanoparticles were prepared
between kaolinite layers. Expansion by hydrazine and NaBH4 reduction
of the interlayer space kaolinite was of palladium ions adsorbed from a
e€ected by intercalation of dimethyl solution of H2PdCl4 (pH 4). The size
S. Papp á I. DeÂkaÂny (&) sulfoxide (DMSO) at 65 °C. The of the palladium particles formed
Nanostructured Materials Research basal spacing increased from 0.72 to was determined by transmission
Group of the Hungarian Academy
of Science, Aradi VeÂrtanuÂk tere 1, 1.12 nm during this process. After electron microscopy measurements
6720 Szeged, Hungary washing with methanol (partial dis- which showed that nearly spherical,
e-mail: [email protected] placement of DMSO ), nonionic nearly monodisperse particles of size
Tel.:+36-62-544211 poly(vinylpyrrolidone)/kaolinite, of about 1 nm were generated.
Fax:+36-62-544042
cationic poly(diallyldimethylammo-
I. DeÂkaÂny nium)/kaolinite and octylammoni-
Department of Colloid Chemistry um/kaolinite complexes were Key words Palladium
University of Szeged,
Aradi VeÂrtanuÂk tere 1, 6720 Szeged, generated by adsorbing the polymer nanoparticles á Kaolinite á
Hungary or the surfactant from solution. Intercalation á Polymer stabilization

Introduction Pd, Pt and Au nanosols stabilized by poly(vinylpyrr-

olidone) (PVP) in aqueous media have been synthesized
Several procedures were devised for the preparation of using alcohol and H2 for reduction [8±10]. Chen and
nanoparticles in the 1±50-nm size range [1]. In these Akashi [11] obtained Pt sols from H2PtCl6 in water±
procedures an important role is assigned to stabilizing ethanol mixtures of a volume fraction of 0.6 with respect
agents which protect the nanoparticles formed against to ethanol and showed the formation of particles in the
aggregation, making possible the preparation of nano- polymer-stabilized system.
particles with diameters of a few nanometers [2, 3]. Transition-metal particles are most conveniently
Polymers and surfactants are most often used as grown within the interlamellar space of clay minerals
stabilizing agents for sols of subcolloidal size. Particles by displacing the exchangeable by precursor transition-
of controlled size can also be prepared within the internal metal cations and by subsequent reduction. Au and Ag
space of micelles and microemulsions [4, 5]. Silicate clusters were obtained in laponite by Aihara et al. [12],
minerals and layer double hydroxides are excellent with hydrazine hydrate, sodium borohydride and UV
supports for the preparation of semiconductor and irradiation as reducing agents.
transition-metal particles with diameters of a few na- In our earlier studies the adsorption layer at the
nometers on the surface of these layered compounds but solid/liquid interface was employed as a ``nanophase
also in the interlamellar space. Clay minerals (montmo- reactor'' for the generation of nanocrystalline semicon-
rillonite, hectorite, etc.) are especially suitable for this ductor particles (CdS, ZnS, TiO2) and for their
purpose because they swell readily in aqueous media and, stabilization [6, 7]. To summarize brie¯y, the procedure
therefore, provide a large (500±800 m2g)1) internal consists of adsorbing the precursor ions of the nano-
surface area [6, 7]. crystalline material in the interfacial adsorption layer of
 95

solid particles (i.e. about 1-nm thick lamellae) dispersed Experimental

in a liquid phase. The synthesis is carried out in the
adsorption layer by introducing the appropriate re- Materials
agent. [6, 7]. The nanoparticles are formed attached to
Supports
the surface in a well-controllable number and size
between the silicate layers. KiraÂly et al. [13, 14] Kaolinite from Zettlitz (Germany, particle diameter: 10±20 lm)
reported the synthesis of Pd nanoparticles in organic was used as a support for the preparation of nanoparticles. The
suspensions on hydrophobized montmorillonite by basal spacing was 0.72 nm. The speci®c surface area as determined
alcohol reduction of Pd acetate. We now present new by N2 adsorption measurement was 14 m2/g.
procedures for the preparation of nanocrystalline
palladium in the interlamellar space of kaolinite, a clay Reagents
mineral that does not swell in water. The large speci®c
surface area necessary for nanoparticle growth is The reagents were used as received without further puri®cation.
The metal precursor PdCl2 (purity 99%) was obtained from
created by breaking the hydrogen bonds between the Aldrich. PVP (K-30, average molecular weight 40,000, Fluka), a
kaolinite lamellae, i.e. by delamination of the mineral 20% aqueous solution of poly(diallyldimethylammonium chlo-
particles. According to Weiss et al. [15], silicate lamel- ride) (PDDA, average molecular weight 40,000±50,000, Aldrich),
lae develop strong dipole±dipole interactions with, for and octylamine (purity 99%, Fluka) were used as protective
agents for the Pd nanoparticles. Methanol (Reanal, Hungary)
example, dimethyl sulfoxide (DMSO), and hydrogen was of analytical purity. DMSO (analytical purity, Reanal,
bonds with formamide, acetamide and hydrazine. The Hungary) was used for delamination of the kaolinte particles.
study of the intercalation of kaolinite with similar The hydrazine hydrate reducing agent was a 55% aqueous
molecules is well known [15±20]. GaÂbor et al. [18] solution (Carlo Erba).
obtained the intercalation complex of kaolinite with
hydrazine and potassium acetate. The basal spacing of Methods
kaolinite is 0.72 nm, that of the kaoline±hydrazine
complex is 1.05 nm and that of the kaoline±potassium Preparation of Pd0 nanoparticles
acetate complex is 1.41 nm. The maximum degree of The kaolinite was expanded by the intercalation of DMSO at
intercalation was shown to increase with the time of 65 °C. The excess DMSO was removed from the sample by several
reaction and the concentration of the guest compound washings with methanol over 5 days. Pd/kaolinite complexes were
but was found to be una€ected by changes in prepared directly by reduction of Pd2+ ions (0.7 mM aqueous
temperature. In the case of hydrazine, the reaction solution) previously adsorbed in the methanol/DMSO/kaolinite
system and by applying a polymer and surfactant to ensure binding
was 94% complete within 1 h, whereas with potassium to the lamellae and steric stabilization. Macromolecules were
acetate the reaction never exceeded 86% completion, adsorbed on the support from a methanol or aqueous solution and
even after prolonged reaction times. this was followed by adsorption and reduction of Pd2+ ions.
Komori et al. [19] cleaved interlamellar hydrogen Intercalation complexes of nonionic PVP/kaolinite and cationic
PDDA/kaolinite (0.02±0.4 g polymer/g kaolinite) were prepared
bonds in kaolinite by N-methylformamide (dL ˆ 1.08 nm) by this method in systems containing various (0.1±2.0%) concen-
and in methanol (dL ˆ 1.11 nm) and their PVP was trations of methanol/PVP, PDDA or water/PVP, PDDA by
incorporated (dL ˆ 1.24 nm). Intercalation of alkylam- polymer adsorption. Intercalation complexes of octylammonium/
ines (C ˆ 6±18) and water was also accomplished by kaolinite (0.12±1.2 g/g kaolinite) were prepared at pH 4.0 in
the same authors [20]. The layers were expanded by systems containing various (0.5±0.05 M) concentrations of water/
octylamin. Methanol/DMSO/kaolinite intercalation compound
N-methylformamide, washed with methanol and the (1 g) was dispersed in 20 ml polymer or surfactant solution, and
methanol-wet product was treated with alkylamine; the mixtures were stirred at room temperature for 24 h. Kaolinite
alternatively, methanol was displaced by treatment samples containing di€erent amounts of palladium were obtained
with water. The basal spacing increased with the alkyl by (0.9±3.6 ml, 0.1 M) hydrazine or (1.8 ml, 0.1 M) NaBH4
reduction of the palladium ions. The metal content of the products
chain length in a linear way in the range 2.69±5.75 nm was 0.45±1.4% (Table 1). The schematic diagram of the synthesis is
with a slope of 0.225 nm per carbon atom. presented in Fig. 1.
We chose direct intercalation of DMSO for ex-
panding the kaolinite structure. The excess DMSO X-ray di€raction experiments
was displaced from the kaolinite by washing with
methanol before the polymer and surfactant were X-ray di€raction measurements were made using a Philips
adsorbed. When palladium ions were added to the PW 1820 di€ractometer (Cu Ka radiation, 40 kV, 35 mA). The
basal spacing was calculated from the (001) Bragg re¯ections using
suspension, they were also adsorbed on the external the PW 1877 automated powder di€raction software.
and internal surfaces and the Pd2+ ions were reduced
by addition of a reducing agent. Thus, the previously Electron microscopy
adsorbed polymer or surfactant promotes the adhesion
of newly formed nanoparticles on the surface of the Transmission electron microscopy (TEM) images were made using
lamellae. a Philips CM-10 transmission electron microscope with an
96

Table 1 Basal spacings of

intercalated kaolinite deriva- Kaolinite samples Pd content Poly(vinylpyrrolidon dL (nm) dave (nm) from
tives and particle diameters (w/w%) e)/poly(diallyldimeth from X-ray transmission
of the Pd0 nanoparticles pro- ylammonium)/C8N di€raction electron
duced content (w/w%) microscopy
Kaolinite 0.00 0.00 0.72 ±
Dimethyl sulfoxide/kaolinite 0.00 0.00 1.12 ±
Methanol/dimethyl 0.00 0.00 1.12 ±
sulfoxide/kaolinite(K)
Rehydrated kaolinite 0.00 0.00 0.72 ±
Poly(vinylpyrrolidone)/meth 0.00 1.90 1.12 ±
anol/kaolinite
Poly(vinylpyrrolidone)/H2O 0.00 1.90 3.64a, 0.72b ±
/kaolinite
Poly(vinylpyrrolidone)/H2O 0.00 1.90 3.92a, 0.74b ±
/kaolinite
C8N/kaolinite 0.00 56.50 2.48a, 1.28b ±
Palladium kaolinite samples Prepared in methanol, reduced by N2H4
PdK 0.47 0.00 7.53 3.25
PVPPdK1 0.47 3.80 2.21a, 1.00b 2.24
PVPPdK2 0.95 3.80 4.56a, 0.72b 2.45
PVPPdK3 0.95 17.00 4.24a, 0.71b 2.45
PVPPdK4 0.95 28.00 0.84 2.59
PVPPdK5 1.41 3.80 0.74 2.10
PDDAPdK1 0.95 3.80 3.52a, 0.82b 6.33
Palladium kaolinite samples Prepared in methanol, reduced by NaBH4
PVPPdK6 0.95 3.80 3.78a, 0.84b 4.16
PDDAPdK2 0.95 3.80 5.07a, 0.83b 2.67
Palladium kaolinite samples Prepared in water, reduced by N2H4
PVPPdK7 0.95 3.80 0.72 2.81
PVPPdK8 1.90 3.80 4.36a, 0.72b 5.83
PDDAPdK3 0.95 3.80 4.24a, 0.72b 4.90
PDDAPdK4 1.90 3.80 4.69a, 0.72b 9.44
C8NPdK1 0.95 11.60 0.73 2.17
C8NPdK2 0.95 20.10 4.42a, 0.73b 2.04
C8NPdK3 0.95 40.00 2.65 1.95
C8NPdK4 0.95 56.50 5.95a, 0.72b 2.22
Palladium kaolinite samples Prepared in water, reduced by NaBH4
PVPPdK9 0.95 3.80 4.62a, 0.72b 4.66
PDDAPdK5 0.95 3.80 6.44a, 0.72b 3.52
a
Basal spacings of intercalated kaolinite
b
Basal spacings of nonintercalated or partially intercalated kaolinite

accelerating voltage of 100 kV. Aliquots of the ethanol suspen- excess DMSO (Fig. 2c). The appearance of a peak at
sions of the samples were dropped on copper grids (diameter 7.53 nm on the XRD pattern of the Pd/kaolinite complex
2 mm) covered with Formvar foil and were then left to stand for
3±40 min and then transferred to the microscope. The particle size prepared by reduction of Pd2+ ions previously adsorbed
distribution was determined using the UTHSCSA Image Tool in the methanol/DMSO/kaolinite system and the disap-
program. pearance of the (001) re¯ection of kaolinite demonstrate
the particle growth in the interlayer space (Fig. 2d). For
the synthesis, macromolecules were ®rst adsorbed on the
Results and discussion support from a methanol or aqueous solution (0.1±2.0%
w/v). The adsorption of the amount of polymer necessary
In order to create the space necessary for the synthesis of for successful particle synthesis (2±20% w/w) did not
the nanoparticles, the hydrogen bonds tightly interlink- increase the basal spacing (Fig. 3a). When palladium
ing the kaolinite layers must be broken. As indicated by particles (0.47±1.41% w/w) were formed, the (001)
XRD experiments, the interlamellar expansion was re¯ection of 2.21 nm proves the incorporation of the
nearly 100% after the formation of the DMSO/kaolinite nanoparticles (Table 1). This peak was much more
intercalation complex. The basal spacing increased from prominent in sample PVPPdK1 than in the other
0.72 to 1.12 nm within 24 h at 65 ° (Fig. 2a, b). The preparations (Fig. 3b). The particle size calculated from
interlamellar distance was unchanged after removal of the position of the new re¯ection (2.21±0.72 ˆ 1.49 nm) is
 97

Fig. 1a±c Schematic illustration of preparation of Pd nanoparticles tion at dL ˆ 2.48 nm indicates the intercalation of
on kaolinite. a Intercalation of kaolinite, b adsorption of poly(vinyl-
pyrrolidone) (PVP) and c octylammonium ions on dimethyl sulfoxide
octylammmonium ions (Fig. 5a). In the course of
(DMSO)/methanol intercalated kaolinite the reduction by hydrazine following the adsorption
of palladium ions, a further shift of the (001) re¯ection
was observed (2.65 nm, Fig. 5b). In the case of
in good agreement with the results of TEM measure- PVPPdK457 and C8NPdK1 Pd nanoparticles only
ments (see later). formed on the external surfaces of the kaolinite
When the aqueous PVP solution was contacted with particles.
kaolinite, the peak characteristic of the intercalation The TEM picture of the PdK sample shows spherical
compound of kaolinite was not observed (Fig. 4a). particles with diameters of 2±4 nm, separately, without
Rather, the initial (001) re¯ection reappeared and a aggregation attached to the lamellae (Fig. 6a). Electron
broadened peak of dL  3.6 nm was observed (Fig. 4b). micrographs of the complexes containing nonionic PVP
This indicates that in contact with the aqueous PVP display relatively small, nearly monodisperse particles
solution some of the kaolinite layers reaggregate, where- (Fig. 6b) which tend to stick together when the polymer
as the remaining layers adsorb PVP. The formation of concentration is increased. The polymer concentration
metal clusters in the interlamellar space was indicated by did not have an e€ect on the Pd particle size (Table 1). In
a shift of the re¯ection from dL ˆ 3.6 to dL ˆ 4.6 nm samples containing cationic PDDA as a stabilizer, the
(Fig. 4c). When sodium borohydride is used for reduc- size distribution of the particles formed was more
tion, the peak appears at higher lamellar distances of polydisperse. The Pd0/kaolinite samples prepared in the
5±6 nm. aqueous system yielded comparatively large palladium
Kaolinite containing palladium was also prepared clusters of polydisperse size distribution (2±5 nm) dense-
using octylamine in acidic media (pH 4.0) to separate ly covering the lamellae (Fig. 6c). The larger particle size
the silicate layers. The amount of octylamine was deduced from the shift of the (001) re¯ection in the
varied between 0.12 and 1.2 g/g kaolinite. The re¯ec- presence of PDDA is supported by the TEM pictures
98

Fig. 4 XRD diagrams: a rehydrated methanol/DMSO kaolinite;

b rehydrated methanol/DMSO kaolinite with adsorbed PVP; c palla-
dium/PVP/kaolinite

(Fig. 6d, e; Table 1). Increasing the palladium content

Fig. 2 X-ray di€raction (XRD) diagrams: a kaolinite; b DMSO-
intercalated kaolinite; c methanol-washed DMSO/kaolinite; d palla-
not only increased the particle size but also broadened
dium nanoparticles between disaggregated kaolinite layers the polydispersity. With octylamine the particle size was

Fig. 3 XRD diagrams: a methanol/DMSO kaolinite sample with Fig. 5 XRD diagrams: a rehydrated methanol/DMSO kaolinite with
adsorbed PVP; b palladium/PVP/kaolinite adsorbed octylamine; b palladium/octylammonium/kaolinite
 99

b
Fig. 6 a Transmission electron microscopy (TEM) image and particle
size distribution of sample PdK (0.47%Pd, reduced by 0.1 M N2H4
solution). b TEM image and particle size distribution of sample
PVPPdK3 (0.95%Pd, 17% PVP, methanol treatment, reduced by
0.1 M N2H4 solution). c TEM image and particle size distribution of
sample PVPPdK7 (0.95%Pd, 3.8% PVP, prepared in aqueous
suspension, reduced by 0.1 M N2H4 solution). d TEM image and
particle size distribution of sample PVPPdK6 (0.95%Pd, 3.8% PVP,
methanol treatment, reduced by 0.1 M NaBH4 solution). e TEM
image and particle size distribution of sample PVPPdK9 (0.95%Pd,
3.8% PVP, prepared in aqueous suspension, reduced by 0.1 M
NaBH4 solution). f TEM image and particle size distribution of
sample C8NPdK2 (0.95%Pd, 20.1% C8 N, methanol treatment,
reduced by 0.1 M N2H4 solution)

similar to that in the presence of polymers; however, even

at the lowest amine concentrations studied the particles
aggregated up to form small islets (Fig. 6f) and, as the
amount of surfactant was increased, large clusters
developed. In each case, even at high metal contents,
the palladium particles remained noncrystalline without
distinct crystal shapes.

Conclusions

Well-crystallized kaolinite intercalated by DMSO served

as an excellent support for the production of metal
nanoparticles. After the adsorption of palladium ion
precursors, metal nanocrystals were formed by reduction
with hydrazine or sodium borohydride. The interlayer
spaces acted as nanoreactors. The intercalation of
nanoparticles into the kaolinite structure was proven
by the XRD measurements. This procedure makes
possible the steric control and restriction of nanoparticle
growth. The stability of the nanoparticles was further
enhanced by the addition of polymers (PVP, PDDA) and
surfactants (alkylammonium salts) which were also
intercalated into the kaolinite. TEM measurements
proved the presence of the particles and yielded reliable
particle sizes and size distributions.

Acknowledgements The authors wish to express their thanks for

the ®nancial support of the FKFP 0402/1999 project of the
Hungarian Ministry of Education and the National Scienti®c
Research Foundation (OTKA T 13/034430).
100

References

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Springer Series in Materials Sciences, JH (1997) J Colloid Interface Sci Z Anorg Allg Chem 320:183
vol 27. Springer, Berlin Heidelberg 195:307 16. Wada K (1961) Am Min 46:78
New York, p 65 8. Teranishi T, Miyake M (1998) Chem 17. Poyato-Ferrera J, Becker H-O, Weiss
2. Henglein A, Guiterrez M, Ber Buns- Mater 10:594 A (1977) Proceedings of the 3th Euro-
enges (1983) Phys Chem 87:474 9. Liu H, Mao G, Meng S (1992) J Mol pean Clay Conference, Oslo, p 148
3. Ueno A, Kakuta N, Park KH, Finlay- Catal 74:275 18. GaÂbor M, ToÂth M, KristoÂf J, KomaÂr-
son MF, Bard AJ, Champion A, Fox 10. Yu W, Liu H (1998) Chem Mater omi-Hiller G (1995) Clays Clay Miner
MA, Webber SE, White JM (1985) J 10:1205 43:223
Phys Chem 89:3828 11. Chen C-W, Akashi M (1997) Langmuir 19. Komori Y, Sugahara Y, Kuroda K
4. Trickot YM, Fendler JH (1984) J Am 13:6465 (1999) Chem Mater 11:3
Chem Soc 106:7359 12. Aihara N, Torigore K, Esumi K (1998) 20. Komori Y, Sugahara Y, Kuroda K
5. Your H-C, Baral S, Fendler JH (1988) Langmuir 14:4945 (1999) Appl Clay Sci 15:241
J Phys Chem 92:6320 13. KiraÂly Z, DeÂkaÂny I, Mastalir AÂ, Bart-
6. DeÂkaÂny I, Nagy L, Turi L, KiraÂly Z, oÂk M (1995) Mag Kem Foly 101:539
Kotov NA, Fendler JH (1996) Lang- 14. KiraÂly Z, DeÂkaÂny I, Mastalir AÂ, Bart-
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Progr Colloid Polym Sci (2001) 117: 101±103
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

Katharina Landfester Quantitative considerations for the

formulation of miniemulsions

Abstract The polymerization of sty- the s1 mechanism, is e€ectively sup-

rene in miniemulsions stabilized with pressed by addition of a very hydro-
anionic sodium dodecyl sulfate or phobic material, whereas droplet
nonionic Lutensol AT50 results in growth by collisions, or the s2
stable polymer dispersions with par- mechanism, is subject to the critical
ticle diameters between 30 and conditions. The growth of the criti-
480 nm and narrow particle size cally stabilized miniemulsion drop-
distributions. Steady-state mini- lets is usually slower than the
emulsi®cation results in a system polymerization time; therefore, in
``with critical stability'', i.e. the ideal cases, a 1:1 copy of droplets to
K. Landfester droplet size is the product of a rate particles is obtained, and the criti-
Max Planck Institute of Colloids equation of ®ssion by ultrasound and cally stabilized state is frozen.
and Interfaces, Am MuÈhlenberg, fusion by collisions, and the mini-
14424 Potsdam/Golm, Germany droplets are as small as possible for Key words Miniemulsion á Critical
e-mail: [email protected]
Tel.:+49-331-5679509 the timescales involved. The droplet stability á Polymerization á Osmotic
Fax:+49-331-5679502 growth by monomer exchange, or pressure á Hydrophobe

Introduction have about the same size as the initial droplets, as shown
by a combination of small-angle neutron scattering,
Regular miniemulsions can be de®ned as aqueous surface tension measurements, and conductometry [2]. In
dispersions of surfactant-stabilized oil droplets within a the case of appropriately formulated miniemulsions
size range of 50±500 nm prepared by shearing a system where polymerization is initiated in each droplet and
containing oil, water, a surfactant, and a strong hydro- the solubility of the monomer in the continuous phase is
phobe. Recently, a quantitative approach for the formu- low, the ideal, limiting case of a 1:1 copy of the droplets
lation of a miniemulsion was given [1]. The hydrophobe to the particles can be obtained; therefore, each droplet
acts as an osmotic agent which stabilizes the system can be considered as a small reactor in which polymer-
against Ostwald ripening. The growth of the droplets by ization reactions takes place. On the basis of the
collision is controlled by the density of the surfactant quantitative understanding of miniemulsions, the process
layer:freshly prepared miniemulsions are ``critically sta- allows new structures in particles to be created by the
bilized'' and show slow, but pronounced growth, where- polymerization, for example, by unusual combinations
as a miniemulsion in equilibrium exhibits constant of monomers or by the incorporation of materials which
particle size on longer time scales. Polymerization of are not soluble in the continuous phase [3].
the oil droplets of such miniemulsions turned out to be
very promising and extends the possibilities of classical
emulsion polymerization. Owing to the fact that the Results and discussion
polymerization time is usually shorter than the growth of
the droplets by collisions, polymerization in carefully Creating a miniemulsion starts with the homogenization
prepared miniemulsions results in latex particles which step. Oil, a hydrophobe, and an aqueous solution of
102

emulsi®er are ®rst mixed by vigorous stirring of droplets Since each droplet behaves as a nanoreactor, many
to obtain droplets in the micrometer range. Then, high application are realized, and only three examples can be
shear, such as ultrasonication, is applied in order to given here:
obtain small monodisperse droplets in the hundred-
± The miniemulsion polymerization process is not
nanometer range. With increasing time of sonication, the
limited to radical polymerizations. Owing to the fact
droplets shrink and the polydispersity decreases till the
that each droplet can be handled as a minireactor,
miniemulsion has reached a steady state. In principle,
there are a lot of new syntheses which can be obtained
there are two possibilities for the degradation of
in miniemulsions but not in conventional emulsion
emulsions:the droplets can grow by di€usion (Ostwald
polymerization processes. We could successfully per-
ripening, s1 mechanism) or the droplets can grow by
form polyaddition reactions with diamines and diep-
collisions (s2 mechanism). The ®rst growth process can
oxides in the droplets [4]. Depending on the type and
be eciently suppressed by the addition of a hydro-
the amount of emulsi®er, particle sizes between 60
phobe, which prevents the droplets from Ostwald
and 400 nm can be obtained. The excess of one
ripening by generating an osmotic pressure in the
component allows the synthesis of particles with
droplets. This osmotic pressure counteracts the Laplace
surface reactivity.
pressure. Directly after sonication, the osmotic pressure
± It was shown that the principle of aqueous miniemul-
is usually smaller than the Laplace pressure. Growth by
sions can be transferred to nonaqueous media. In
the s1 mechanism is not observed; however, it was found
direct miniemulsions using polar media such as
that growth by collision can not be fully suppressed.
formamide or glycol instead of water and hydropho-
Therefore the droplets grow very slowly till the Laplace
bic monomer, the miniemulsion stability was obtained
pressure and the osmotic pressure are equal. This
by a hydrophobic agent, which prevents the droplets
scenario of equal pressure can also be reached intention-
from Ostwald ripening. In the case of inverse systems,
ally by adding an adequate additional amount of
hydrophilic monomers were miniemulsi®ed in a
emulsi®er.
nonpolar medium, such as cyclohexane. In order to
The size of the droplets in freshly prepared miniemul-
provide osmotic-stabilized droplets, a lipophobe has
sions and after polymerization of the resulting polymer
to be added to the monomer phase. This allows the
particles mainly depends on the amount of emulsi®er
synthesis of homogeneous structured particles con-
used. As an example, the dependence of the amount of
taining water-soluble monomers [5].
the anionic emulsi®er sodium dodecyl sulfate on the size
± The miniemulsion polymerization enables the forma-
of polystyrene particles is shown in Fig. 1. Particle sizes
tion of nanocrystalline particles consisting of pure
between 180 and 30 nm can be obtained. As a compar-
polyacrylonitrile (PAN) in the size range between 100
ison, the nonionic emulsi®er Lutensol AT50 is shown,
and 180 nm. Since the polymer is insoluble in the
where particle sizes between 480 and 70 nm are realized.
monomer, the polymer formed precipitates during the
The domain of the miniemulsion is in the low surfactant
polymerization within the droplets, and large polymer
load. In all cases, the droplets and the ®nal particles are
nanocrystals (about 10 nm) are formed. Pure PAN
incompletely covered by surfactant molecules. At a
latexes have a crumpled appearance [6].
surfactant amount of more than about 50 %, one leaves
the domain of miniemulsions since full coverage of the
particles is obtained. Conclusion

Steady-state dispersed miniemulsions are osmotically

stable but are critically stabilized with respect to their
colloidal stability. The interface energy between the oil
and water phase in a miniemulsion is greater than zero.
The surface coverage of the droplets by surfactant
molecules is incomplete. The formation of a miniemulsion
requires high mechanical agitation to reach a steady state
given by a rate equilibrium of droplet ®ssion and fusion.
The osmotic stability of miniemulsion droplets results
from an osmotic pressure in the droplets, which controls
the solvent or monomer evaporation. The osmotic
pressure results from the addition of a hydrophobe, which
has an extremely low water solubility. During polymer-
Fig. 1 The size of polystyrene particles obtained in miniemulsion ization each droplet behaves like a nanoreactor. This
polymerization by using di€erent amounts of anionic sodium dodecyl allows the formation of particles which are not accessible
sulfate or nonionic Lutensol AT50 by other types of heterogeneous polymerization.
 103

References

1. Landfester K, Bechthold N, Tiarks F, 3. Bechthold N, Tiarks F, Willert M, 5. Landfester K, Willert M, Antonietti M

Antonietti M (1999) Macromolecules Landfester K, Antonietti M (2000) Mac- (2000) Macromolecules 33:2370
32:5222 romol Symp 150:549 6. Landfester K, Antonietti M (2000) Mac-
2. Landfester K, Bechthold N, FoÈrster S, 4. Landfester K, Tiarks F, Hentze HP, romol Rapid Commun 21:820
Antonietti M (1999) Macromol Rapid Antonietti M (2000) Macromol Chem
Commun 20:81 Phys 201:1
Progr Colloid Polym Sci (2001) 117: 104±109
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

L. VeÂkaÂs Concentration and composition dependence

D. Bica
I. Potencz of rheological and magnetorheological
D. Gheorghe
O. BaÄlaÄu properties of some magnetic ¯uids
M. RasË a

Abstract Rheological and mag- an applied magnetic ®eld is strongly

netorheological behaviour of mag- dependent on microstructural char-
netic ¯uids with nonpolar and polar acteristics. A relatively large, almost
carrier liquids were investigated, us- 1 order of magnitude, increase in the
ing capillary and rotary viscometers, relative viscosity was measured for
the measuring cells being completed medium-concentration water-based
with specially designed electromag- magnetic ¯uids, with large secondary
nets. In the absence of a magnetic agglomerates. The magnetoviscous
®eld the relative viscosity±hydrody- e€ect was found to be rather small,
namic particle volume fraction de- below 10%, for highly stable mag-
L. VeÂkaÂs (&) á D. Bica á I. Potencz
Centre for Fundamental and Advanced pendence is well ®tted especially by netic ¯uid samples on decahydron-
Technical Research, Romanian Academy, the formulas of Vand, Krieger± aphathalene and pentanol carriers.
TimisË oara Branch, Dougherty and Chow. The ®tted
Bd. Mihai Viteazul no. 24, values of the Chow interaction co-
1900 TimisË oara, Romania
ecient are close to the theoretical Key words Magnetic ¯uids
D. Gheorghe á O. BaÄlaÄu á M. RasË a value, except at low temperatures (ferro¯uids) á Rheological
Institute for Complex Fluids and close packing of magnetic properties á Magnetorheological
Politehnica University of TimisËoara
Bd. Mihai Viteazul, no. 1 nanoparticles. The e€ective viscosity properties á Colloidal stability á
1900 TimisË oara, Romania of various types of magnetic ¯uids in Chemical composition

Introduction structural characteristics; therefore, the macroscopic

treatment of the rheological behaviour is not adequate.
Magnetic ¯uids are a special category of colloids. In a recent investigation conducted in the absence of a
Magnetic nanoparticles (Fe3O4, c-Fe2O3, CoFe2O4, Co, magnetic ®eld [2] we showed that composition details, for
Fe, etc.) of about 7±10-nm mean physical diameter are example, the nature and chemical purity of the surfac-
dispersed using suitable surfactants and by applying tants used, as well as the hydrodynamic volumic fraction
various stabilisation procedures in nonpolar and polar of the nanoparticles, strongly in¯uence the ¯ow proper-
carrier liquids, like hydrocarbons, synthetic oils, water or ties of magnetic ¯uids.
alcohols, to mention only a few possible carrier liquids. In this article we present experimental results
The most important feature of these magnetic colloids is concerning the rheological and magnetorheological
that they maintain their high degree of colloidal stability behaviour of several nonpolar and polar magnetic
even in intense and very nonuniform magnetic ®elds, i.e. ¯uids, as well as ®ts of the data to appropriate
from a macroscopic point of view magnetic ¯uids are semiempirical and theoretical formulae concerning the
quasihomogeneous magnetisable liquid media Many dependence of the dynamic viscosity on the volumic
details of the preparation, properties, magnetohydrody- concentration of the nanoparticles and the details of
namics and applications of magnetic ¯uids may be found their surface coverage (nature and quality of the
in Ref. [1]. surfactant/s, e€ective thickness of the surfactant layer),
The rheological and magnetorheological properties of in the absence or the presence of an applied magnetic
magnetic ¯uids are strongly dependent on the micro- ®eld.
 105

Magnetic ¯uid samples and experimental methods Experimental results and discussion

High-concentration magnetic ¯uid samples were pre- As was shown [2, 10, 11], the magnetic, rheological,
pared up to the upper limit of the hydrodynamic volume magnetorheological and magnetooptical properties of
fraction of magnetic nanoparticles, uh @ 0.6. The Fe3O4 magnetic ¯uids strongly depends on the microstructural
nanoparticles were synthesised by chemical coprecipita- characteristics, in particular, on aggregate formation.
tion of Fe2+ and Fe3+ ions in the presence of excess 25% Particle agglomeration processes may be induced, among
NH4OH at 80±82 °C [3].
Depending on the nonpolar or polar character of the
carrier, for example, transformer oil, decahydronaphtha-
lene (DHN), dioctylsebacate, alcohol, and water, the
dispersion of magnetic nanoparticles was performed by a
monolayer or a double-layer steric stabilisation procedure
[3, 4]. The ®rst chemisorbed surfactant layer, which
consists of technical grade oleic acid (TOA) or chemically
pure oleic acid (POA), ensures the stability of nonpolar
magnetic ¯uids. The free oleic acid was eliminated from
the magnetic ¯uid. In order to ensure the dispersion of
oleic acid covered Fe3O4 nanoparticles in polar carriers, a
suitable secondary surfactant has to be used [dodecyl
benzene sulfonic acid, poly(isobutylene succinanhydride),
etc.], which is physically adsorbed on the oleic acid
covered Fe3O4 particles. The stabilisation of magnetic
nanoparticles, in particular, in strongly polar carriers, like
in medium-chain and short-chain alcohols or water, is a
dicult task [4±6]. The preparation of very high concen-
tration C3±C10 alcohol based magnetic ¯uids was reported
recently [7]. The pentanol (C5) based samples of this series
were thoroughly investigated in this work. The excellent
colloidal stability of this type of magnetic ¯uid was shown
in Refs [8, 9] by applying various physical methods of
analysis of microstructural properties, in particular,
sedimentation velocity analysis and electrophoresis. Sev-
eral results of magnetic, electronic micrography, rheolog-
ical, magnetorheological and magnetooptical methods
applied to microstructural characterisation of various
type of magnetic ¯uids may be found in Refs. [10±12].
These investigations evidenced the e€ects of composi-
tion and particle concentration on the agglomerate
formation process and implicitly on the macroscopic
behaviour of di€erent samples. For the investigations
performed in this work the following nonpolar and polar
magnetic ¯uids were selected: magnetic ¯uid/DHN
(300 G), magnetic ¯uid/pentanol (830 G) and magnetic
¯uid/H2O (300 and 420 G), as well as a series of dilute
samples of the concentrated magnetic ¯uid/pentanol
liquid.
The rheological behaviour of the samples was inves-
tigated with an Ubbelohde-type capillary viscometer and
with a Couette-type rotary rheometer (Rheotest 2). The
experimental cells were completed with a magnetic-®eld
source, an electromagnet with plane-parallel pole pieces
(Fig. 1a; Bmax @ 0.3 T) and a specially designed electro- Fig. 1 a Ubbelohde-type capillary viscometer (1 ± capillary tube, 2 ±
magnet (Fig. 1b; Bmax @ 0.1 T), for the magnetorheolog- polar pieces, 3 ± support cylinder, 4 ± water entrance/exit), b Couette-
ical measurements. type rotary rheometer
106

others, by insucient covering of particles owing to the The values of the maximum hydrodynamic volume
low chemical purity of the surfactant (e.g. with a large fraction, um, were determined by ®tting the data to the
fraction of shorter chain length carboxylic acids in TOA), well-known two-parameter formula of Krieger and
by the reduction of the mean distance between magnetic Dougherty [14],
dipole particles owing to the increase in the particle ‰gŠum
volume fraction or by the application of a strong g=g0 ˆ 1 uh =um † ; 2†
magnetic ®eld. where [g] is the intrinsic viscosity (Table 1).
The mixed stabilisation mechanism, double-layer Note that the [g] values obtained are not far from that
steric and electrostatic, appropriate for pentanol-based corresponding to spherically shaped particles, [g] ˆ 2.5.
magnetic ¯uids [8] and for other polar magnetic ¯uids Also, it may be observed that p and consequently d, um
prepared by the same method [4], allowed n-pentanol and [g] are slightly temperature dependent. Indeed, the
magnetic ¯uid samples of very high solid volume fraction e€ective surfactant layer thickness, d, depends on the
to be obtained (up @ 19.4% and with correspondingly temperature and has greater values at lower tempera-
high saturation magnetisation, Ms ˆ 800±900 G, which tures, especially because the physically adsorbed second-
are the highest reported up to now [5, 7]). ary surfactant layer is more in¯uenced by the thermal
The dependence of relative viscosity, g/go, where g is motion.
the dynamic viscosity of the magnetic ¯uid and go is the In the Refs. [15, 16] Chow performed a thorough
dynamic viscosity of the pentanol carrier liquid, on the theoretical analysis of concentrated suspensions, taking
solid particle volume fraction, T, was determined at into account the contribution of many-body particle
various temperatures in the )10±70 °C interval. In order interactions on the e€ective viscosity. On the basis of a
to determine the hydrodynamic volume fraction, uh, i.e. liquid lattice model, the low-shear limiting viscosity
the e€ective volume fraction of the double-layer-covered resulted as
Fe3O4 nanoparticles, the data were ®tted to the Vand  
g 2:5uh Au2h
formula using the ®t parameter p ˆ uh/uq : ˆ exp ‡
; 3†
g0 1 uh 1 Au2h um
g=g0 ˆ exp‰ 2:5p/q ‡ 2:7p2 /2q †Š= 1 0:609p/q † : 1†
where A is the coupling coecient. Without considering
The ®tted g/go ˆ f(us) curves at various temperatures are dipole±dipole type interactions between particles, the
presented in Fig. 2 together with the detailed results of theoretical value of A was determined to be 4.67.
the ®ts and the Vand formula [13]. Using the ®tted p The theoretical formula (Eq. 3) obtained by Chow
values, the e€ective mean surfactant layer thickness may proved to be well ®tted by viscosity data for various
be obtained, d ˆ (p1/3 ) 1)D/2 (Table 1). magnetic ¯uids at 20 °C [2]. The ®tted values of A are

Fig. 2 Dependence of relative

viscosity on physical volume
fraction for a series of pentanol-
based magnetic ¯uids
 107

Table 1 Fit parameters from -D

Vand, Krieger±Dougherty T (°C) p (Vand) d (nm) um (K-D) [g] (K-D) A (Chow) with uK
m
(K-D) and Chow relations
(pentanol magnetic ¯uids) ±10 3.896 2.466 0.670 2.858 3.317
0 3.765 2.389 0.654 2.886 3.663
10 3.624 2.305 0.637 2.925 3.975
20 3.543 2.255 0.625 2.953 4.170
30 3.426 2.182 0.614 2.971 4.356
40 3.369 2.146 0.607 2.980 4.460
50 3.310 2.108 0.600 2.988 4.552
60 3.271 2.083 0.596 2.997 4.599
70 3.247 2.967 0.593 3.000 4.627
Atheor (Chow) = 4.67

close to the theoretical one for uh £ 0.45. At higher Under the in¯uence of a magnetic ®eld, magnetic
values of the hydrodynamic volume fraction, the result- ¯uids increase their e€ective viscosity owing to the
ing A value is lower, evidencing the role of dipolar supplementary dissipation due to the motion of particles
interactions at close packing. relative to the surrounding carrier liquid.
The results of a ®t of all the viscosity data corre- The magnetorheological e€ect is described by the
sponding to the temperature interval )10±70 °C and up model developed by Shliomis [17], but its validity is
to the highest hydrodynamic volume fraction, um ~ 0.6, limited to a very low volumic concentration of particles
are shown in Fig. 3. The experimental data are well ®tted even if we take into account the size distribution of the
by the Chow formula (Eq. 3), the resulting overall particles and the Shliomis diameter, as in the generalised
coupling coecient being 3.78. This ®t and the previous formula proposed in Ref. [10].
one [2] show that A is smaller than the theoretical value The intensity of the magnetorheological e€ect, will be
of 4.67 at lower temperatures and at close packing of shown, is strongly dependent on various microstructural
particles when the role of dipolar interactions cannot be processes, especially on those relating to agglomerates.
neglected, even in the case of a magnetic ¯uid of very high Incomplete surfactant covering of particles initiates the
degree of colloidal stability. Note, that at T > 50 °C, the formation of agglomerates, which signi®cantly change
®tted values of A approach the theoretical one, the the behaviour of magnetic ¯uids in a magnetic ®eld. This
increased thermal motion diminishing the in¯uence of is well illustrated by the experimental data represented in
dipolar interactions. Fig. 4 for two decahydronaphthalene-based magnetic

Fig. 3 Dependence of relative

viscosity on hydrodynamic
volume fraction for a series of
pentanol-based magnetic ¯uids
108

Fig. 4 The in¯uence of the

degree of purity of chemisorbed
surfactant on the magnetovis-
cous e€ect

¯uid samples of the same magnetisation, but stabilised large fraction of primary agglomerates, which develop
with technical grade and chemically pure surfactant further into secondary, large agglomerates under the
(TOA and POA, respectively). in¯uence of an applied magnetic ®eld of moderate or
Water-based magnetic ¯uids, except those with low even low magnetic induction (B @ 0.01 T). The process
particle volume fraction, up ~ 0.05, present a relatively of agglomerate formation in water-based samples pre-

Fig. 5 Magnetorheological
behaviour of water-based
magnetic ¯uids
 109

pared according to the procedure given in Ref. [6] was ± The relative viscosity±volumic concentration depen-
recently investigated by magnetic [18] and magnetoopti- dence, at various temperatures, is well ®tted, especially
cal [11] methods. Magnetic-induced phase condensation by the formulae of Vand, Krieger±Dougherty and
occurs, i.e. the magnetic ¯uid becomes a biphasic system Chow. This is well illustrated by the data for a series of
in an external magnetic ®eld. The microstructural pentanol-based magnetic ¯uids. The ®tted values of
changes, in particular, the formation of condensed-phase the Chow interaction parameter, A, are very close to
droplets, signi®cantly modify the magnetisation curve, the theoretical one (4.67). Somewhat lower values
especially in the low-®eld region [18], as well as the resulted at lower temperatures (T £ 20 °C) and at close
magnetic dichroism e€ect [11], compared to other highly packing of magnetic nanoparticles (uh @ 0.6).
stable magnetic ¯uids. ± The magnetorheological behaviour of magnetic ¯uids
The signi®cant, almost 1 order of magnitude, increase is very sensitive to microstructural processes, in
of the relative viscosity, g(B)/g(0), may be observed in the particular, to agglomerate formation induced by
case of two medium-concentration water-based magnetic low-quality stabilisation. Water-based magnetic ¯u-
¯uids in Fig. 5. The large e€ects observed illustrate the ids, with large secondary agglomerates, show an
high sensitivity of magnetorheological measurements almost 1 order of magnitude increase of relative
concerning microstructural changes in magnetic colloids. viscosity in a magnetic ®eld.

Acknowledgements The permanent support of Prof. I. Anton

Conclusions (Romanian Academy ± Tourizoara Branch) is gratefully acknowl-
edged. We are indebted to A. Philipse (University of Utrecht) for
many helpful discussions on the stability and microstructural
± Rheological and magnetorheological properties of charactersitics of polar magnetic ¯uids. The present work was
partly supported by a grant of the Romanian Academy (contract
magnetic ¯uids are strongly dependent on the nature no. 64/2000). The ®nancial support of the Romanian Agency for
and quality of surfactant(s), as well as on the volumic Science, Technology and Innovation (contract no. 91/1996) is also
concentration of magnetic nanoparticles. gratefully acknowledged.

References

1. Berkovski B, Bashtovoi V (eds) (1996) 7. Bica D, VeÂkaÂs L (2000) Concentrated 13. Vand V (1984) J Phys Colloid Chem
Magnetic ¯uids and applications hand- magnetic ¯uids on various alcohol carri- 52:277±321
book. Begell House, New York er liquids, ``last-minute poster''. Interna- 14. Barnes HA, Hutton JF, Walters K
2. VeÂkaÂs L, Bica D, Gheorghe D, Potencz tional conference ``Adsorption and (1989) An introduction to rheology.
I, RasË a M (1999) J Magn Magn Mater nanostructures ± from theory to applica- Elsevier, Amsterdam, p 199
201:159±162 tion'', 25±28 September 2000, Budapest 15. Chow TS (1993) Phys Rev E 48:1997
3. Bica D (1995) Rom Rep Phys 47: 8. Donselaar LN, Philipse AP, Surmond 16. Chow TS (1994) Phys Rev E 50:1274
265±272 J (1997) Langmuir 13:6018 17. Shliomis MF (1972) J Exp Theor Phys
4. Bica D, VeÂkaÂs L (1994) Magn Gidro- 9. Donselaar L (1998) PhD thesis. Uni- 61:2411
din (Magnetohydrodynamics), 30: versity of Utrecht 18. VeÂkaÂs L, RasË a M, Bica D (2000) CAS
194±196 10. VeÂkaÂs L, RasË a M, Bica D (2000) 2000 Proceedings of the 23rd Interna-
5. Fujita T, Miyazaki T, Nishiyama H, J Colloid Interface Sci 231:247±254 tional Semiconductor Conference, 10±
Jeyadevan B (1999) J Magn Magn 11. Socoliuc V, Bica D (2001) Prog Colloid 14 October 2000, Sinaia, Romania,
Mater 201:14±17 Polym Sci 117:131±135 vol 2. Institute of Electrical and Elec-
6. Bica D (1985) Romanian Patent RO 12. Schott M, VeÂkaÂs L, Bica D (1995) Rom tronics Engineers, pp 495±498
90078 Rep Phys 47:411±436
Progr Colloid Polym Sci (2001) 117: 110±112
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

F. Tiarks The controlled generation of nanosized

M. Willert
K. Landfester structures in miniemulsions
M. Antonietti

Abstract In this article the e€ective ration of particles consisting of hy-

F. Tiarks á M. Willert á K. Landfester (&)
M. Antonietti encapsulation of carbon black with drophilic polymers.
Max Planck Institute of Colloids polymers by cosonication of a car-
and Interfaces, Research Campus Golm, bon black dispersion and a mini- Key words Miniemulsion
14424 Potsdam, Germany emulsion is decribed. The inverse polymerization á Encapsulation á
e-mail: [email protected]
Tel.: +49-331-5679509 miniemulsion process is shown to be Carbon black á Cosonication á
Fax: +49-331-5679502 an excellent method for the prepa- Polar monomers

Introduction Results
Regular miniemulsions are aqueous dispersions of Encapsulation of carbon black
relatively stable oil droplets with a size between 50
and 500 nm prepared by shearing a system containing
In previous experiments encapsulated carbon black
oil, water, a surfactant, and a hydrophobe. The
particles were obtained by ®rst mixing carbon into the
polymerization of miniemulsions extends the possibil-
monomer and then formulating a miniemulsion of the
ities of the emulsion polymerization and provides
monomer/carbon black dispersion in water [1]. Owing to
advantages with respect to copolymerization reactions
aggregation of carbon black clusters and the coupled
of monomers with di€erent polarity, incorporation of
viscosity problems, the amount of carbon black in the
hydrophobic materials, or the stability of the latexes
monomer can be only as high as 10 wt%. To enable any
formed [1, 2]. In this article the e€ective encapsulation
ratio between the monomer and carbon black, another
of carbon black with polymers by cosonication of a
approach has to be developed. Both components have to
carbon black dispersion and a miniemulsion polymer-
be independently dispersed in water and mixed after-
ization recipe is described. Another subject of this
wards in the right proportion. The controlled ®ssion/
article is the preparation of polymer particles from
fusion process in the miniemulsi®cation destroys the
inverse miniemulsions. Inverse miniemulsions consist of
aggregates and liquid droplets, and only hybrid particles
a hydrophilic monomer, like acrylic acid, dispersed in a
remain owing to their higher stability. This process can
nonpolar continuous phase, for example, cyclohexane
be realized by high-energy ultrasound or high-pressure
and a surfactant [3]. To stabilize the droplets against
homogenization.
Ostwald ripening a strong lipophobe, like sodium
By screening experiments, it was shown that a
chloride, has to be added. It could be shown that
hydrophobic polyurethane is a favorable choice as the
miniemulsions can also be made in organic systems
osmotic agent: It is not volatile in ®lm formation
with monomers, like acrylamide, styrene sulfonic acid
processes, and the interaction with carbon black is
sodium salt, or hydroxyethyl methacrylate, and show
strong, leading to a homogeneous and well-coupled
the typical characteristics of miniemulsions, i.e. incom-
polymer layer on the carbon. In addition, it diminishes
plete coverage of the particles with surfactants and
the speci®c surface area of the carbon (presumably by
preservation of droplet number.
 111

Fig. 1 Principle of encapsula-

tion of carbon black

Table 1 Comparison between stirred and sonicated emulsions. FW18 was used as carbon black and FTPUR1 as the optimized hydro-
phobe. The miniemulsions comprised 1.0 g styrene, 0.025 g 2,2¢-azobis(isobutyronitrile), 7.0 g water, and 0.03 g FTPUR1. A carbon
black dispersion (10.0 g, c = 43.5) was added

Latex Surfactant (g) cmini ccarbon US % polystyrene± Particle Poly-

(mNm)1) (mNm)1) %C (thermogravi diameter dispersity
metric analysis) (nm)
FTC88 No 27:73 128 0.35
FTC89 Sodium 0.033 48.7 43.5 Yes 62:38 70 0.49
dodecyl
sulfate

``plugging'' cavities and the inner surface), which results Table 2 Characteristics of latexes consisting of di€erent polymers
in a lower surfactant demand. For optimization of the obtained by inverse miniemulsion polymerization in cyclohexane
technical parameters, the weight ratio of carbon to (25 g)
monomer was kept at 50:50, and the in¯uence of Monomer Amount of Emulsi®er Water/ Particle
sonication was studied. monomer (mg) NaCl diameter
The characteristics of the dispersion with and without (g) (nm)
sonication treatment are summarized in Table 1. The Acrylamide 3 255 4 142
surface tension of the ®nal dispersion is above the Acrylic acid 1 250 1 145
minimal surface tension of sodium dodecyl sulfate, Styrene 1 204 5 206
indicating the absence of micelles and incomplete sulfonic acid
coverage of the polymer±carbon hybrid particles. As sodium salt
Acrylic acid- 1 200 1 205
studied by sedimentation experiments in a preparative (3-sulfopropylester)
ultracentrifuge, the sample without sonication treatment potassium salt
consists of di€erent species: a white fraction composed of
carbon-black-free homopolystyrene particles and a black
fraction with densities higher than 1.13 g/l. In the case of
that they are coated with a thin layer of polymer which
sonication treatment (FTC89) only one particle fraction,
screens the carbon±carbon interaction.
with a narrow density distribution (1.2 g/l), is detected,
indicating that all the particles formed show a very
similar carbon/polymer composition or degree of encap-
sulation. The absence of pure polystyrene particles or Inverse miniemulsions
pure pigment aggregates is clearly proven. This compo-
sition heterogeneity is also observed by electron micro- Inverse miniemulsions allow the synthesis of particles
scopy. In the transmission electron microscopy picture consisting of polar polymers. For the dispersion of polar
no pure polystyrene particles are detected (not shown). monomers in nonpolar dispersion media, surfactants with
The carbon particles are well separated, which means low hydrophile-lipophile balance values are required. The
112

additional lipophobic agent to increase the stability of

the miniemulsions, and the continuous phase was
cyclohexane. The polymerization was started by adding
100 mg 2,2¢-azobis(isobutyronitrile) to the continuous
phase after miniemulsi®cation. The characteristics of the
®nal latexes are shown in Table 2. In the case of
acrylamide and acrylic acid, particle sizes of about
140 nm are found; the particles in the case of styrene
sulfonic acid sodium salt and acrylic acid-(3-sulfopropy-
lester) potassium salt are larger (205 nm).

Fig. 2 Transmission electron micrograph of particles consisting of

a poly(acrylic acid) and b polyacrylamide Conclusion

It was shown that the cosonication of a carbon black

concept of using a hydrophobe to stabilize the disperse dispersion and a miniemulsion leads to the e€ective
droplets has to be adapted by adding a very lipophobic encapsulation of the pigment particles. It is our model
substance. A number of surfactants were screened. The that the fusion/®ssion process induced by ultrasound is
nonionic block copolymer stabilizer poly(ethylene-co- only e€ective for the monomer droplets, whereas the
butylene)-b-poly(ethylene oxide) (KLE3729) and sorbi- monomer-coated carbon is not splittable. In this way,
tan monooleate (Span80) turned out to be the most monomer redistribution takes place until all droplet
ecient surfactants for inverse miniemulsions. To obtain fragments are heteronucleated onto the carbon to form a
stable miniemulsions, the strong ``lipophobe'' NaCl was monomer ®lm; the thickness of the ®lm depending on the
mixed with the monomeric phase in order to build up an amount of monomer.
osmotic pressure in the droplets. The inverse miniemulsion polymerization enables the
For polymerization in inverse miniemulsions, a large formation of homogeneous particles consisting of polar
variety of hydrophilic monomers can be used, such as polymers such as acrylamide, acrylic acid, styrene
acrylamide, acrylic acid-(3-sulfopropylester) potassium sulfonic acid sodium salt, or acrylic acid-(3-sulfopropy-
salt, styrene sulfonate, or acrylic acid. For the formula- lester) potassium salt and extends the possibilities of
tion of the miniemulsions, the solid crystalline monomers inverse emulsion and precipitation polymerization in a
have to be dissolved in water. NaCl was added as an meaningful way.

References

1. Bechthold N, Tiarks F, Willert M, 2. Tiarks F, Landfester K, Antonietti M 3. Landfester K, Willert M, Antonietti M

Landfester K, Antonietti M (2000) Mac- (2001) Macromol Chem Phys 202:51 (2000) Macromolecules 33:2370
romol Symp 151:549
Progr Colloid Polym Sci (2001) 117: 113±116
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

Wolfram HaÈrtl The glass transition and propagating

Christian Beck
transverse phonons in colloidal systems

Abstract The dynamics of mono- transverse phonons, which are char-

disperse, highly charged colloidal acteristic of the glassy state.
W. HaÈrtl (&) á C. Beck
Physikalische Chemie, systems are investigated in the glassy
University of SaarbruÈcken, GebaÈude 9.2, phase. The Debye±Waller factors
Im Stadtwald, 66123 SaarbruÈcken, obtained are compared to calcula-
Germany tions based on the mode-coupling
e-mail: [email protected]
Tel: + 49-681-3024881 theory. For small Q values, low-
Fax: + 49-681-3024759 frequency oscillations appear in the
C. Beck
time correlation functions. An in-
Paul Scherrer Institute, terpretation of these oscillations is Key words Glass transition á
5232 Villingen, Switzerland given in terms of long-wavelength Colloids á Dynamic light scattering

(TEOS), which was hydrolysed according to the StoÈber synthesis

Introduction [7]. The silica particles obtained were functionalised with carboxylic
acid groups according to a procedure which was described in detail
Monodisperse colloidal particles are well-suited model recently [8].
systems to investigate the liquid±solid phase transition. The second model system was prepared by emulsion polymeri-
The main advantage compared to atomic systems is the sation of ¯uorinated poly(acrylic ester) monomers [9]. Both model
possibility to study the dynamics directly in the time systems were index-matched in a mixture of water/glycerol in order
to suppress multiple scattering. Our light scattering setup consisted
domain over several orders of magnitudes. of a photon correlation spectrometer from ALV Laservertriebsge-
Whereas colloidal systems, which interact with a hard- sellschaft, Germany. The correlation functions were obtained with
sphere potential, were investigated extensively during the an ALV-5000 E fast correlator. As light source we used an He±Ne
last decade [1, 2] only few experiments on charged laser with a power of 33 mW (Zeiss). The scattered light was
colloidal systems are known which deal with the glass focused on a monomode cable and transferred to the detection
unit, which consisted of two photomultipliers. The digitalised
transition [3, 4]. signals were cross-correlated in order to eliminate dead-time e€ects.
In the hard-sphere systems the phase diagram and the All the measurements were done at 25 °C and the dust in the
glass-transition point were determined from experiments samples was removed with membrane ®lters of 0.8-lm pore size.
and good agreement with theoretical predictions was
obtained [5]. In case of charged colloidal particles, which
interact via a Yukawa potential, the exact conditions for
Theory
obtaining a glassy phase are still unknown, but a recent
theoretical investigation in the framework of the mode-
The interpretation of dynamic light scattering data from
coupling theory (MCT) seems to support the experimen-
glassy colloidal suspensions has to take into account the
tal data [6].
nonergodic character of the system. The obtained time
correlation functions are no longer identical with the
Preparation and characterisation ensemble-averaged correlation functions; however, it has
been shown by Pusey et al. [10] that it is possible to
For our investigations we prepared two di€erent model systems. convert them to the ensemble-averaged correlation
The starting material for the silica colloids was tetraethoxysilane functions. In the case of the monomode ®bre system,
114

only one coherence area is detected and the ensemble- correlation functions of these samples showed the
averaged ®eld correlation function can be expressed as characteristic plateau values for a glassy state. The
q  ensemble-averaged ®eld correlation functions are con-
IT
f Q; t† ˆ 1 ‡ 2 2
gT Q; t† gT Q; 0† ‡ 1 1 ; 1† structed from Eq. (1) and the measured intensity corre-
IE lation function. The f(Q,1) values are extracted from the
where IT and IE are the time- and ensemble-averaged long-time limits of the ®eld correlation functions. In
scattering intensities and gT2(Q,t) is the time-averaged a next step we calculated the f(Q,1) function within
intensity correlation function. IE was obtained by the idealised MCT approach and used as an input the
rotating the sample at constant speed during the corresponding experimental structure factors of the
measurements. The main features of the glass transition samples [12]. A comparison of the experimental and
in colloidal systems can be described by two distinct theoretical values is shown in Fig. 1. The agreement is
relaxation processes, a and b, with the relaxation times sa remarkable if one keeps in mind that there are no free
and sb. The a process, which exists only in the liquidlike parameters involved. The main di€erence to the Debye±
state of the colloidal system, describes the decay of Waller factors of hard-sphere colloid particles can be
density ¯uctuations at long times. The b process exists found at small Q vectors. Here the Debye±Waller factors
both in the liquidlike and in the glassy state and can be are much smaller, which means that for charged systems
interpreted as the particle motion within the neighbour- the long-wavelength density ¯uctuations are less frozen
ing cages. The MCT makes precise predictions about the in as in the case of hard-sphere systems.
dynamics in the vicinity of the glass-transition point. For To investigate the dynamics of glassy colloidal
hard-sphere colloids the separation parameter, e, is systems at even smaller Q values compared to the
de®ned as maximum of the structure factor we synthesised per¯uo-
rinated colloids of diameter 110 nm. After concentrating
U the suspension to a volume fraction of 0.25 and treating it
eˆ 1 ; 2†
UG with an ionic exchanger we obtained a glassy phase,
which can be identi®ed unambiguously by the plateau
where FG is the volume fraction at the glass-transition
values in the time correlation function. The intensity
point. The idealised MCT approach leads to the
correlation functions are shown in Fig. 2 for the sample
following result for the intermediate scattering function:
p at Q* ˆ 0.23 (Q* ˆ Q/Qmax) during the deionisation
f Q; t † ˆ f Q; 1† ‡ hQ eg t † : 3† process with ionic exchanger. After 3 h a well-developed
plateau, which manifests the slowing down of the density
The rescaled time, t*, is connected to e and diverges at ¯uctuations, can be observed. After 7-h deionisation the
the glass-transition point. The amplitude function. hQ, a process has disappeared and a phase transition into a
and the master function, g ‹ (t*), are independent of e glassy phase has occurred. Additionally, a new feature in
and were calculated for the hard-sphere system [11]. The the correlation functions emerges. In the time range 0.01±
Debye±Waller factors, f(Q,1), can be obtained from the 0.1 s characteristic oscillations in the correlation func-
long-time plateaus of the intermediate scattering func- tions can be seen. To investigate this in more detail we
tion and compared with the MCT predictions if one performed a Q-dependent measurement of the sample.
knows the static properties of the system. The only inputs
in these calculations are the static structure factor, S(Q),
and the direct correlation function, c(Q) [11].

Results and discussion

First, we present some results we obtained for the highly

charged silica systems. The samples we investigated had a
mean diameter of 272 nm and were index-matched in a
water/glycerol mixture. For our system we obtained from
MCT calculations a glass transition at a volume fraction,
F, of 0.175 if one uses 550 e€ective charges in the rescaled
mean spherical approximation (RMSA) calculations of
the structure factor. This result is in good agreement with
recent calculations of Wang and Lai [6] on a similar
system. The structure factors of our samples at volume Fig. 1 Experimental Debye±Waller factors, f(Q,1), at F ˆ 0.27
fractions F ˆ 0.21 and F ˆ 0.28 could be modelled by (closed symbols) and F ˆ 0.21 (open symbols). The solid lines are
RMSA calculations with 550 e€ective charges. The time calculations according to the mode-coupling-theory approach
 115

Fig. 2 Intensity correlation functions during the deionisation process Fig. 4 Field autocorrelation functions of the sample in Fig. 2 for two
for a highly charged sample at F ˆ 0.25 composed of per¯uorinated di€erent experimental con®gurations
colloidal particles at Q* ˆ 0.23

brane [13]. The second possibility to explain the exper-

imental ®ndings are intrinsic transverse phonons which
are present in the glassy samples. The existence of long-
wavelength transverse phonons have been discussed in
the literature for crystalline samples but until now only
overdamped modes could be detected [14]. To rule out
the possibility of shear waves excited by external sources
we performed a measurement of the sample with a
di€erent instrumental setup. As a light source a Nd:yt-
trium aluminium garnet laser was utilised and the whole
setup was isolated from external vibrations by a marble
table and a sand bed. The result of the measurement is
compared with the data obtained from our setup. As can
be seen in Fig. 4 the oscillations are still present and have
the same frequency.
A second point which supports the picture of
transverse phonons is given by the fact that the resonance
frequency of the standing shear waves can be estimated
Fig. 3 Characteristic oscillations in the intensity correlation function to be between 200±600 Hz if one takes the elastic
of the sample in Fig. 2 for Q* ˆ 0.23 and Q* ˆ 0.63 modulus values given in the literature for similar systems
[15]. This frequency is at least 1 order of magnitude
larger than the observed frequency in our measurements;
As shown in Fig. 3 the oscillation frequency is not Q- therefore, we attribute the oscillations to propagating
dependent and only a slight decrease in the oscillation transverse phonons, which are characteristic for colloidal
amplitude is detected with increasing Q values. glasses. In a recent investigation of a hard-sphere
One explanation of the observed oscillations could be colloidal silica system in a low-viscosity solvent we could
propagating shear waves, which are excited by vibrations con®rm the present results.
of the whole experimental setup. The method of standing
shear waves has been used to determine the elastic Acknowledgements We want to thank H. Versmold for the use of
modulus of crystalline and glassy samples. Here the shear his dynamic light scattering spectrometer and H. LoÈwen for helpful
waves are excited mechanically by a loudspeaker mem- discussions.
116

References

1. van Megen W, Underwood SM (1993) 6. Wang GF, Lai SK (1999) Phys Rev 11. Fuchs M, GoÈtze W, Hildebrand S, Latz
Phys Rev Lett 70:2766 Lett 82:3645 A (1992) J Phys Condens Matter 87:43
2. van Megen W, Underwood SM (1994) 7. StoÈber W, Fink A, Bohn E (1968) J 12. Beck C, HaÈrtl W, Hempelmann R
Phys Rev E 49:4206 Colloid Interface Sci 26:62 (1999) J Chem Phys 111:8209
3. Sirota EB, Ou Yang HD, Sinha SK, 8. Beck C, HaÈrtl W, Hempelmann R 13. Dubois-Violette E, Pieranski P, Rothen
Chaikin PM (1989) Phys Rev Lett (1999) Angew Chem 111:1380 F, Strzelecki L (1980) J Phys 41:369
62:1524 9. HaÈrtl W, Zhang-Heider X (1996) J 14. Hurd AJ, Clark NA, Mockler RC,
4. HaÈrtl W, Versmold H, Zhang-Heider X Colloid Interface Sci 185:398 O'Sullivan WJ (1982) Phys Rev A
(1995) J Chem Phys 102:6613 10. van Megen W, Underwood SM, 26:2869
5. GoÈtze W (1999) J Phys Condens Mat- Pusey PN (1991) Phys Rev Lett 67: 15. Benzing DW, Russel WB (1981)
ter 11:A1 1586 J Colloid Interface Sci 83:178
Progr Colloid Polym Sci (2001) 117: 117±119
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

N. M. Nagy Lead accumulation on montmorillonite

J. KoÂnya
M. Beszeda
I. Beszeda
E. KaÂlmaÂn
Z. Keresztes
K. Papp

Abstract The structure of lead and the mean surface concentration. The
N. M. Nagy (&) á J. KoÂnya á M. Beszeda calcium±lead montmorillonites was diameter of them is less than 1 lm.
Isotope Laboratory, Faculty of Natural studied by IR spectroscopy and Similar lead enrichments were found
Sciences, University of Debrecen, scanning electron microscopy. The on a natural clay sediment of a lake
P.O. Box 8, 4010 Debrecen, Hungary
e-mail: [email protected] IR spectra showed no structural in Hungary. Lead ions adsorb on
Tel.: +36-52-310122 changes of the montmorillonite montmorillonite by cation exchange
Fax: +36-52-310122 crystal lattice during calcium±lead in the interlayer space and a heter-
I. Beszeda cation exchange, only the intensities ogeneous nucleation on the particle
Department of Solid State Physics, of hydrate water of the interlayer surface followed by crystal growth.
Faculty of Natural Sciences, cation vary and the OH band on the
University of Debrecen, edges disappears. Scanning electron
4010 Debrecen, Hungary
microscopic studies showed that the
E. KaÂlmaÂn á Z. Keresztes á K. Papp distribution of lead is fairly even on Key words Lead ion á Calcium
Institute of Chemistry, the major part of the surface; how- montmorillonite á Microparticles á
Chemical Research Center,
Hungarian Academy of Sciences, ever, there are places where the IR spectroscopy á Scanning
P.O. Box 17, 1525 Budapest, Hungary concentration of lead is higher than electron microscopy

Introduction In this article, studies of the physical and chemical

formations of sorbed lead ions on calcium montmorill-
Nowadays the heavy-metal concentration of soils in- onite and a Hungarian lake sediment by IR spectros-
creases because of anthropogenic activity. Heavy-metal copy and scanning electron microscopy (SEM) are
ions, including lead ions, can be present as di€erent reported.
species, depending on the environmental conditions. The
adsorption of lead ions on clay minerals has been studied
by several authors; the important results have been Experimental
summarized by Shen et al. [1]. They explained the
adsorbed quantity of lead on montmorillonite by chem- Calcium montmorillonite was a product of the Central Laboratory
ical speciation of lead. of the National Mining Company, Hungary. X-ray di€raction and
By the X-ray absorption ®ne structure method thermoanalysis showed 83% montmorillonite content, the other
constituents were kaolinite (3%), calcite (5%), and quartz in trace
Strawn and Sparks [2] indicated that lead could adsorb and amorphous form (9%). The cation-exchange capacity was
via two mechanisms, depending on the ionic strength. determined by the ammonium acetate method [3] and it was found
At low ionic strength, lead adsorption is pH-indepen- to be 52 mmol/100 g for calcium ions (i.e. 104 mEq/100 g).
dent, consistent with an outer-sphere complexation. At Air-dried calcium montmorillonite (40.0 mg) was measured into
a beaker and 20.0 cm3 bidistilled water and perchloric acid solution
high ionic strength, lead adsorption is pH-dependent, of di€erent concentration was added and the mixture was stirred at
suggesting inner-sphere complexation, in which lead constant speed for 3 min. Then, lead perchlorate solutions with
forms covalent bonds [Pb(OH)24 (aq)]. di€erent concentrations and labeled by radioactive 212Pb isotope
118

was added to the suspension and stirred again for 60 min. The of lead adsorption. Since this band belongs to the OH
concentration of the solution at the time of the addition of lead vibrations at the edges [4], the disappearance of the band
perchlorate was 5 ´ 10)4, 1 ´ 10)3, or 5 ´ 10)3 mol/dm3 Pb2+ ion.
The phases were separated with a membrane ®lter (0.45-lm pore can be identi®ed as proton±lead exchange on the edge
size) and the pH of the liquid was measured. The solid was dried at charges of montmorillonite.
room temperature (25 °C). The c activity of the solid and the SEM studies showed that the distribution of lead is
solution was measured using a NaI(Tl) scintillation detector. The fairly even on the major part of the surface; however,
adsorbed quantity of lead was calculated from the radioactivities.
IR spectra, and SEM images were taken after the complete decay of
there are places where the concentration of lead is higher
212
Pb (about 5 days). than the mean lead concentration (Fig. 1).
The experiments were repeated in suspensions containing The results show that lead ions are adsorbed on
5 ´ 10)4 mol/dm3 lead ion and citric acid as a complex forming montmorillonite by two processes: by cation exchange in
agent. The pH was adjusted to 3.2. the interlayer space (outer-sphere complexation) and by
The experiments were made at room temperature. IR spectra of
the dried solid samples were taken using a PerkinElmer Paragon adsorption on the edge sites (inner-sphere complexation).
1000 PC Fourier transform IR spectrometer after the samples had Cation exchange leads to the even distribution of the
been pressed with KBr. The dried solid samples were studied using ions, while the adsorption on the edge site can act as the
an Amray-1830 and a Hitachi S-570 I scanning electron micro- initial nucleus of precipitation of lead hydroxide ob-
scope and an RoÈntec EDR288 energy-dispersive X-ray spectrom-
eter. Sediments from Lake Prod (next to road number 33 in eastern served by Strawn and Sparks [2]. The nanoparticles and
Hungary) were also studied. The lead content of the sediments was microparticles (lead enrichments) seen by SEM can
determined using a Spectro¯ame inductively coupled plasma probably be formed on these nuclei.
optical emission spectrometer and was above 30 mg/kg. The production of these particles is not expected from
the thermodynamic properties under conditions of the
bulk solution and cannot be observed in the absence of
clay. On the basis of the solubility product of Pb(OH)2
Results and discussion (L ˆ 6.8 ´ 10)13) lead is present as Pb2+ at the pH values
of the experiments (pH 3±5). The formation of lead
IR spectrometric studies of the lead montmorillonites enrichments requires the presence of the clay. In the
showed no structural changes of the montmorillonite presence of clay, lead enrichments are formed even in a
crystal lattice. The intensities of the hydrate water of the solution containing a complex-forming agent (citric acid).
cation in the interlayer space vary during cation ex- The chemical analysis by SEM shows that the
change. The band at 2,920 cm)1 disappeared as a result elementary composition of lead enrichments (except

Fig. 1 Scanning electron

microscope picture of mont-
morillonite treated with 5 ´
10)4 moldm)3 lead perchlorate
solution, pH 4.18. Left: mor-
phology of the sample made by
backscattered electrons. Right:
lead map made by characteristic
X-ray photons
 119

Fig. 2 Scanning electron mi-

croscope picture of a natural
clay sediment. The mean lead
concentration is 36 mg/kg, lead
map in the window

lead, of course) is usually the same as the mean the interlayer space and a heterogeneous nucleation on
composition of montmorillonite, so the enrichments are the particle surface followed by crystal growth. Cation
formed on montmorillonite, not on the impurities. exchange leads to the even distribution of the ions, while
Similar lead enrichments were found on a natural the heterogeneous nucleation and crystal growth causes
clay sediment of a lake in Hungary (Fig. 2). The the formation of the enrichment of the lead ions. The
production of nanoparticles and microparticles con- production of these particles is not expected from
taining lead ions under environmental conditions is thermodynamic aspects of the solution and cannot be
especially interesting. observed in the absence of clay.

Conclusions Acknowledgements The authors thank M. FoÈldvaÂri and P.

KovaÂcs-PaÂl€y for X-ray di€raction studies and P. KovaÂcs for
the clay sediment samples. The work was supported ®nancially
The results show that lead ions are adsorbed on by the National Research Foundation (OTKA T23905 and
montmorillonite by two processes: cation exchange in CO278).

References

1. Shen S, Taylor WT, Bart H, Tu S-I 3. Richards LA (1957) Diagnosis and 4. Peker S, Yapar S, BesuÈn N (1995)
(1999) Commun Soil Sci Plant Anal improvement of saline and alkaline Colloids Surf 104:249
30:2711 soils.US Department of Agriculture
2. Strawn DG, Sparks DL (1999) J Colloid Handbook, p 60
Interface Sci 216:257
Progr Colloid Polym Sci (2001) 117: 120±125
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

A. Pozsgay Polypropylene /montmorillonite

L. Papp
T. FraÂter nanocomposites prepared
B. PukaÂnszky
by the delamination of the ®ller

Abstract Polypropylene/montmo- organophilization of NaMMT was

rillonite (PP/MMT) nanocomposites not complete, which hindered the
were prepared by the exfoliation of perfect exfoliation of the MMT lay-
the nanoclay during processing. The ers. Sieved bentonite and NaMMT
®ller was used in various forms behaved like traditional ®llers,
(sieved bentonite, sodium and while the incorporation of the
organophillic MMT) in order to organoclay into PP yielded a true
determine the e€ect of subsequent nanocomposite. Because of incom-
stages of organoclay preparation on plete exfoliation and poor adhesion
the structure and properties of the only a moderate improvement of
composite. The ®ller content was mechanical properties was achieved
varied over a relatively wide range to in the study. Reinforcement depends
determine the extent of maximum on composition; above a certain
reinforcement and the range of ®ller content the nanoclay behaves
practically relevant compositions. like a particulate ®ller possibly
Specimens were injection-molded owing to the stacking of exfoliated
A. Pozsgay á L. Papp á T. FraÂter
with various weak sites (weld lines, layers. The weld line strength of PP
B. PukaÂnszky (&) gate section) in the test area to see nanocomposites is very low; exfoli-
Budapest University of Technology and the performance of the nanocom- ated clay particles orientate parallel
Economics, Department of Plastics and posite under practically relevant to the weld line and strongly deteri-
Rubber Technology, 1521 Budapest,
P.O. Box 92, Hungary, and
conditions. The results proved that orate the properties.
Institute of Chemistry, Chemical Research extensive exfoliation of the organo-
Center, Hungarian Academy of Sciences philic MMT occurred during the
1525 Budapest, P.O. Box 17, Hungary homogenization and subsequent in- Key words Nanocomposite á
e-mail: [email protected]
Tel.:+36-1-4632015 jection molding of the PP compos- Delamination á Organoclay á
Fax:+36-1-4633474 ites studied; however, Strength á Weld line

Introduction contain exfoliated clay particles [8]. This third class of

composites can be prepared by intercalation and in situ
Recently, interest in nanocomposites has increased polymerization of a monomer in the galleries of the
enormously both in industry [1] and academia [2±5]. nanoclay or by the exfoliation of the layers during
This new class of materials can be prepared by various processing [2].
routes, resulting in composites with di€erent structures. Layered silicate nanocomposites are claimed to have
Molecular composites consist of rigid molecules embed- numerous advantages. The homogeneously dispersed thin
ded into a softer polymer matrix [6], colloidal composites clay layers increase sti€ness and strength considerably
are usually prepared by in situ sol±gel precipitation of the even at very low ®ller contents. In contrast to traditional
®ller particles [7], while layered silicate nanocomposites particulate-®lled composites, in nanocomposites ecient
 121

reinforcement can be achieved at ®ller content as low as Table 1 Characteristics of the ®ller used in the experiments (cata-
3±5 wt%. Further advantages of these materials are their logue data)
low ¯ammability [1, 2], increased dimensional stability Mineral composition (wt%)
and heat de¯ection temperature as well as decreased
permeability. Owing to the combination of the previous- Montmorillonite 70
Quartz 30
ly mentioned properties the potential application ®elds of
these materials are mainly the automotive and the Chemical composition (wt%)
packaging industries [1]. However, in spite of their SiO2 76.0
Al2O3 15.0
potential as well as the intensive research and develop- Fe2O3 2.6
ment carried out on them, technical problems and their CaO 2.0
relatively high price hinder the extensive application of MgO 1.4
these materials; obviously further research is needed Other 3.0
before a real breakthrough is achieved. Properties
The goal of the present study was to prepare Particle size (lm) 0±60
polypropylene/montmorillonite (PP/MMT) nanocom- Bulk density (g/cm3) 0.55
posites by the exfoliation of the nanoclay during Moisture content (wt%) 7.5
Speci®c surface area (m2/g) 375
processing. The ®ller was used in various forms in order
to determine the e€ect of the various stages of organoclay
preparation on the structure and properties of the com-
posite. The ®ller content was varied over a relatively wide ray scattering (WAXS) using a Phillips PW 1830/PW 1050 instru-
range to determine the extent of maximum reinforcement ment with Cu Ka radiation at 40 kV and 35 mA. The same
and the range of practically relevant compositions. technique and conditions were used for the characterization of the
PP/clay composites. The dispersion and orientation of the ®ller, as
Specimens were injection-molded with various weak sites well as the failure behavior of the composites, were studied by
(weld lines, gate section) in the test area to see the scanning electron microscopy (SEM) using a JEOL JSM-5600 LV
performance of the nanocomposite under practically instrument. The melting and crystallization characteristics of the
relevant conditions. composites were determined using a PerkinElmer DSC 7 apparatus
on 5-mg samples with heating and cooling rates of 10 °C. Tensile
properties were measured using a Zwick 1445 machine at 10-mm
gauge length and 50 mm/min cross-head speed.
Experimental

A PP homopolymer (Tipplen H 377, melt ¯ow index of 9 g/10 min Results

at 21.6 N and 230 °C) produced by TVK, Hungary, was used as a
matrix material in the experiments. Bentonite mined in MaÂd,
Hungary, was selected as the starting material for the preparation The results of the study are discussed in three sections.
of organophillic MMT. The most important characteristics of the First, we present the changes in the MMT structure
®ller are compiled in Table 1. The ®ller consists of large aggregated during the course of organoclay preparation. Subse-
particles with a layered structure. The raw mineral was sieved to
obtain a ®ller of less then 90-lm maximum particle size (sieved quently, the structure and properties of the nanocom-
sample). In the next step the bentonite containing mostly CaMMT posites are discussed separately for the perfect part and
was subjected to ion exchange in order to produce NaMMT. Ion for the specimen containing the weld line. Compared to
exchange was carried out with NaCl solution of 1.0 mol/l the perfect specimen the presence of the gate in the test
concentration at 20 °C and was repeated three times. Subsequently, area did not change the properties of the composite
the product was treated with an amount of N-cetyl pyridinium
chloride corresponding to the theoretical ion-exchange capacity of signi®cantly; thus we refrain from the discussion of these
the ®ller in order to obtain the organoclay (organophillic MMT). results in order to save space.
The three samples (sieved, Na and organophillic MMT) were
prepared in sucient quantities and homogenized with PP to
produce nanocomposites of 1, 2, 5, 10 15 and 20 v% ®ller content.
Homogenization was carried out in a Brabender DSK 42/7 twin MMT structure
screw compounder at set temperatures of 195, 200 and 205 °C. The
granules produced in the compounder were injection-molded using One of the ®ller samples introduced into the PP matrix
a Battenfeld BA 200 CD machine at barrel temperatures of 205, was produced by the sieving of the raw mineral obtained
215 and 225 °C into dog-bone tensile bars of 3 ´ 2-mm dimensions
in their test section. The temperature of the mold was set to 30 °C. from the mine. Sieving was expected to remove very large
The design of the mold made possible the simultaneous preparation particles, which deteriorate mechanical properties. In the
of three kind of specimens representing various practical molding presence of large spherical particles the dominating
con®gurations. They di€ered in the position of the gate, which was deformation mechanism of composites is debonding
located at one end, at both ends to produce a weld line in the test
area, or in the mid section of the specimen, respectively.
[9±11] and both yield stress and strength decrease with
Changes in the structure of the ®ller as an e€ect of treatment increasing particle size [12, 13]. The maximum size of
(ion exchange, organophilization) was followed by wide-angle X- 90 lm used in the experiments is well over the usual
122

particle size range of commercial ®llers; however, the peak at 7.3 , which indicates the presence of nontreated
initial size of the particles does not play a role in bentonite with closed galleries.
nanocomposites, where complete exfoliation is assumed.
The particle size of the sieved sample and NaMMT,
where exfoliation does not take place, had to be the same Structure and properties of nanocomposites: perfect
to allow comparison. Moreover, the ®ller used in the parts
experiments contains a signi®cant amount of microcrys-
talline quartz, which may also in¯uence the properties. Fillers and reinforcements often modify the morphology
The WAXS di€ractogram of the three samples is of crystalline polymers. Nucleation usually leads to a
presented in Fig. 1. Figure 1A shows the di€ractogram change in lamella thickness, spherulite size and crystal-
taken from the sieved sample and indicates the presence linity, but occasionally modi®es the crystal form as well
of quartz, shown by the characteristic peak appearing at [14±16]. The e€ect of the three ®llers on the temperature
the 2h angle of 26.7°. of crystallization of PP is presented in Fig. 2 as a
The procedure to produce NaMMT from the sieved function of composition. There may be several reasons
sample considerably changed the di€ractogram (Fig. 1B); for the changes observed in the ®gure. The sieved
only small traces of quartz can be detected in this sample. bentonite contains both MMT and quartz particles;
The peaks of MMT remain practically unaltered. Quartz both may nucleate PP. The layered structure of bentonite
obviously settles in and can be removed from the vessel is somewhat similar to that of talc and may result in
used for the ion exchange. As a consequence, this step of increased nucleation [16]. On the other hand, most of the
sample preparation has two results:exchange of Ca2+ by quartz was removed during ion exchange and the
Na+ and removal of quartz. It is interesting to note that nucleating e€ect of the ®ller decreased simultaneously,
the gallery distance of MMT decreased in this step, i.e. quartz might also be the nucleating component. We
probably owing to the intensive drying of the ion- are convinced that the layered particle structure of
exchanged ®ller (see WAXS peak at around 7.8°). The bentonite is the source of strong nucleation. During ion
treatment of NaMMT with a solution of N-cetyl exchange, MMT layers are separated, then they reform
pyridinium chloride leads to further ion exchange. The again during drying with a smaller gallery distance
success of the treatment is clearly proved by the increase (Fig. 1). The ®ller particles formed in this process have a
in the gallery distance of the layers. After treatment, the weaker nucleation e€ect than the original bentonite,
peak detected at 7.3° shifts towards lower angles and probably owing to this change in the distance of the
appears at 4.2°, which corresponds to a gallery thickness layers. As an e€ect of organophilization the layer thickness
of 21.3 AÊ. Unfortunately, the organophilization process increases signi®cantly and a large part of the layered
was imperfect as shown by the appearance of the WAXS structure is destroyed during processing. Both processes

Fig. 1 Wide-angle X-ray scattering di€ractogram of the ®ller samples Fig. 2 Nucleation e€ect of the various ®ller samples in the
used in the experiments:A sieved bentonite; B sodium montmorillonite polypropylene (PP) matrix used:sieved bentonite (h); NaMMT (n);
(NaMMT); C organoclay organoclay (s)
 123

change the distance of the layers and thus in¯uence the both strength and deformation increase. At high ®ller
nucleation eciency of the ®ller. In this case nucleation is loadings, however, the bene®t is lost. Either exfoliation
not observed at all. does not take place or the layers organize into large
The SEM micrograph taken from the fracture surface stacks and behave like commodity ®llers. These re-
of the composite containing the sieved ®ller in 0.05 sults verify earlier observations which indicate that the
volume fraction is presented in Fig. 3. Very large advantages of nanocomposites appear only at low ®ller
particles can be observed on the surface and the content in a limited composition range.
dominating deformation mechanism is clearly debond- WAXS di€ractograms were taken from the compos-
ing. The micrograph forecasts poor mechanical proper- ites to check the extent of exfoliation and the structure of
ties:the complete lack of a reinforcing e€ect. In other the composites. The di€ractograms, not presented here
areas parallel orientation of plateletlike particles can be to save space, show the characteristic peaks of PP, but at
observed on the surface. This latter structure may result low angles two other peaks appear as well, which belong
in reinforcement, but the local areas represented in Fig. 3 to the closed gallery structure of bentonite (6.7°) and to
dominate the response of the material towards external the opened layers of the organoclay (4.4°). Their presence
loading. indicates both incomplete organophilization and imper-
The properties of the composites follow exactly the fect exfoliation. The composition dependence of the
prediction made by the analysis of the SEM micrographs. extent of exfoliation is expressed quantitatively as the
The composition dependence of the yield stress is ratio of the intensity of the two peaks (organophilic/
presented in Fig. 4. A strong decrease in this property bentonite) in Fig. 5. The intensity of the organoclay-
occurs when the composite contains sieved bentonite and related peak decreases with increasing ®ller content,
NaMMT, while the organoclay reinforces PP. The which indicates increasing exfoliation, since delaminated
composites prepared with the ®rst two ®llers failed MMT sheets do not give a WAXS pattern. The viscosity
without yielding at very low ®ller contents, which proves increases with ®ller content, which results in higher shear
again that debonding takes place during deformation and a more complete exfoliation of the organophilized
and the voids formed merge rapidly into critical cracks. clay; however, the di€ractograms reveal that a consider-
On the other hand, exfoliation changes the deformation able amount of bentonite is also present in the composite,
mechanism, yielding dominates at low ®ller contents and i.e. organophilization was not complete, resulting in the
moderate improvement in properties.

Weld lines

The study of specimens containing weld lines might

supply further information about exfoliation and the

Fig. 3 Scanning electron microscopy (SEM) micrograph taken from

the fracture surface of a PP nanocomposite containing 0.05 volume Fig. 4 Comparison of the yield stress of PP nanocomposites
fraction sieved bentonite; large particles, debonding containing sieved bentonite (h), NaMMT (n) and organoclay (s)
124

Fig. 5 Composition dependence of the relative intensity (organoclay/

bentonite) of the two peaks assigned to closed and open gallery
distance of the organoclay
Fig. 7 SEM micrograph taken from the fractured weld line of an
injection-molded specimen prepared from a composite containing 0.05
volume fraction organoclay

decrease the strength with increasing ®ller content, which

is in line both with the structure and with the deforma-
tion mechanism (Fig. 3) of the composites as discussed
earlier. The composite containing the organoclay pos-
sesses a strongly decreased strength. Obviously exfoliated
clay sheets orientate in the plane of the weld line and
inhibit interdi€usion of molecules in the merging melt
fronts. This result proves again that a considerable
amount of the organoclay exfoliates during homogeni-
zation and the processing of composite parts. This
statement is further corroborated by Fig. 7, which shows
a SEM micrograph taken from the fracture surface of the
weld line. Very large, 200±400-lm smooth areas appear
on the surface as an e€ect of a rapidly propagating crack
front. The crack apparently proceeds along the weld line
containing the clay sheets of parallel alignment.
Fig. 6 Weld-line strength of nanocomposites containing the three
®llers; sieved bentonite (h); NaMMT (n); organoclay (s)

Conclusions
structure of the composites, but it also has practical
relevance. Anisotropic particles were shown to orientate The study of PP composites containing a bentonite ®ller
in the plane of the weld line and to considerably in the various stages of organophilization proved that
deteriorate the mechanical properties of injection molded extensive exfoliation of organophilic MMT occurred
parts [17±19]. The tensile strength of the composite parts during the homogenization and subsequent injection
containing a weld line is plotted against composition in molding of the PP composites studied; however, organ-
Fig. 6. A very signi®cant di€erence can be seen between ophilization of NaMMT was not complete in the study,
the organoclay and the other two ®llers in their e€ect on which hindered the perfect exfoliation of the MMT
weld-line strength. The sieved bentonite and NaMMT layers. Sieved bentonite and NaMMT behaved like
 125

traditional ®llers, while the incorporation of the organo- weld line and they strongly deteriorate the properties.
clay into PP yielded a true nanocomposite. Because of Both treatment and processing technology must be
incomplete exfoliation, and probably owing to poor improved in order to utilize all the potential of nanoclays
adhesion, only a moderate improvement in the mechan- and achieve maximum reinforcement.
ical properties was achieved in the study. Reinforcement
depends on composition; above a certain ®ller content Acknowledgements The authors are truly indebted to TamaÂs GroÂsz
the nanoclay behaves like a particulate ®ller, possibly and IstvaÂn Sajo for their assistance in completing the WAXS
owing to the stacking of exfoliated layers. As a conse- measurements. PeÂter Hargitai is acknowledged for the preparation
quence,theadvantagesofnanocompositescanbeexploited of the SEM micrographs. The National Fund for Scienti®c
Research (OTKA T 30579) and the Varga JoÂzsef Fund of the
only at low ®ller contents in a limited composition range. Faculty of Chemical Engineering at the Budapest University of
The weld line strength of the PP nanocomposites is very Technology and Economics is greatly appreciated for the ®nancial
low, exfoliated clay particles orientate parallel to the support of the research.

References

1. Sherman LM (1999) Plast Technol 45:52 8. Liu P, Qi Z, Zhu Z (1999) J Appl 13. PukaÂnszky B (1990) Composites 21:255
2. Giannelis EP (1996) Adv Mater 8:29 Polym Sci 71:1133 14. Fujimama M, Wakino T (1991) J Appl
3. Giannelis EP (1998) Appl Organometal 9. Vollenberg P, Heikens D, Ladan HCB Polym Sci 42:2739
Chem 12:675 (1988) Polym Compos 9:382 15. Varga J (1989) J Thermal Anal 35:1891
4. MuÈlhaupt R, Stricker F (1997) Kustst- 10. PukaÂnszky B, VoÈroÈs G (1993) Compos 16. PukaÂnszky B, Belina K, Rockenbauer
o€e 87:482 Interfaces 1:411 A, Maurer FHJ (1994) Composites
5. Herron N, Thorn DL (1998) Adv 11. VoÈroÈs G, Fekete E, PukaÂnszky B 25:205
Mater 10:1173 (1997) J Adhes 64:229 17. Christie M (1986) Plast Eng 42:41
6. Ruckenstein E, Yuan Y (1997) Poly- 12. PukaÂnszky B, TurcsaÂnyi B, TuÈdos F 18. Fisa KB, Dufour J, Vu-Khanh T
mer 38:3855 (1988) In:Isida H (ed) Interfaces in (1987) Polym Compos 8:408
7. Schmidt HK, Geiter E, Mennig M, polymer, ceramic, and metal matrix 19. Waxman A, Narkis M (1991) Polym
Krug H, Becker C, Winkler RP (1998) composites. Elsevier, New York, Compos 12:161
J Sol-Gel Sci Technol 13:397 pp 467±477
Progr Colloid Polym Sci (2001) 117: 126±130
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

C. Beck Fullerenes as new colloidal model systems

W. HaÈrtl

Abstract Water-soluble C60(OH)22±27 attributed to the di€usion of

(fullerol) particles with di€erent C60(OH)22±27 colloidal particles in
concentrations in D2O as solvents the solvents, whereas the broad
were used as colloidal spheres. By Lorentzian is due to the motion of
means of quasielastic neutron scat- the solvents molecules themselves.
tering (QENS) we determined the From the width of the narrow line
dynamic structure factor, S(Q,x), we ®nd the translational di€usion
for samples with concentrations coecient of the fullerol particles to
ranging from 1 to 6 vol%. Recently, be about 2.74á10)10 m2s)1. Taking
it has been shown that C60 in CS2 is into consideration the hydrodynam-
a new hard-sphere colloidal model ic shell and the resulting larger
system. In contrast to this lipophilic e€ective hydrodynamic diameter of
system with only low solubility in the particles this value is comparable
most solvents, hydrophilic to those obtained from the Stokes±
C60(OH)22±27 can be treated as a new Einstein relation. Additionally, we
soft-sphere colloidal model system show that the self-di€usion coe-
for weakly or even highly charged cient is signi®cantly in¯uenced by
particles. We show that QENS is the volume fractions of the fullerol
C. Beck (&)
Paul Scherrer Institute, well suited for studying the dynamic particles in D2O. This is a direct hint
Laboratory for Neutron Scattering, and static behavior of these fullerol± for the beginning of particle±particle
5232 Villigen, Switzerland D2O systems with di€erent concen- self-organization in the sense of a
e-mail: [email protected] trations. At 1 bar and 298 K, for
Tel.: + 41-56-3104621 liquid-like-ordered system.
Fax: + 41-56-3102939 scattering vectorsQ ˆ 0.4 AÊ)1 up to
C. Beck á W. HaÈrtl
Q ˆ 2.6 AÊ)1 S(Q,x) can be well Key words Fullerenes á
University of SaarbruÈcken, described by a sum of a narrow and Scattering á Colloids á Di€usion á
66123 SaarbruÈcken, Germany a broad Lorentzian line. The ®rst is Self-organization

Introduction transition in systems of highly charged and hard-sphere

particles [3].
The dynamics of dilute monodisperse suspensions of In this article we report a study of the dynamic
spherical colloidal particles has been extensively studied behavior of hydroxylated fullerene molecules, i.e. so-
by means of dynamic light scattering [1] to prove their called fullerol C60(OH)22±27, which are intermediate
model system character for the atomic state, which is due between classical colloidal suspensions and binary mix-
to the similar interparticle interaction potential. A tures of atomic liquids. We consider at a temperature of
tremendous amount of work has been done in the ®eld 298 K dispersions of fullerol, which are highly soluble in
of soft-condensed-matter research to study and reveal the polar liquids, in D2O with di€erent volume fractions, /,
hydrodynamic behavior [2] or even the liquid±glass ranging from dilute up to 6%. Each of these systems is
 127

between the monochromator and the sample at a distance of 0.5 m

in front of the sample. The elastic energy resolution ranges from
50 leV (full width at half maximum, FWHM) at ki ˆ 6 AÊ to
131 leV at 4 AÊ and 1300 leV at 2 AÊ [4]. An elastic scattering
vector Q range from 0.2 to 5.6 AÊ)1 can be applied with the
following relationship for Q:
4p
Qˆ sin H ; 1†
k
with Q the scattering angle and k the wavelength. The optical
parameters of FOCUS can be adapted to the requirements of the
experiment by the variable curvatures of the monochromator in
the horizontal and vertical directions and ¯exible distances
between the main spectrometer components. A novel concept of
FOCUS consists of the option to operate the machine either in
Fig. 1 Brief sketch of the spectrometer FOCUS time-focusing or in monochromatic-focusing conditions [5].
Whereas the time-focusing option allows a sharp energy resolution
with enhanced intensity at a certain energy transfer window, the
monochromatic-focusing option of the instrument provides an
essentially a monodisperse solution of perfect almost constant resolution within a broad range of energy
C60(OH)22±27 with a calculated crystallographic (powder) transfers, especially on the neutron-energy-loss side of the
diameter of about 0.9 nm. spectrum.
We show that neutron time-of-¯ight (TOF) spectro- We performed all measurements using a conventional closed-
cycle refrigerator at 298 K with a standard aluminum hollow
scopy is a powerful tool to study these dynamic processes cylinder sample can. As a ®rst instrumental setup we chose an
of fullerol particles in D2O as a solvent by analyzing the incident wavelength of 6 AÊ, which corresponds to a primary
quasielastic broadening of the elastic scattered intensity energy, E, of 2.27 meV, with an instrumental resolution of
at Q values between Bragg re¯ections. The momentum DE ˆ 50 leV covering a scattering vector window between
Q ˆ 0.3 and Q ˆ 2.0 AÊ)1. The second setting consisted of
transfer, Q, and the energy transfer, x, of the neutron to k ˆ 4.2 AÊ and E ˆ 4.6 meV with DE ˆ 120 leV and an elastic Q
the sample during the scattering process mainly charac- range of 0.8±2.6 AÊ)1. Di€erent detector eciencies were corrected
terize the method. In contrast to a triple-axis spectrom- using the completely incoherent and elastic scatterer vanadium in
eter, a TOF experiment simultaneously detects several the same sample geometry.
points in the (Q,x) phase space by time-resolved neutron
detection within a large solid angle by the use of typically Sample
several hundreds of detectors. TOF spectroscopy uses the
de Broglie relation between the wavelength of the The hydroxylated fullerene, i.e. so-called fullerol, was purchased
neutron and its velocity: from MER, Tucson, USA, as a dry powder. The particles were
further dissolved in analytical grade D2O. All scattering curves
from the sample were corrected using pure D2O in an aluminum
k ˆ h=mv ) k ˆ 3956=v : cuvette in order to gather the pure contribution of the fullerol. The
determinations of the dynamic character of the more highly
Typical neutron velocities used in a scattering exper- concentrated samples were carried out in the presence of a
iment range from 200 to 3000 ms)1; therefore, the ¯ight mixed-bed ion exchanger (Fluka) in the deuterated modi®cation
times for experimentally relevant distances of several in order to remove all excess ions within the sample; only the
counterions of the surface were present.
meters are of the order of milliseconds. By measuring the
time the neutrons need to pass a known distance one can
calculate the wavelength that directly yields the energy, E.
Theory

Experimental Static properties

Spectrometer The molecule has a total scattering cross-section of

2,485 barn (1 barn equals 10)24 cm2), which is built up
The SINQ TOF spectrometer FOCUS, Fig. 1, is based on the by an incoherent scattering cross-section of 2,005 barn
hybrid-TOF principle and combines a double-focusing crystal mainly caused by the hydrogen atoms and a coherent
monochromator with a Fermichopper. The disc chopper in front of
the monochromator serves as an antioverlap device. At a distance scattering cross-section of 480 barn resulting from the
of 2.5 m from the sample position, three banks of detectors carbon and the oxygen atoms. In a thought experiment,
equipped with 383 3He single-tube detectors cover a range of ®lling the volume of one particle completely with D2O
scattering angles between 30° and 130°. One main purpose of the means that the particle scatters 1.5 times more strongly
concept is the high ¯exibility of the instrument. The pyrolythic
graphite monochromator allows a continuous and large range of than the solvent particles themselves, which is not the
initial energies, Ei: 2.3 meV < Ei < 20 meV. A Fermichopper case for pure C60. For a spherical, monodisperse hollow
with a straight collimation of 2.0° and 1°, respectively, is located particle the normalized integrated scattering intensity
128

Dynamic properties

The neutron spectra of a di€using particle are given by

Z 1
I Q; x† ˆ IP Q† S Q; x0 †R Q; x x0 †dx0 ; 4†
1

where I is a Q- and x-independent normalization factor,

P(Q) is the normalized single particle form factor,
S(Q,x) represents the dynamic structure factor of the
di€using species and R(x) is the resolution function of
the spectrometer. For isotropic processes S(Q,x) is
described by a Lorentzian line [6]:
1 C Q†
S Q; x† ˆ ; 5†
p C Q†2 ‡ hx†2

Fig. 2 The fullerol particle: C60(OH)22±27 with G(Q) the Q-dependent half width at half maximum
(HWHM) and hx the energy transfer with respect to the
sample. The HWHM is directly connected to the nature
due to intraparticle interactions, Pcoh(Q), the single- of di€usion. The rotational di€usion is considered to be
particle form factor, is: too fast and so with our instrumental setup not
determinable [7]. For translational di€usive processes
 2
A Q† the well-known Q2D law, with D the di€usive constant,
Pcoh Q† ˆ 2† describes the HWHM. For particles much larger then the
C
solvent molecules, the Stokes±Einstein continuum rela-
and tion for solvents with viscosity, g, holds for the free
! di€usion constant, Dfree:
sin QRo † QRo cos QRo † kB T
A Q† ˆ 3 3 Dfree ˆ : 6†
QRo † 6pgR
!
sin QRi † QRi cos QRi † 3† That is why we are on the cutting edge when applying this
3 3 theory because the fullerol particles are only about
QRi †

10 times larger then D2O [8].
C ˆ 1=3 R3o 3
Ri ; As mentioned earlier the incoherent scattering hydro-
gen atoms on the surface dominate the scattering
with Ri and Ro the inner radius and the outer radius of
the hollow sphere, respectively. This relation only holds
for the situation of coherently scattering surface
elements in the sense that the scattered waves are able
to interfere in a coherent manner and is directly related
to the scattering properties of the carbon and the
oxygen atoms of fullerol. By considering the scattering
behavior of the hydrogen atoms a completely di€erent
picture is drawn. The incoherent scattered waves
originating from the hydrogen atoms on the surface
are not able to interfere coherently, with the result that
Pinc(Q) ˆ 1 over the complete Q range; therefore, the
complete form factor should consist of 20% Pcoh(Q)
and 80% Pinc(Q).
For interacting particles a second static contribution,
that is to say the static structure factor, S(Q), also plays a
prominent role. For a 20% coherent scatterer and the
volume fractions we are dealing with this means that the
static coherent scattering intensity is additionally super-
imposed by a 5±10% e€ect, which is essentially is
negligible. Fig. 3 Raw scattering function at highest applied Q (2.6 AÊ)1)
 129

function of the fullerol particles. The direct consequence a ®xed inner radius of 3.5 AÊ for pure C60 and an outer
is the determination of the free di€usion constant for the radius of 4.7 AÊ by taking into consideration the contri-
dilute systems and a self-di€usion constant for the more bution ratio of the coherent and incoherent surface
highly concentrated samples. scattering of one particle, i.e. Pcoh(Q) and Pinc(Q).

Results and discussion Concentrated systems

Dilute systems The high solubility of the fullerol particles in polar

solvents makes a determination of the dynamic proper-
The raw scattering curves of all the samples investigated ties at high volume fractions possible; therefore, we were
are excellently describable by two Lorentzian curves due able to probe samples at a volume fraction of / ˆ 1, 4
to the motion of water molecules and fullerol plus an and 6%. The particle dispersions in D2O showed an
elastic contribution of the aluminum container (Fig. 3). acidic pH of about 5, which can be interpreted as a direct
The data were further corrected with the neutron spectra hint for the partial deprotonation of the surface hydroxyl
of pure D2O in the same cuvette to collect only the groups and leads to a categorization of the particles as at
scattering curves of the colloidal fullerol particles. least weakly charged systems. After removing all the
For the dilute sample we determined from the Q excess ions by means of a mixed-bed ion exchanger only
dependence of the FWHM, G(Q), at room temperature a the counterions are present and the surface charges are
di€usion constant of 2.74 ´ 10)10 m2s)1 which, by not shielded anymore. The direct consequence is a
applying the Stokes±Einstein relation leads to an e€ec- relatively long range repulsion, which at appropriate
tive particle radius of about 8.0 AÊ; for pure C60 the number densities can cause collective ordering phenom-
radius is about 3.5 AÊ [9] and for dilute C60 in CS2 a value ena, like a liquid-like-order phase, a crystalline phase or
of 4.5 AÊ was recently obtained by Smorenburg et al. [8]. even a glassy phase [10].
Taking into consideration the hydrodynamic solvent The FWHM is displayed in Fig. 5 with respect to Q2
shell of one or even more molecular layer on the surface for the three di€erent volume fractions. The in¯uence of
of all the di€using particles in solution the discrepancy of the increasing concentration on the velocity of the
the values is reasonable. particles is clearly visible. For the most concentrated
To gather information about the static properties of system we determined a di€usion constant of
the dilute colloidal fullerol, i.e. the single particle form 1.36 ´ 10)10 m2s)1, whereas the dilute system revealed
factor, we illustrate in Fig. 4 the intensity of the a value of 2.74 ´ 10)10 m2s)1 (Table 1). The slowing of
quasielastic peak with respect to Q. Using the function the di€usion has to be interpreted in terms of the
for a hollow sphere with nonnegligible thickness, Eq. (2), beginning of self-organization of the system, i.e. a liquid-
the Q dependence of the intensity is well describable with like-ordered system. Thus the di€usion constant, D,

Fig. 5 Following the Q2D law for fullerol samples with a volume
Fig. 4 Single-particle form factor, P(Q), for a dilute fullerol system fraction, /, of 1, 4 and 6%
130

Table 1 Di€usion constants of the fullerol systems in comparison facility FOCUS was used to determine the dynamic and
to dilute, pure C60 [8] static behavior for samples with concentrations ranging
System D (m2s)1) D* ˆ D/Dfree from 1 to 6 vol%. In contrast to the lipophilic hard-
sphere C60 system in nonpolar solvents, hydrophilic
Fullerol: / ˆ 1% 2.74 ´ 10)10 1 fullerol can be treated as a new soft-sphere colloidal
Fullerol: / ˆ 4% 2.02 ´ 10)10 0.7
Fullerol: / ˆ 6% 1.36 ´ 10)10 0.5
model system for weakly or even highly charged
Pure C60: / < 1% 1.5 ´ 10)9 1 particles. After the correction of the raw scattering data
the scattering function can be well described by a single
Lorentzian line, which is attributed to the di€usion of
mirrors the self-di€usional behavior of the colloidal colloidal particles in D2O. For a dilute system we
fullerol particles: D shows no Q dependence in contrast extracted from the FWHM the self-di€usion coecient
to the collective di€usion constant [2]. The reduced self- of the spheres to be about 2.74 ´ 10)10 m2s)1. By taking
di€usion constant, D* ˆ D/Dfree, will slow to a value of into consideration the hydrodynamic shell and the
0.1 with respect to the concentration, where a phase resulting larger e€ective hydrodynamic diameter of the
transition will occur [11]. For our colloidal systems we particles this value is comparable to those obtained from
measured a course of the value of D* from 1 to 0.7 to 0.5, the Stokes±Einstein relation. A direct hint for the
which indicates the regime of a liquid-like-ordered beginning of particle±particle self-organization in the
system. sense of a liquid-like-ordered system is revealed by
the reduced self-di€usion constant with respect to the
free counterpart.
Conclusion
Acknowledgements FOCUS was built and is being operated in
close cooperation between the University of SaarbruÈcken, Germany,
We showed that water-soluble fullerol particles with and the Paul Scherrer Institute, Switzerland. Generous ®nancial
di€erent concentrations in D2O as a solvent are suitable support by the German BMBF (project nos. 03-HE4SA2 and 03-
colloidal model systems. The inelastic neutron scattering HE5SA2) is gratefully acknowledged.

References

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freezing and glass transition. Elsevier, 6. Bee M (1988) Quasielastic neutron Rev E 52:2742
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(1999) J Chem Phys 110:7074 RL, Kamitakahara WA, Lindstrom 10. HaÈrtl W, Beck, CH, Hempelmann R
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(1999) J Chem Phys 11:3209 now WJ, Coustel N, McCauley HP Jr, 117:113±116
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Progr Colloid Polym Sci (2001) 117: 131±135
Ó Springer-Verlag 2001 NANOSTRUCTURED MATERIALS

V. Socoliuc Experimental investigation of magnetic-

D. Bica
induced phase-separation kinetics in aqueous
ferro¯uids

Abstract In this article we report Key words Ferro¯uids á Colloidal

V. Socoliuc (&) microscopy and light scattering in- stability á Phase transition á Phase
National Institute for Research vestigation of phase-separation phe- separation
and Development in Electrochemistry
and Condensed Matter, Tirnava 1, nomenon in ferro¯uids. The
1900 Timisoara, Romania in¯uence of the temperature and an
e-mail: [email protected] external magnetic ®eld on the kinet-
D. Bica ics and on the quantitative extent of
Center for Fundamental and Advanced the phase separation was investigat-
Technical Research, Romanian Academy, ed.
Bd. Mihai Viteazul 24, Timisoara,
Romania

Introduction stabilized with dodecyl benzene sulfonic acid produced

by means of a chemical coprecipitation method [2, 3].
Ferro¯uids, or magnetic colloids, are suspensions of
magnetic nanoparticles dispersed in a carrier liquid. In
order to prevent agglomeration due to attractive van der Experimental
Waals or magnetic dipole±dipole interactions, in addition
to the Brownian motion, a repulsive force between the Optical microscopy investigations of the ferro¯uid condensation
particles is created by means of steric hindrance or phenomena were carried out. A special electromagnet and a sample
electrostatic repulsion. The ideal ferro¯uid is a homog- thermostat were designed and adapted to a metallographic
microscope with a maximum magni®cation of 1500 ´. The
enous dispersion of isolated particles. Phase separation is magnetic ®eld range was 0±1.5kOe, the ®eld gradient in the sample
one of the main phenomena that leads to radical changes region was less than 10Oe/mm at 0.5 kOe and about 50Oe/mm at
in the ferro¯uid colloidal stability and structure [1]. When 1.5kOe and the magnetic ®eld transient time was less than 1 s.
the temperature or the external magnetic ®eld strength Wide-angle forward scattering of light was investigated by
recording the scattering pattern projected on a screen with a
exceed their critical values, the formation of highly charge-coupled-device camera (Fig. 1). This technique allows the
concentrated phase droplets may occur in the ferro¯uid. instantaneous sampling of the entire scattering pattern and the
In this article we present the results of research on the recording of its time evolution. A He±Ne laser beam polarized
in¯uence of the temperature and an external magnetic perpendicular to the magnetic ®eld direction was used as incident
light.
®eld on the kinetics of phase-separation phenomena in an Detection of the light transmitted in the incident beam direction
aqueous ferro¯uid as well as on the size, shape and space was performed (Fig. 2). The He±Ne laser incident beam was
con®guration of the condensed-phase drops. polarized at 54.7° with respect to the ®eld direction in order to
annul the dichroism induced by the magnetic particle orientation
and agglomeration [4]. The scattered light was ®ltered out with an
iris. In order to compensate the laser emission ¯uctuations the
Sample description incident beam was split and both beams were ®ltered and focused
on two identical large-area photodetectors (IPL10530DAW Inte-
grated Photomatrix) with incorporated operational ampli®ers. The
An aqueous ferro¯uid was prepared for the investiga- signals from the photodetectors were fed into a National Instru-
tions with a volume fraction of 3% magnetic particles ments LabPC+ data acquisition board; data processing and signal
132

Fig. 1 Wide-angle light scattering experiment setup Fig. 2 Forward scattering experiment setup

referencing were made with a virtual instrument developed with temperature decrease. At low temperatures the density
LabView. The ferro¯uid was contained in a 10-lm light-path cell of the drops increases signi®cantly with increasing ®eld
with a detachable window. The magnetic ®eld was perpendicular to
the incident light beam and parallel to the cell plates. A Weiss
intensity.
electromagnet was used to produce a static magnetic ®eld in the At temperatures above 30 °C no condensed-phase
range 0±4kOe with less than 10Oe/cm gradient. The magnetic ®eld drops were observed even at the highest ®eld value
strength was measured with 10Oe precision. The sample temper- (1.5kOe), while at temperatures below 20 °C condensed-
ature was measured with 0.1 °C precision and was controlled with a phase drops were observed for ®eld values as low as
water thermostat system and a specially designed cell mount.
10Oe.

Results and discussion

Light scattering experiment
Optical microscopy investigation
The pasted (negative) images of the scattering pattern at
After the sudden onset of the 1.5kOe magnetic ®eld, a several moments of time after the ®eld settling subse-
high density of small acicular drops (primary drops) of quent to its sudden onset are shown in Fig. 4. The spots
the condensed state form in the ferro¯uid, aligned at the bottom of the picture are the images of the
parallel to the magnetic ®eld direction. Their length is unscattered light beam projection. The sample temper-
about 5 lm and the thickness was estimated to be less ature was 27 °C, the applied ®eld was 3kOe and the ®eld
than 1 lm. From the beginning of their formation the transient time was less than 1 s. The pronounced lack of
primary drops move chaotically inside the cell, while circular symmetry of the scattering pattern is character-
the formation of larger drops (secondary drops about istic for very elongated scatterers [7]. One can observe
20 lm long and 1 lm thick) begins (Fig. 3). The that immediately after the onset of the ®eld the
primary drops vanish as the number of secondary di€raction pattern presents a minimum in the vicinity
drops increases. The secondary drops also drift within of the central spot. Over time the minimum moves
the uncondensed ferro¯uid but their motion is much toward the central spot and the scattered light intensity
slower than that of the primary drops. Owing to their increases over the entire angular range. The angular
large magnetic moment aligned in the ®eld direction dependence of the scattered light intensity is plotted in
and to the magnetic dipole attraction, the secondary Fig. 5 for several moments after the onset of the ®eld.
drops stick together head to tail, thus leading to the The data were obtained from vertical gray-level distri-
formation of very elongated drops (some of them bution sampling of the patterns plotted in Fig. 4. Once
exceeding 100 lm). Similar evolution resulted from again one can observe the displacement of the minimum
theoretical modeling of phase condensation in ferro¯- toward the central spot and also the increase in the
uids [5] and was also observed experimentally [6]. scattered intensity at the minimum corresponding angle.
After about 1 min the drops no longer grew and An important question arises regarding the origin of
they settled in a fairly stable space con®guration the local minim in the scattered light pattern (Fig. 5). It
owing to magnetic lateral repulsion. The temperature is well known that light scattering in ferro¯uids with
was found to have little in¯uence on the dimensions droplike aggregates originates from the light di€raction
of the drops but their density increases with a on the drops of the condensed phase which, since their
 133

Fig. 3 Optical microscopy

image of the condensed phase
drops elongated in the external
magnetic ®eld direction for
H ˆ 1.5kOe at a 21 °C and
b 28 °C

particle density is much greater than the uncondensed where u ˆ 2pns/kásin(h/2), where s is the drop thickness,
state, are opaque to visible light. Following Ref. [7], in n is the refractive index of the uncondensed phase, k is
the case of very elongated scatterers, the scattered light the wavelength of light in a vacuum and h is the
angular dependence can be well approximated as scattering angle. If one assumes that the light scattered
  by the ferro¯uid sample is the result of the incoherent
sin u 2 superposition of light di€racted by individual drops, the
I h†  ; 1†
u di€raction function (sinu/u)2 should ®t the experimental

Fig. 4 Time evolution of the scattered light patterns after the ®eld
setup as recorded with a charge-coupled-device camera (27 °C, Fig. 5 Angular distribution of the scattered light at several moments
H ˆ 3kOe) of time after the onset of the ®eld
134

data quite well. The di€raction function with a ®rst- 0 2p ns† sin h=2†12
order minimum angle and a ®rst-order maximum sin k
amplitude corresponding to the experimental data at I h†  cos4 h@ 2p ns† sin h=2† A : 4†
k
t ˆ 0.3 s is plotted in Fig. 4. The experimental angle of
the ®rst-order maximum is nearly twice the theoretical Following the previous discussion one can use Eq. (3)
value and both the width and magnitude of the to compute the mean distance between drops and
experimental zero-order maximum are much smaller Eq. (4) to determine the mean thickness of the drops
then the theoretical values. On the other hand, the drops times the uncondensed phase refractive index by ®tting
thickness that results from Eq. (1) with the minimum the experimental data at high scattering angles. The time
corresponding angle and the refractive index of water dependence of the mean thickness and spacing of the
(n ˆ 1.5) is about 10 nm, which is an order of magnitude drops times the matrix refractive index is plotted in
greater than the value estimated from microscopy Fig. 7. At the beginning of the condensation process the
investigations; therefore, we infer that the minimum in drops thickness is constant at about 0.8 lm for about 5 s
the scattered light originates from the coherent interfer- and afterwards it slowly and asymptotically increases
ence of the light di€racted by individual drops. The toward about 1.1 lm. The spacing between the drops
space con®guration of the condensed-phase drops in the increases constantly from 3 to 8 lm, mainly owing to the
ferro¯uid could be modeled as the superposition of the process of coalescence of primary drops as observed in
light scattered by a series of ideal di€raction gratings the microscopy investigations. Although it was not
with the space between neighboring drops distributed possible to determine the refractive index of the
over a certain range of values. Thus, one can model the condensed phase, it is reasonable to assume that it is
angular dependence of the scattered light as the independent of the drop size.
incoherent superposition of the light coherently scat-
tered by pairs of neighboring drops as
0 2pns sin h=2†12 Light extinction experiment
sin k
I h†  cos4 h@ A
2pns sin h=2† The time dependence of the scattered light intensity
k (normalized to the transmitted intensity in the absence of
Z
! 2 the ®eld) was measured between 15 and 35 °C, after the
sin pNnDk sin h sudden onset of the magnetic ®eld for several values of its

g D; d0 ; w†dD : 2†
sin pnDksin h magnitude (the data measured at 23 °C are plotted in
D
Fig. 8). The magnetic ®eld transient time was less than 1 s.
The term cos4(h) describes the perpendicular polari- It was found, as an example, that for ®eld values below
zation of light relative to the elongation direction of the 0.5kOe no light scattering occurs at 27 °C, while at 23 °C
drops, the second term describes the angular dependence light scattering occurs at ®eld values as low as 0.15kOe.
of the light di€racted by individual drops and the The lower the temperature and the higher the magnetic
integral describes the incoherent summation of the inter- ®eld value, the more pronounced the light scattering.
ference term of pairs of drops (N ˆ 2) over the distribu-
tion g(D,d0,w) of the distance between neighboring
drops, where d0 and w are the distribution parameters.
In Fig. 6 the angular dependence of the interference
integral is plotted for d0 ˆ 2.5 lm and several values of w
assuming a Gaussian distribution of the distance
between drops and for d0 ˆ 5 lm and w ˆ 2 lm. As the
distribution width increases, the integral becomes
smother and constant at high values of the scattering
angle, while the ®rst-order minimum remains dependent
on d0. The minimum corresponding angle is related to
the mean distance between drops by the following
approximate equation
ˆ k
nD ; 3†
2 sin hmin
while at high scattering angles the experimental data are
approximately well described by the polarization term Fig. 6 The interference term for a pair of drops integrated over the
times the di€raction term, since the integral of the Gaussian distribution of the spacing between drops for several values
interference term is independent of the scattering angle: of the parameter w
 135

Fig. 7 Time dependence of the mean thickness of the drops and the Fig. 8 Time dependence of the scattered light intensity normalized to
mean spacing between drops the transmitted intensity in the absence of the ®eld at 23 °C for several
values of the magnetic ®eld intensity
Depending on temperature, above a certain value of
the magnetic ®eld the scattered light intensity reaches a where t1 is the temperature above which phase conden-
local maximum. The time until the scattered light sation does not occur no matter how strong the magnetic
intensity reaches the local maximum increases with ®eld is. As a result of the ®tting of the experimental data
temperature and decreases with magnetic ®eld value. with Eq. (5), a value of 31.7 °C was found for t1 , which
One can divide the time evolution of the scattered light is in good agreement with the observations from
into two stages: prior and subsequent to the local microscopy and scattering investigations.
maximum corresponding moment. On basis of the
microscopy observations one can infer that at the
Conclusions
beginning of the ®rst stage light scattering is mainly
due to the formation of primary drops. The transient
The e€ect of magnetic-induced phase condensation on
time of the scattered light was found to be independent
the aqueous ferro¯uid investigated is that the ferro¯uid
of ®eld intensity but it increases with decreasing
becomes a biphasic system i.e. condensed-phase droplets
temperature.
form in equilibrium with the uncondensed phase matrix.
At temperatures below 20 °C light scattering occurs
The density of the condensed-phase droplets increases
for magnetic ®eld values as low as 10Oe and above
with decreasing temperature and increasing magnetic
30 °C no scattering was observed even at the highest
®eld intensity. While the length of the droplets at
magnetic ®eld value (3kOe), in good agreement with
equilibrium increases with ®eld intensity, their thickness
microscopy observations. For several temperature val-
is independent both of temperature and ®eld intensity.
ues the critical ®eld value (Hc) was determined at which
Above 32 °C, magnetic-induced phase condensation
the drops begin to scatter the light. The data was ®tted
does not occur.
with the equation derived by Cebers [8] for the
The kinetics of phase condensation was found to be
dependence on temperature of the critical ®eld at which
in¯uenced mainly by the temperature. The growing
phase condensation occurs:
process of the condensed-phase drops was found to
1 evolve in two stages: small primary drops grow and stick
Hc t †  ; 5† together into large secondary drops, similar to the
t t1
theoretical predictions reported in Ref. [4].

References

1. Berkovski B, Bashtovoy V (1996) 4. Kopcansky P, Koneracka M, Toma- 7. van de Hulst HC (1957) Light scatter-
Magnetic ¯uids and applications sovicova N, Tomco L (1999) J Magn ing by small particles. Wiley, New
handbook. Begell House, New York Magn Mater 201:204 York
2. Bica D (1985) Romanian Patent 5. Yu Zubarev A, Ivanov AO (1997) 8. Cebers A (1991) Physical properties
90078 Phys Rev E 55:7192 and models of magnetic ¯uids. Euro-
3. Bica D (1995) Rom Rep Phys 47:265 6. Jayedevan B, Nakatani I (1999) J pean Advanced Course of UNESCO,
Magn Magn Mater 201:62 Minsk, April 1991
Progr Colloid Polym Sci (2001) 117: 136±140
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

I. Varga Characterisation of ionic surfactant

T. GilaÂnyi
R. MeÂszaÂros aggregates by means of activity
measurements of a trace probe electrolyte

Abstract On the basis of the Pois- new ®nding of the experimental part
son±Boltzmann cell model a new of this work is that the aggregation
trace probe electrolyte method was number depends only on the equi-
applied to determine the surfactant librium surfactant concentration and
aggregation number in Poly(ethylene is independent of the polymer con-
oxide)± Sodium dodecyl sulphate centration.
systems. It is demonstrated that
I. Varga (&) á T. GilaÂnyi á R. MeÂszaÂros activity measurements on a probe
Department of Colloid Chemistry, electrolyte added to a polymer/sur- Key words Polymer-surfactant
LoraÂnd EoÈtvoÈs University, factant solution in a trace amount complex á Aggregation number á
P.O. Box 32, 1518 Budapest 112, Hungary can be used for the determination of Poisson±Boltzmann theory á
e-mail: [email protected]
Tel.: 36-1-2090555 the mean aggregation number of the Poly(ethylene oxide) á Sodium
Fax.: 36-1-2090602 surfactant aggregates. An important dodecyl sulphate

Introduction The polymer±surfactant complex has been described

as a ``string of beads'' in which the polymer chain
The interaction of surfactants with macromolecules has connects micellelike surfactant aggregates by wrapping
been the subject of investigations since the early 1950s. around them [4]. This illustrative picture probably well
First, the protein±surfactant systems were investigated characterises the separated individual complex mole-
owing to their biological importance. Later, with the cules, for example, at low polymer concentration of long-
appearance of well-de®ned synthetic polymers the re- chain polymers with high degree of surfactant binding.
search was extended to the polymer±surfactant interac- For the description of the polymer±surfactant inter-
tion. Beyond their scienti®c interest, polymer±surfactant action several thermodynamic and molecular interaction
systems have received considerable attention because of models have been proposed [5±9]. A common feature of
their numerous industrial applications (e.g. in pharma- these models is that one of their central parameters is
ceutical and biomedical applications, oil recovery, food usually the surfactant aggregation number. The number
and mineral processing) [1±3]. of methods available for the determination of the
The binding of ionic surfactants to nonionic polymers surfactant aggregation number in the polymer±surfac-
is a cooperative process which starts at a well-de®ned tant complex is rather limited. In a few cases small-angle
concentration that is often called the critical aggregation neutron scattering measurements were used [10], while
concentration (cac). Below this concentration there is no recently mainly ¯uorescence probe methods have been
interaction between the surfactant and the polymer. applied for this purpose [11]; however, these techniques
Above the cac the surfactant starts to bind to the require quite special and expensive instrumentation,
polymer. With increasing amount of bound surfactant which makes their use rather limited.
the equilibrium surfactant concentration increases. When Recently, we have described a new trace probe
it reaches the critical micelle formation concentration electrolyte method that is suitable for the determination
(cmc) free micelles form and the equilibrium surfactant of the surfactant aggregation numbers [12]. In this
concentration becomes practically constant [3]. contribution we demonstrate the usefulness of this
 137

method by its application to the poly(ethylene oxide) The main lesson from Eq. (2) is that if a (polymer±
(PEO)/sodium dodecyl sulphate (NaDS) system. surfactant) solution contains macroions (y ¹ 0) then the
analytical concentration of the small ions cannot be
equal to their concentration in the equilibrium solution.
Experimental The traditional interpretation of this experience is based
Materials
on the counterion dissociation of the macroions:


The polymer investigated was PEO (Aldrich Mw ˆ 1.0 ´ 105 and c0B c0B ‡ aZcmac ˆ c2e ; 3†
Mw ˆ 1.0 ´ 106). The PEO solutions were puri®ed by mixed-bed
anion-cation exchange, by a similar method to that used in case of
latex dispersions [13] for the elimination of ionic contaminants. where ce refers to the concentration of the monomeric
This puri®cation was necessary in order to obtain well-reproducible surfactant, a is the degree of counterion dissociation and
results. Z and cmac are the total charge and the concentration of
The surfactant was NaDS (Merck) recrystallised twice from a the macroions, respectively. However, it can be shown
1:1 hot benzene±alcohol mixture. The cmc was found to be 8.2 mM
from conductometric measurements.
that the experimentally determinable apparent degree of
dissociation does not have the physical meaning that is
usually attributed to it [14].
Potentiometric measurements
The e€ect of a macroion on the distribution of an
The electromotive force (emf). values of the following two galvanic electrolyte is demonstrated in Fig. 1. In the absence of
cells were determined by means of a Radelkis research pH meter at macroions the electrolyte is distributed uniformly in the
25.0 ‹ 0.1  C: volume of the solution. When macroions are added to the
1. Cell 1: Na±glass| c NaDS, cp PEO |Au|Hg|HgIDS solution then the ions having similar charge are expelled
2. Cell 2: Na±glass| 10)4 M NaI, c NaDS, cp PEO|Ag|AgI from the close vicinity of the macroions. Owing to this
The emf values were converted into mean activities (aNaDS and exclusion e€ect the equilibrium concentration of these
aNaI) using the Nernst equation. NaI was chosen as a probe ions is increased. This concentration increase can also be
electrolyte, but this choice is not exclusive. The trace electrolyte viewed as if the free volume available for the electrolyte
should meet the following requirements: it does not bind specif-
ically (chemically) to the polymer or to the surfactant and
decreased. This is demonstrated by the square concen-
reversible electrodes are available to measure its mean activity. tration pro®le in the ®gure. Using the latter approach we
The binding on PEO was checked by emf measurements against the can de®ne the excluded volume of the system (V*):
polymer concentration at constant 10)4 M NaI concentration. The  
emf was constant within 0.5 mV, i.e. binding of the iodide ions to  c0B
PEO in the concentration range investigated cannot be detected. It V ˆ 1 V : 4†
cB;e
was checked experimentally that the iodide ion electrode was not
sensitive to the presence of the surfactant ions. In order to evaluate the integral in Eq. (2) the
``chemical'' structure of the system under consideration
Theory: trace probe electrolyte method must be speci®ed. For the sake of simplicity we assumed
that the aggregate distribution is statistically uniform in
The distribution of small ions in a solution is strongly the solution. Certainly, this assumption is ful®lled only in
in¯uenced by the presence of macroions. Consequently, special cases (e.g. when the polymer concentration is high
if we can ®nd an appropriate method for monitoring this enough). Our model and measurements were restricted to
in¯uence we can get information about the characteristic these cases.
features of the macroions. The addition of a probe Dividing the volume of the solution into electrically
electrolyte in a trace amount to a polymer±surfactant neutral equivalent spherical cells in such a manner that
solution can be such a method if there is no speci®c every cell contains a single aggregate and the appropriate
interaction between the probe electrolyte and the poly- amount of electrolyte [15, 16], the excluded volume of the
mer molecules. In this case the local distribution of the system can be expressed in the following form:
small ions can be given by the following equation: Z R
V 3
ˆ1 exp y†r2 dr ; 5†
cB x† ˆ cB;e exp y† ; 1† V R3 a 3 a
where y ˆ eY/kT is the reduced electric potential with a where R is the radius of the cell,
zero point chosen in a polyme-free equilibrium solution.  1=3
The analytical concentration of the small ions can be 3m
Rˆ ; 6†
given by the integration of their local concentration for 4pNA cmac
the volume of the solution: a is the core radius of a surfactant aggregate,
Z
1  
0
cB ˆ cB;e exp y†dV : 2† 3mV0 1=3
V aˆ ; 7†
V 4pNA
138

Fig. 2 Scheme of an osmotic and a nonosmotic membrane equilib-

rium to study the polymer±ionic surfactant solutions

radius of the surfactant aggregate. The polymer segment

density is assumed to be small and its e€ect on the ion
distribution is neglected. In the close vicinity of the core
this model is probably not correct, but fortunately the
integral in Eq. (5) is not sensitive to the inner electrical
structure of the aggregate.
The scheme of di€erent experimental arrangements
for the determination of the excluded volume of a
polymer±surfactant system is depicted in Fig. 1. One of
the cells (cell I) contains the polymer±surfactant solution
and a 1:1 probe electrolyte in a trace amount. Let us
suppose that cell I is in a nonosmotic membrane
equilibrium with cell II. This means that the temperature
and the pressure are equal in the two cells and the
membrane is permeable only for ions. The condition of
the thermodynamic equilibrium between the two cells is
the constancy of the electrochemical potential of the
mobile components. Since the pressure and the temper-
Fig. 1 The local distribution of small ions a in the absence and b in ature are equal in the two cells this condition reduces to
the presence of a macroion the equality of the mean activities of the surfactant
(ASurf) and the probe electrolyte (AB) in the cells:

V0 ˆ 212.4 cm3mol)1 [17] is the molar volume of the aIASurf ˆ aASurf;e ˆ cASurf;e cA;e cSurf;e †1=2 ; 9†
surfactant aggregates and m is the surfactant aggregation
number. The reduced electric potential, y(r), can be aIAB ˆ aAB;e ˆ cAB;e cA;e cB;e †1=2 ; 10†
computed from the Poisson±Boltzmann equation for
spherical symmetry and 1:1 electrolytes by means of the where c is the corresponding mean activity coecient and
following equation the indexes I and e refer to the polymer±surfactant
  solution in cell I and the equilibrium solution (cell II),
2 d 2 dy 2e2 cB;e respectively. Consequently, the emf measured either in
r r ˆ sinh y 8†
dr dr ekT the polymer±surfactant solution (cell I) or in its equilib-
rium solution (cell II) is the same:
using the boundary conditions y ˆ y0 at r ˆ a and
(dy/dr)R ˆ 0. This means that the surfactant aggregation kT  2 
E ˆ E0 ln cAB;e cA;e cB;e : 11†
number can be calculated if we determine the excluded e
volume of the system experimentally. Taking into account that cA,e ˆ cSurf,e+cB,e and
In the previous calculations the electrical structure of cSurf.ecB,e
the aggregate surface is approximated by the simplest
Gouy±Chapman model. The closest distance of ap- kT  2 
E ˆ E0 ln cAB;e cSurf;e cB;e : 12†
proach of the mobile ions to the surface is a, the core e
 139

If the surfactant concentration is below the cac the

ions are in single dispersed form and both the surfactant
and the probe ion concentration are the same in the
polymer±surfactant solution and in its equilibrium
solution, i.e. cB,e ˆ cIB and cSurf,e ˆ cISurf. Furthermore,
the equilibrium solution is a dilute electrolyte and
according to the Debye±HuÈckel theory at constant
temperature and Po its activity coecient depends only
on the ionic strength, which is cASurf,e in cell II since cB,e
is negligible. The change in cAB,e in the concentration
range between ccac and the cmc is usually negligible, so
the di€erence between the emf values measured at cASurf
and ccac can be given as
kT cB;e cSurf;e
E cASurf † E ccac † ˆ ln 0 : 13† Fig. 3 The relative excluded volume against the concentration of the
e cB ccac
aggregated surfactant for the poly(ethylene oxide) (PEO)±sodium
Following the determination of cSurf,e (e.g. by means dodecyl sulphate (NaDS) system
of galvanic cell 1), Eq. (13) can be used for the calcula-
tion of the quotient cB,e/c0B and consequently for the
determination of the excluded volume of the system. This qualitatively indicates that the surfactant aggregates
It is noted that the potentiometric method is only a in the polymer complex are smaller than the free micelles.
tool for the rapid determination of cI,e. The measure- With increasing complex concentration all the parame-
ments can be performed in a real Donnan equilibrium ters a€ecting V*/V tend to lower the excluded volume:
(between cells I and III in Fig. 1) by analysing the the ionic strength increases from 5 mM to the cmc and
composition (c¢Surf,e and c¢B,e) of the equilibrium solution the aggregation number and the interaction between the
and correcting the activities because of the pressure aggregates also increase.
di€erence between the two cells. The pressure correction For the free micelle formation the trace probe
on the activity is usually negligible and c¢B,e @ cB,e. electrolyte method yields m ˆ 57, which is in good
agreement with the aggregation number measured by
static light scattering [18].
Results and discussion The aggregation numbers calculated from the trace
probe electrolyte measurements for the PEO±NaDS
We made excluded-volume measurements in PEO± solutions are plotted against the equilibrium surfactant
NaDS solutions at several polymer concentration in the concentration in Fig. 4. The reproducibility is good: the
case of two di€erent molecular mass PEOs (1 ´ 105, m values fall into a narrow range (r ˆ ‹3), although they
1 ´ 106). were measured at several polymer concentrations of two
The relative excluded volume, V*/V, is plotted di€erent molecular weight polymers. From these mea-
against the concentration of the surfactant in complex surements the following statements can be made:
form (caggr ˆ cNaDS)ccac) in Fig. 3 at di€erent constant
± The aggregation numbers are signi®cantly smaller
polymer concentrations. V*/V depends on the number
than those of ordinary micelles.
and the size of the surfactant aggregates, the ionic
± The aggregation number increases monotonously with
strength of the solution and the interaction between the
the equilibrium surfactant concentration.
aggregates.
± Within experimental error the aggregation number is
In the case of ordinary micelle formation (cp ˆ 0) the
invariant to the polymer concentration and the poly-
ionic strength is approximately constant and for nonin-
mer molecular weight and depends only on the
teracting micelles with constant size V*/V should increase
equilibrium surfactant concentration (which is the
linearly with the complex concentration. In fact, the V*/V
ionic strength in these experiments performed without
function increases linearly at low micelle concentrations
addition of supporting electrolyte).
but declines from linearity at higher micelle concentra-
tions, which can be interpreted by an increase in the The dependence of the aggregation number on the
aggregation number and/or micelle±micelle interactions equilibrium surfactant concentration can be partly
because both lead to smaller excluded volumes at the explained by the well-known e€ect of the ionic strength
same micelle concentration. on the electrical free energy of the micelle formation [19].
In the presence of polymer the V*/V versus caggr The equilibrium surfactant concentration determines the
function is a saturation-type curve. The initial slope is ionic strength of the solution. cNaDS,e increases from the
signi®cantly higher than in the case of micelle formation. critical interaction concentration up to the cmc, while
140

for the more simple ordinary micelle formation because

the existing models are restricted for noninteracting
dilute micellar systems.
In the literature the aggregation numbers are usually
plotted against the total surfactant concentration, which
results in di€erent curves in the case of di€erent polymer
concentrations, implying the dependence of m on the
polymer concentration. In order to demonstrate that this
dependence is only an apparent one we collected the
NaDS aggregation numbers from the literature measured
in PEO±NaDS solutions [20, 21, 22]. In Fig. 4 we also
plotted these aggregation numbers against the equilibri-
um surfactant concentration. The equilibrium surfactant
concentrations were calculated from the total concen-
trations using the binding isotherms of the PEO±NaDS
system [23]. Although, these aggregation numbers were
measured over a very wide polymer and surfactant
concentration range they transformed practically to the
Fig. 4 The aggregation number of NaDS in a PEO complex against same curve that we measured by the trace probe
the equilibrium surfactant concentration. Solid symbols: trace probe
electrolyte method; M ˆ 1.0 ´ 105 ( ), M ˆ 1.0 ´ 106 (d). Open
electrolyte method.
symbols: Zana et al. [20] ( ), van Stam et al. [22] (h), Francois et al.
[21] (n)
Conclusion
the amount of the polymer-bound surfactant tends to
saturation. The electrical free energy of micelle formation Summarising our results it can be concluded that the
increases with increasing aggregation number and coun- activity measurements on a probe electrolyte added to a
teracts with the growth of the micelles. At higher ionic surfactant solution in a trace amount give a simple
strength the electrical free energy is smaller, leading to experimental method to estimate the mean aggregation
the formation of larger micelles. On the other hand, for number of the surfactant aggregates either in the form of
entropy reasons the increase in the equilibrium concen- a polymer±surfactant complex or in the form of free
tration in itself leads to the shift of the distribution curve micelles. An important new ®nding of the experimental
of the aggregation number to higher values, resulting in part of this work is that the aggregation number depends
larger mean aggregates. The third e€ect that may a€ect only on the equilibrium surfactant concentration and is
the aggregation number is the interaction between the independent of the polymer concentration.
aggregates. The equilibrium aggregate size is determined
by the free-energy minimum of the system and not that of Acknowledgement This work was supported by the Hungarian
a single aggregate. This e€ect has not been analysed even Scienti®c Research Fund (no. T029780).

References

1. Li Y, Dubin PL (1994) In: Herb CA, 8. Ruckenstein E, Huber G, Ho€mann H 17. Vass S, ToÈroÈk T, JaÂkli G, Berecz E
Prud'homme RK (eds) Structure and (1987) Langmuir 3:382 (1989) J Phys Chem 93:1758
¯ow in surfactant solutions. ACS sym- 9. Nikas YJ, Blankschtein D (1994) Lang- 18. Huisman HF (1964) Proc K Ned Akad
posium series 578. American Chemical muir 10:3512 Wet Ser B 57:407
Society, Washington, DC, pp 320±336 10. Cabane B, Duplessix R (1982) J Phys 19. Stigter D (1975) In: van Olphen H,
2. Goddard ED (1986) Colloids Surf 43:1529 Mysels KJ (eds) Physical chemistry:
19:255 11. Zana R (1986) In: Zana R (ed) Surfac- enriching topics from colloid and sur-
3. Goddard ED, Ananthapadmanabhan tant solutions. Surfactant science series, face science. Theorex, La Yolla, p 181
KP (1992) Interaction of surfactants vol 22. Dekker, New York, pp 241±294 20. Zana R, Lang J, Lianos P (1985) In:
with polymers and proteins. CRC, 12. Gilanyi T, Varga I (1998) Langmuir Dubin PL (ed) Microdomains in poly-
Boca Raton, 14:7397 mer solutions. Plenum, New York,
4. Nagarajan R, Kalpakci K (1982) 13. Vanderho€ JW (1980) Pure Appl p 357
Polym Prep Am Chem Soc Div Polym Chem 52:1263 21. Francois J, Dayantis J, Sabbadin J
Chem 23:41 14. GilaÂnyi T (1988) J Colloid Interface Sci (1985) Eur Polym J 21:165
5. Nagarajan R (1985) Colloid Surf 13:1 125:641 22. van Stam J, Almgren M, Lindblad C
6. Nagarajan R (1986) Adv Colloid In- 15. Gunnarson G, JoÈnsson B, Wen- (1991) Prog Colloid Polym Sci 84:13
terface Sci 26:205 nerstroÈm H (1980) J Phys Chem 23. GilaÂnyi T, Wolfram E (1985) In: Dubin
7. Nagarajan R (1989) J Chem Phys 84:3114 PL (ed) Microdomains in polymer
90:1980 16. Marcus RA (1955) J Chem Phys 23:1057 solutions. Plenum, New York, p 383
Progr Colloid Polym Sci (2001) 117: 141±144
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

T. GilaÂnyi Determination of binding isotherms of ionic

R. MeÂszaÂros
I. Varga surfactants in polymer gels

Abstract A thermodynamic analysis ments. A trace probe electrolyte

of the equilibrium of ionic surfactant method is suggested for the deter-
solutions with polymer solutions, mination of the binding isotherm of
polymer microgels and macrogels is the surfactant.
T. GilaÂnyi (&) á R. MeÂszaÂros á I. Varga given. It is concluded that the
Department of Colloid Chemistry,
LoraÂnd EoÈtvoÈs University, P.O. Box 32, amount of surfactant bound to the
1518 Budapest 112, Hungary polymer cannot be calculated exactly Key words Binding isotherm á
e-mail: [email protected] from the total and equilibrium sur- Surfactant á Microgel á
Tel.: +36-1-2090555 factant concentration measure- Macrogel á Thermodynamics
Fax: +36-1-2090602

Introduction Concerning the interaction between surfactants and

polymer gels one of the most important pieces of
Surfactants associate into micelles above a critical thermodynamic information is the binding isotherm of
micelle concentration (cmc) in aqueous solution. In the surfactant on the gel. On one hand, this function is
the presence of water-soluble polymers polymer±sur- necessary to the correct evaluation of several physico-
factant complexes form in which surfactant aggregates chemical and scattering measurements. On the other
are distributed along the polymer chains [1±3]. The hand, the isotherm itself provides basic information
main driving force of the surfactant aggregation, about the way of binding (e.g. monomer binding or
known as the ``hydrophobic e€ect'', is the transfer of micelle-like collective interaction) and the standard free-
the surfactant hydrocarbon chain from water into the energy change of the interaction.
micelle-like aggregate core. One of the manifestations Surfactant binding measurements on gels are rare and
of the polymer±surfactant interaction is the interaction the results are contradictory [5]. Abuin et al. [6] studied
of surfactants with polymer gels. In principle, concep- the interaction between sodium dodecyl sulphate (NaDS)
tual di€erences cannot be expected in the polymer± and poly(N-isopropylacrylamide) (PNIPAM) microgel
surfactant interaction; either the polymer is free or it is particles. Surface tension measurements indicated that
in a loosely cross-linked gel. the interaction was similar to that of the surfactant with
Several studies have been reported in the last decade free polymer. The interaction starts from a critical
on stimuli-responsive hydrogels, which can change their surfactant concentration (cac1 » 1 mM) and above a
swelling and shrinking in response to external stimuli. second critical concentration (cac2) there is no further
The discovery of a discontinuous volume-phase transi- surfactant binding, as is the general experience in the case
tion in gels, which is often called a collapse transition, of surfactant±(free) polymer interaction [1, 2]. Mylonas
has rendered such soft materials technologically useful at al. [7] determined the binding of NaDS on PNIPAM
[4]. The stimuli that have been investigated to induce polymer by equilibrium dialysis method. They esti-
changes in polymer gels are diverse and they include mated a cac1 value that was similar to the one found
temperature, pH, solvent and ionic composition, elec- previously in case of PNIPAM microgel. Mears at al. [5]
tric ®eld, light intensity and speci®c molecules such as determined the binding of NaDS in PNIPAM microgel
surfactants. particles by separating the equilibrium surfactant
142

solution by centrifugation. They did not observe a well- bound surfactants and ``free'' micelles) in the microgel
de®ned cac; however, the bound amount increased latex can be given as
sharply above 3 mM equilibrium NaDS concentration.
A further increase in binding was experienced when co V ˆ hSi ‡ cmic †C ‡ Bcp V 1†
the equilibrium surfactant concentration exceeded the or by treating the latex as a two-phase system as
cmc.
The discrepancies in these investigations have di€er- co V ˆ hSig ‡ cmic;g †Vg ‡ hSis ‡ cmic;s †Vs ‡ Bcp V ; 2†
ent reasons. There may be a di€erence in the interaction
if the polymer is in the form of free coils, macrogel or where the subscripts g and s refer to the gel and solution
microgel latex particles. The di€erences in the sample phase, respectively, co is the total (analytical) surfactant
preparation, for example, the degree of cross-linking and concentration, hSi is the volume-average free surfactant
the type of the cross-linking monomer may play a role as monomer concentration, V is the volume of the system,
well. A sound basis for the evaluation of the di€erent cmic is the concentration of the surfactant micelles, cp is
experimental methods used to calculate the surfactant the polymer concentration (mass/volume) and B is the
binding isotherm is also lacking. The general route of number of moles of bound surfactant per unit mass of
calculating the amount of bound surfactant as a di€er- polymer.
ence of the total and equilibrium surfactant concentra- Equation (2) can also be applied for a macrogel
tion seems to be trivial but, as will be shown in this work, (Vs ˆ 0, V ˆ Vg) and for a polymer solution (Vg ˆ 0,
is erroneous. V ˆ Vs). Independently of the model investigated (mac-
In order to investigate the role of the previously rogel, microgel latex or polymer solution) we are facing
mentioned parameters in the interaction systematically, the same problem: Eq. (1) or Eq. (2) de®nes the amount
the ®rst step is the de®nition of the binding isotherm and of bound surfactant, B, but the quantities in brackets,
the determination of an exact way to calculate it from hSi, cannot be measured directly. The experimentally
experiments. In this work an analysis is given to explore available quantities are the mean surfactant activity in
the relation of the amount of bound surfactant to the the microgel latex (a‹) and either the mean surfactant
measurable quantities. activity (a‹e) or the surfactant concentration (c) in the
gel (polymer)-free solution which is in equilibrium with
the latex. The scheme of the system investigated is given
Binding isotherm in Fig. 1a. In the following we discuss the relation
between B and the measurable quantities.
The mass balance of the surfactant distributed in The thermodynamic condition of the equilibrium
di€erent molecular forms (as free monomers, polymer- in the system concerned is the constancy of the

Fig. 1 Scheme of the microgel

latex±ionic surfactant system in
equilibrium with a polymer-free
reference solution. The solid
spheres represent the surfactant
aggregates bound in the micro-
gel particles and the c(x) func-
tion denotes the local
concentration of the free sur-
factant ions
 143

electrochemical potential of the surfactant ion, (^

l ), ae ˆ ce c‡ c †1=2  ce ; 8†
throughout the system:
where the symbols refer to the polymer-free surfactant
l^ ˆ l ‡ ez w ; 3†
solution in equilibrium with the gel±surfactant±solvent
where l) is the chemical potential of the surfactant ion system. c+ and c) are the concentration of the surfactant
with valency z) and Y is the electrical potential. For the monomer and its counterion, respectively. By neglecting
sake of simplicity, systems containing a 1:1 surfactant the small ion interactions for dilute surfactant solutions
electrolyte without added foreign salt will be discussed (c‹e » 1) and by taking into account that c+ ˆ c) ˆ ce
here. In order to eliminate the electrical potential from the mean activity of the surfactant electrolyte can be
Eq. (3) the mean chemical potential of the surfactant approximated by ce, called the equilibrium monomer
electrolyte can be given as l ˆ l^‡ ‡ l^ †=2. The concentration (a‹e » ce). Note that ce is not the total
equilibrium condition of the system is the invariance of surfactant concentration of the equilibrium solution; it is
the mean chemical potential in the gel phase (l‹g), in the the surfactant monomer concentration. This is important
solution phase (l‹s) and in the gel-free equilibrium if the equilibrium concentration (c) exceeds the cmc and
solution (l‹e). As an alternative view we can consider micelles form. In this concentration range c ˆ ce+cmic »
the microgel solution as a one-phase system. In this case cmc+cmic.
the equilibrium is determined by the constancy of the By taking into account only the electrostatic interac-
mean chemical potential in the latex phase (l‹) and in tions the relation between hSi and ce can be formally
the gel-free equilibrium solution (l‹e). The mean expressed in case of a 1:1 surfactant electrolyte as
chemical potential of the surfactant electrolyte in the Z
latex can be expressed as ce
hSi ˆ 0 e y dV 0 ˆ ce he y i ; 9†
V
l ˆ lo ‡ KT ln a latex† ; 4† V

where lo is the standard-state chemical potential de®ned where y ˆ ew/kT is the reduced electrical potential with a
at temperature T and pressure p. If we assume that owing reference potential chosen as w ˆ 0 at the polymer-free
to the very low segment density in the polymer-contain- reference system and V¢ is the volume of the system
ing phases (latex, gel) the segment density dependence of concerned. y and the surfactant monomer concentration
the standard potential can be neglected and we suppose are local functions of the space coordinates as depicted
that the partial molar volume of the surfactant electro- schematically in Fig. 1. The concentration of the surfac-
lyte (V ) does not depend on the pressure then the mean tant anions is lower than ce around the negatively
chemical potential of the solution, gel and equilibrium charged micelles and polymer-bound surfactant aggre-
phases can be given in the following forms: gates; consequently, he yi may be signi®cantly smaller
ls ˆ lo ‡ kT ln as solution phase† ; 5† than unity. By rewriting Eqs. (1) and (2) by means of
Eq. (9) one obtains
lg ˆ lo ‡ pg p†V ‡ kT ln ag gel phase† ; 6†
co ˆ fhe y ig U ‡ he y is 1 U†gce ‡ cmic;g U
le ˆ lo ‡ pe p†V ‡ cmic;s 1 U† ‡ Bcp ; 10†
‡ kT ln ae equilibrium solution† ; 7†
where F is the volume fraction of the gel phase.
where a‹ is the mean activity of the surfactant electrolyte The binding isotherm is de®ned by the B(ce) function.
and p is the pressure in the appropriate phases. It can be As a route B is generally calculated from the relation
shown that the pressure term is negligible compared to [5±8]
the activity term in Eq. (7) if the pressure di€erence
between the latex and its equilibrium solution is small c0 c
Bˆ ; 11†
enough (e.g. less than 1 atm). The contribution of the cp
pressure di€erence to the chemical potential in Eq. (6) is
and plotted against c, the total equilibrium surfactant
also neglected although it is questionable that the
concentration.
pressure di€erence between the gel phase and its
By comparing Eq. (11) to Eq. (10) it can be stated that
environmental solution is suciently small in the case
of strongly interacting polyelectrolyte type gels. 1. If c>cmc, the calculated B is not the amount of the
If it is justi®ed to neglect the terms just discussed the surfactant bound.
equilibrium condition reduces to the constancy of the 2. Plotting B against c has no thermodynamic signi®-
mean surfactant activity in the di€erent phases: cance above the cmc because c ¹ ce.
a‹ ˆ a‹s @ a‹g @ a‹e. This means that in an equilibri- 3. The calculated B values can be accepted as an
um we may express the mean surfactant activity by approximation if c<cmc when c » ce (the error in B
means of the polymer-free reference solution changes with the volume fraction of the gel and with
144

the amount of bound surfactant via the value of the ce c

hS i ˆ hTri : 12†
he yi term). ce;Tr
The concentration of the equilibrium solution can be In the right-hand side of Eq. (12) all the quantities are
determined by analysing the supernatant solution sepa- determinable experimentally. Further details of the
rated from the microgel particles by ultra®ltration and application of the trace probe electrolyte method are
ultracentrifugation [5], assuming that the separation does given in Refs. [10, 11]. Another possibility to calculate B
not in¯uence the equilibrium concentration, or by the from Eq. (10) is to perform the measurements in the
equilibrium dialysis method [7]. The separation of the presence of a large amount of inert electrolyte when
microgel particles from a polymer-free equilibrium he yi » 1; however, in this case the system investigated is
solution is not necessary. Potentiometric measurements di€erent from the salt-free one because the salt may
with two reversible electrodes for the surfactant ion and in¯uence the interaction between the polymer and
its counterion yield directly the mean surfactant activity surfactant.
or ce independently of the concentration range investi- The previous discussion considers the interaction of
gated. However, it is important to note that a surfactant- an ionic surfactant with electrically neutral gels (poly-
sensitive electrode [8] cannot be applied against a mers). In case of polyelectrolyte solutions or polyelec-
reference electrode connected via a salt bridge because trolyte gels an ion-exchange process must also be taken
of the development of an anomalous di€usion potential into account. In these cases the determination of the
(the so-called suspension potential [9]) in the presence of binding isotherms requires further analysis. It should
colloid electrolytes, which is the case concerned here. also be stressed that in Eq. (9) only electrostatic inter-
In order to determine the correct binding isotherm the actions were taken into account; however, the surfactant
he yi term in Eq. (8) must be determined from indepen- ions may be excluded from the vicinity of the polymer
dent measurements. Recently, we suggested a method for chain owing to nonelectrostatic interactions (e.g. because
the determination of he yi. This method is based on the of the preferential sorption of water). This exclusion
activity measurements of a foreign electrolyte added to theoretically leads to negative B values (negative surfac-
the system in a trace amount. The probe electrolyte tant adsorption) at low surfactant concentrations if the
should meet the following requirements: it does not bind surfactant does not bind speci®cally to the polymer.
speci®cally to the polymer or to the surfactant and its Negative surfactant binding (i.e. exclusion of the surfac-
concentration is negligible compared to that of the tant) was measured below the critical interaction con-
surfactant. If we write an equation analogous to Eq. (9) centration for poly(vinyl alcohol) macrogel and alkyl
for the anion of an added 1:1 trace electrolyte sulfate systems [12].
[hTri ˆ ce,Trhe yi, where hTri and ce,Tr are the total
(analytical) and the equilibrium concentrations of the Acknowledgement This work was supported by the Hungarian
trace anion, respectively] then the he yi term can be Scienti®c Research Fund (no. T029780).
eliminated from Eq. (9):

References

1. Goddard ED (1986) Colloids Surf 4. Gandhi MV, Thomson BS (1992) 8. Okuzaki H, Osada Y (1991) Macro-
19:255 Smart materials and structures. Chap- molecules 28:4554
2. Goddard ED, Ananthapadmanabham man and Hall, London 9. Overbeek JTG (1956) Prog Biophys
KP (1992) Interaction of surfactants 5. Mears SJ, Deng Y, Cosgrove T, Pelton Biophys Chem 6:58
with polymers and proteins. CRC, R (1997) Langmuir 13:1901 10. Gilanyi T, Varga I (1998) Langmuir
Boca Raton 6. Abuin E, Leon A, Lissi E, Varas JM 14:7397
3. Nagarajan R, Kalpakci (1982) Polym (1999) Colloids Surf 147:55 11. Varga I, Gilanyi T, Meszaros R (2000)
Prep Am Chem Soc Div Polym Chem 7. Mylonas Y, Staikos G, Lianos P (1999) Prog Colloid Interface Sci 117
23:41 Langmuir 15:7172 12. Kralova K (1970) Thesis. LoraÂnd
EoÈtvoÈs University, Budapest
Progr Colloid Polym Sci (2001) 117: 145±152
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

AÂ. CsiszaÂr Changes in the thermotropic

A. BoÂta
C. NovaÂk and the structural behaviour
E. Klumpp
G. Subklew of 1,2-dipalmitoyl-sn-glycero-3-
phosphatidylcholine/water liposomes
effected by 2,4-dichlorphenol

Abstract Toxic 2,4-dichlorophenol changes in the ®rst Bragg pro®les of

(DCP) molecules, originating from the SAXS curves depend not only on
the environment, drastically a€ect the temperature but also very
the main functions of organic cell strongly on the DCP/DPPC molar
membranes. To yield some infor- ratios. Especially, at higher concen-
mation on the destroyed membrane trations DCP causes a strong
structures, 1,2-dipalmitoyl-sn- broadening in the Bragg pro®les and
glycero-3-phosphatidylcholine a di€erence from the pro®les of the
(DPPC)/water liposome systems nonrippled phase. The general de-
containing di€erent amounts of struction in the layer arrangements
DCP were studied by di€erential and the reductions in the transition
scanning calorimetry and small-an- enthalpies between them indicate
gle X-ray scattering (SAXS) meth- defect structures consisting of do-
AÂ. CsiszaÂr á A. BoÂta (&) á C. NovaÂk ods. The transition points of the mains with nonlayer structure which
Department of Physical Chemistry,
Department of General main transition and its enthalpy are are formed simultaneously by DCP
and Analytical Chemistry, changed only in a relatively narrow molecules.
Budapest University of Technology range of about 0±2.5%, while the
and Economics, MuÈegyetem rkp 3. 1111 enthalpy of the pretransition is af-
Budapest, Hungary
e-mail: [email protected] fected by DCP more strongly. The Key words Liposome á
disappearance of the pretransition Multilamellar structure á Phase
E. Klumpp á G. Subklew occurs in a range of about 3 orders transition á Di€erential
Institute of Applied Physical Chemistry,
Research Centre JuÈlich, 52428 JuÈlich, of magnitude of the DCP/DPPC scanning calorimetry á
Germany ratio (from 10)5 to 10)2). The Small-angle X-ray di€raction

Introduction shells. The lamellar arrangement is the main structural

feature of liposomes. Moreover, within the hydrocarbon
1,2-Dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC) region of the shells the chain packing is also varied and
is one of the most common phospholipid components in di€erent subcells are formed. On increasing the temper-
biological membranes [1]. On dispersing this molecule in ature, di€erent multilamellar phases are formed: a
water, concentric onion-like shells of alternating water crystalline phase, Lc; a nonrippled gel phase, Lb¢; a
and lipid±bilayer regions form spontaneously as unila- rippled gel phase, Pb¢; and a liquid-crystalline phase, La.
mellar or multilamellar vesicles (liposomes); therefore, These four parent phases consist of regular multilamellar
DPPC is widely applied for the preparation of vesicles structures with periodicities of 59, 64, 70, and 67 AÊ, for
which are considered as model systems of membranes in the Lc, Lb¢, Pb¢, and La phases, respectively as measured
living cells. DPPC liposomes exhibit at least four by small-angle X-ray scattering (SAXS). These structures
di€erent multilamellar structures in excess water, de- are depicted schematically in Fig. 1. Accordingly, there
pending on the temperature [2±5]. These structures are are three phase transitions: the subtransition (Lc±Lb¢) at
characterized by speci®c lattice parameters of periodical Tm1(about 18 °C), the pretransition (Lb¢,±Pb¢,) at Tm2
146

di€erential scanning calorimetry (DSC) and SAXS

measurements in DPPC/water liposome systems con-
taining di€erent amounts of DCP. Calorimetric data
(e.g. the change in the transition enthalpy, the temper-
ature range of the transition) are fundamental to
characterize the system and to distinguish between the
di€erent states related to the di€erent phases [12, 13].
The changes in the calorimetric data compared to those
of the pure system also indicate changes in the structure.
As the periodicity of the lamellar arrangement of
liposomes falls between 60 and 70 AÊ, SAXS is very
powerful for the study of this structure [14, 15]. The
periodic, unoriented liposomes show radially symmetric
SAXS patterns, which are detected in one-dimensional
forms and are presented as the scattering intensity as a
function of the scattering variable. The incorporation of
DCP into the double layers can be proved by means of
¯uorescence spectroscopy. For steady-state measure-
ments pyrene is widely used as a ¯uorescence label in
studies of vesicle systems [16, 17]. Using these methods,
we have concentrated on the changes in the thermotropic
behaviour and on the destruction of the layer arrange-
ment of the gel and liquid phases of the liposome systems.

Experimental
Materials and preparation

Synthetic L-a-dipalmitoylphosphatydilcholine (DPPC, purity high-

er than 99%) was purchased from Avanti Polar Lipids (Alabaster,
Ala, USA) and was used without further puri®cation. Deionized,
Fig. 1 Layer structures of the fully hydrated 1,2-dipalmitoyl-sn- triple-quartz-distilled water was added to the dry lipid powder
glycero-3-phosphatidylcholine (DPPC)/water liposomes as a function under a nitrogen gas atmosphere to yield a lipid concentration of
of temperature 30 w/w%. The mixture was kept at 50 °C for about 10 h and
vortexed frequently. After incubation the sample was quenched to
(about 33 °C), and the main transition (Pb¢±La) at Tm3 4 °C, then reheated to 50 °C again and vortexed intensively. The
(about 41 °C). The enthalpy changes accompanying the process was repeated ten times to achieve homogeneous hydration.
three transitions are about 14.2, 5.6, and 32.2 kJ/mol The sample was stored at 40 °C. The preparation of the systems
lipid, respectively. The value of the pretransition enth- consisting of DCP was the same, only DCP solutions with di€erent
concentrations were used instead of pure water. The half value of
alpy is signi®cantly smaller than the other two e€ects the solubility of DCP was chosen as the maximal DCP concentra-
observed for the subtranstion and the main transition. tion, which yielded a molar ratio of 0.04 (DCP/DPPC). The DCP
During the pretransition, ¯uctuations and correlation concentration was varied in a range of 3 orders of magnitude of the
distances increase signi®cantly in the whole system and molar ratio down to 4 ´ 10)5. For ¯uorescence spectroscopy, the
samples were diluted to about 0.1 w/w% by water. The incorpo-
defect structures can be formed [6, 7]; therefore the e€ect ration of DCP into the vesicle bilayers was veri®ed by ¯uorescence
of impurities becomes very strong. The e€ect of each spectroscopy, but the distribution ratios of DCP between the
molecule, the molecules being known to be toxic, can be liposomes and the excess water were not measured. Therefore the
especially drastic. The toxic molecules can induce molar ratios of DCP referred to DPPC are expressed for the whole
aqueous systems and not only for the bilayer regions.
nonlamellar local structures [8±10]. If the temperature
of the organism falls into the transitional region of the
lipid domains of the membrane, the transport properties Methods
can be drastically changed; therefore, studies on the The DSC measurements were made with a TA Instruments
transitional states of the model system are expected to DSC 2920 instrument. The scan rate was 1 °C/min and the
have considerable relevance in biology. Toxic 2,4- reproducibility of the measurements of the temperature values
dichlorophenol (DCP) molecules, originating from the was within ‹0.005 °C. The DSC curves were recorded in the
heating direction in all cases and they are presented in w/g unit.
environment, drastically a€ect the main functions of The SAXS measurements were performed using a Kratky
organic cell membranes [11]. To yield some information camera and a proportional counter (Anton Paar, Graz, Austria).
on the destroyed membrane structures we performed The scattering of Ni-®ltered Cu Ka radiation (k ˆ 1.542 AÊ) was
 147

recorded in the 6 ´ 10)3±0.6 1/nm range of the scattering variable, subtranstion, pretransition, and main transition, as can
de®ned as h ˆ (4p sin h)/k, where 2h is the scattering. The primary be seen in Fig. 2. The explanation of the characteristic
beam was line-focused. The intensity curves were corrected
considering the geometry of the beam pro®le in order to obtain data (transition enthalpy, transition point, Tm, beginning
point-focused curves. For X-ray measurements the lipid dispersion point of the transition, i.e. onset temperature, Tos) is
was transferred into thin-walled quartz capillaries (Hilgenberg, presented in Fig. 2b. It is noteworthy that the subtran-
Germany) with a diameter of 1 mm. In order to remove air bubbles sition can be detected in the ®rst scan and only when the
the capillaries were centrifuged for 5 min at 500g at room
temperature. The capillaries were sealed with a two-component
sample has been kept for several hours below 4 °C. The
synthetic resin and transferred into metal capillary holders placed two other transitions were reversible when the DSC
into an aluminium block. This block was positioned directly into measurements were carried out in the temperature range
the beamline and was used as a thermal gradient incubator for from 4 to 50 °C and were repeated in this temperature
controlled annealing at di€erent temperatures around the pretran- range. DCP causes changes in the thermograms over a
sition.
The ¯uorescence spectra were recorded using a luminescence wide concentration range. The dimensions of the changes
spectrometer (PerkinElmer, LS 50, UK). The ¯uorescence activity of the transition signals are very di€erent; therefore, the
was measured on pyrene molecules added to the systems using DSC curves related to the main transition, the pretran-
10)3 mol/mol pyrene/DPPC ratios. The pyrene was weighed into sition and the subtransition are presented separately in
the empty ¯uorescence capillary as a solution in chloroform, then it
was dried and ®nally the liposome system was added. After 1-h Figs. 3, 4, and 5. The main transition can be observed for
incubation, the ¯uorescence activity was maximal and nearly the entire concentration range over 3 orders of magni-
constant for 6 h at the reference temperature (26 °C). The pyrene tude of the DCP and are found not to be a€ected strongly
molecules are solubilised in the chain region of the double layers by the actual concentration. The transition point is
and are sensitive to all changes which are in progress in the lipid
region.
shifted to lower temperature values for higher DCP
concentrations only, as can be seen in Fig. 3. The
transition enthalpy decreases slightly as the DCP ratio
Results increases. The characteristic parameters of the main
transition are summarized in Table 1. The pretransition
Thermal behaviour of the systems

The pure, fully hydrated DPPC/water system shows

three transitions in the DSC curves, which are the

Fig. 2 a Typical di€erential scanning calorimetry (DSC) curves of Fig. 3 DSC curves of the main transition in the pure and in the 2,4-
fully hydrated DPPC/water liposomes in the temperature range from dichlorophenol (DCP) loaded DPPC/water systems. The concentra-
4 to 50 °C. b The characteristic temperature data (transition point, tion of DCP is expressed as the molar ratios of DCP related to DPPC
Tm, beginning point of the transition, i.e., onset temperature, Tos) and is marked on each curve
148

Fig. 4 DSC curves of the pretransition in the pure and in the DCP-
loaded DPPC/water systems. The concentration of DCP is expressed Fig. 5 DSC curves of the subtransition in the pure and in the DCP-
as the molar ratios of DCP related to DPPC and is marked on each loaded DPPC/water systems. The concentration of DCP is expressed
curve as the molar ratios of DCP related to DPPC and is marked to each
curve
is much more strongly a€ected by DCP than the main
transition, especially in the higher DCP molar ratio Table 1 The characteristic parameters of the main transition.
1,2-Dipalmitoyl-sn-glycero-3-phosphatidylcholine (DPPC), 2,4-
regime. The pretransition point is higher in the presence dichlorophenol (DCP)
of the smallest DCP quantity applied than that measured
in the pure DPPC/water system. At a DCP/DPPC molar DCP/DPPC Tos (°C) ‹0.1 Tm (°C) ‹0.1 DH (kJ/mol
ratio of 4 ´ 10)3 the same pretransition point can be (mol/mol) lipid) ‹0.5
observed as in the pure system. Above this ratio, the
Pure DPPC 40.7 41.3 32.2
higher the DCP/DPPC molar ratio, the stronger the 4 ´ 10)5 40.6 41.6 30.5
e€ect of DCP on the calorimetric data. At a DCP/DPPC 4 ´ 10)4 40.6 41.3 30.1
molar ratio of 0.04 the pretransition cannot be identi®ed 4 ´ 10)3 40.5 41.2 30.9
at all. The calorimetric data for the pretransition are 2 ´ 10)2 39.6 40.9 31.8
summarized in Table 2. The subtransition is a€ected by 4 ´ 10)2 38.7 40.3 30.5
DCP, but not strongly, similarly to the case of the main
transition, as can be observed in Fig. 5. The transition relatively narrow range of about 0±2.5%, while the
point is shifted to lower temperature values as a function enthalpy of the pretransition is a€ected by DCP more
of the DCP/DPPC ratio, while the changes in the strongly. The changes in enthalpy related to the pure
enthalpy are not monotonous. The calorimetric data system are demonstrated as a function of the DCP/
for the subtransition are shown in Table 3. DPPC ratio in Fig. 6. This ®gure shows that the
The calorimetric data for the pure system are in good disappearance of the pretransition occurs over a range
agreement with the values published in the literature. of about 3 orders of magnitude of the DCP/DPPC ratio
Having the biological relevance in sight, we focused on (from 10)5 to 10)2). The relative changes in the transition
the changes in the pretransition and the main transition. points extend to about 10% in the case of the pretran-
It may be concluded that the transition points of the sition and are more drastic than those observed for the
main transition and its enthalpy are changed only in a main transition as can be seen in Fig. 7. It must be
 149

Table 2 The characteristic parameters of the pretransition mentioned that the measurement of the calorimetric data
of the pretransition is questionable at the highest DCP
DCP/DPPC Tos (°C) ‹0.2 Tp (°C) ‹0.1 DH (kJ/mol
(mol/mol) lipid) ‹0.5 concentration, as the base line of the curves is uncertain.

Pure DPPC 33.0 34.8 5.6

4 ´ 10)5 33.7 35.5 5.3 SAXS studies on the layer structure
4 ´ 10)4 33.3 35.1 4.0
4 ´ 10)3 33.2 34.7 2.8
2 ´ 10)2 29.6 32.0 0.8 Study of the parent phases
4 ´ 10)2 ± ± ±

The scattering curves (the intensity as a function of the

absolute value of the scattering variable) exhibit more-
Table 3 The characteristic parameters of the subtransition
or-less sharp small-angle di€raction peaks, indicating
DCP/DPPC Tos (°C) ‹0.2 Ts (°C) ‹0.2 DH (kJ/mol long-range correlation between the lamellae. The refer-
(mol/mol) lipid)‹0.5 ence parent phases, for example, the gel and liquid phases
show characteristic small-angle X-ray di€raction pat-
Pure DPPC 15.8 19.10 14.2 terns corresponding to the regular lamellar arrangements
4 ´ 10)5 17.0 19.78 13.8
4 ´ 10)4 17.3 19.66 11.7 of the DPPC/water liposomes investigated. The e€ect of
4 ´ 10)3 17.6 20.30 15.5 the DCP concentration was studied at 26, 38, and 44 °C,
2 ´ 10)2 17.7 22.60 14.6 i.e., in the temperature domains of the nonrippled gel
4 ´ 10)2 17.2 21.25 14.6 (Lb¢), the rippled gel (Pb¢), and the liquid-crystalline (La)
phases, respectively. The Bragg pro®les of the reference
and perturbed states measured at 26 °C can be observed
in Fig. 8.
Samples which contain DCP in small quantities
(DCP/DPPC molar ratios of 4 ´ 10)5 and 4 ´ 10)4)
exhibit higher and sharper Bragg maxima than the pure
system. In the higher molar-ratio range (between
4 ´ 10)3 and 4 ´ 10)2) drastic changes in the Bragg
pro®les can be observed. In this range the Bragg
maximum diminishes signi®cantly and the positions of
the Bragg maxima shift from s ˆ 0.0159 to s ˆ 0.0141 1/AÊ
The lamellar structure related to the 2 ´ 10)2 molar ratio
has a higher periodic distance than the regular Lb¢ phase;
moreover, the other lamellar structure related to the
4 ´ 10)2 molar ratio exhibits a slightly larger periodic

Fig. 6 Relative changes of the transition enthalpies in the pretransi-

tion and the main transition

Fig. 8 First Bragg pro®le of the small-angle X-ray scattering (SAXS)

curve detected in the pure and in the DCP-loaded DPPC/water
Fig. 7 Relative shifts of the transition points in the pretransition and systems at 26 °C. (pure: solid line; 4 ´ 10)5: squares; 4 ´ 10)4:
the main transition triangles; 4 ´ 10)3: circles; 2 ´ 10)2: crosses; 4 ´ 10)2: rhomboids)
150

distance than the Pb¢ phase. Considering the calorimetric Figs. 9 and 10. In the SAXS patterns detected at 38 and
data, as no transition occurs between the subtransition 44 °C the e€ect of the DCP concentration is similar; this
and the main transition regions in the systems loaded means that only the maximum of the Bragg peaks is
with the highest DCP concentration, these shifts in Bragg reduced, except for the system having a DCP molar ratio
re¯ections cannot be interpreted as the appearance of the of 4 ´ 10)2. The latter system exhibits an average
Pb¢ phase, but rather as the direct e€ect of the high DCP periodic distance of about 66.8 AÊ instead of 63.4 AÊ in
concentration on the layer structure. The broadening of the temperature domains of the Lb¢ and Pb¢ phases and
these Bragg pro®les is enormous, indicating a drastic loss shifts to the value of 61.8 AÊ instead of 66.7 AÊ in the
in the layer regularity in the systems. temperature domain of the Lb¢ phase.
The Bragg pro®les observed at 38 and 44 °C exhibit
the same shape and their maxima are located at
s ˆ 0.0144 and s ˆ 0.0150 1/AÊ, corresponding to the Studies in the pretransition range
characteristic periodic distances of the rippled gel and
liquid-crystalline phases, respectively, as can be seen in The pretransition was strongly a€ected by DCP; there-
fore, the states of this transition were studied closely. The
SAXS curves of the transitional states were recorded over
a wide temperature range from 28 to 38 °C with a step
width of 2 °C. The changes in the ®rst Bragg pro®les
depend not only on the temperature but also very
strongly on the DCP/DPPC molar ratios. Especially,
higher DCP concentrations caused a strong broadening
in the Bragg pro®les and a di€erence from the pro®les of
the parent (nonrippled and rippled) phases. The charac-
teristic changes induced by DCP can be expressed by a
control parameter. The reciprocal value of the full width
at half maximum (FWHM) was de®ned as a control
parameter. The reciprocal value of FWHM (n) recorded
for the ®rst Bragg pro®le in the Lb¢ phase of the pure
system at 28 °C was used for the normalization of the
other cases. This parameter indicates that the Lb¢ phase
has a higher degree of order than the Pb¢ phase because
the latter has a signi®cantly wider ®rst Bragg pro®le. A
Fig. 9 First Bragg pro®le of the SAXS curve detected in the pure and multilamellar system with no regular layer correlation
in the DCP-loaded DPPC/water systems at 38 °C. (pure: solid line; would have a control parameter of n ˆ 0. It must be
4 ´ 10)5: squares; 4 ´ 10)4: triangles; 4 ´ 10)3: circles; 2 ´ 10)2: pointed out that this parameterisation serves only to
crosses)
quantify the di€erences of the Bragg pro®les of the SAXS
curves and should not be taken as a physical de®nition of
the order parameter. The n versus T functions are shown
in Fig. 11. The changes in the control parameter
demonstrate the di€erent regularities of the lamellar
packing in the parent phases and thereby re¯ect the e€ect
of DCP concentration. The local minimum of the n(T)
functions indicates temperature values which are close to
the transition points in the three systems investigated
(pure and systems with DCP at molar ratios of 4 ´ 10)3
and 2 ´ 10)2). It can be seen that the pretransition is in
progress in the temperature domain from about 31 to
36 °C in the pure system. The characteristic di€erence
between the gel and rippled gel phases expressed by the
di€erence in the n values at the lower and higher
temperature ranges (28±30 °C and 36±38 °C, respective-
ly) was diminished at a DCP/DPPC molar ratio of 10)3
and turned into the opposite direction at the highest DCP
Fig. 10 First Bragg pro®le of the SAXS curve detected in the pure
and in the DCP-loaded DPPC/water systems at 46 °C. (pure: solid concentration. In the latter case the change in the control
line; 4 ´ 10)5: squares; 4 ´ 10)4: triangles; 4 ´ 10)3: circles; 2 ´ 10)2: parameter also indicates that the pretransition ceases to
crosses) exist in this DPC concentration domain.
 151

Fig. 12 Change in the intensity ratio of the ®rst and the third peak, I1
(at 383 nm)/I3 (at 394 nm) during the pretransition observed in the
Fig. 11 Change of the control parameter in the pretransition range
¯uorescence emission spectra of pyrene
(pure: solid line; 4 ´ 10)3: triangles; 2 ´ 10)2: squares)

nonrippled phase being more rigid than the rippled

Fluorescence spectroscopy study on the location
phase, the latter having ¯uid crystalline-phase behaviour.
of DCP molecules

The e€ect of DCP on the vesicles can be directly observed

in the ¯uorescence emission spectra of pyrene. The higher Conclusion
the DCP/DPPC molar ratio, the more drastic the
decrease in the ¯uorescence intensity. This e€ect can be The changes in the pretransition were expected to be the
observed in the entire temperature domains of rippled strongest of the three transitions. This prediction,
and nonrippled gel phases. The tendency of the decrease mentioned in the Introduction, was supported by DSC
is the same in both phases. Presumably, the interaction and SAXS measurements. DCP causes drastic changes in
between the label and the DCP molecules yields a both the calorimetric and structural behaviour at higher
decrease in the ¯uorescence intensity. However, the concentrations. The di€raction peaks in the SAXS
shape of the spectra remains characteristic of the parent patterns show very similar shapes at 26 and 38 °C in
phases, indicating the thermotropic character of the the samples containing the highest quantity of DCP;
double-layer matrix. The ratio of the intensity values of moreover, the pretransition disappears between these
the ®rst and the third peaks, I1 (at 383 nm)/I3 (at states. We conclude that the changes occur in the
394 nm), is characteristic of the parent phases [18], temperature domain of the gel phase. However, it still
namely the I1/I3 ratio quanti®es the hydrophobicity of remains unclear whether the same Bragg pro®le indicates
the surroundings of the pyrene molecules. The ¯uores- identical or di€erent structures.
cence spectra were recorded in the wide temperature DCP a€ects the transition temperatures, especially for
range of the pretransition and the I1/I3 ratios are plotted the pretransition. A small quantity of DCP causes a
as a function of the temperature in Fig. 12. In the pure slightly higher transition point than that of the pure
DPPC/water system the changes in the I1/I3 ratio indicate system for all three transitions. Presumably, the defect
that the hydrophobicity of the surrounding of pyrene is structures present in the pure system can be changed to
less in the rippled gel phase than in the nonrippled gel more regular forms by addition of small quantities of
phase. The change in this character is continuous during DCP.
the pretransition. The change is more pronounced in the The shifts of the transition points revealed by the DSC
presence of DCP molecules, but no dependence on the curves can be interpreted as a direct e€ect of DCP on the
DCP concentration was observed. It is noteworthy that melting points of the self-organized phospholipid bilay-
in the nonrippled gel phase the I1/I3 ratio re¯ects a higher ers, but the transition points themselves are higher than
hydrophobicity in the systems which are loaded with those connected to the equilibrium states. Namely, the
DCP molecules than in the pure system. We can conclude slow scan rates applied in the experiments proved not to
that the chemical character of the surroundings of the be slow enough to attain the thermodynamic equilibrium
pyrene molecules is formed already at the lowest DCP states during the transition. In these cases, like in our
concentration and this character is connected to the calorimetric experiments, the transition point appears at
152

a higher temperature than that observed by means of rippled gel phase, but in all thermally adjacent phases.
SAXS measurements. The results, i.e., the general destruction in the layer
Knowing the chemical character of chlorinated phe- arrangements and the reductions in the transition
nol, we can suppose that DCP molecules are located enthalpies between them, do not exclude the possibility
close to the polar groups in the bilayers. This assumption of the existence of defect structures consisting of domains
was supported by ¯uorescence measurements. The with nonlayer structure which are formed simultaneously
existence of the rippled gel phase is connected with the by DCP molecules.
hydrophobic e€ect of the polar headgroup, especially to
that of the choline group; therefore, the hydrophobic Acknowledgements This work was supported by the Hungarian
interaction is strongly perturbed by DCP molecules. Scienti®c Funds OTKA (T 014396, T 21781) and a bilateral
However, destruction was observed not only in the German±Hungarian Program TEÂT (D-42/1998).

References

1. Cevc G., Marsh D (1987) Phospholipid 7. Bota A, Drucker T, Kriechbaurm M, 13. Grabielle-Madelmont C, Perron R
bilayers. Physical principles and Pal®a Z, Rez G (1998) Langmuir (1983) J Colloid Interface Sci 95:471±482
models. Wiley, New York 15:3101±3108 14. Luzatti V (1968) In: Chapman D (ed)
2. Tardieu A, Luzatti V, Reman FC 8. Lohner K (1991) Chem Phys Lipids Biological membranes, vol 1. Academ-
(1973) J Mol Biol 75:711±733 57:341±362 ic, New York, pp
3. Ruocco MJ, Shipley GG (1982) Bio- 9. Lohner K, Degovics G, Laggner P, 15. Laggner P (1988) Top Curr Chem
chim Biophys Acta 684:59±66 Gnamusch E, Paltauf F (1993) Biochim 145:173±200
4. Ruocco MJ, Shipley GG (1992) Bio- Biophys Acta 1152:69±77 16. Lehtonen JYA, Holopainen JM, Kinn-
chim et Biophys Acta 691:309±320 10. Weber FJ, de Bout JAM (1996) Bio- unenPKJ(1996)BiophysJ70:1753±1760
5. Maulik PR, Ruocco MJ, Shipley chim Biophys Acta 1286:225±245 17. Socaciu C, Lausch C, Diehl HA (1999)
GG (1990) ChemPhys Lipids 56:123± 11. Escher BI, Schwarzenbach RP (1996) Spectrochim Acta A 55:2289±2297
133 Environ Sci Technol 30:260±270 18. Somasundaran P, Krishnakumar S
6. Bota A, Kriechbaurm M (1998) Col- 12. Biltonen RL, Freire E (1978) CRC Crit (1997) Colloids Surf A 123/124:491±
loids Surf A 141:441±448 Rev Biochem 5:85±124 513
Progr Colloid Polym Sci (2001) 117: 153±158
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

A. Marton Correlation between equilibrium and NMR

Y. Miyazaki
spectroscopic data in the study
of the selectivity of cross-linked
ionic polymers

Abstract Ion-exchange equilibrium the resin phase the chemical shifts of

and 31P NMR measurements were the monovalent and bivalent anions
used for the study of the ion-ex- were calculated. The linear relation-
change distribution of phosphonic ship observed between the calculated
acid anions in various types of ion- selectivity coecients and the resin-
exchange materials. An equation phase 31P chemical shifts proves that
was derived for the calculation of interactions responsible for ion-ex-
ion-exchange selectivity coecients change selectivity (thermodynamic
of the monovalent and bivalent data) and chemical shifts (spectro-
anions from the pH dependence of scopic data) are strongly correlated
A. Marton (&) the measured distribution coecient in the systems studied.
Atmospheric Chemistry Research Group
of the Hungarian Academy of Sciences, of the acid. The equation derived
University of VeszpreÂm, 8201 VeszpreÂm, was also used to calculate the hy-
P.O. Box 158, Hungary drogen ion concentration inside the
e-mail: [email protected] polymer phase. 31P NMR spectra of Key words Ion exchange á
Tel.: +36-88-422022
Fax: +36-88-423203 the equilibrium resin phase were Selectivity á 31P NMR
studied as a function of pH. On the spectroscopy á Phosphonic acid á
Y. Miyazaki basis of the relationship derived for Probing interactions
Department of Chemistry,
Fukuoka University of Education, the pH dependence of the observed in swollen gels á Ions in macromo-
31
Fukuoka 811-4192, Japan P NMR shift of phosphonic acid lecular systems

Introduction di€usion coecients [6, 7] and hydration properties of

the counterions [8] have been measured in various
The selectivity of ion-exchange reactions is usually synthetic ion-exchange resins and membranes. The
characterised by the thermodynamic equilibrium con- chemical shift [9] and the relaxation time [10] of the
stant calculated either by the Gaines and Thomas water protons in the hydration sphere of the counterion
equation [1] or by the relationship recently suggested have also been studied with the intention to predict ion-
by HoÈgfeldt [2] or by using the equation derived on the exchange selectivity. Our current article is concerned
basis of the concentrated electrolyte solution model of with the observation of the NMR spectra of the
ion-exchange polymers [3]. Enthalpy and entropy data of counterion itself and with the study of the expected
the ion-exchange reactions may further contribute to our correlation between its resin-phase chemical shift and its
understanding of selectivity [4] but the interpretation of selectivity coecient. In our studies phosphonic acid was
these data in terms of the physicochemical properties of selected as a particular model compound because of the
the exchanging counterions still remains to be studied. similarity of its protonation sites to the proton binding
Although a direct thermodynamic study of the interac- groups of biological energy-transfer molecules [11]. The
tions in the resin itself is hardly possible NMR spectros- intracellular ionisation of these groups was successfully
copy provides a unique method to probe the chemical followed by the sensitive pH dependence of the
31
environment inside the polymer phase. Ion pairing [5], P NMR signal [12].
154

Experimental solution was measured. The concentration of the phosphonate was

determined by a spectrophotometric method [14] both in the starting
and in the equilibrium solutions (co and ce). The overall distribution
Materials
coecient, Dm, was calculated using the following equation:
Analytical grade disodium phosphonate (Na2PHO3) was obtained V c0 ce †
from Wako Pure Chemicals, Japan. Strongly basic polystyrene- Dm ˆ ; 1†
mce
based anion exchange resins (100±200 mesh) with tetramethyl
ammonium functionalities were obtained in various cross-linkings where V is the volume of the solution (20 cm3) and m is the mass of
(1-X2, 1-X4 and 1-X8) from Muromac, Japan. Polysaccharide gel- the weighed-chloride-form air-dried resin. The change in the
type exchanger QAE Sephadex A-25 was received from Pharmacia distribution coecient as a function of the pH of the equilibrium
Biotech, Sweden. The ion exchangers were converted into chloride solution is shown for the systems studied in Fig. 1.
form, washed free from all invaded electrolyte and were stored in
an air-dried form. The ion-exchange capacities (Q), determined by
31
the usual standard method [13], were as follows 1-X2: 3.39, 1-X4: Measurement of P NMR spectra
3.44, 1-X8: 3.00, QAE A-25: 2.69.
31
P NMR spectra of the equilibrium system were recorded using a
JEOL JNM-GSX 500 spectrometer with a 10-mm multinuclear
Equilibrium measurements probe at a resonance frequency of 202.5 MHz. Typical instrumen-
tal parameters used to obtain spectra of the equilibrium systems
Exactly known amounts of each resin sample (1-X2: 0.65 g, 1-X4: were as follows: ¯ip angle 45° (10 ls), pulse repetition time 3 s,
1.2 g, 1-X8: 1.6 g, QAE A-15: 0.5 g) were weighed into 25-cm3 ¯asks spectral width 36 kHz, lock D2O containing 0.0125% H3PO4 in a
into which 20 cm3 disodium phosphonate solution 2-mm coaxial capillary. The chloride concentration of the resin
(1.5 ´ 10 moldm)3) was added. The ionic strength of the systems
)3 phase was also determined by an NMR spectroscopic technique
was set to 0.1 moldm)3 by sodium chloride. The pH of the solution according to the procedure described in our earlier publication [15].
was varied in the range 1±12 by addition of concentrated The variation of the measured 31P NMR chemical shifts is shown
hydrochloric acid or sodium hydroxide solutions. The pH was in Fig. 2 as a function of the pH.
measured using a glass electrode (Horiba 6069-10C) calibrated for
three bu€er solutions. The systems were placed in a thermostatted
water bath set to 25 °C. After equilibration overnight the resin and
solution phases were separated by ®ltration and the pH of the
Results and discussion

Fig. 1 Distribution coecient of phosphonic acid (Dm) as a function In order to simplify notation, the various phosphonic
of pH acid species (PHO32), HPHO3) and H2PHO3) will be
 155

Fig. 2 31P chemical shift as a

function of pH of the solution.
For the curve ``solution''
chemical shifts are solution-
phase data which were used to
calculate the protonation con-
stants. For the rest of the curves
the chemical shifts were mea-
sured in the resin phase

denoted as P2), HP) and H2P. Using these symbols the bi ‰H‡ Ši
ion-exchange reaction, the selectivity coecient (KHP) /i ˆ ; 9†
P
2
‡ i
and the distribution coecient (dHP) of the monovalent bi ‰H Š
ions can be described by the following equations: iˆ0

RCl ‡ HP ˆ RHP ‡ Cl ; 2† de®ned in terms of the cumulative protonation constant

bi:
HP †‰Cl Š
KHP ˆ ˆ dHP ‰Cl Š= Cl † ; 3† bi ˆ K0 K1 K2 i ˆ 0; 1; 2 and K0 ˆ 1† : 10†
‰HP Š Cl †
It is noted here that the values of the K1 and K2
HP † constants were calculated from the pH dependence of the
dHP ˆ : 4† 31
‰HP Š P NMR chemical shift of the 1.5 ´ 10)3 mol/dm3
disodium phosphonate solution (Fig. 2). By performing
The exchange equilibria of the bivalent ions can be
the least-squares calculation according to Eq. (16) the
represented by a similar set of equations:
following values were obtained: K1 ˆ 106.34, K2 ˆ 101.12.
2RCl ‡ P2 ˆ R2 P ‡ 2Cl ; 5† The set of dP and dHP distribution coecients giving
the minimum sum of the squares of the deviations,
P2 †‰Cl Š2 X
KP ˆ 2 2
ˆ dP f‰Cl Š= Cl †g2 ; 6† D m D c †2 ; 11†
‰P Š Cl †
was obtained by a nonlinear regression. The calculated
P2 † distribution coecients are shown in the second and
dP ˆ 2 : 7† third columns of Table 1.
‰P Š
Ion-exchange selectivity coecients were calculated
In these equations the parentheses and the square for the resins studied using Eqs. (3) and (6) and are also
brackets indicate resin- and solution-phase equilibrium presented in Table 1. (columns four and ®ve). As a
concentrations respectively. The resin invasion of the consequence of the electroselectivity of the resin the
neutral species will be neglected. Since the overall distribution coecients are higher for the bivalent ions
distribution coecient (Dc) is de®ned as the ratio of the than for the monovalent phosphonate ions.
analytical concentration of the phosphonic acid in the Knowing the pH dependence of the distribution
resin and in the solution phases it can be shown that Dc is coecient (Fig. 1.) Eq. (8) o€ers a convenient way to
related to the ionic distribution coecients (dHP and dP) estimate the internal pH of the resin phase. For this the
by the following equation: protonation equilibria of the phosphonate anion are
Dc ˆ /0 dP ‡ /1 dHP ; 8† expressed in terms of resin-phase components and, in the
absence of a better approximation, the values of the
where / is the mole fraction of the phosphonic acid protonation constants are assumed to be the same as in
species, the solution phase. This consideration leads to a
156

Table 1 Ion-exchange
equilibrium data (d, K) and dHP DP KHP KP dHP dP
31 
P NMR chemical shifts (d) AG 1-X2 3.62 13.1 0.25 0.066 2.42 3.15
calculated for the monovalent
AG 1-X4 4.19 15.3 0.20 0.035 2.15 3.05
and bivalent phosphonate ions
AG 1-X8 3.53 11.33 0.12 0.012 1.81 2.91
(HP) and P2))
QAE A25 2.08 7.29 0.366 0.25 2.55 3.20
Solution 3.01 3.43

relationship similar to Eq. (8) except that [H+] is now phase NMR parameters the measured chemical shifts
replaced by ‰H ‡ Š (the bar refers to the resin phase). The have to be decomposed into the contribution character-
quadratic equation obtained can be solved for ‰H  ‡ Š and istics for the individual phosphonic acid species. These
the pH inside the resin phase can be estimated. It should data are not directly accessible from the NMR spectra but
be born in mind, however, that the protonation constants they can be calculated by the method shown later. In the
of the base studied in the resin and in the solution phases evaluation of the NMR spectra the following two features
are certainly di€erent owing to the high density of the of the system have to be kept in mind. The rate of exchange
positive charges of the immobilised cationic functional of the phosphonic acid species between the solution and
groups. If Y designates the average electrostatic potential resin phases is very slow on the time scale of the NMR
generated by these charges then it can be shown that the experiment. For this reason, the 31P NMR spectra of the
protonation constants in the resin and solution phases equilibrium system exhibit two well-separated resonance
are interrelated by the following general equation: signals (the high-®eld signal is due to the resin-phase
zeW species, while the lower-®eld signal is due to the solution-
 ˆ log K ‡ 0:434
log K ; 12† phase phosphonic acid species). This feature of the system
kT o€ers a convenient way to study the pH dependence of the
where z is the valence of the ion (including sign), e is the chemical shifts in both the solution and the resin phases.
electronic charge of the proton, k is Boltzmann's As opposed to the slow exchange of the phosphonic
constant and T is the temperature [16]. Since the K acid species between the equilibrium phases, the rate of
values in the two phases are equal only when Y ˆ 0 proton exchange among the phosphonic acid species is
(which obviously does not apply here), the calculated fast on the time scale of the NMR spectroscopy. As a
resin phase pH values should be considered as estimates. consequence, the species are indistinguishable and in
When the calculated pH values were plotted as a each phase only one 31P signal can be detected at a so-
function of the pH of the solution then a linear called population-averaged chemical shift value [17]. In
relationship was obtained: the case of fast-exchange conditions the resin-phase
h i chemical shift (dc ) is de®ned as
 ‡ ˆ a log‰H‡ Š ‡ b :
log H 13†
dc ˆ / dP ‡ / dHP ‡ / dH P ;
0 1 2 2
14†
The values of the parameters a and b are given for the
systems studied in Table 2. where d represents the individual chemical shift of the
As can be seen, the slope of the straight lines is very species shown in the subscript and the bars above the
close to unity in all the cases, while the intercept varies symbols indicate resin-phase parameters. A similar
for the di€erent types of resins and indicates a higher pH equation (without the bar) can, of course, also be written
value inside the resin than in the outside equilibrium for the solution-phase 31P chemical shifts. If the previous
solution phase. hypothesis for the protonation constants is accepted (i.e.
 1 ˆ K1 and K
K  2 ˆ K2 ) then by using Eqs. (9) and (14) the
In order to correlate the calculated ion-exchange
selectivity data (KHP and KP) to the appropriate resin- following relationship can be derived for the interpreta-
tion of the pH dependence of the experimentally
measured population-averaged chemical shift:
Table 2 Values of the parameters a and b of Eq. (13) calculated dP ‡ dHP K  ‡ Š ‡ dH2 P K
 1 ‰H 1K
 2 ‰H ‡ Š2
from pH data (values in parentheses were estimated from 31P NMR dc ˆ : 15†
1‡K  ‡Š ‡ K
 1 ‰H 1K  ‡ Š2
 2 ‰H
shifts)
Knowing the measured resin-phase chemical shifts
a b
(dm ) and the chemical shifts calculated by Eq. (15) at
AG 1-X2 0.994 0.598 (0.544) di€erent pH values (dc ) the resin-phase chemical shifts of
AG 1-X4 1.010 0.567 (0.614) the monovalent and bivalent phosphonic acid anions
AG 1-X8 0.999 0.524 (0.456)
(dHP and dP ) can be calculated by ®nding the minima of
QAE A25 0.995 0.614 (0.565)
the function
 157

Fig. 3 Calculated resin-phase

31
P chemical shifts of the
monovalent and bivalent phos-
phonic acid species as a func-
tion of their ion-exchange
selectivity coecients calculated
for the resins studied (KHP and
KP)

X
dm dc †2 16† of a strong correlation between selectivity and NMR
spectroscopic data.
by using the least-squares approximation. The calculated The observed correlation can be interpreted theoret-
chemical shift characteristics for the resin-phase envi- ically by considering the origin of the electronic screening
ronment of the anionic species studied are shown in of the 31P nuclei and their relation to the thermodynamic
Table 1. The correlation between the ion-exchange parameters controlling ion-exchange selectivity.
selectivity coecients and the 31P chemical shifts calcu-
lated for the various resins are presented for the
monovalent and bivalent ions in Fig. 3. The ®gure Conclusion
indicates a linear correlation between the interactions
governing the selective uptake of ions and the chemical The correlation between the ion-exchange selectivity
environment controlling the 31P chemical shift of these coecient and 31P NMR chemical shifts has been
species in the polymer phase. A further support to this proved and discussed for the ion-exchange distribution
correlation is obtained if the value of the b coecient is of monovalent and bivalent phosphonic acid anions on
calculated from the available NMR data. For this resins with various cross-linkages. A similar relation-
purpose, the resin-phase hydrogen ion concentration in ship may be expected to exist in systems where a
Eq. (15) is substituted by the expression ‰H  ‡Š ˆ
pH‡b† selective uptake of ions takes place in phases like
10 . In this way the b coecient de®ned by polyelectrolyte gels, synthetic or natural membranes or
Eq. (13) can be estimated from the spectroscopic data living cells.
by applying the least-squares calculation procedure
according to Eq. (16). Values of the b parameter
Acknowledgements Thanks are due to Hirofumi Sakashita for
calculated from pH and from 31P chemical shift data obtaining NMR data at the Centre of Advanced Instrumental
are compared in Table 2. The good agreement between Analysis, Kyushu University, Japan. The JSPS grant (no. L97541)
the two sets of data is a further indication of the existence to A.M. is hereby acknowledged.
158

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1. Gaines GL, Thomas HC (1953) J Phys 7. Ohuchi M, Horiuchi H, Sakai Y (1995) 13. InczeÂdy J (1966) Analytical applica-
Chem 21:714 Kobunshi Ronbunshu 52:512 tions of ion exchangers. Pergamon,
2. HoÈgfeldt E (1988) React Polym 7:81 8. Busch M, Boldammer EV (1982) New York, pp 116±130
3. Marton A (1997) Pure Appl Chem J Solution Chem 11:777 14. Murphy J, Riley JP (1962) Anal Chim
69:1481 9. Reichenberg D, Lawrenson I J (1963) Acta 27:31
4. Marton A, InczeÂdy J (1995) In: Ohya H Trans Faraday Soc 59:141 15. Kura G, Miyazaki Y, Marton A (1998)
(ed) Proceedings of the International 10. Marton A, Elvidge J A InczeÂdy J (1980) React Polym 38:197
Conference on Ion Exchange. Japan J Chromatogr 201:79 16. Daune M (1999) Molecular biophysics.
Association of Ion Exchange, Takama- 11. Brindle KM, Fulton AM, Williams S Oxford University Press, Oxford,
tsu, pp 87±93 (1995) In: Brown GC, Cooper CE (eds) pp 332±339
5. Komoroski RA, Mauritz KA (1978) Bioenergetics. Oxford University Press, 17. Popov AI, Hallenga K (1991) Modern
J Am Chem Soc 100:7487 Oxford, pp 159±187 NMR techniques and their application
6. Zawodzinski T, Neeman M, Sillerud L 12. Cantor CL, Schimmel PR (1980) Bio- in chemistry. Dekker, New York,
O, Gottesfeld S (1991) J Phys Chem physical Chemistry. Freeman, New pp 485±520
95:6040 York, pp 481±538
Progr Colloid Polym Sci (2001) 117 :159±166
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

L. HalaÂsz Structural and viscoelastic properties of

Z. NeÂmeth
J. P. T. HoraÂnyi lamellar systems formed from concentrated
A. BoÂta
nonionic surfactant solutions

Abstract The structure and rheolog- function were measured at di€erent

ical properties of a concentrated temperatures with systems contain-
lamellar liquid-crystalline nonionic ing surfactant in di€erent concen-
surfactant system were investigated. trations. The rheological properties
The morphology of the samples was were described by the modi®ed slip-
analyzed by polarization light plane theory. Discrepancies between
L. HalaÂsz (&) microscopy, electron microscopy and the ®tted curves of the model and the
Technikon Pretoria, P.O. Box X 680,
Pretoria 0001, South Africa small-angle X-ray scattering mea- experimental curves were estimated
surements. The rheological proper- as the result of the Frank stress.
Z. NeÂmeth á J. P. T. HoraÂnyi ties, the frequency-dependent storage
A. BoÂta
Technical University of Budapest, and loss modulus, the creep compli- Key words Rehology á Lamellar
1111 Budapest, BudafokiuÂt 8, Hungary ance and the steady-state viscosity structure á Surfactant self-assembly

Introduction higher temperature range the number of the dislocation

loops.
Surfactant-based liquid crystals have a broad range of The viscoelastic behavior of a lamellar anionic
application in the cosmetic and food industries [1±6]. surfactant, Aerosol OT±water system was investigated
The most important systems are those in which bilayers by Robles-Vasquez and coworkers [13, 14]. They con-
are formed from the surfactants: these are the lamellar sidered the lamellar mesophase as a weak gel, but
mesophase, the bicontinous cubic phase, the liposome quantitative descriptions were not used for the explana-
phase and the so-called onion phase. The rheological tion of the experimental results.
properties of such systems were reported in some Other authors [9±11] believe in the importance of the
articles [7±17]. In spite of its importance, the micro- orientation of lamellae under shear. The orientation of
scopic origin of the rheological behavior is not yet well domains in the case of an unsheared sample is dependent
understood. on the domain±domain interaction. If stress is applied to
In explaining the ¯ow curves of a three-component the sample the orientation changes and the competition
lamellar mesophase Bohlin and Fontell [7] modeled the between the interactions and the external stress de®ne the
lamellar structure as ¯exible layers of water in a liquid viscosity of the system. Penfold et al. [12] investigated the
hydrocarbon chain environment. Flow was associated shear-induced ordering of the lamellar phase of hexa-
with cooperative changes of conformation of ¯exible ethylene glycol monohexadecyl ether in a Couette shear
layers subject to frictional forces in the liquid layers. The cell by small-angle neutron scattering. Two distinct
¯ow coecients were found to be dependent on the lamellae orientations were identi®ed. At low shear rates
thickness of the water layer, the bilayer interaction and the lamellae are ordered parallel to the ¯ow-vorticity
the mobility in the hydrocarbon chain layer. plane, whereas at higher shear rates the lamellae order
In investigations of the temperature dependence of parallel to the ¯ow-shear gradient plane.
¯ow Oswald and Allain [8] took into consideration the Viscoelastic behaviour of liposomes was investigated
importance of the undulation of the bilayers and in the intensively by Ho€mann and coworkers [15, 16] and
160

they found a frequency-independent storage and loss diagram do not change markedly with temperature, but the
modulus. lamallae melt at about 50 °C and at a higher temperature an
optical isotropic liquid forms with low viscosity.
Onion phases was investigated by Panizza et al. [17]. The lamellar samples were prepared by heating the aqueous
The creep compliance curve was described well by a mixtures to about 50±55 °C, where they were easily homogenized
Burger model, consisting of a Maxwell and a Voigt and, after homogenization, the mixtures were left to cool to room
element in series. In the analysis of the results of the temperature. Then, the samples were stored for a 1-week period
before the measurements. Special care was taken to prevent the
dynamic tests the same model was used with a Laplace evaporation of the water content of the samples during both their
transformation of the creep equation. The calculated and preparation and their storage. Mixtures were prepared with
measured results were in good agreement in the case of distilled water having a surface tension of 72±73 mN/m. The
the storage modulus but a signi®cant di€erence could be samples prepared in this way were checked by observing the texture
observed in the case of the loss modulus, especially in the of the samples in a polarization microscope before the rheological
measurements.
high-frequency region.
Jones and McLeish [18] and Radiman et al. [19] used a
Methods
slip-plane theory to describe the frequency dependence of
the storage and loss moduli of cubic phases. The theory Rheological measurements were done with a Haake RS 100
used the results of Doi et al. [20] and Harden and Doi apparatus. A cone±plate sensor was used, with diameter of
[21] which were given for the ordered phases of block 20 mm, and cone angle of 4°. The sample thickness in the middle
of the sensor was 0.134 mm, so in each case about 0.15 ml sample
copolymers. For describing the rheological properties of was tested rheologically. During the measurements the maximum
liquid-crystalline phases formed from polymer melts allowed deviance in temperature was ‹ 0.2 °C. The samples were
Larson and Doi [22] introduced the so-called Frank kept in nearly saturated water vapor during the whole time of the
stress, which was used ®rst by Marucci and Ma€ettone measurements. Because the rheological properties of such systems
are dependent on the shear±deformation history, the sample was
[23] for other systems. The role of the Frank stress is to gently inserted in the top of the plate of the sensor and then the
change the orientation of the domains by the shear. plate was slowly elevated to its measuring position always with the
In our previous work [24, 25] we investigated the same velocity. The sample squeezed out from the sensor system was
rheological and structural properties of nonionic, lamel- removed gently. Measurements were carried out after a 10-min
lar surfactant system. We tried to describe the rheological waiting (relaxation±thermostation±saturation) period.
The dynamic (oscillation) tests were done in the viscoelastic
properties of these system by an empirical equation and region on all the samples. First, the linear viscoelastic region was
the original form of the slip-plane theory. In the present determined by measuring the complex modulus versus the stress at
article we summarize the results of the rheological a given low frequency and then 2.5 Pa was chosen as a stress
investigation done both in and out of the linear visco- amplitude, which was found to be in the linear viscoelastic region in
all cases.
elastic region of a nonionic lamellar system as a function The viscosity was measured as a function of the shear in a
of the surfactant concentration and the temperature. We steady-state way. The viscosity was measured as a function of time
use the modi®ed version of the slip-plane theory to at each stress value and the result was accepted if its change was
describe the rheological properties of the system. lower than 0.05%/s.
For the small-angle X-ray scattering (SAXS) measurements the
samples were transferred into thin-walled Mark quartz capillaries
(Hilgenberg, Germany) of 1-mm diameter. The capillaries were closed
Experimental with a two-component synthetic resin and were transferred in metal
capillary holders into an aluminum block. This block was settled
Materials directly in the beamline and used as a thermal incubator for controlled
annealing at di€erent temperatures. The block was held at the desired
We studied a lamellar liquid-crystal system consisting of a nonionic temperatures by a thermostat. The actual temperatures were constant
surfactant (Synperonic A7, ICI) and water. The surfactants were to within less than 0.05 °C as measured by a thermocouple. The
used as supplied. Synperonics were made by ethoxylation of windows of the block were covered with Mylar foil.
synperonic alcohol, which consists of 66% C13 and 34% C15 alkyl The SAXS camera was a Kratky camera (Anton Paar, Graz,
chains. The ethoxylation process gives rise to a wide distribution of Austria) attached to the line-focus window of a Cu tube at a
poly(ethylene oxide) chains; therefore, only the average ethoxyla- generator (Seifert, Ahrensburg, Germany) operated at 40 kV and 20
tion number can be declared. Though the properties of the samples mA. A Ni ®lter was used to eliminate Kb radiation. The scattering
should not change from batch to batch, the preparation of the data were collected with a proportional counter. The scattering data
lamellar systems investigated here was always done from surfac- curves were normalized and desmeared for the slit geometry.
tants from the same batch.
The phase diagram of the synperonic A7±water system was
established by HalaÂsz and MacskaÂsi [26] and Dimitrova et al. [27]
by rheological, calorimetric and NMR measurements and by Results
polarization microscopic observations. They found normal micellar
(L1), hexagonal liquid-crystalline (H1), lamellar liquid-crystalline Structure of the lamellar phase
(La) and inverse micellar (L2) phases with increasing surfactant
concentration at 23 °C. At this temperature the lamellar phase
exists in a concentration range between 55 and 80% (w/w). The
In the lamellar region the samples showed double
coexistence of the hexagonal and lamellar phases was observed at refraction between crossed polarizers. In the texture
50±55% (w/w). The boundaries of the lamellar phase in the phase many Maltese crosses, crosses which open if the sample
 161

position is rotating and stripes are visible. While Maltese

crosses are characteristic of crystals with one optical axis,
the opening crosses indicate the presence of crystals with
two optical axes. From this fact it is clear that the sample
is heterogeneous on a microscopic scale; it contains
di€erent types of lamellar domains: probably some of the
carbon chains are in a frozen state and some are probably
molten. Moreover, all the samples were pseudoisotropic;
after some minutes of waiting large black regions were
visible between crossed polarizers. When the slide was
tilted, strong double re¯ection occurred again. This
phenomenon is due to the alignment of lamellae parallel
to the plane of the slide [26]. In the case of the
pseudoisotropic samples, between the black regions
some Maltese crosses were also visible. It is probable
that the parallelly aligned lamellae with originally two
optical axes cause these crosses, but the presence of some
nonoriented domains is also possible.
In the case of A7, with increasing concentration a
change in the structure occurs. While at lower concen-
tration under a polarization microscope the sample
shows big crosses and small more-or-less statistically
aligned stripes, at 80% (w/w) A7 concentration the
texture is strongly striped, the stripes are long and are
aligned parallel to one another. This change in the
texture may be due to a transition which causes a
stronger ordering in the sample; probably the domains Fig. 1 Typical results of small-angle scattering measurements at
order more parallelly to one another. At this concentra- 25 °C. The calculated repeat distance is also shown in the ®gure for
samples containing A7 in di€erent concentrations
tion the sample is also pseudoisotropic.
The change in the repeat distance of a nonionic
lamellar surfactant±water system during the shearing Table 1 Repeat distance of lamellae of the samples investigated
was measured by SAXS [28] and it was found that the measured by small-angle X-ray scattering
repeat distance decreased from 4.83 to 4.68 nm when
the shear deformation was increased. After a 3-h shearing Surfactant concentration Temperature Repeat distance
(% w/w) (°C) (nm)
the ordering of the domain structure was increased but the
average number of layers in a domain remained constant. 60 25 5.22
The change in the repeat distance of the lamellae was 70 25 4.61
measured by SAXS for all the samples investigated. 80 25 4.35
70 40 4.61
Typical results of the scattering experiments are shown in 70 50 4.61
Fig. 1. It can be seen that in all cases a marked maximum
occurs owing to the strong ordering of the lamellae. From
the maximum of the peaks, repeat distances were calcu-
lated and these are summarized in Table 1. As is shown, to about 10 Pa. This range is called the linear viscoelastic
the repeat distance decreases with increasing surfactant region. Here the applied stress does not cause a marked
concentration, shows no dependence on temperature and change in the sample or, in other words, we gain
is a function of the ethoxylation number of the surfactant. information on a slightly perturbed sample. Above
The interlamellar water layer thickness decreases with the 10 Pa, G* decreases strongly with stress, which indicates
increase in the surfactant concentration. that the structure of the sample is changed. The limit of
the linear viscoelastic region is dependent on the
Rheological properties composition and the temperature, but we found it to be
higher than 2.5 Pa in all cases.
Dynamic measurements Typical results of the storage modulus, the loss
modulus and the complex viscosity of the lamellar
Typical complex modulus (G*) versus stress curves at low mesophase, formed from aqueous Synperonic A7, as a
frequency of the applied stress are shown in Fig. 2. G* function of the frequency in the linear viscoelastic region
shows only a slight dependence on the applied stress up can be seen in Fig. 3. The system is more elastic than
162

change with the concentration of the surfactants. A

summary of the results can be seen in Fig. 4, where we
show the storage modulus, the loss modulus and their
ratio (tan d) as a function of the surfactant concentration
at a given frequency. It can be seen that both the storage
modulus and the loss modulus increase with increasing
concentration, but the rate of their increase is di€erent.
As the system becomes more concentrated the sample
behaves more and more elastically, as can be seen from
the decrease in tan d. At the highest concentration region
both the storage modulus and the loss modulus begin to
decrease. On investigating the structure of the sample
with a polarization microscope a change in texture can be
observed at 80% (w/w) concentration. While in the case
of the concentration range 60±75% (w/w) Maltese
Fig. 2 Complex modulus (G*) of a lamellar sample of 70% (w/w) A7 crosses are seen, in the case of 80% (w/w) concentration,
solution as a function of the applied stress (s) at a constant (low) the texture is of the oily striped type. This change in
frequency (0.036 Hz) at 25 °C texture indicates an orientation change of the domains,
which is connected to the deviation of the trend of the
storage modulus. These observations are in good agree-
ment with the ®ndings of Simitrova [27].
The e€ect of temperature was also examined for the 70
% (w/w) Synperonic A7 lamellar system. The shape of
the storage modulus, the loss modulus and the complex
viscosity as a function of frequency does not change with
temperature until the phase boundary. Above this
temperature the system shows rheological behavior
characteristic of the system consisting of inverse micelles.
This was found at the same temperature where the
scattering experiments indicate the complete disappear-
ance of the lamellar mesophase. In the lamellar region
the quantitative results of dynamic tests are strongly
temperature dependent (Fig. 5). Both the storage mod-
ulus and the loss modulus decrease with increasing
temperature, but the rate of their change is di€erent, the
Fig. 3 Storage modulus (G¢), loss modulus (G¢¢) and complex
viscosity (g*) of the 70% (w/w) aqueous A7 lamellar system as a decrease of the elastic component being much more
function of the frequency (x) at a stress of 2.5 Pa at 25 °C pronounced. This can be evaluated from tang d, which

viscous in the range of frequency investigated, the

storage modulus is higher by about 1 order of magnitude
than the loss modulus throughout the whole frequency
range. While the storage modulus has a weak dependence
on the applied frequency, the loss modulus shows a
minimum. The complex viscosity is strongly frequency
dependent: the higher the frequency the lower the
complex viscosity. The picture described here is charac-
teristic only of the lamellar mesophase, both of the other
phases (hexagonal phase and inverse micellar phase)
which surround the lamellar phase in the phase diagram
show completely di€erent behavior as a function of
frequency.
The e€ect of concentration on the storage and loss
moduli was examined within the lamellar concentration
region at 25 °C. The shape of the previously mentioned Fig. 4 The concentration dependence of G¢, G¢¢ and their ratio (tan d)
characteristics as a function of frequency does not at 1 Hz, measured with a stress amplitude of 2.5 Pa at 25 °C
 163

Fig. 5 The temperature dependence of G¢, G¢¢ and their ratio (tan d)
at 1 Hz measured with a stress amplitude of 2.5 Pa
Fig. 6 Complex and shear viscosity versus frequency or e€ective
strain of a 70% (w/w) aqueous A7 lamellar system at 25 °C
increases with temperature. The change in the storage
modulus is more pronounced in the lower-temperature
region (between about 5 and 25 °C). The elastic compo- statically (with creep tests and steady-state viscosity
nent of ¯ow diminishes as the phase boundary is reached measurements). In the linear viscoelastic region, where
with increasing temperature. The change in the storage the structure of the system does not change signi®cantly
modulus can be characterized by two straight lines and during the rheological measurements, the lamellar mes-
the break point of the lines is at 25 °C. This value is very ophase behaves as an elastic gel; its storage modulus is
close to the melting point of the water-free surfactant. higher by about 1 order of magnitude than its loss
Assuming that the melting point of the carbon chains is modulus.
not in¯uenced strongly by the aqueous layers which are Lamellar phases formed from other aqueous surfac-
separated from these chains with the ethoxylate groups, tant mixtures have a similar viscoelastic behavior to the
this break point seems to be a transition temperature system studied here, for example Robles±VaÂsquez and
between the gel and the liquid-crystalline phases of the coworkers [13, 14] reported similar behavior for a
lamellar domains. lamellar mesophase of aqueous Aerosol OT; in that case
the storage modulus was nearly independent of frequen-
Steady-state viscosity measurements cy, the loss modulus showed a minimum and the complex
viscosity decreased with increasing frequency and did not
A typical complex viscosity versus frequency curve for obey the Cox±Merz rule. According to this we can
di€erent surfactant concentrations is shown in Fig. 2. conclude that this type of behavior is observed in the
Both the shear viscosity and the complex viscosity are lamellar phases and is a characteristic of such phases.
decreasing functions of the shear rate and the frequency, The results of the rheological behavior in the linear
respectively; however, neither the Cox±Merz rule nor the viscoelastic range were evaluated by using the slip-plane
modi®ed Cox±Merz rule is followed (i.e. the complex theory developed by Jones and McLeish [18] for cubic
viscosity is equal to the shear viscosity if the shear rate is phases. This theory assumes that parallelly aligned
the same as the frequency or the e€ective strain ± which is planes exist in the sample, and the shear stress acting
equal to the strain amplitude multiplied by the frequen- tangentially results in a displacement between them
cy). Both the shear viscosity and the complex viscosity (Fig. 7). When we apply a ®xed strain to the sample, if no
increase with an increase in the surfactant concentration slipping occurs, the stress exerted at the top surface of the
in all regions of the shear rate and frequency, respective- sample is
ly. They decrease with an increase in temperature. as can
s ˆ GP ‡ gP_ ; 1†
be seen from Fig. 6 for the shear viscosity.
where G is the bulk modulus, g is the bulk viscosity of the
liquid-crystalline phase, P is the gradient of displacement
Discussion and P_ is its time derivative. Equation (1) is a simple
Voigt±Kelvin equation. Once a slip has occurred, the
The rheological properties of the lamellar mesophase strain in one layer is large but in all others is very small.
formed from the nonionic Synperonic systems were The deformation in the slip plane is very large and is
investigated both dynamically (with oscillation tests) and mainly viscous. The viscous interaction between domains
164

for G¢ and G¢¢ using the slip±stick model (assuming a

ratio of 0.8 for e/c0 and the G value was taken as the
inverse of the instantaneous creep compliance.) The
agreement between the calculated and measured values is
rather good.
The ®tted curves can describe the experimental curves
rather well in the case of the storage modulus, but the
agreement is not too good in the case of the loss modulus
curves: the minimum values of the ®tted curves are
sharper than the experimentally measured ones. When
we took into consideration the e€ect of the lattice
potential by the perturbation method the results did not
improve signi®cantly and the agreement remained poor
between the experimental and calculated results. As an
example we show the ®tted results as a function of
Fig. 7 Slip-plane model frequency in the case of 70 wt% Synperonic A7 at 25 °C
in Fig. 8.
The density of the slip planes calculated from k with G
(in the slip plane) is disturbed by an elastic lattice
(G is kept equal to AG, because A@1 if k and k1 are
potential. The force balance in the slip plane is
strongly di€erent) strongly dependent on g2, which is
g2 2p unknown. The two limits for g2 are the viscosity of pure
GP ‡ g P_ xn xn 1 † G2 sin xn xn 1 † ˆ 0 ;
a a water and the calculated viscosity between two lamellae
2† (g). With this we get a range of values for N between 103
and 107; this range seems to be too high.
where G2 is an elastic modulus at the slip plane. If we
neglect the e€ect of the lattice potential we can get for the
components of the complex modulus Table 2 Measured and calculated moduli at 10)2 Hz for samples
2
at 25 °C containing surfactant in di€erent concentrations
0 k x†2 k1 x†
G x† ˆ AG ; 3† Concentration Storage Modulus Loss Modulus
1 ‡ k x †2 (% w/w) measured calculated measured calculated
(Pa) (Pa) (Pa) (Pa)


00 k x 1 ‡ k k1 x2 60 220 198 35 40
G x† ˆ AG ; 4†
1 ‡ k x †2 70 606 636 113 97
80 1,250 1,050 202 200
N g2 g‡N g2
where k1 ˆ g/G and A ˆ g‡N g2 . k ˆ G is the relaxation
time.
This linear model was extended by introducing a weak
elastic force at the slip plane owing to the connectivity of
the structure. The components of the complex modulus
were considered as a series, and the higher terms were
calculated by the perturbation method.
It was supposed that at low frequencies there is a slip±
stick phenomenon, there is no slip below a critical stress
value. In this region the two components of the complex
modulus are
"   #12
0 Ge e 2 3
G ˆ 1 1  c0 2 ; 5†
c0 c0
 
00 Ge e
G ˆ 1  c0 1 ; 6†
c0 c0
where e is the critical value of the strain. Considering the
shape of our modulus curves it seemed to us that the slip±
Fig. 8 G¢ and G¢¢ of a 70% (w/w) aqueous A7 lamellar system as a
stick model and the linear model may describe our function of the frequency at a stress of 2.5 Pa at 25 °C. Comparison
curves. In Table 2 we summarize the calculated values of the measured and calculated values
 165

G increases with increasing surfactant concentration orientation of the domains (Frank stress) and which is
and decreases with increasing temperature. It seems that not included in the theory of Doi, Ohta and McLeish. If
G is a function of the lamellar±lamellar interactions. At a we take into consideration the Frank stress, the left side
given temperature the repeat distance of the lamellae of Eq. (1) consists of two terms: the Frank stress and the
decreases and this means an increased interaction shear stress. Applying the common form of the Frank
between lamellae, which causes an increase in G. At a stress leads to
given surfactant concentration the repeat distance is
sF ˆ KE=a2 ; 7†
independent of the temperature, but naturally the
interactions depend on temperature. In the case of where K is a characteristic Frank elastic constant which
lamellae formed from nonionic surfactants the interac- has a typical value of 10)11±10)10 N, E is an orientation-
tions originate from the van der Waals forces and steric± dependent dimensionless tensor and a is the domain size.
hydration forces. The hydration repulsion is strongly Assuming that sF simply equals b/G00min ˆ G00E minus the
temperature dependent. From these facts it seems Frank modulus and considering a b value of 10 as is
reasonable to conclude that steric±hydration interactions typical for polymer systems we get a domain size of the
play an important role in determining the interlamellae order of 100 nm, which is a more acceptable estimation.
elastic modulus (G). The same conclusion (the impor- The steady-state ¯ow curves show the yield value. The
tance of repulsion forces) was drawn by Robles-Vasquez theory given by Doi et al. [20] predicted a yield value for
and coworkers [13, 14]. block copolymer liquid crystals but their simple equation
k shows a maximum as a function of temperature. It is describing the steady-state viscosity versus the shear rate
dependent on the viscosity values, the elastic modulus did not give a good approximation for our experimental
and the rheological domain size (N). While the ratio of results. In our system the shear rate causes some
the viscosities against elastic modulus increases with orientation and some change in the structure, which at
increasing temperature, N may decrease (the enhanced higher shear rates should be di€erent than in the linear
temperature may increase the number of slip planes) and viscoelastic region. The steady-state ¯ow curves were
the superposition of these changes can cause the described by a Carreau-type equation:
maximum in k. ga c_
k1 (the ratio of the interlamellar viscosity and s s0 ˆ ; 8†
elasticity) is a monotonically decreasing function of the 1 ‡ a k c_ †m
concentration. This is in good agreement with the the where s0 is the yield value, ga is the viscosity extrapolated
ratio of the macroscopical elasticity (G¢) and viscous to s)s0 ˆ 0, k is a characteristic time and a and m are
component (G¢¢), tang d, which is a monotonic increasing constants. Equation (8) can be simply derived if we
function of the concentration. assume breaking kinetics for the domain contact loss.
If we use a modi®ed form of Eqs. (3) and (4) in which Equation (4) was used for the evaluation of the ¯ow
a constant was added to the right side of the equations we curves of the samples; the results can be seen in Table 4.
obtain excellent agreement between the measured and ga increases with increasing concentration and decreases
the ®tted values. The calculated parameters are summa- with increasing temperature. The decrease in ga with
rized in Table 3. The data in the table show that the value temperature is exponential and can be characterized by
of the constant is very close to the minimum value of the an Arrhenius-type equation. The activation energy was
loss modulus. determined to be 2 J/mol for 70% concentration. The m
The GE term of the model might be explained by that value is independent of the A7 concentration; only the m
part of the applied stress which is used to change the value of the sample containing 60 wt% A7 is lower than
the other values. m is a decreasing function of the
Table 3 Fitting results of the linear slip-plane theory for samples
as a function of the surfactant concentration and sample tem- Table 4 Fitted constants of Eq. (8) as a function of the surfactant
perature (GE is the extra modulus needed for better ®tting) concentration and the temperature
c (% w/w) T (°C) AG (Pa) k (s) k1 (s) GE (Pa) c (% w/w) T so(Pa) ga (Pas) b k (s) m
(°C)
60 25 220 161 0.0317 48.2
65 25 360 85 0.0240 53.1 60 25 4 19.03 8.988 0.111 0.446
70 25 560 132 0.0184 46.7 65 25 14 80.38 7.277 0.810 0.633
75 25 1,010 122 0.0082 68.3 70 25 28 144.70 3.926 1.544 0.782
80 25 1,010 152 0.0103 75.0 75 25 33 220.4 2.109 0.227 0.751
70 5 2,040 24 0.0154 184.3 80 25 39 250 16 0.388 0.758
70 15 1,375 38 0.0086 89.1 80 30 35 78.6 0.392 48.967 0.667
70 40 320 65 0.0189 43.1 80 40 25 6.5 2.246 321.6 0.308
70 50 110 10 0.0346 41.0 80 50 8 0.6 8.905 985.9 0.022
166

temperature. From the experimental data it seems to us by the slip-plane theory but in the case of the loss
that in shear ¯ow the lamellar system changes its modulus we obtained a signi®cant deviation from the
orientation at low shear rate and at higher shear rates theoretical value. The modi®ed version of the theory
the structure of the system starts to change by changing gave excellent agreement with the experiments. The
the connectivity or the size of the domains. Equation (9) necessity of the modi®cation was estimated to be due to
has a similar form as the temporary network equations the existence of the Frank stress, which has the role to
[22]. change the orientation of domains under shear. The
steady-state ¯ow curves were well described in the
framework of slip-plane theory if we introduce
Conclusions the breaking kinetics of the domain structure and we
can get a modi®ed Carreau-type equation. The fact
The complex rheological behavior of a liquid-crystal- that the system does not obey the modi®ed Cox±Merz
line surfactant±water system was investigated. The rule indicates that breaking of the domains does not
storage modulus versus frequency was well described occur in the linear viscoelastic region.

References

1. (a) Brown GH (ed) (1975) Advances in 8. Oswald P, Allain MJ (1988) Colloid 19. Radiman S, Toprakcioglu C, McLeish
liquid crystals, vol 1. Academic, New Interface Sci 126:45 TCB (1994) Langmuir 10:61
York; (b) Brown GH (ed) (1976) 9. Galleos C, Nieto M, Nieto C, Munoz J 20. Doi M, Harden JL, Ohta T (1993)
Advances in liquid crystals, vol 2. Ac- (1991) J Prog Colloid Polym Sci 84:236 Macromolecules 26:4935
ademic, New York; (c) Brown GH (ed) 10. Alcantara MR, Vanin JA (1995) Col- 21. Harden JL, Doi M (1996) J Rheol
(1978) Advances in liquid crystals, loids Surf 97:151 40:187
vol 3. Academic, New York; Brown 11. Valiente M (1995) Colloids Surf 22. Larson GR, Doi M (1991) J Rheol
GH (ed) (1979) Advances in liquid 105:265 35:539
crystals, vol 4. Academic, New York; 12. Penfold J, Staples E, Lodhi A, Tucker 23. Marucci M, Ma€ettone PL (1985) Pure
(e) Brown GH (ed) (1982) Advances in L, Tiddy GJT (1997) J Phys Chem B Appl Chem 57:1545
liquid crystals, vol 5. Academic, New 101:66 24. NeÂmeth Z, HalaÂsz L, PaÂlinkaÂs J, BoÂta
York 13. Robles-Vasquez O, Corona-Galvan S, A, HoraÂnyi T (1998) Colloids Surf A
2. Gray G, Winsor PE (1974) Liquid Sottero JFA, Puig JE (1993) J Colloid 145:107
crystals and plastic crystals. Wiley, Interface Sci 160:65 25. NeÂmeth Z, PaÂlinkaÂs J, HalaÂsz L, BoÂta
New York 14. Robles-Vasquez O, Sottero JFA, Puig A, HoraÂnyi T (1999) Tenside Surfac-
3. Oswald A, Huang H, Huang J, Valint JE, Monero O (1994) J Colloid Inter- tants Deterg 36:88
P (1984) US Patent 4,434,062 face Sci 160:436 26. Tamamushi B (1976) Pure Appl Chem
4. Brown GH, Walker JJ (1979) Liquid 15. Ho€mann H, Thuing C, Schmeidel P, 48:441
crystals and biological structures. Aca- Munkert V (1994) Langmuir 10:3972 25. Paasch S, Schambil F, Schwunger MJ
demic, New York 16. Ho€mann H, Thuing C, Schmeidel P, (1989) Langmuir 5:1344
5. KruÈssmann H, Bercovici R (1993) Munkert V, Ulbricht W (1994) Tenside 26. HalaÂsz L, MacskaÂsi L (1996) Plast
Tenside Surfactants Deterg 30:99 Surfactants Deterg 31:389 Rubber 33:146
6. Suzuki T, Tsutsumi H, Ishida A (1982) 17. Panizza P, Roux D, Vuillame V, Lu 27. Dimitrova GT, Tadros TF, Luckham
12th International Congress IFSCC CYD, Cates ME (1996) Langmuir PF, Kipps MR (1996) 12:315
Paris 1:117 12:248 28 BoÂta A (1999) J Hung Chem Soc
7. Bohlin L, Fontell KJ (1978) Colloid 18. Jones JL, McLeish TCB (1995) Lang- 105:270
Interface Sci 67:273 muir 11:785
Progr Colloid Polym Sci (2001) 117: 167±171
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

EÂ. Kiss Surface characterization of polylactide/

C. N. C. Lam
T. M. Duc polyglycolide copolymers
E. I. Vargha-Butler

Abstract The wettability and the spectroscopy at various takeo€ an-

surface composition of biodegrad- gles to get information on the depth
able polymers used as drug delivery distribution of the components.
particles were determined and com- Surface enrichment of the nonpolar
pared. Films of poly(lactic acid), (lactide) component in the outer-
poly(glycolic acid), and their co- most layer of the copolymer ®lms
polymers with four di€erent lactide/ was detected. The wettability be-
glycolide ratios of 85/15, 75/25, havior was in accordance with the
65/35 and 50/50 were formed by surface composition results, sug-
solvent-casting on polar (silicon gesting a surface activity e€ect
wafer, glass and mica) substrates. resulting in the orientation of the
Advancing and receding water con- nonpolar segments of the copolymer
EÂ. Kiss (&) tact angles were measured gonio- chains towards the surface of the
Department of Colloid Chemistry, metrically and also by using the ®lm and hence producing more hy-
L. EoÈtvoÈs University, P.O. Box 32, automated axisymmetric drop shape drophobic character for the copoly-
1518 Budapest 112, Hungary analysis method. Both the advancing mer ®lms than should be due to their
e-mail: [email protected]
Tel.: +36-1-2090555 and the receding water contact an- bulk composition.
Fax: +36-1-2090602 gles of the copolymers were higher
than was expected from the values
C. N. C. Lam á E. I. Vargha-Butler
Department of Mechanical and Industrial obtained for the two homopolymers Key words Wettability á
Engineering, University of Toronto, considering the increasing glycolide Biodegradable polymers á Drug
Toronto, ON, M5S 3G8, Canada content of the copolymers. Surface carrier á X-ray photoelectron
T. M. Duc analysis of the polyester ®lms was spectroscopy surface analysis á
Biophy Research S.A., Marseille, France performed by X-ray photoelectron Lactide/glycolide copolymers

Introduction Considering the applications, it is important to

establish whether the surface characteristics of the
Poly(lactic acid), DL-PLA, and its copolymers with homopolymers and the copolymers are di€erent from
poly(glycolic acid) (PGA), DL-PLGA, (with di€erent each other, because the interchange of these drug carrier
copolymer ratios) are widely recommended [1±5] as polymers, owing to their similar wetting characteristics,
polymeric drug delivery systems. The wettability of these could be bene®ciary for di€erent industries. In recent
biodegradable drug carriers in¯uences pharmaceutically literature [9±11] only few wettability data on these
important processes such as drug encapsulation and copolymers can be found. In these studies, the advancing
release mechanisms. Furthermore, the hydrophobicity of contact angles decreased with increasing PGA ratio, as
the polymer determines the extent of the surface expected.
modi®cation for the purpose of enhancing the biocom- The purpose of the present work was to study the
patibility of the microspheres and the nanospheres in wettability of DL-PLA and DL-PLGA copolymer surfac-
pharmaceutical, and medical applications [6±8]. es. The other homopolymer of the series, PGA, was also
168

studied for comparison only, since PGA is not a metric drop shape analysis pro®le (ADSA-P) a hole 1 mm in
substance considered for the preparation of a micropar- diameter was drilled in the centre of each wafer by using a diamond
drill bit from Lunzer (New York, N.Y., SMS ±0.027). The wafer
ticulate drug carrier owing to its nonsuitable physico- surfaces and similarly the glass plates were then soaked in freshly
chemical properties. The interpretation of the wettability prepared persulphuric acid (volume ratio of concentrated sulphuric
results was carried out using the chemical composition acid: hydrogen peroxide, 30 w/v% solution of 2:1) at least for 2 h.
data obtained by X-ray photoelectron spectroscopy The samples were thoroughly washed with double-distilled water
and dried under an IR lamp for 15 min before the coating process.
(XPS) on the surface layer of the polymer ®lms. The mica plates were freshly cleaved before the polymer deposition
The outcome of this study might provide a guideline in order to minimize carbonaceous contamination.
regarding the surface hydrophobicity of the lactide/ The polymer ®lms (except PGA) were prepared by a solvent-
glycolide-type polymers, and the data can be used to casting technique on the hydrophilic substrates. The polymers were
prepare drug carriers for successful and optimized drug dissolved in dichloromethane (2 w/v%) and 200 ll of each polymer
solution was deposited onto the relevant substrate with a pipette.
delivery. To prevent fast evaporation of solvent (hence to enhance the ®lm
smoothness) the samples were covered for 20 min, allowing the
solution to spread on the surface. Then, the polymer ®lms were
Experimental dried in a vacuum oven overnight. A PGA layer was formed from a
polymer melt on a glass substrate at 230 °C, then the ®lm was
cooled slowly to room temperature and stored in a vacuum box
Materials until the measurements were performed.
DL-PLA (Mw: 106,000), PGA, and four of their random copoly-
Methods
mers, DL-PLGA, with 85/15 and 75/25 (Mw: 90,000±126,000), as
well as with 65/35 and 50/50 (Mw: 40,000±75,000) component ratios
Contact-angle measurement
of lactide/glycolide obtained from Sigma-Aldrich Canada (Oak-
ville, Ontario, Canada) were used for polymer ®lm preparation.
The structural compositions of the homopolymers, i.e., DL-PLA Water contact angles were measured goniometrically using a
and PGA are illustrated in Fig. 1. Rame-Hart M2033 (Mt Lakes, N.J., USA) instrument. Water
Dichloromethane (ACS reagent high-performance liquid chro- droplets on the polymer surface were formed in a closed chamber
matography grade) supplied by Sigma-Aldrich was used for sample saturated with liquid vapour. The volume of the drop was increased
®lm preparation. Double-distilled water was applied as the step by step with a micropipette ®xed to the measuring chamber
measuring liquid. and the static advancing angles were determined. Then, while
Silicon wafers h100i (Silicon Sense, Naschua, N.H., USA) with withdrawing the liquid in a similar way, the receding angles were
a thickness of 525  50 lm, glass plates (microscopic cover measured. Generally, 16±20 advancing and receding contact angles
glasses: 22 ´ 40 ´ 0.16 mm, Menzel-Glaser, Germany) and mica were determined at 25.0  0.5 °C and were used to calculate the
sheets (Mica Supply, UK) were used as substrates for the polymer average values on each ®lm.
®lms. The ADSA-P technique as an automated and more accurate
dynamic method producing reliable contact-angle data was also
applied to characterize the wetting properties of the polymer and
Sample preparation copolymer surfaces. The principle of the method is the ®tting of the
experimental pro®le of a sessile drop by the Laplacian theoretical
The silicon wafers were cut into a rectangular shape of about drop pro®le. Mathematical derivations and computational proce-
2.5 ´ 1.5 cm. For contact-angle measurements using the axisym- dures can be found in previous work [12±15]. The volume of the
droplet on the solid surface is increased and decreased continuously
with a low rate, resulting in a contact line motion with a velocity of
0.1±1.0 mm/min for advancing and 0.3±2.0 mm/min for receding
three-phase contact lines, respectively. The liquid drop is formed on
the surface from below through a hole drilled into the solid sample
before measurement. The shape of the drop is recorded by a
microscope/charge-coupled-device camera and is processed by a
computer operating at a rate of one picture in every 2 s. Individual
sessile drops (4±10) were formed on each polymer and approxi-
mately 200 images were processed per drop. The measurements
were performed at 23.0  0.5 °C and at 45% relative humidity in a
temperature-controlled room. Besides providing a large amount of
accurate contact-angle data in an automated way, an additional
bene®t of the method is that the surface tension of the measuring
liquid is monitored simultaneously during the contact-angle
measurement.
The average advancing and receding contact angles were plotted
with the corresponding 95% con®dence limits which did not exceed
0.9° for the ADSA-P and 1.2° (with one exception: receding angle
on PGA) for the goniometric method, respectively.

Fig. 1 Chemical composition of the homopolymers: poly(lactic acid) Surface analysis

(PLA) and poly(glycolic acid) (PGA). The numbers mark the carbon
atoms in di€erent chemical environments resulting in C 1s electrons Chemical analysis of the polymer (DL-PLA) and two selected
with various binding energies copolymer (DL-PLGA 85/15 and DL-PLGA 50/50) ®lms deposited
 169

on hydrophilic mica substrate was performed by XPS. Measure- ADSA-P technique or goniometrically on the copolymer
ments were made using a SCIENTA 200 spectrometer using a surfaces do not change with the copolymer composition.
monochromatized X-ray source (Al Ka at 1,486.6 eV) with a spot
size of 4 mm ´ 1 mm. A ¯ood gun with characteristics of 3 eV and The expected values are represented by dotted lines in
30% emission (0.3 mA) was necessary for charge compensation. Fig. 2 using the simple approximation that the hydro-
The relative atomic composition of the surface layer of the polymer phobic character of the copolymers can be estimated
®lms was determined from the spectra, while the chemical structure from the properties of the homopolymers taking into
of the surface layer was deduced using the chemical shift e€ect in
the C 1s signal. In addition to the usually employed 90° takeo€
account the component ratio. There is a signi®cant
angle relative to the sample surface, the measurement for each deviation from this expectation; the advancing water
sample was repeated at a grazing 25° takeo€ angle, in order to contact angles of the copolymers do not di€er from that
study the surface composition of the outermost (2.4 times thinner) determined for PLA. The results obtained by using
layer of the polymer ®lms as well, and hence to get information on organic liquids besides water also provided constant
the depth distribution of the components. All spectra were
calibrated to the position of the aliphatic component of C 1s peak advancing angles on the copolymers [16].
at 285.0 eV binding energy. Considering the receding contact angles there is also a
notable deviation from the expected values. The mea-
sured angles are much higher than those predicted from
Results and discussion the composition of the copolymers. In contrast to the
advancing angles, the receding contact angles are not
Wettability of the polymer and copolymer surfaces constant for the various copolymers but a slight but
signi®cant decrease was observed with decreasing poly-
The mean advancing and receding contact angles of lactide ratio. The trend is clear in the receding angles
water measured on the polymer and copolymer surfaces measured by the ADSA-P technique.
are plotted in Fig. 2. The wettability is displayed as a From the wetting behaviour reported here we can
function of the lactide content of the copolymers; thus conclude that the surfaces of PLGA copolymers do not
100% corresponds to the homopolymer PLA, while 0% di€er or just slightly di€er from that of a PLA ®lm under
represents the other homopolymer, PGA. the conditions of advancing contact with water.
The wettability of the homopolymers indicates that
PLA is rather hydrophobic (QA » 80°), but PGA seems
to be considerably less hydrophobic (QA » 57°). The Surface composition
di€erences in the advancing and receding angles of water
are about 20° and 30°, respectively; however, the The atomic compositions of the surface layer of one
advancing contact angles measured either by the homopolymer (PLA) and two copolymer (PLGA with
85/15 and 50/50 component ratios) ®lms were determined
by the XPS technique. The overview spectra indicated the
presence of only carbon and oxygen originating from the
polymer ®lms; no signal from the mica substrate was
detected, which means that the polymers formed contin-
uous ®lms with a thickness greater than the analysis
depth of the XPS experiment. The C/O atomic ratios
characterizing the chemical composition measured at the
two angles are summarized in Table 1. They di€ered
slightly from the expected values of the stoichiometric
ratio for PLA, while the C/O ratios obtained for
PLGA85/15 and PLGA50/50 are in better agreement
with the expected value. The XPS atomic ratios are to be
considered only on a relative level and the most
signi®cant information is the surface carbon enrichment
indicated by the higher C/O values at a 25° takeo€ angle
compared to those at 90°. This carbon enrichment
increases relatively with the bulk PGA content in the
polymer ®lms.
Decomposition of the carbon signals into their
Fig. 2 Advancing (n) and receding (d) water contact angles di€erent chemical components and their angular depen-
measured with the axisymmetric drop shape analysis pro®le and dence provided further and more relevant information
goniometric (h, s) methods on PLA/PGA ®lms with various lactide
contents. The dotted lines represent the expectable values of the on the structure of the surface ®lms [17±19]. Peak
contact angles considering the ratio of the components in the synthesis was performed on the C 1s spectra with the
copolymers following chemical shifts: C±C and C±H at 285.0 eV,
170

Table 1 Chemical composition of the surface layer of poly(lactic C±O at 287.0 eV, O±CˆO at 289.0 eV (Fig. 3). The
acid) (PLA) and PLA/poly(glycolic acid) copolymer ®lms (PLGA) results of the peak synthesis as well with the numbers
determined by X-ray photoelectron spectroscopy (XPS)
referring to the various carbons from Fig. 1 are collected
Polymer Stoichiometry Carbon components (%) in Table 1. From the analysis performed at a 90° takeo€
C/O angle the carbon component values found for PLA were
C±C (1) C±O (2) O±C=O (3) in good agreement with the theoretical composition;
however, the experimentally determined composition of
PLA
Theoretical 1.5 33.3 33.3 33.3 the ®lm re¯ected a higher C±C content at the expense of
XPS at 90° 1.33 34.1 33.6 32.3 the more polar C±O and O±CˆO components in the
XPS at 25° 1.37 33.3 34.3 32.4 surface layer of the PLGA copolymers. This e€ect
PLGA 85/15 became more pronounced for higher PGA content
Theoretical 1.41 28.4 35.8 35.8 (PLGA50/50). The component analysis was also per-
XPS at 90° 1.30 31.4 34.2 34.4 formed at a 25° takeo€ angle, which provided data
XPS at 25° 1.40 32.8 34.1 33.1 corresponding to the chemical composition of the
PLGA 50/50 outermost layer owing to the sampling of a 2.4 times
Theoretical 1.22 16.6 41.7 41.7 thinner layer than at 90°. The deviation of the XPS data
XPS at 90° 1.18 23.4 38.6 38.0 obtained in this case from the theoretical values was
XPS at 25° 1.29 26.1 37.2 36.7 above 15 and 50% for PLGA85/15 and PLGA50/50

Fig. 3 Deconvoluted peaks of

C 1s X-ray photoelectron spec-
troscopy signals obtained for
PLA and PLGA50/50 copoly-
mer ®lms at 90°and 25° takeo€
angles
 171

copolymer ®lms, respectively. This indicates a consider- the surface composition of the copolymers can change
able alteration of the composition of the surface layer owing to the presence of a polar liquid at the interface if
characterized by a surface enrichment of aliphatic carbon the segments have the freedom to orient to an energet-
related to that of the ``bulk'' phase of the copolymer ically preferable position [20]. That change in the surface
®lms. distribution or the orientation of the polymer segments
Both the wettability and the surface composition was indicated by the lower receding water contact angles,
studies revealed that DL-PLGA copolymer ®lms repre- but those values were still higher than the values expected
sent a more hydrophobic surface than would be expected from the bulk composition.
according to their bulk composition. A reasonable The behaviour of the copolymer surfaces, namely the
explanation for that might be the surface orientation of ability to adapt to some extent the surface composition to
the nonpolar groups of the copolymers allowed by a the properties of the neighbouring phase further supports
certain segment mobility at room temperature. The e€ect the hypothesis that the surface polarity of DL-PLGA)
of that kind of surface activity was proved to increase copolymer ®lms is dominated by the nonpolar groups
with higher glycolide content. The results show that oriented at the solid/air interface.
DL-PLGA copolymer surfaces up to 50/50 component
ratio are of similar hydrophobicity to the PLA homo- Acknowledgements We give our special thanks to A.W. Neumann
polymer under dry conditions, when the polymer surface for using his facilities. This research was supported by the
®rst contacts with water (advancing contact angles). Ministry of Culture and Education (Hungary) through Research
and Development Project FKFP 0156/1997, by the Natural
It is worth noting, however, that the receding water Sciences and Engineering Research Council of Canada through
contact angles determined by the ADSA±P technique grant no. OGPOO37393 and by a grant from Merck Frosst
decreased with increasing glycolide (polar) component of Centre for Therapeutic Research (Canada). The authors express
the copolymers. Receding angles are formed in ADSA-P their appreciation to Z. Policova, J.Y. Lu and L. Zhang
(Department of Mechanical and Industrial Engineering, Univer-
measurements on a solid surface in a controlled way sity of Toronto, Canada) and to Mrs. HoÂrvoÈlgyi (EoÈtvoÈs
following a well-de®ned contact with water, leading to University, Budapest) for their valuable help in the measurements
hydrated state of the surface. During the contact time, and technical evaluation.

References

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Chemical Society Symposium Series PJ (1999) J Controlled Release 59:173 The Scienta ESCA300 Database. Wi-
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Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

H.-G. Kilian Model of reversible aggregation: universal

M. Koepf
V. I. Vettegren features of ¯uctuating ensembles

Abstract The model of reversible black and liquids, of defects on the

H.-G. Kilian (&) á M. Koepf aggregation predicts universal surface of loaded metals and of cells
Experimentelle Physik, University of Ulm, reduced ensemble number or energy of bacteria and yeast.
Albert-Einstein-Allee 11, 89069 Ulm, distributions described by
Germany
G-functions of di€erent classes,
V. I. Vettegren typi®ed by the value of a single
AF Jo€e Physico-Technical Institute, parameter, p. The universality of Key words Aggregation á Ensemble
Russian Academy of Science,
Polytechnichaja ul. 26, St. Petersburg, the model is evidenced by the structure á Fluctuation á
194021 Russia description of ensembles of carbon Universality á Glasses

Introduction The model of reversible aggregation

Reversible aggregation of atoms, molecules or molecu- The key assumption [3] is that ``units'' form metastable
lar units (``particles'') [1±3] is typi®ed by weak particle- aggregates with a liquidlike anisotropic internal struc-
to-particle contact energies in the range of the mean ture. Equivalent ensemble con®gurations are generated
thermal energy. The con®guration of aggregate ensem- consecutively. Described analogously to many simulta-
bles and the intraaggregate states ¯uctuate. Such neously and reversibly running linear chemical reac-
conditions are met in very di€erent systems. The tions [3, 9] the thermodynamic interpretation of the
aggregate ensemble of carbon black [4±6] produced in reaction constant reveals that aggregation should
a gas stream at very high temperatures (around 1800 K) mainly be controlled by the standard aggregation
within extremely short times (microseconds) is depicted energy, Dup. For all the di€erent systems studied until
in Fig. 1 [7]. In liquids, aggregates ``collapse'' forming now Dup is constantly assigned to a positive value
densely packed patterns as it is evidenced by the surface identifying aggregates as dynamic clusters. The energy
structure of glassy poly(methyl methacrylate) [3] and of of internal modes of motion overpowers the negative
a monolayer of bottle-brush molecules [3, 8] depicted in ``contact energy'' per unit. This is illustrated in Fig. 3.
Fig. 2. Since bottle-brush molecules have a diameter of This aggregation energy of an aggregate with y
about 6 nm the chains can be seen. The anisotropic contacts may then be written as [3]
intraaggregate patterns show that folded loops or
chain ends are concentrated in the boundaries of the
aggregates. Dupy ˆ yDup : 1†
The model of reversible aggregation [3] allows us to
describe the stationary ensemble properties and to Neglecting ``extra contacts'' as in branched con®gura-
discover universal features as demonstrated later for tions, the number of contacts, y, is y ˆ ya 1 (ya: number
carbon black, liquids, defect ensembles at the surface of of units). The number of aggregates with y contacts,
loaded metals and for bacteria and yeast. n0p y†, is then written as
 173

Fig. 1 Transmission electron microscopic picture of carbon black

N358 according to Ref. [7]

np y † ˆ n0 y p exp byDup ;
1 2†
bˆ ;
kB T
where n0 is the normalization factor, kB is the Boltzmann
constant and T is the absolute temperature. The value of
the exponent p of the front factor of Eq. (2) de®nes
di€erent ``classes of aggregate ensembles''. For isotropic
Fig. 2 A Pulsed force scanning microscopic picture of poly(methyl
aggregates p is zero. An ensemble of randomly oriented methacrylate) (PMMA) in the glassy state wetted with alcohol [3].
aggregates the anisotropy of which grows with y is B Tapping-mode image of a monolayer of bottle-brush molecules
characterized by p ˆ 2 owing to the additional orienta- depleted on mica [3]
tion ensemble entropy. Dup may depend on the value of p.
The size distribution of aggregates (``mass distribu-
tion'') is then given by



np gpy
k B T †p
hp y † ˆ ynp y† ˆ n0 y p‡1 exp byDup ; 3† npr ˆ ˆ gppy exp gpy ; npg ˆ C ;
npy Dupp
so the energy distribution is equal to


hpu gpy
kB T †p‡1
hpu y † ˆ n0 y p‡1 Du0 exp byDup 4† hpur ˆ ˆ gp‡1 exp g ; h pg ˆ C ;
hpg py py
Dupp
With Dup > 0 the mean size of the aggregates, hy(T)i, gpy ˆ byDup :
should grow proportionally to the absolute temperature 6†
[3].
From Eqs. (2) and (4) the reduced number distribu- Quasistationary aggregate ensembles of the same class
tion, npr, and the conjugated energy distribution, hpur, are (parameter p) are predicted to show the same reduced
deduced to be given by [3] distribution.
174

always running aggregation phenomena. The anisotropy

of the particles should grow with y.
The particles undergo aggregation. The frequency of
the ``particle aggregates'' as a function of the diameter
(deduced from such electron microscopy images by Hess
and Herd [7]) is also reproduced by the (p ˆ 2) version of
Eq. (3) (Fig. 5B). The aggregation energy of the particles
is larger than that of the aggregates. This is a necessary
condition for getting hierarchically organized ensembles
independently ``optimized'' on each level (maximum
ensemble entropy [10]).

Quasistationary dynamic states

The invariant frequency distribution of the aggregates as

function of y/hyi obtained by solving Smoluchovsky's
Fig. 3 The process of aggregation. The internal energy of all the di€erential equation [1, 11, 12] is depicted in Fig. 6 (the
modes of oscillation per unit, uos, should exceed the weak contact size of the aggregates increases continuously). The
energy, ucon
distribution corresponds to a stationary (p ˆ 2) class of
our model (solid line). The internal anisotropy of the
aggregates should grow with y. Apparently, in the course
Experiments of time the cluster ensemble runs through equivalent
con®gurations with a maximized ensemble entropy. The
The reduced frequency distribution of aggregates entropy production is minimized [13]. This explains
deduced from the images in Fig. 2 is shown in Fig. 4. straightforwardly why, under the given conditions,
The solid line is computed with the (p ˆ 1) version of carbon black shows the same reduced size distribution
Eq. (3) (``two-dimensional!'' layer). For each class this for particles and aggregates.
leads to the general conclusion that the mean aggregate
size at the glass temperature should be identical [3]. The
anisotropic intraaggregate structure growing with y An important test
should be ®xed during the life time of an aggregate.
The frequency of particles of di€erent types of carbon For Dup > 0 the size of the aggregates should grow
black [7] is plotted against the diameter in Fig. 5A. The proportionally to T (Eq. 5). This can be scrutinized by
(p ˆ 2) version of Eq. (3) reproduces the data fairly well. comparing the distribution of carbon black generated at
The particle ensemble is optimized irrespective of the about 1600 K with that after special treatment of
cellulose acetate butyrate (CAB) chip dispersions at
about 450 K [14]. ``Process-induced activation'' should
be accounted for by introducing the ``e€ective temper-
ature'' T* > T.
Herd et al. [14] deduced the volume fraction, V¢(ya)/
V(ya), of aggregates as a function of the ``relative free
volume'' fraction, v¢(ya)/v(ya). v¢(ya)/v(ya) is described by
[9]
v0 ya † veq ya †
ˆ ˆ vya2j 1 : 7†
v v
V¢(ya)/V(ya) is then written as
V 0 ya †

ˆ CV 0 ya3j 1 ya2 exp byDup ;
V 8†
CV 0 ˆ vC0 :
The constants CV¢ and C0 are linked by the parameter
Fig. 4 Reduced frequency distribution of aggregates at the glassy v (Eq. 7). After the CAB treatment, the size of the
surface of PMMA and for a frozen monolayer of bottle-brush aggregates is reduced as shown in Fig. 7, where the
molecules as a function of the reduced area distribution V(ya)¢/V(ya) of a ``dry ensemble'' is com-
 175

Fig. 5 A Frequency distribu-

tion of particles of di€erent
mean diameters (dexp) of parti-
cles of carbon black against the
diameter deduced from electron
microscope pictures [7]. The
solid lines represent data com-
puted with the (p ˆ 2) version of
Eq. (2). dya is de®ned by
dya ˆ 2yaflo (lo set equal to
1 nm). The parameter f is 1/3
for densely packed particles in a
cubic lattice. For loosely ar-
ranged aggregates f increases.
Parameters are indicated.
B Mass fraction of aggregates
plotted against the diameter
deduced from electron micro-
scope pictures [7]. The solid
lines represent data computed
with the (p ˆ 2) version of
Eq. (3).

pared with the CAB pattern. The data can be ®tted with loaded metals (copper, gold, molybdenum and palladi-
Eqs. (7) and (8) by only replacing T* ˆ 1600 K by um) [15±18]. As a representative example, the pattern of
T* ˆ 563 K in full accordance with Eq. (5). copper under constant stress (r ˆ 350 MPa) after 16 h is
depicted in Fig. 8.
In loaded metals, dislocations can move at least within
Defect ensemble of the surface of loaded metals conservative sliding planes which are segregated at the
surface. Fluctuating defect ensembles are generated
Scanning tunnelling microscopy reveals a ¯uctuating (Fig. 8A), characterized by a mean life time of the order
ensemble of submicroscopic defects on the surface of of 20 h. The data here are ®tted with the (p ˆ 1) version
176

of Eq. (2). The reduced size distributions of loaded Bacteria and yeast ensembles
metals (copper, gold, molybdenum and palladium) fall
on a master curve (Fig. 9). Images of Escherichia coli and of yeast ensembles [19] are
Since defects with the same shape are oriented shown in Fig. 10. Embedded in a culture medium the
(Fig. 8A, B) the (p ˆ 1) class representation of Eq. (2) cells grow, whereby the internal properties and functions
demands that defects should exhibit di€erent randomly of each cell are at each moment entirely determined by
generated metastable internal structures. The ensemble the proteins made according to the genetic instructions
entropy increases, and p becomes equal to 1. stored in the DNA molecules [19]. The cytoplasm of the
cells seems to be gelatinized since the constituents are
linked to each other.
A key point is that the cells reproduce quickly by
dividing in two [19]. Under optimum conditions, when
food is plentiful, a bacterium can duplicate itself in as
little as 20 min, depending, of course, on environmental
conditions. If growth and decomposition rates are
identical a stationary ensemble with a more-or-less
broad cell size distribution should be constituted. The
size should now be characterized by the number of
``units''. A unit is possibly represented by the chain-
standing molecular group with a side-standing amino
acid and the environment each unit is, on average,
surrounded by. Yet, at the moment it is not necessary
to identify these units. When a new unit is generated
within the cell the energy should increase by the
standard energy Dup, which is comparably large since
it includes covalent peptide bonds. The state of
reference is the ``nonrealizable system'' without con-
Fig. 6 Reduced number distribution of aggregates of di€erent size as tacts between the units. Dup should be positive, i.e. the
a function of y/hyi obtained by a numerical solution of the
Smoluchovski equation according to Refs. [11, 12]. The solid line energy of ``internal modes of motion'' is supposed to
represents data computed with the use of the (p ˆ 2) version of Eq. (6) overpower the negative contact energy. Dup is likely to
(hyi  1/bDu1) depend on the properties of the culture medium.

Fig. 7 Volume fraction of

N358 carbon black against
v¢(y)/v(y) according to Herd
et al. [14]: A h dry, s CAB,
B master curve. The solid lines
represent data computed with
Eqs. (7) and (8) and the
parameters indicated
 177

Fig. 8 A Tunnelling micro-

scopic topogram of the defect
ensemble of copper under a
stress of r ˆ 350 MPa at
t ˆ 16 h according to Kilian
et al. [18]. B Single defects at
the surface of loaded copper
and gold crystals [18]

Fig. 9 Master curve of the

number distributions of the
defects at the surface of crystals
of loaded copper, gold and
molybdenum as function of the
reduced depths, ya,red [15, 16,
17, 18]. The solid line represents
data computed with the (p ˆ 1)
version of Eq. (2)

Living cell ensembles show a ``birth volume'' (yb), i.e. be activated. This distribution is a ``maximum entropy
a smallest cell. The number of ``contacts'' between units pattern'' [3]. The parameter p should not depend on
in a cell set equal to y ˆ ya 1 the quasistationary environmental conditions. Rewriting Eq. (9) in terms of
number distribution, np(y), should be given by the the reduced variable gyb we are led to the universal relation
modi®ed version of Eq. (2) gyb

  gred ˆ ˆ gpys exp gyb ;
np y† ˆ n0 y yb †p exp b y yb †Dup ; 9† C
p 10†
gyb ˆ b y yb †Dup ; C ˆ bDup :
where 1/b represents the mean energy stored in enzymat-
ically excited intermediate states in the cell cytoplasm; it The proof of our conception is thus easily done by
exceeds the standard energy Dup, so ¯uctuations can easily verifying that the reduced quasistatic number distribu-
178

Fig. 10 A Escherichia coli

according to Ref. [19]. B Yeast
cells according to Ref. [19]

Fig. 11A±C Frequency distributions of the bacteria at di€erent The cell size distribution
doubling times, s2 [20] and di€erent growth rates, r [21]. The lines
represent data computed with the (p ˆ 3) version with the parameters
in the micrometre representation of Eq. (2) We present in Fig. 11 the frequency of bacteria as a
function of the length at di€erent mean duplication
times, s2 [20] i.e. under di€erent growth rates, r [21]
tions of bacteria or yeast cells of di€erent sizes, typi®ed (r ˆ ln2/s2). The data are fairly well reproduced with the
by p, are universal. (p ˆ 3) version of Eq. (9). According to results not
 179

Fig. 12 Frequency distribu-

tions of di€erent mutants of
yeast cells as a function of the
cell volume according to
Ref. [22]. The solid lines
represent data computed with
the (p ˆ 3) version of Eq. (2)
with the parameters in the
nanometre representation as
indicated

reported here bacteria establish quasistationary ensem-

bles of this class even when irreversible processes run o€.
Ensembles of mutants of yeast show analogous
volume distributions of the (p ˆ 3) type [22] (Fig. 12).
The data represented by the solid lines were computed
with Eq. (9). Du3 changes slightly with a modi®cation of
the genetic code, i.e. the conformation within the cells of
yeast depends on the individual structure of the various
proteins. The bDu3 values cover the usual range.
The internal structure of bacteria is likely to be
anisotropic showing an uniaxial ®bre symmetry [19]. If
the bacteria are randomly oriented and if the internal
structure is ®xed p should be equal to 2. Yet, according to
the energy landscape of a protein molecule depicted in
Fig. 13 [23] di€erent ``quasi-one-dimensional metastable
con®gurations'' of the intracellular protein complex can
be generated thermally. The ensemble entropy increases
and p goes to 3.
It was not expected that the frequency of the cell Fig. 13 Sketch of the energy landscape of a folded protein according
to Fraunfelder et al. [23], which is typi®ed by a pocket with a set of
volume of yeast cells also belongs to the (p ˆ 3) class. The low-energy potential walls. They characterize the many metastable
anisotropic properties of the cell should in both cases con®gurations (or conformations?) the folded protein with an
exhibit a ®bre texture, the con®guration of which should invariant global structure is able to visit in the course of time
¯uctuate topologically analogously to the behaviour of (thermally activated)
bacteria.
lengths has been determined for bacteria and yeast
cells by decoding the genome. The number of proteins
The length distribution of the proteins of three di€erent bacteria and for yeast (Saccharomy-
ces cerevisia) is plotted against their length (i.e. the
The proteins constitute most of the dry mass of a cell number of amino acids per strand) [19, 24] in Fig. 14.
[19]. The prospective number of proteins of di€erent For both systems the data represented by the solid
180

Fig. 14 Plot of proteins encod-

ed by several chromosomes [19]
of di€erent bacteria and of the
yeast Saccharomyces cerevisia
showing the numbers of pre-
dicted proteins of di€erent sizes
according to Ref. [24]. The solid
lines represent data computed
with the (p ˆ 1) version of
Eq. (2) with the parameters as
indicated. The lowest panel
shows the master curve of all
the distributions shown above

lines were computed with the (p ˆ 1) version of Despite the di€erences in the structure of bacteria or
Eq. (9). Rapid enzyme catalyzed generation or decom- yeast cells the reduced size distribution of the intracell
position of proteins is necessary to permit optimiza- proteins [24] belongs to the same universal (p ˆ 1) class.
tion of the intracell protein sequences as observed Hence, in both cell types many statistically equivalent
here. con®gurations of the proteins should continuously be
 181

generated or decomposed. Since the cytoplasm is gela- logical parameters, the values of which do not ¯uctuate
tinized, any free orientation of the proteins is inhibited. to measurable extents.
The same argument holds for yeast cells. By having the The mechanisms of reversible aggregation rely on
proteins linked in an intracell sca€old, the thermally having weak long-range interaction energies. The global
activated ¯uctuation of their ``chainlike'' con®gurations properties are controlled by the ®nite size of the
should be represented by quasi-one-dimensional random aggregates, while their individual characteristics are
statistics (p ˆ 1). Du1 falls in the usual range of determined by the properties of the units. Aggregates
0.004 £ bDu1 £ 0.008. are, in any case, metastable dynamic entities (Dup > 0!).
Despite the remarkable di€erences of the individual The isoenergetic ensemble con®gurations ¯uctuate so as
properties (di€erent molecular units, di€erent intracel- to maximize the ensemble entropy. Controlled by these
lular structures, no nucleus in the cells of bacteria in boundary conditions, ensembles constituted by very
contrast to yeast cells, di€erent complex structures of the di€erent units (carbon black, liquids, loaded metals and
various folded proteins), bacteria and yeast cells seem to simple living systems) generate their structure analo-
be able to optimize their ensemble structure adequately gously. Each class (p) turns out to be characterized by
and independently on each level according to the generalized symmetries which are typical for the model
extremum principles of thermodynamics: Both cell of reversible aggregation. Moreover, the ensembles are,
ensembles belong to the (p ˆ 3) class, while the ``intracell by de®nition, ``perfect'' and are able to ``heal them-
ensemble'' is of the (p ˆ 1) type. This is manifested by the selves'' via structure-controlled relaxation processes.
master curve of the length distributions of both cell types This guarantees unsurpassed perfection and reproduc-
(Fig. 14). The reduced cell size distributions of both tion, impressively proven with the description of
systems are, of course, also identical. ensemble properties of bacteria and yeast cells, which
are ``globally'' controlled by the extremum principles of
thermodynamics. This is an important matter since the
Final comments statistical identity of cell ensembles is guaranteed. A
genesis of complex individual ensemble structures,
The results presented here identify universal features of essentially as in ensembles of simple living systems, is
¯uctuating ensembles. Aggregates and their analogues not impeded at all. A unique correlation between
should behave like metastable microphases, so their ensemble structure and cell functions is likely to be
internal properties can be characterized by phenomeno- individually installed in each case.

References

1. Smoluchovski M (1916) Phys Z 17:585 8. Pieper B, Dulfer N, Kilian HG, Wol€ S 17. Vettegren VI, Rakhimov SS, Svetlov
2. Botet R, Jullien R., Kolb M (1984) (1992) Colloid Polym Sci 270:29 VN (1997) Proc SPIE 33:226
Phys Rev A 30:2150 9. Kilian HG (2001) Colloid Polym Sci (in 18. Kilian HG, Vettegren VI, Svetlov VN
3. Kilian HG, Zink B, Metzler R (1997) press) (2000) Physics Solid State 42:2083
J Chem Phys 107:8697 10. Montroll EW, Shlesinger MF (1983) 19. Alberts B, Bray D, Johnson A, Lewis J,
4. Donnet JB, Bansal RC, Wang MJ (eds) J Stat Phys 32:209 Ra€ M, Roberts K, Walter P (1998)
(1993) Carbon black. Dekker, New 11. Jullien R (1990) New J Chem 14:239 Essential cell biology. Garlan, New
York 12. Botet R, Jullien R, Kolb M (1984) Phys York
5. Donnet JB, Voet A (1976) Carbon Rev A 30:2150 20. Kubitchek HE (1969) Biophys J 9:792
black. Dekker, New York 13. Prigogine I (1961) Introduction to 21. Ecker RE, Schaechter M (1963) Ann
6. Wagner HG (1081) In: Siegela DC, thermodynamics of irreversible pro- NY Acad Sci 102:549
Smitter GW (eds) Particle formation cesses. Wiley, New York 22. Gross FR (1989) J Cell Sci 12:117
during combustion. Plenum, New 14. Herd CR, McDonald GC, Hess WM 23. Fraunfelder H, Wolynes PG, Austin
York, pp 1 (1991) Rubber Chem Technol 65:1 RH (1999) Rev Mod Phys 71:419
7. Hess WM, Herd CR (1993) In: 15. Vettegren VI, Rakhimov SS, Svetlov 24. Netzer WJ, Hartl WU (1997) Nature
Donnet JB, Bansal RC, Wang MJ VN (1996) Phys Solid State 38:323 388:343
(eds) Carbon black. Dekker, New 16. Vettegren VI, Rakhimov SS, Svetlov
York, p 89 VN (1997) Phys Solid State 39:1389
Progr Colloid Polym Sci (2001) 117: 182±188
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

D. Pawlowski Change of structure and phase behaviour

B. Tieke
during homo- and copolymerisation
of (2-methacryloyloxyethyl)dodecyldimethyl-
ammonium bromide in a hexagonal
lyotropic mesophase

Abstract The c-ray initiated poly- to the binary system results in a

merisation of (2-methacryloyloxy- decrease in the transition tempera-
ethyl)dodecyldimethylammonium ture from the hexagonal phase to the
bromide in a hexagonal lyotropic isotropic solution until for a system
mesophase was investigated. The with (2-methacryloyloxyethyl)dode-
binary mixture with water and the cyldimethylammonium bromide and
ternary mixture with water and acrylamide in equimolar ratio the
acrylamide were studied. Especially mesophase has completely disap-
the changes in the structure and the peared at room temperature.
phase behaviour during polymerisa- However, upon c-ray irradiation the
tion were investigated. Small-angle transition temperature is raised again
X-ray scattering indicates that the and for systems which are not liquid-
polymerisation of the binary mixture crystalline in the monomeric state a
is accompanied by a discontinuous mesophase is eventually induced.
increase of the d spacing from 3.08 to The polymerisation rate of the
3.36 nm at about 5% conversion ternary system is lower because the
although the hexagonal order of the acrylamide induces a di€erent
system is retained. The increase surfactant conformation in the
originates from a conformational mesophase. IR spectroscopic analy-
transition in the headgroup region of sis of the copolymer formed in the
(2-methacryloyloxyethyl)dodecyl- ternary system indicates that acryla-
dimethylammonium bromide and mide is enriched at low conversion.
leads to a strong acceleration of the
D. Pawlowski á B. Tieke (&) reaction rate. Evidence for the ther-
Institut fuÈr Physikalische Chemie der modynamic stability of the system Key words c-ray irradiation á Poly-
UniversitaÈt zu KoÈln,
Luxemburger Strasse 116, during the entire reaction process is merisation á Cationic surfactant
50939 Cologne, Germany presented. Admixture of acrylamide monomer á Lyotropic phase

Introduction studies were carried out in order to prepare more stable

LLC nanostructures, either by mixing amphiphilic
Highly concentrated aqueous solutions of surfactants polymers and water [5±7], by growth of polymers within
often exhibit lyotropic liquid-crystalline (LLC) phase the hydrophilic regions of LLC phases of commercial,
behaviour [1±3]. In the LLC phase well-de®ned nanom- nonpolymerisable surfactants [8±10] or by the in situ
eter-scale architectures are present; these exhibit inter- polymerisation of reactive surfactants in the LLC phase
esting material properties and are useful for a variety of [11±20]. Especially the latter method appears to be very
applications [4]. Unfortunately, they are rather instable straightforward and elegant; however, recent studies
to perturbations such as a change of pressure, temper- indicate that the in situ polymerisation may proceed
ature and composition of the mixture. Therefore, several under a phase change [20], be incomplete [15±17], not
 183

occur at all [15] or the resultant polymeric nanostructures 60

Polymerisation was carried out by subjecting the samples to
are the result of a phase separation and are not from the Co c-ray irradiation (dose rate 0.388 kGyh)1). The conversion to
polymer was determined gravimetrically after leaching out the
monomeric LLC arrays [9, 21, 22]. water-soluble monomer from the water-swellable (but not water-
A big problem of the in situ polymerisation in the soluble) polymer and after subsequent drying of the polymer gel in
LLC phase is that a general understanding of the poly- a vacuum at room temperature until a constant weight was
merisation process is still missing. Most of the studies obtained.
only dealt with the characterisation of the system before
and after polymerisation, but the systems were not Methods
examined during polymerisation. In order to elucidate The composition of the copolymer was determined using IR
the optimum reaction conditions and to prepare stable spectroscopy. The ratio of the band intensities of the C ˆ O
LLC materials suitable for applications, more detailed stretching modes at 1,650 cm)1 (ester group) and 1,720 cm)1
studies of the polymerisation process itself are necessary, (amide I) was used to evaluate the composition.
for example, by investigating the phase behaviour and The phase behaviour was studied using a standard Zeiss
polarising microscope equipped with hot stage and a camera (Zeiss
the structural changes during the polymerisation. MC 80). To investigate the phase diagrams, a few drops of the
The purpose of our contribution is therefore to aqueous solution were placed between two glass slides, heated to
present a detailed study of the polymerisation process the isotropic state, sheared and recooled to room temperature.
of a reactive surfactant in a LLC phase. (2-Methacry- Subsequently, the phase-transition temperature was determined by
viewing the samples in the polarising microscope during slow and
loyloxyethyl)dodecyldimethylammonium bromide (1) constant heating at a rate of about 0.2 °Cmin)1.
(Scheme 1) was chosen for this purpose as this compound Small-angle X-ray scattering (SAXS) was carried out on sealed
samples in ®ne-glass capillary tubes (1 mm diameter) using a
Kratky compact camera (Anton Paar) with block collimation. Ni-
®ltered Cu Ka radiation with k ˆ 0.154 nm was used. The acceler-
ation voltage was 40 kV at an anode current of 30 mA. Re¯exes
were monitored in continuous scan mode. The scattering curves
were corrected for slit-smearing e€ects by a computational
desmearing procedure.

Scheme 1 Structure of (2-methacryloyloxyethyl)dodecyldimethylam-

monium bromide 1
Results and discussion
is known to completely polymerise upon c-ray irradia-
tion in the hexagonal phase under retention of the Polymerisation of the 1/water binary mixture
macroscopic order [23]. Here the changes in the phase
behaviour and the structure during the polymerisation as As previously described [23], 1 forms LLC phases in
well as the reaction kinetics are described in detail. In aqueous solution at a surfactant concentration above
addition, the copolymerisation of 1 and acrylamide in the 55 wt%. The phase diagram in Fig. 1 (lower part)
ternary hexagonal phase is reported and is compared indicates the formation of hexagonal (Ha), cubic (Qa)
with the polymerisation behaviour of 1 in the binary and lamellar (La) phases. In the following, we concen-
mixture with water. trate on a detailed study of the polymerisation in the
hexagonal phase, the surfactant concentration being
70 wt%. As indicated in Fig. 1 (middle and upper part),
Experimental the phase-transition temperature from the hexagonal
phase to the micellar solution constantly increases upon
Materials exposure to c-rays. At a dose of 3.9 kGy the maximum
transition temperature has increased from 55 to 72 °C.
1 was prepared by reaction of dimethylaminoethyl methacrylate This is a rather strong e€ect, especially if one takes into
with 1-bromododecane in acetone at 41 °C according to procedures
described in the literature [23, 24]. A white solid was obtained account that only 5 wt% of polymer has been formed in
which was recrystallized from ethyl acetate and dried in vacuum the sample, as can be concluded from the conversion
(m.p. 84 °C). Acrylamide was used as received from Fluka. versus dose curve shown in Fig. 2. The fact that the
Deionized water was used for all the experiments (MilliQ water). transition temperature goes up may be taken as the
Lyotropic solutions of the 1/water binary system were prepared
by mixing the surfactant with previously degassed water, followed indication of the miscibility of monomer and polymer.
by stirring for 10 min under purging with nitrogen to keep the Further indication of the miscibility results from the
oxygen content as low as possible. Subsequently, the samples were SAXS diagrams taken after di€erent radiation doses of
sealed and stored at 5 °C in the dark for 24±48 h. Lyotropic the sample. All the diagrams indicate a strong ®rst-order
solutions of the 1/acrylamide/water ternary system were prepared
by mixing solid 1 and acrylamide in molar ratios of 1:1, 2:1 or 4:1
peak of the hexagonal phase, which is retained during the
using a vibrating mill. Subsequently, the lyotropic solutions were entire reaction (Fig. 3). The half width of the peak also
prepared as described for the binary mixtures. remains nearly constant. This indicates the presence of a
184

Fig. 2 Plot of the d spacing of the hexagonal phase and the

conversion as a function of the c-ray dose (surfactant concentration:
70 wt%)

Fig. 1 Phase diagram of the (2-methacryloyloxyethyl)dodecyldime-

thylammonium bromide (1)/water binary system without c-ray
irradiation (lower part) and after exposure to 1.3 kGy (middle) and
3.9 kGy (upper part) (hatched areas indicate two-phase regions)

homogeneous hexagonal phase independent of the

polymer content of the sample, in good agreement with
the polarising micrographs reported earlier [23]. From
the angular position of the ®rst-order peak the d spacing
of the hexagonal phase was evaluated as a function of the
radiation dose. As shown in Fig. 2, the original d spacing Fig. 3 Small-angle X-ray scattering patterns of aqueous mixtures of
of 3.08 nm of the monomer remains constant until a 1 in the hexagonal-phase region (concentration 70 wt%) before and
after irradiation with various c-ray doses
c-ray dose of approximately 4 kGy is reached, which
corresponds to a polymer content of about 5 wt%. Then,
the d spacing abruptly changes to a value of 3.36 nm and polymer (and/or oligomer) chains until ®nally the
again remains constant until the polymerisation has gone transition into the more stable phase II takes place.
to completion. The abrupt change indicates a structural The sudden increase in the d value by almost 10%
transition within the hexagonal phase, which we denote indicates a pronounced conformational transition of the
as a transition from hexagonal phase I to hexagonal surfactant molecules. In agreement with Hamid and
phase II. Sherrington [25] we believe that the monomer molecules
As the conversion versus dose curve in Fig. 2 originally show intramolecular interaction of the meth-
indicates, the polymerisation proceeds very slowly in acryloyloxy group with the onium nitrogen centre, which
phase I, while in phase II an accelerated reaction which could explain the small d spacing found in phase I. The
®nally goes to completion is found. We believe that exothermic polymerisation could easily provide the
phase I becomes increasingly destabilized by the growing energy necessary to overcome this interaction so that
 185

phase II with a larger d spacing is formed, in which the acrylamide and its polymer are highly water-soluble and
molecules attain a more elongated shape. The rearrange- thus in the case of copolymerisation with 1 an amphi-
ment in the headgroup region leads to a di€erent mutual philic copolymer with potentially interesting self-organ-
orientation of the vinyl groups, which in phase II is ising properties could result and because the system is
sterically more favourable for polymerisation. This may well comparable with the binary system described
explain the rapider reaction in phase II. previously. Copolymerisation of water-soluble mono-
The monomer/polymer mixture formed upon irradi- mers and reactive surfactant monomers in LLC meso-
ation might be either a thermodynamically stable or phases is still a new area and very little information is
only a so-called frozen-in structure in which demixing is available in the literature.
kinetically hindered by the high viscosity of the polymer. As the partial phase diagram of Fig. 5a indicates, the
In the latter case, all attempts to prepare a homoge- addition of acrylamide to the 1/water binary system
neous hexagonal phase by simply dissolving correspond- with an initial surfactant concentration of 70 wt% leads
ing amounts of monomer and polymer in water would to a continuous decrease in the stability of the
fail. Instead of a homogeneous mesophase, a two-phase hexagonal-phase region. As can be seen, the transition
system recognisable by SAXS peaks of either phase temperature from the hexagonal to the isotropic phase
would result. In order to prove the thermodynamic decreases from 55 °C for the acrylamide-free mixture to
stability, we ®rst mixed solid monomer and polymer in 35 °C for the comonomer mixture of 1 and acrylamide
di€erent ratios and then prepared aqueous solutions in a 2:1 molar ratio. However, as shown in Fig. 5b, the
with a solid content of 70 wt%. As shown in Fig. 4, the phase-transition temperature is raised upon c-ray irra-
SAXS data of the monomer/polymer mixed systems diation, quite similar to the binary mixture shown in
exhibit nearly the same d spacing of 3.36 nm as the in Fig. 1. In the case of an equimolar aqueous mixture of
situ polymerised system of identical composition. This 1 and acrylamide with a total monomer content of
indicates the spontaneous formation of hexagonal 75 wt% the hexagonal phase has completely disap-
phase II and can be taken as proof of the thermody- peared at room temperature. Since we are presently not
namic stability of the in situ polymerised samples. able to study samples below room temperature, it is not
possible to decide whether the hexagonal phase has
completely disappeared at all temperatures or whether
Copolymerisation of the 1/acrylamide/water ternary the phase-transition temperature has dropped to a value
system below 20 °C. The interesting point is that a mesoscale
structure reappears at 20 °C once the sample is exposed
In addition to the 1/water binary system we also to c-rays. Obviously the increasing polymer content
investigated the polymerisation of the 1/acrylamide/ stabilises the LLC phase and causes the system to form
water ternary system. This system was chosen because a hexagonal phase up to elevated temperature. Relevant
polarising micrographs showing the ternary system
before and after c-ray rradiation are shown in Fig. 6.
The conversion to polymer of the ternary system was
determined gravimetrically. The possible formation of
the water-soluble acrylamide±homopolymer was
checked, but no indications could be found. As shown
in the conversion versus dose curves of Fig. 7, the
polymerisation rate increases as the acrylamide content
becomes higher, but the high rate of the binary system is
not reached in any of the ternary mixtures (see also
Fig. 2). The di€erent reaction rates might be a conse-
quence of interactions between the acrylamide and the
surfactant molecules. Interactions are evident from the
di€erences in the d spacing of the ternary and the binary
system. While the d spacing of the ternary mixture
containing 1 and acrylamide in a 4:1 molar ratio is
3.42 nm (Fig. 8), the binary system exhibits a value of
3.25 nm (Fig. 2). We therefore denote the new structure
as hexagonal phase III. As also shown in Fig. 8, the d
Fig. 4 Plot of the d spacing of the hexagonal phase as a function of spacing ®rst decreases to a value of 3.25 nm during
the polymer content of the sample (the total concentration of
monomeric plus polymeric 1 is always 70 wt%). Samples were polymerisation, and then increases to the ®nal value of
prepared upon in situ polymerisation of the mesophase or upon 3.31 nm. This value agrees with the value of the
admixture of polymer to the monomer phase polymerised binary system denoted as hexagonal pha-
186

Fig. 5 Change of a the hexago-

nal-phase region of the 1/water
system upon addition of acryla-
mide (2) and of b the 1/2/water
system (with a 4:1 molar ratio of
1 and 2) upon c-ray irradiation
(hatched areas indicate two-phase
regions)

Fig. 6 Polarising micrographs of an aqueous mixture containing

75 wt% of an equimolar mixture of 1 and 2 before (inset) and after Fig. 7 Conversion versus dose curves of 1/2/water ternary mixtures
c-ray irradiation with a dose of 110 kGy at room temperature containing 75 wt% 1 and 2 in di€erent molar ratio
 187

Fig. 8 Plot of the d spacing of a 1/2/water ternary system containing

75 wt% 1 and 2 in a 4:1 molar ratio versus the c-ray irradiation dose Fig. 9 Composition of the copolymer formed in the 1/2/water ternary
system containing 75 wt% 1 and 2 in di€erent molar ratios as a
function of the irradiation dose
se II. It is likely that a transition from phase III to II
occurs at a dose of 35 kGy, when the lowest d value of
3.25 nm is reached. The half width of the ®rst-order acceleration once a certain polymer content is formed
X-ray peak does not signi®cantly change upon the generally renders the control of the polymerisation of 1
transition, which is an indication that the order of the dicult. This may explain the inconsistent results
system is retained. previously reported on the polymerisation of this com-
The di€erent polymerisation rates of the binary and pound in mesoscale systems [23, 26]. The fact that a
the ternary systems can be ascribed to a di€erent simple mixing of monomer, polymer and water leads to
molecular conformation of the surfactant resulting in a the same hexagonal order as obtained in the in situ
lower reactivity in case of hexagonal phase III. The fact polymerisation of the system can be taken as proof of the
that in the ternary mixture the reaction rate increases thermodynamic stability of the mesophase during the
with the acrylamide content might be due to the entire polymerisation process.
preferential polymerisation of acrylamide in the aqueous Our study also indicates that the addition of a water-
phase so that copolymers with a higher polyacrylamide soluble comonomer signi®cantly alters the phase and
content are formed. A detailed analysis of the copoly- polymerisation behaviour and is even able to suppress
mer composition by IR spectroscopy indeed indicates a LLC phase behaviour completely. In contrast, c-ray
preferential incorporation of acrylamide monomer in polymerisation increases the stability of the lyotropic
the initially formed copolymer (Fig. 9), while the phase and even induces liquid-crystalline phase beha-
copolymer obtained at high conversion has the same viour in systems which in the monomeric state are not
composition as the original monomer mixture. liquid-crystalline.
The study also shows that the change in structure and
phase behaviour of 1 during polymerisation is quite
Conclusions di€erent from other surfactant monomers and makes it
dicult to draw more general conclusions from the
Our study demonstrates that the polymerisation of present results. Besides the pressure, the temperature and
surfactant monomer 1 in a hexagonal mesophase pro- the composition of the system, the molecular conforma-
ceeds without loss of the mesoscale order. Structural tion, the mutual arrangement of the reactive units and
studies during the polymerisation indicate that the the conversion to polymer are important parameters
polymerisation is accompanied by a discontinuous controlling the phase behaviour, the structure and the
change in the d spacing at about 5% conversion, while reactivity of the system in a complex manner. Clearly, the
the hexagonal order is completely retained. The change study of other systems of reactive monomers in a LLC
in the d spacing can be ascribed to a conformational phase is necessary to fully understand the in situ
transition in the headgroup region of the surfactant polymerisation in a mesoscale solution.
molecules. The new conformation is sterically more
favourable for polymerisation, so the reaction rate Acknowledgement The authors thank Astrid Haibel, II. Physika-
strongly increases after the transition has taken place. lisches Institut der UniversitaÈt zu KoÈln, for the SAXS measure-
The low initial reaction rate combined with the sudden ments.
188

References

1. Winsor PA (1968) Chem Rev 68:1 10. Candau F, Zekhini Z, Durand JP 18. Lester CL, Guymon CA (2000) Mac-
2. Gray GW, Winsor PA (eds) (1974) (1986) J Colloid Interface Sci 114:398 romolecules 33:5448
Liquid crystals and plastic crystals, 11. Herz J, Reiss-Husson F, Rempp P, 19. Srisiri W, Benedicto A, O'Brien DF,
vol 1, 1st edn. Wiley, New York Luzatti V (1963) J Polym Sci Part C Trouard TP (1998) Langmuir 14:1921
3. Kelker H, Hatz R (1980) Handbook of 4:1275 20. Thundatil R, Sto€er JO, Friberg SE
liquid crystals, 1st edn. Verlag Chemie, 12. O'Brien DF, Armilage B, Benedicto A, (1980) J Polym Sci Part A Polym Chem
Weinheim Bennett DE, Lamparski HG, Lee YS, 18:2629
4. Engels T, v Rybinski W (1998) J Mater Srisiri W, Sisson TM (1998) Acc Chem 21. Antonietti M, Hentze HP (1996) Col-
Chem 8:1313 Res 31:861 loid Polym Sci 274:696
5. Finkelmann H, LuÈhmann B, Rehage G 13. Meier W (1998) Macromolecules 22. GoÈltner CG, Antonietti M (1997) Adv
(1982) Colloid Polym Sci 260:56 31:2212 Mater 9:431
6. Hill RM, He M, Liu Z, Davis HT, 14. Miller SA, Ding JH, Gin DL (1999) 23. Pawlowski D, Haibel A, Tieke B (1998)
Scriven LE (1993) Langmuir 9:2789 Curr Opin Colloid Interface Sci 4:338 Ber Bunsenges Phys Chem 102:1865
7. Wang W, Lieser G, Wegner G (1993) 15. McGrath KM, Drummond CJ (1996) 24. Nagai K, Ohishi Y (1994) J Polym Sci
Liq Cryst 15:1 Colloid Polym Sci 274:316 Part A Polym Chem 32:445
8. Laversanne R (1992) Macromolecules 16. McGrath KM (1996) Colloid Polym 25. Hamid SM, Sherrington DC (1987)
25:489 Sci 274:399 Polymer 28:325
9. Antonietti M, Caruso RA, GoÈltner 17. McGrath KM (1996) Colloid Polym 26. McGrath KM, Drummond CJ (1996)
CG, Weissenberger MC (1999) Marco- Sci 274:499 Colloid Polym Sci 274:612
molecules 32:1383
Progr Colloid Polym Sci (2001) 117: 189±194
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

R. BorbaÂs Elastic properties of protein gels obtained

EÂ. Kiss
M. Nagy by three-phase partitioning

Abstract A special combination of structure. The viscoelastic properties

alcoholic precipitation and salting were determined by measuring the
out of proteins was described as deformation as a function of time.
three-phase partitioning [1]. Proteins The BSA gels showed higher elastic
are accumulated in a coherent mid- and viscous deformation and lower
dle phase in the partitioning system viscosity than the ovalbumin gels.
composed of tert-butanol, ammoni- The rheological behaviour of protein
um sulphate and water. The me- gels is consistent with the previous
chanical properties of the middle results obtained from the analysis of
phase were determined in model middle-phase components, which
systems using bovine serum albumin indicate that the middle phase
(BSA) or ovalbumin. The stress± formed in three-phase partitioning is
deformation relationship obtained an emulsion gel.
by uniaxial compression showed the
R. BorbaÂs á EÂ. Kiss (&) á M. Nagy
LoraÂnd EoÈtvoÈs University, elastic behaviour of the middle
Department of Colloid Chemistry, phase. It was found that the elastic
Budapest 112, modulus of the protein gel changed Key words Three-phase partition-
P.O. Box 32, Hungary-1518 with stress. The middle phase be- ing á Rheology of bovine serum
e-mail: [email protected]
Tel.: +36-1-2090555 came harder upon compression, albumin and ovalbumin gels á
Fax: +36-1-2090602 possibly owing to some change in Emulsion gel á Protein separation

Introduction mechanical properties of the gel-like middle phases of

TPP.
Three-phase partitioning (TPP) is a protein separation Gels can be classi®ed either by the forces acting in the
method based on heterogeneous systems consisting of junction points or by the basic elements forming the
tert-butanol, ammonium sulphate and water. tert-Buta- network. Physical and chemical gels can be distinguished
nol has limited miscibility with water in the presence of on the basis of the forces. The basic forming elements of
ammonium sulphate; the mixture separates into two the network can be either macromolecules or other kinds
liquid phases [1, 2]. Applying this type of heterogeneous of colloidal particles. A special type of particle gel is a
system to a protein solution leads to the appearance of a protein-stabilised emulsion gel, made of protein-coated
coherent protein-rich disc (a third phase) between the droplets aggregated in a liquid which is immiscible with
two liquid phases [1±4]. It was proved to be an e€ective the interior of the droplets [6, 7].
method in the prepuri®cation of proteins [3, 4] or the Mechanical measurement is a typical tool for the
preparation of high activity horseradish peroxidase [5]. characterisation of protein gels. The knowledge of the
Several parameters a€ecting the behaviour of proteins mechanical properties gives indirect information on
during TPP have been studied so far in order to exploit the strength of the forces acting in the junction zones
the full potential of the method, but there are still many of the gel network, the ¯exibility of network elements
aspects uncovered in this area. This article focuses on the and the concentration of cross-links. A gel is properly
190

characterised rheologically by the elastic modulus and protein, which are determined by the amino acid seque-
viscous components of deformation [7]. The mechanical nce of the molecule. In addition, the conformation of
measurements monitor network continuity over macro- protein molecules can change in the presence of an
scopic dimensions on a supramolecular level, surveying interface (owing to partial unfolding), and this e€ect may
the arrangement of molecules [8]. contribute to the mechanical properties of the interfacial
There are many fundamental works on the rheological ®lm. An adsorbed protein layer at the interface of
characterisation of gels. Both the theoretical [8±13] and droplets dispersed in an immiscible liquid controls the
the experimental [11, 12, 14, 15] aspects of this subject stability of the emulsion and, hence, the structure of an
have been widely studied. emulsion gel [6, 7].
The theoretical approach is based on a model with
ideally elastic Gaussian chains. By considering the elas-
ticity of one chain, the force acting between the two ends
of the network chain, the Brownian motion of the
Experimental
segments, and using physical and statistical methods the
Bovine serum albumin (BSA) fraction V (from Reanal) and
following basic equation can be deduced: chicken egg ovalbumin (OVA) (from Sigma) lyophilised and with
2 m
purity above 98% were used. tert-Butanol, high-performance liquid
rcr 2 chromatography grade, was obtained from Sigma. All other
r ˆ K1 kT 2 V
k k ; 1†
rmp reagents were of analytical grade and each reagent was used
without further puri®cation.
which provides a connection between stress and defor- Five partitioning systems were used during the measurements,
mation. r stands for the applied force per unit unde- which di€ered in the ratio of tert-butanol, ammonium sulphate and
water. The compositions in mass ratio are (listed in the manner of
formed area, K1 is a constant, k is the Boltzmann factor, T tert-butanol:ammonium sulphate:water) system 1 0.16:0.18:0.66;
is the absolute temperature, rcr2 is the mean-square end-to-
system 2 0.58:0.09:0.33; system 3 0.56:0.06:0.38; system 4 0.71:0.04:
2
end distance, rmp is the most probable distance of the ends 0.25; system 5 0.18:0.11:0.71. The interfacial tension of the protein-
of network chains, m is the number of elastically active free heterogeneous systems were 1 (system 5), 2 (systems 1 and 3)
and 4.5 mNm)1 (systems 2 and 4).
network chains in the volume, V, of the gel and k is Aqueous protein solution was mixed with aqueous ammonium
de®ned as the extension ratio of the gel: the actual length sulphate solution to obtain a protein concentration of 3.5 gdm)3,
of the gel under r stress per the initial length (l0) of the gel. and ®nally tert-butanol was added to the system after 1 h. The
The rearrangement of Eq. (1) results in the following system was thoroughly mixed by turning the tubes upside down
20 times and was centrifuged after standing for 1 h. The centrif-
expression: ugation was performed at 2,000 rpm (672g) for 10 min. The system
r K1 kT was kept at 25 °C during the whole procedure.
‰rŠ ˆ 2
/ m ; 2† The gel-like middle phase was separated, and then two
k k l0 deformation tests were performed using an apparatus developed
where l0 replaces V1/3 in the case of uniaxial compression. in our department [16]. This equipment allowed the vertical
compression of the sample with measurement of deformation and
This expression de®nes the reduced stress, [r], which is force within a wide range, from 10)5 to 2 ´ 10)3 m and from 10)4
independent of the extension ratio and the stress. to 2 N, respectively. The gel sample was placed and compressed
The connection between stress and the deformation between parallel glass plates. The samples were loaded and the
parameter can be written in another form [8]: deformation was measured on a scale proportional to the change in
sample height with an accuracy of 10)5 m. The samples were either
  loaded step by step in the range 0±5 g and the deformation was
E 2 1
rˆ k ; 3† measured as a function of stress (method 1) or they were loaded
3 k with a given weight (0.5 and 1 g) and the deformation was
measured as a function of time (method 2).
where E stands for Young's modulus. Information could be obtained on the reversibility of deforma-
Equations (1) and (3) work well for many synthetic tion from both types of methods. The gel size was measured when
polymer gels or heat-set protein gels, but in several cases the sample was loaded with the smallest possible weight, 0.01 g,
nonideality has also been observed where this equation is (which corresponds to a stress of ) 0.15 Nm)2). This condition is
mentioned as unloaded in the following. The reversibility of
no longer valid. For example, the Mooney±Rivlin formu- deformation was checked twice on the sample during the whole
la or the equation of Blatz, Sharda and Tschoegl (which procedure of method 1, once after reaching a stress of ) 2.2 Nm)2
can be found in Refs [8, 11]) can be used in this cases. and once after ) 75 Nm)2. In method 2 the reversibility was
The previously discussed model of rubber elasticity checked by unloading the sample at 600 s and measuring the gel
size for 300 s.
and the equations derived from it have been applied to
biopolymer gels [8]; however, this model can be consid-
ered as a rough approximation of the behaviour of
biopolymer gels. The network-forming protein is not a Results and discussion
random coil and with the exception of a few cases, its
end-to-end distance, conformations are regulated by the Proteins accumulate into a coherent third phase when
secondary, tertiary and quaternary structures of the treated with a heterogeneous two-liquid-system of TPP.
 191

A gel-like phase is formed, which contains all four units of newtons per square metre. The higher the slope
components of the two-liquid-phase system. The protein the harder the gel because a larger step in stress caused a
content of the gel is low (3±9 w/w% in the case of BSA, smaller step in deformation. The slope of the second
0.4±2 w/w% in the case of OVA), and the tert-butanol/ linear region is 1 magnitude higher than that of the ®rst
ammonium sulphate/water ratio in the gel is a function of region, which means that the gels became considerably
the initial composition of the system [17]. harder during compression. It can be seen that the OVA
The coherent phase produced by TPP is a physical gel gels were not so hard as the BSA gels: the slopes of OVA
because the mild conditions during which the gel was curves were slightly smaller than those of BSA. The
formed do not induce chemical reaction, i.e. no oxidising di€erences between the hardness of the two types of
or reducing agents were present in the system, ammoni- protein gels were not so high as was expected from the
um sulphate and tert-butanol are protein friendly and the di€erences in their protein content.
system was held at standard temperature. These condi- The comparison of the gels developed from a single
tions permit the formation of physical connections only protein in ®ve di€erent systems led to the conclusion that
between the network elements. BSA gels were harder if they were formed in a system
The mechanical properties of protein gels were studied with higher interfacial tension. The system with an
in two ways. The deformation of the sample was mea- interfacial tension of 1 mNm)1 produced a curve with
sured as a function of stress (method 1) and time the lowest value of the slope (431 ‹ 17 Nm)2), while the
(method 2). The stress±deformation curves of BSA and highest slopes (952 ‹ 72 and 796 ‹ 49 Nm)2) were
OVA gels developed in ®ve di€erent systems are dis- measured in the system with the highest interfacial
played in Fig. 1a and b, respectively. The abscissa shows tension. No such tendency could be observed in the case
the extension ratio (k) while the ordinate shows the stress of OVA.
(r), which is negative because the applied force was There should be a linear relationship between stress
compressive. and k ) k)2 for macromolecular gels according to
Figure 1 shows that Hooke's law is valid for the gels Eq. (1). The gel-like middle phase of TPP had an elastic
in the initial (see insert of Fig. 1b) and the ®nal sections behaviour similar to the gel in the model of rubber
of the stress±deformation curves, i.e. stress is linearly elasticity, even though it possessed a more complex
proportional to deformation. The initial region was structure. A linear relationship could be detected be-
within 0.96 or 0.94 £ k £ 1 (depending on the protein tween stress and k ) k)2 around stress values above
studied) with stress values above )2 Nm)2; the ®nal ) 2 Nm)2 and below ) 15 Nm)2 (data not displayed).
region was below a stress of )15 Nm)2. There was a turn There was a break between these two regions similarly to
between the two linear regions. the stress±deformation curves.
The hardness of the gel is indicated by the slope of the The rearrangement of Eq. (1) results in the reduced
linear region of the curves. The slopes of the second stress, [r], de®ned by Eq. (2). The reduced stress should
linear section are displayed beside the curves in Fig. 1 in be independent of r and k, but in this case the relation

Fig. 1 The applied stress (force

per unit undeformed area) as a
function of extension ratio in
the case of a bovine serum
albumin (BSA) and b ovalbu-
min (OVA) gels, obtained by
applying ®ve di€erent parti-
tioning systems: systems 1 (h),
2 (s), 3 (n), 4 (,), 5 (e). The
initial section of the curves of
the OVA gels is shown as an
insert. The slopes of the re-
gressed lines are displayed next
to the lines
192

seemed to be not generally valid. The actual relationship deviations from a ratio of 3 were calculated for k < 0.9.)
between the reduced stress and the stress for protein gels Hence, it could be concluded that the elastic modulus of
developed by TPP is displayed in Fig. 2: [r] grew with the the protein gels became higher as the sample was loaded
load (as r became lower). In the case of OVA this value with a higher weight.
became almost constant in the region ) 30 Nm)2 ³ r ³ The viscoelastic properties of the middle phases were
) 75 Nm)2 (except in system 5). The right-hand side of also studied by measuring the deformation of the sample
Eq. (2) contains a few constants (K1, k, T, l0) beside the loaded with a constant weight as a function of time. The
factor m. There was no detectable change in the volume of results for BSA and OVA gels developed in TPP system 1
the gels during the measurements, so the growing value are shown in Fig. 3. The instant deformation value
of the reduced stress can be due to the change in the (1 ) k1) was measured directly after loading the protein
concentration of physical bonds relevant to the elastic (BSA or OVA) gel. The elastic region of the gel extended
property. A possible explanation could be that new to the point where the deformation versus time curve
interparticle interactions are formed because of the became linear; the value characterising this region is the
compression, and the new cross-links harden the gel. elastic deformation, 1 ) k2 (calculated by subtracting
The syneresis (which could be observed to a small extent) 1 ) k1 from the intercept of the regressed linear line). The
can also induce some change in the structure of the gels. viscous component of deformation was active from 0 s,
The reduced stress is a modulus-type quantity which but when the elastic deformation vanished, this was the
can approximate the value of the shear modulus of the only component present. The extent of viscous deforma-
sample [10] (if k does not di€er much from 1). Young's tion at the end of the period of loading (1 ) k3) can be
modulus of the protein gels calculated from Eq. (3) is calculated by subtracting 1 ) k1 and 1 ) k2 from the
almost equal to the 3 times the value of the reduced maximum value of 1 ) k. The load was removed from
stress, which is expected from the literature [18]. (Greater the sample at 600 s, and after that the instant, elastic and
viscous deformations could be measured in a similar way
to the loaded section (signed by primes), giving infor-
mation on reversibility [19]. These values of the defor-
mations are summarised in Table 1.
The comparison of the di€erent deformation values
leads to interesting observations. It can be generally
concluded that the higher the load the higher the
deformation in the case of a single protein. No great
di€erence was measured between the 1 ) k1 values of
OVA and BSA if they were loaded with the same
weight; however, di€erences between the deformation
of the two proteins appeared both in the elastic and in
the viscous region: the elastic and viscous deforma-
tions of BSA gels signi®cantly exceeded those of OVA
gels. The elastic component of deformation of BSA
gels was about 3 times higher than the viscous compo-
nent (considering the measuring period), while the
1 ) k2 and 1 ) k3 values of the OVA gels were quite
similar.
In the unloaded section 1 ) k1¢ did not di€er much
from 1 ) k1 in the case of both protein gels loaded
previously with 0.5 g. The 1 ) k1¢ value of the sample
loaded previously with the heavier weight was much
smaller than the instant deformation at loading. Possibly
the original structure of the sample could not be regained
if a larger force compressed the sample. In the unloaded
section the elastic deformation decreased and the re-
maining deformation increased in every case compared
to the corresponding values observed in the loaded
section. The reversibility of the elasticity of protein gels
was not high (92±79%), owing to either the compression
Fig. 2 The reduced stress as a function of stress in case of a BSA and or the ¯ow of the gel.
b OVA gels, obtained by applying ®ve di€erent partitioning systems: The reversibility of the protein gels was also
systems 1 (h), 2 (s), 3 (n), 4 (,), 5 (e) measured during method 1. It was found that the
 193

Fig. 3 The deformation (1 ) k)

as a function of time in case of
BSA (h) and OVA (s) gels.
Solid and open symbols corre-
spond to the samples loaded
with 0.5 and 1 g, respectively

Table 1 The deformation d 1 k†  105 (s)

parameters of bovine serum Protein Load (g) Loaded Unloaded
dt
albumin (BSA) and ovalbumin
(OVA) gels 1)k1 1)k2 1)k3 1)k1¢ 1)k2¢ 1)k3¢

BSA 0.5 0.014 0.107 0.039 7 0.019 0.026 0.116

BSA 1 0.089 0.165 0.048 8 0.029 0.062 0.211
OVA 0.5 0.015 0.011 0.009 2 0.013 0.003 0.019
OVA 1 0.091 0.015 0.012 2 0.025 0.006 0.087

gels were reversibly deformed up to r ˆ ) 2.2 Nm)2

(k ³ 0.95), and the degree of reversibility decreased to Conclusions
k ˆ 0.88 or 0.95 for BSA and OVA after the turn in the
stress±deformation curves. The comparison of these An aqueous protein solution treated with tert-butanol,
values and the 1 ) k3¢ values in Table 1 suggest that ammonium sulphate and water (in a suitable ratio)
both compression and the viscous deformation played results in the enrichment of the protein as a coherent disc.
an important role in the alteration of gel structure. The gel appears between two immiscible liquid phases.
The rate of ¯ow of the gels was also acquired from The protein disc was supposed to be an emulsion gel
Fig. 3. The slope of because it is formed after the emulsi®cation of the two
 the linear region of the deforma- immiscible liquid phases of the heterogeneous TPP
tion±time curves, d 1 k† , was calculated form the system. Mechanical characterisation of the middle phas-
dt r;T
measurements and is listed in Table 1. The rate of ¯ow es was carried out to study the nature of the protein gel.
is inversely proportional to viscosity. The comparison Stress±deformation curves were obtained for two
of BSA and OVA showed that OVA was more viscous di€erent proteins, BSA and OVA, in ®ve di€erent
than BSA. There was no great di€erence between the partitioning systems. It was found that the gels became
rate values of BSA loaded with 0.5 and 1 g, and OVA harder when they were compressed, which was shown by
behaved similarly to BSA. This suggested that the gel the increasing slope of the curves and also from the fact
showed higher viscosity at higher compressing force. that the reduced stress increased with stress. A possible
The increased viscosity upon compression also suggest- reason for hardening is that the structure of the gel
ed that the protein gel underwent a certain change in changes owing to deformation.
structure as a result of deformation. The deformation±time measurements provided infor-
The way in which the middle phases were formed by mation on the elastic and viscous deformations, on the
TPP advocated that the middle phases are emulsion gels. ¯ow of the gels and on the reversibility of deformation.
Enzyme-set emulsion gels were reported to have an BSA gels showed higher elastic and viscous deforma-
increasing shear modulus with increasing deformation tions compared to OVA gels, but their reversibility was
[7]. Hence, the mechanical behaviour suggests that the lower. The viscous component of the deformation of
gels are really a kind of particle gel. BSA gels was higher, but the viscosity was calculated to
194

be lower than that of OVA gels, which re¯ects that BSA are planned in order to gain further information on the
lost more of its network structure as a consequence of formation of the middle phase and its connection with
compression. the interfacial properties of proteins, probably by
It can be concluded from the mechanical characteri- microscopic and other techniques.
sation of the TPP middle phases that there might be a
certain alteration in the structure of the gels as a result of Acknowledgements The work was supported by the Hungarian
compression and also that the gel is supposedly a Research Foundation (OTKA) project no. T 033065. The authors
concentrated emulsion. Investigations of the structure are indebted to Mrs. HoÂrvoÈlgyi for helpful technical assistance.

References

1. Kiss EÂ, Szamos J, TamaÂs B, BorbaÂs R 7. Dickinson E (1998) J Chem Soc Fara- 15. Palusson M (1990) PhD thesis. Univer-
(1998) Colloids Surf A 142:295 day Trans 94:1657 sity of Lund
2. Szamos J, Kiss EÂ (1995) J Colloid 8. Clark AH, Ross-Murphy SB (1987) 16. Horkay F, Nagy M, Zrinyi M (1980)
Interface Sci 170:290 Adv Polym Sci 83:57 Acta Chim Acad Sci 103:387
3. Tan KH, Lovrien R (1972) J Biol 9. Ferry JD (1948) Adv Protein Chem 4:1 17. BorbaÂs R, Turza S, Szamos J, Kiss EÂ
Chem 247:3278 10. Treolar LRG (1975) The physics of (2001) Colloid Polym Sci (in press)
4. Lovrien R, Goldensoph C, Anderson rubber elasticity. Clarendon, Oxford 18. Grosberg AY, Khokhlov AR (1997)
PC, Odegaard B (1987) In: Burgess R 11. Nagy M (1985) Colloid Polym Sci Giant molecules. Academic, San
(ed) Protein puri®cation: micro to 263:245 Diego, p 103
macro. Liss, New York, pp 131±148 12. Nagy M (1993) Magy Kem Foly 1:8 19. Rohrsetzer S (1996) In: Rohrsetzer S
5. Szamos J, Horschke AÂ (1992) Acta 13. Nagy M, Nagy A (1996) Magy Kem (ed) Kolloidika. TankoÈnyvkiadoÂ,
Alimen 21:253 Foly 10:427 Budapest, pp 306±308
6. Dickinson E (1994) J Chem Soc Fara- 14. Van Kleef FSM, Boskamp JV, van der
day Trans 90:173 Tempel M (1978) Biopolymers 17:225
Progr Colloid Polym Sci (2001) 117: 195±199
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

B. Kolaric Interactions between polyelectrolyte brushes

S. FoÈrster
Regine v. Klitzing in free-standing liquid ®lms: in¯uence
of ionic strength

Abstract Foam ®lms of charged out of the ®lm in analogy to usual

amphiphilic diblock copolymers are foam ®lms containing micelles of
B. Kolaric á Regine v. Klitzing (&) investigated using a thin-®lm bal- small surfactant molecules. With
Iwan-N.-Stranski-Institut fuÈr ance. At low polymer concentrations increasing salt concentration the ®lm
Physikalische und Theoretische Chemie,
Technische UniversitaÈt Berlin, the disjoining pressure shows a con- becomes thinner as the charged part
Strasse des 17. Juni 112, tinuous exponential decay as a becomes more and more coiled and
10623 Berlin, Germany function of the thickness This indi- the surface charges more screened.
e-mail: [email protected] cates ®lm stabilization by electro-
Tel.: +49-30-31426774
Fax: +49-30-31426602 static repulsion. At higher polymer
concentration strati®cation occurs Key words Polymer brushes á Foam
S. FoÈrster with increasing pressure. This is due ®lm á Amphiphilic diblock copoly-
Institut fuÈr Physikalische Chemie,
UniversitaÈt Hamburg, Bundesstrasse 45, to the formation of a layer of block mer á Strati®cation á Disjoining
20145 Hamburg, Germany copolymer micelles which is pressed pressure

Introduction trolytes [7±9] adsorbed at solid interfaces has already

been investigated using a surface force apparatus. The
In aqueous solutions diblock copolymers consisting of a di€erence to liquid interfaces (liquid/liquid or air/liquid
hydrophobic and a hydrophilic part can form many interface) is the constant packing density after the
di€erent kinds of aggregates, such as micelles, vesicles, adsorption process is ®nished [10]. At liquid interfaces
wormlike or networklike structures [1±3]. The spherical the density of surface-active molecules is variable
micelles have a core of an insoluble block and a shell of a depending on the di€erent parameters, such as concen-
soluble block. The shape of the aggregates is a€ected by tration, ionic strength or pH. Especially, in foam ®lms
the polymer concentration, the ionic strength or the pH (two opposing liquid interfaces) the surface density
of the solution or in the case of adsorbed aggregates by increases with decreasing ®lm thickness [11].
the hydrophobicity of the substrate [4]. The variety of Investigations of the structure at one liquid interface
geometrical structures is similar to that of surfactants of (air/water) show that amphiphilic diblock copolymers
low molecular weight but on a nanometer scale. If the present polymer brushes which are anchored by the
hydrophilic block is a polyelectrolyte the quality of the hydrophobic block on the interface [12, 13]. In the
solvent provides additional facilities to tune the shape present study ®rst disjoining pressure measurements
and the interactions between the aggregates. This leads to between two opposing charged polymer brushes between
new approaches to biological systems and new technical liquid interfaces are described. An amphiphilic copoly-
applications (e.g. stabilization of microemulsions, nano- mer consisting of a hydrophobic and a polyelectrolyte
casting); therefore, the aggregation has to be controlled block is investigated in the con®ned geometry of free-
in solution. In this context, more information about the standing foam ®lms. These ®lms give the opportunity to
interactions between the aggregates is required. The control the thickness and, therefore, the degree of
diblock copolymers are assumed to form a brushlike con®nement and the interaction between the brushes.
structure at the interface of the aggregate. The interac- The term ``geometrical con®nement'' means that the ®lm
tion between polyelectrolyte brushes [5, 6] or polyelec- thickness is of the same order of magnitude as the
196

diameter of a micelle (several tens of nanometers). The

®lm consists of two air/water interfaces and the question
arises if the second interfaces in¯uence the formation of
polymer brushes which is assumed at a single air/water
interface. Furthermore, it should be clari®ed if the
amphiphilic block copolymer behaves in a foam ®lm like
a ``big surfactant'' and what in¯uence the polyelectrolyte
part has. For this reason the solvent quality was impaired
for the polyelectrolyte part by the addition of salt.

Experimental

The amphiphilic diblock copolymer used for the present studies

consists of a poly(styrene sulfonic acid) (PSSH) block of 144
monomers and a hydrophobic poly(ethylethylene) (PEE) block of
136 monomers. Synthetic details are described elsewhere [3]. All
solutions were prepared with MilliQ water and the salt (NaCl) was Fig. 1 Disjoining pressure isotherms of a poly(styrene sulfonic acid)±
purchased from Merck. The measurements were carried out with a poly(ethylethylene) (PSSH±PEE) at two di€erent concentrations: 1.8
thin-®lm balance using the porous-plate technique. This method and 3 g/l. The solid line corresponds to an exponential ®t of the
was developed by Mysels and Jones [14] and subsequently en- experimental data. For details see text
hanced by Exerova and coworkers [15, 16] for measuring the
disjoining pressure, P(h), in the ®lm as a function of the ®lm
thickness, h (disjoining pressure isotherm). The ®lm is formed from length corresponds to a counterion concentration of
an aqueous polymer solution over the (1 mm) hole drilled in a 4.4 ´ 10)4 mol/l. Using this concentration the ®tted
porous plate. The ®lm holder is enclosed in a cell and the pressure value of P0 results in a surface potential of around
inside the cell is changed using a syringe pump. The ®lm thickness
is determined by an interferometric method [17]. The equilibrium 20 mV (using Eqs. 2, 3). The sign of the potential cannot
thickness is reached when the intensity is constant over a period of be determined by this method. The exponential decay
20 min. Further details are described elsewhere [18]. indicates an electrostatic repulsion between the two ®lm
interfaces.
At a higher concentration of 3 g/l the ®lm shows a
Results discontinuous strati®cation. The isotherm shows a step
in ®lm thickness of approximately 32 nm (from 103 to
In¯uence of polymer concentration 71 nm). This step size is in good correlation with the size
of PSSH±PEE micelles in solution, which have a
Foam ®lms of pure PSSH±PEE are stable without any diameter of approximately 30 nm [4]. After the step the
additional surfactant. The disjoining pressure isotherms ®lm is thinner than in the case of the lower concentration.
at PSSH±PEE concentrations of 1.8 and 3 g/l are shown The ®lm is less stable and breaks at a pressure of about
in Fig. 1. At a concentration of 1.8 g/l the ®lm drains 300 Pa. The transition from a thicker ®lm (h~100 nm) to
continuously and the data points can be ®tted with an a thinner ®lm (h~70 nm) starts in the form of darker
exponential function: spots (Fig. 2) which extend to the ``new'' (smaller)
Pel ˆ P0 exp‰ j h 2h0 †Š ; 1† thickness.
with the Debye±HuÈckel length 1/j and the interface layer
thickness h0. P is connected to the surface potential, Y0, In¯uence of ionic strength
by the relation [19]
P h† ˆ 64kT q1 c2 exp jh† The disjoining pressure isotherms at a polymer concen-
8 2 tration of 1.8 g/l without additional salt and at a NaCl
ˆ 1:59  10 †‰cel Šc exp jh†; 2†
concentration of 50 mmol/l are shown in Fig. 3. After
addition of salt the ®lm becomes thinner and the
c ˆ tanh zeW0 =4kT † : 3†
isotherm is steeper. This is an additional proof that the
The second part of Eq. (2) is valid at 298 K for ®lm is stabilized by electrostatic repulsion at low ionic
monovalent ions and the unit of the pressure is pascals. strength. The repulsive interactions are screened partially
The thickness of the imterface h0 was estimated with at higher salt concentrations. The in¯uence of salt at the
22.5 nm as found by Helm et al. for the thickness of one higher polymer concentration of 3 g/l is shown in Fig. 4.
(PSSH144-PEE136) brush at the air/water interface With increasing ionic strength the ®lm becomes thinner
(private communication). The ®t results in a Debye after the step and the ®lm becomes less stable. After the
length of 15 nm and a P0 of around 2,200 Pa. The Debye addition of salt an experimental problem occurred: Since
 197

Fig. 2 Photograph of a PSSH±PEE ®lm at a concentration of 3 g/l Fig. 4 Part of the disjoining pressure isotherm after the step in ®lm
during the discontinuous transition from a thicker to a thinner ®lm. In thickness at a ®xed PSSH±PEE concentration of 3 g/l and at di€erent
the area of the darker spots the ®lm has a thickness of around 70 nm, NaCl concentrations: 0, 0.1, 0.2, 0.3, 0.5 mol/l
in the bright part the ®lm is around 100-nm thick. The dark grey area
on the left side is the meniscus of the ®lm but is not considered in this
work
interaction between the interfaces. The 22.5-nm-thick
interface layer indicates the formation of polymer
brushes at the opposing interfaces which are anchored
at the ®lm surface with the hydrophobic PEE block
(Fig. 5a).
At the air/water interface X-ray measurement results
of a similar system (PSSH83±PEE114) are interpreted in
the way that the hydrophobic PEE block forms a
collapsed 1-nm-thick layer at the interface and the
hydrophilic PSS chains are extended into the solution.
So, the copolymer molecules form a brush at the
interface [12, 13]. X-ray measurements at vertical free-
standing ®lms of amphiphilic blockcopolmers (Pt-PSS)
also led to the conclusion that polymer brushes are
formed at the ®lm interfaces [20]. In these studies the ®lm
is drained by gravitation forces at atmospheric pressure.
With increasing pressure the opposing brushes are
pressed together. In the present study they do not seem
Fig. 3 Disjoining pressure isotherms of PSSH±PEE at a ®xed to interdigitate. If they were in contact, the electrostatic
concentration of 1.8 g/l without additional salt and at a NaCl repulsive force would increase with decreasing h as 1/h
concentration of 0.05 mol/l. The curve without salt is the same as in
Fig. 1 instead of the exponential increase found [21].
The data points of the measurement at a lower
concentration (1.8 g/l) can be ®tted by an exponential
the ®lm was not in equilibrium before the step we were function, which indicates an electrostatic repulsion
not able to estimate precisely the size of the jump. So, between the brushes grafted at the interfaces. The
only the part of the disjoining pressure isotherm after the ``surface potential'' of around 20 mV corresponds to
step is shown in Fig. 4. Without any additional salt this the potential at the brush/solution interface. After Odijk
problem was less pronounced and we were able to [22] the Debye length consists of a part which is due to
determine the complete isotherm as shown in Fig. 1. the counterions of the polylectrolyte and to the ions of
additional salt. In the present case there is no salt;
therefore, we can only argue with the counterion
Discussion concentration of the PSS part to discuss the screening
length of the electrostatic repulsion between the brushes.
At lower polymer concentrations the foam ®lm drains The experimentally determined Debye length is rather
continuously and it seems to be stabilized by electrostatic large with respect to the counterion concentration.
198

Fig. 5 Assumed structures

of a PSSH±PEE ®lm: a approach
of two brushes at low polymer
concentration, b in¯uence
of ionic strength and c expulsion
of one layer of micelles at high
polymer concentration

A PSSH±PEE concentration of 1.8 g/l corresponds to ene oxide) triblock copolymer (Synperonic) results in the
7.4 ´ 10)3 mol/l monomer units of PSS. The distance transition from Derjaguin±Landau±Verwey±Overbeek
between two charges along the PSS chain is about 2.5 AÊ (DLVO) forces to steric interactions as forces that
and is smaller than the so-called Bjerrum length, lB stabilize the ®lm. This indicates a brush-to-brush contact
(7.1 AÊ in water). In this regime counterion condensation at higher capillary pressure [25]. In the present study, the
must be taken into account [23, 24]. This gives a ®lms were not stable at high pressure. Consequently, it is
concentration of free counterions of about one-third of not possible to state whether a comparable transition
the total number of counterions, i.e. 2.5 ´ 10)3 mol/l, would also occur in ®lms of charged block copolymers.
which results in a Debye length of about 6 nm. The A ®lm thinning is also measured after the increase in
deviation from the experimentally determined value of PSSH±PEE concentration (Fig. 1). The free counterions
15 nm could mean that almost all counterions are in the introduced by the PSS part lead to a screening of
brush (osmotically swollen brush) and that the counte- electrostatic repulsion between the brushes and along
rion concentration in the ®lm core between the brushes is one brush. This leads to a coiling of the PSS part and also
much lower: 1/j ˆ 15 nm is equivalent to a counterion causes a decrease in ®lm thickness with increasing
concentration of about 4 ´ 10)4 mol/l.1 polymer concentration. With respect to small surfactant
At a salt concentration of 50 mmol/l the Debye length molecules, this thinning of the interface layer after
is about 1.4 nm. (This value is smaller than the precision increasing the polymer concentration is counterintuitive
of the ®t.) So, the isotherm becomes steeper (Fig. 3). since usually the packing of surface-active molecules
Additionally, the conformation of the polyelectrolytes increases with increasing concentration.
changes with the ionic strength and becomes more coiled At a higher concentration (3 g/l) the isotherm is not
(Fig. 5b). Both e€ects result in a reduction in ®lm continuous anymore: a step in ®lm thickness occurs. The
thickness. This salt in¯uence is observed at both polymer step size is similar to the diameter of the micelle in an
concentrations. A decrease in ®lm thickness, after aqueous solution [4]; therefore, a layer of micelles is
addition of salt, was also observed in vertical ®lms of assumed to be embedded in the ®lm (Fig. 5c, left). In
charged diblock copolymers where the drainage is driven analogy to the solvation forces between spherical parti-
by gravitation [20]. cles [19] the interfaces induce a lateral ordering of the
Investigations of horizontal foam ®lms of nonionic micelles. The micelles are squeezed out of the ®lm
poly(ethylene oxide)±poly(propylene oxide)±poly(ethyl- (Fig. 5c, right) into the surrounding bulk phase, which
leads to a lower concentration in the ®lm. This results in
attractive depletion forces and in oscillation in the
1
The pH of the water was 5.5. So, the concentration of hydronium disjoining pressure. In the thin-®lm balance only the
and hydroxide ions was much lower than 4 ´ 10)4 mol/l repulsive parts of a pressure oscillation can be measured,
 199

resulting in steps in ®lm thickness. A similar picture exists used and it is assumed that they are caused by a
for foam ®lms of small surfactant molecules [26]. Foam mesoscopic ordering of nonanchored polyelectrolyte
®lms made from surfactant solutions above the critical chains in the ®lm core.
micelle concentration shows several steps in ®lm thick-
ness which cannot be explained by DLVO forces. This
strati®cation is explained by layer-by-layer expulsion of
Conclusions
the micelles. In the present study a maximum of one step
can be observed. A possible explanation could be that the
Foam ®lms of charged amphiphilic diblock copolymers
pressure barrier which has to be overcome to squeeze out
have a kind of ``sandwich'' structure of two opposing
one layer is too small to observe a multilayer ordering
polymer brushes and are stabilized by electrostatic
between the interfaces. This could be due to a ``softer''
repulsion between the brushes. Further, the exponential
ordering of micelle layers than in the case of small
decay of the P(h) isotherm indicates that the brushes do
surfactant micelles. So, just one oscillation could be
not interdigitate. The ®lm thickness decreases with
measured resulting from a single layer of micelles in the
increasing salt concentration for two reasons:
®lm core. Since the step in ®lm thickness and the
diameter of the micelle (in solution) are of similar size 1. As in ®lms of small surfactant molecules the electro-
it is assumed that the micelle is not compressed in the static repulsion between the two ®lm interfaces is
®lm. In this picture the amphiphilic PSSH±PEE molecule screened.
can be considered as a ``big surfactant'', which leads to a 2. In contrast to foam ®lms of small surfactant mole-
similar ®lm strati®cation behavior as in the case of small cules the thickness of the interfacial (stagnant) layer
surfactant but on a larger length scale. shrinks in the case of polyelectrolyte brushes with
Foam ®lms consisting of hydrophilic polyelectrolytes increasing ionic strength.
also show stepwise drainage on a mesoscopic length scale
In analogy to ®lms of small surfactant molecules,
[18, 27, 28] but the reason is di€erent. In contrast to the
micelles are embedded which can be squeezed out of the
foam ®lms of amphiphilic diblock copolymer, ®lms of
®lm. This is noticeable as steps in the ®lm thickness.
hydrophilic polyelectrolytes are not stable. Surfactant
has to be added and the interfacial layer is formed by a Acknowledgements We thank the DFG (Schwerpunkt Polyelek-
layer of surfactant or surfactant/polyelectrolytes com- trolyte mit de®nierter MolekuÈlarchitektur) for ®nancial support
plexes. The step sizes are independent of the surfactant and Deven D. Parghi for reading the manuscript.

References

1. Gast A (1997) Curr Opin Colloid 10. Steitz R, Leiner V, Siebrecht R, v. 20. Guenoun P, Scalchli A, Sentenac D,
Interface Sci 2:258 Klitzing R (2000) Colloids Surf A 163:63 Mays JW, Benattar JJ (1995) Phys Rev
2. Alexandridis P (1997) Curr Opin 11. Exerowa D, Nikolov A, Zacharieva M Lett 74:3628
Colloid Interface Sci 2:478 (1981) J Colloid Interface Sci 81:419 21. Ohshima H (1999) Colloid Polym Sci
3. FoÈrster S, Hermsdorf S, Leube W, 12. Ahrens H, FoÈrster S, Helm CA (1997) 277:535
Schnablegger H, Regenbrecht M, Macromolecules 30:8447 21. Odijk T (1979) Macromolecules 12:688
Akari S (1999) J Phys Chem B 103: 13. Ahrens H, FoÈrster S, Helm CA (1998) 22. Manning GS (1969) J Chem Phys
6657 Phys Rev Lett 81:4172 51:924
4. Regenbrecht M, Akari S, FoÈrster S, 14. Mysels KJ, Jones MN (1966) Discuss 23. Ray J, Manning GS (1997) Macromol-
MoÈhwald H (1999) J Phys Chem B Faraday Soc 42:42 ecules 30:5739
103:6669 15. Exerova D, Schedulko A (1971) Chim 24. Sedev R, Exerowa D (1999) Adv
5. Kurihara K, Kunitake T, Higashi N, Phys 24:47 Colloid Interface Sci 83:111
Niwa M (1992) Langmuir 8:2087 16. Exerova D, Kolarov T, Khristov KHR 25. Bergeron V, Radke CJ (1992) Lang-
6. Abe T, Higashi N, Niwa M, Kurihara (1987) Colloids Surf A 22:171 muir 8:3020
K (1999) Langmuir 15:7725 17. Schedulko A (1967) Adv Colloid Inter- 26. Asnacios A, Espert A, Colin A, Lange-
7. Klein J, Luckham PF (1984) Colloids face Sci 1:391 vin D (1997) Phys Rev Lett 78:4974
Surf 10:65 18. v Klitzing R, Espert A, Asnacios A, 27. Kolaric B, Jaeger W, v Klitzing R
8. Komiyama Y, Israelachvili J (1992) Hellweg T, Colin A, Langevin D (1999) (2000) J Phys Chem B 104:5096
Macromolecules 25:5081 Colloids Surf A 149:131
9. Dahlgreen MAG, Hollenberg HCM, 19. Israelachvili J (1997) Intermolecular
Claesson PM (1995) Langmuir 11:4480 and surface forces. Academic, London
Progr Colloid Polym Sci (2001) 117: 200±203
Ó Springer-Verlag 2001 SURFACTANTS, POLYMERS

H. CoÈlfen The mechanism of the morphogenesis

L. Qi
of CaCO3 in the presence of poly(ethylene
glycol)-b -poly(methacrylic acid)

Abstract The morphogenesis of cess, whereas at high pH or high

crystalline CaCO3 in calcite modi®- polymer concentration, spherical
cation was systematically investigat- structures dominated originating
ed in the presence of poly(ethylene from a more complicated growth
glycol)-b-poly(methacrylic acid) with scenario: polymer adsorption onto
respect to pH, polymer and mineral the nanocrystals with subsequent
concentration. A variety of di€erent de®ned aggregation into a super-
particle morphologies was observed structure. Here, the elongated crystal
H. CoÈlfen (&) and at least two di€erent mecha- is stabilized on the nanometer scale
Max Planck Institute of Colloids and nisms for the formation of the ®nal with a growth self-termination and
Interfaces, Colloid Chemistry,
Research Campus Golm, CaCO3 structures are proposed. At an acting electric multipole ®eld
Am MuÈhlenberg 2, low polymer concentration or pH, arranges later nucleated particles
14424 Potsdam, Germany the basis of the mechanism is that into the observed superstructures.
e-mail: [email protected] the polymer could selectively adsorb
Tel.: +49-331-5679513
Fax: +49-331-5679502 onto speci®c crystal surfaces leading
to morphologies elongated along the
L. Qi crystal c-axis. At low pH, macro- Key words Morphogenesis á
College of Chemistry
Peking University scopic elongated crystals were found CaCO3 á Block copolymers á
Beijing 100871, China resulting from a slow growth pro- Crystal design á Aggregation

Introduction the so-called double-hydrophilic block copolymers [7],

turned out to be very e€ective for the morphogenesis of
Living organisms are well able to synthesize highly inorganic crystals, such as calcium carbonate [7±9],
optimized organic±inorganic hybrid materials with often calcium phosphate [10], barium sulfate [11, 12] and zinc
complex forms by biomineralization (e.g., seashells, oxide [13], owing to the separation of binding and
bone, teeth, diatomea and many others). For this, solvating moiety. For CaCO3, di€erent morphologies
biological systems use organic molecules (mostly pro- were reported for the same polymer additive but for
teins and polysaccharides) that function variously as various experimental conditions [8, 9], suggesting the
nucleators, cooperative modi®ers and matrices or molds importance of experimental parameters such as pH, ionic
for minerals so that they exert exquisite control over the strength and polymer as well as mineral concentration in
crystallization processes [1±5]. The strategy that organic a complex overall morphogenesis scenario. These pa-
additives and/or templates with complex functionaliza- rameters were varied in a recent study on the CaCO3
tion patterns are used to control the nucleation, growth, crystallization in presence of poly(ethylene glycol)-b-
and alignment of inorganic crystals has been universally poly(methacrylic acid) (PEG-b-PMAA) and their in¯u-
applied for the biomimetic synthesis of inorganic mate- ence on the CaCO3 morphology was elaborated [14]. In
rials with complex form [6]. A recently developed class of this work, we propose two mechanisms for the observed
functional block copolymers as crystal growth modi®ers, morphogenesis.
 201

Experimental preferential adsorption to these faces, thus making those

unusual faces the most stable, hindering further crystal
The experimental conditions for CaCO3 crystallization with PEG- growth and leading to the observed elongated structures.
b-PMAA as a growth modi®er as well as the characterization However, it must be stated that the observed crystal
methods have been described in previous work [14]. morphologies show some diversity, so the morphology
control by polymer adsorption does not seem to be
perfect. It is remarkable that these three faces are
Results and conclusion identical and expose dense, regular arrays of Ca2+ ions
at their surface, which explains the preferred interaction
At pH 9 CaCO3 crystallization occurs more slowly of the polyanionic polymer block with these faces. At the
compared to at higher pH owing to the lower supersat- crystal tips, however, the CO23 triangles are exposed to
uration which is determined by the pH-dependent the surface, leading to a negative charge. The Ca2+ ions
carbonate±hydrogen carbonate equilibrium. Here, in are distributed on a regular lattice on the elongated faces;
the presence of PEG-b-PMAA (0.2 g/l), elongated their distances in perpendicular directions being 499 and
CaCO3 single microcrystals are formed and are shown 405 pm. The distance between the carbon atoms on the
in Fig. 1a and c. edge of a tetrahedron in the PMAA backbone is 252 pm,
These crystals show the calcite )1, 1, )4, )1, 0, 4 and so the COOH groups attached to every second carbon on
0,1,4 faces (or the three symmetry-related ones at the the PMMA backbone favourably match the crystal
other end) at their tips and are elongated along the c-axis, lattice; we call this soft epitaxy. The elongated structures
which is the growth axis (see also Fig. 1c). This mor- grow slowly to their ®nal microcrystal size (Fig. 2,
phology is remarkably di€erent from the normal calcite mechanism c).
rhombohedrons and is not the obvious result of a At higher polymer concentrations, however, a di€er-
preferential polymer adsorption on one or more of the 1, ent scenario is observed as the polymer is now well able
0, 1; 1, )1, )1 or 0, 1, )1 (or the three symmetry-related) to stabilize the higher surface area of nanoparticles
faces of rhombohedral calcite which show a quite even (Fig. 2, mechanisms a, b).
distribution of Ca2+ and CO23 at the surface. However, The adsorption does not become selective anymore
a matching of the functional polymer block to the 0, 16, and the polymer adsorbs on all crystal faces, which leads
)1, 16, 0, 1 and 16, )16, )1 faces would result in the to a stabilization of the nanoparticles, preventing them

Fig. 1 CaCO3 particles obtained

in the presence of poly(ethylene
glycol)-b-poly(methacrylic
acid). [CaCO3] ˆ 8 mM
(a) [polymer] ˆ 0.2 g/l, pH 9;
b [polymer] ˆ 0.5 g/l, pH 10;
c zoom in of the crystal in the
lower-right-hand corner of a with
the corresponding calcite Groth/
Krantz crystal model 267 [18]
202

Fig. 2 Proposed mechanisms for

the formation of various CaCO3
morphologies resulting from the
de®ned superstructuration of
the nanoparticles

from further growth. Here, dumbbell (Fig. 1b) and surface-recognition process and the PEG extending into
spherical particle morphologies are observed and these the solution and thus providing partial steric stabiliza-
are polycrystalline according to transmission electron tion depending on the amount of polymer adsorbed,
microscopy thin cuts. Here, a completely di€erent which is mostly not sucient to prevent aggregation [14].
growth mechanism is observed and is shown schemati- From the results in Ref. [14], these nanoparticles are
cally in Fig. 2. amorphous. As the PEG block is rather short (3000
As soon as amorphous nanoparticles are nucleated g/mol) extending approximately 3±4 nm into the solu-
[14], the block copolymer becomes surface-active with tion, the steric stabilization is insucient as the steric
the PMAA block adsorbing onto the particle surface by a barrier is still in the range of the attractive van der Waals
 203

forces, which have a range of 5±10 nm. The particles are aggregating nanoparticles with respect to the primary
not completely stabilized and dipolar interactions can crystals along these ®eld lines. It is now the interplay
range through the stabilization layer and lead to directed between the van der Waals and dielectric forces and the
particle aggregation. As a consequence of the solution quadrupole ®eld which determines the superstructure of
ionic strength of about 0.01 mol/l, there is only little the compound particle. If attractive forces prevail, a side-
electrostatic shielding, so overall, the attractive van der by-side aggegation is favoured (for instance by lowering
Waals forces prevail, leading to particle aggregation. the pH and thus decreasing the negative charge at the
Owing to surface-energy minimization as well as to crystal tips). If the quadrupole ®eld is strong, it depends
di€usion e€ects, a spherical superstructure shape is on the shielding of the ®eld by the polymer on the
favoured. The particle size, on the other hand, is elongated faces (Fig. 2, mechanisms a, b), which mor-
determined by the minimum of the free enthalpy where phology is favoured. Poor shielding results in the
the enthalpy decrease owing to surface minimization is reproduction of the polar ®eld [17], whereas sucient
balanced by the entropy loss owing to the superstructure shielding results in peanutlike particles (Fig. 2, mecha-
formation, so remarkably monodisperse spherical parti- nism a, structure 1) or dumbbells (Fig. 2, mechanism a,
cles are often obtained [8]. structure 2) depending on whether further nanoparticles
The dumbbell particle morphology is regarded as an are structured along the ®eld lines of the primary polar
intermediate case of the sphere formation; however, it ®eld (Fig. 2, mechanism a, structure 1) or if the ®eld of
cannot be explained by such mechanism. Here, a mech- the previously deposited particle is at least partly
anism suggested by Kniep and coworkers [15, 16] for the responsible for the orientation of the next deposited
fractal growth of ¯uorapatite in a gelatin matrix is closely particle (Fig. 2, mechanism a, structure 2).
related to the observed morphology. If elongated parti- This results in the observed dumbbell shape where
cles are nucleated as the ®rst crystalline species from the both ends of the dumbbells can grow together at later
pool of the amorphous CaCO3 nanoparticles and the stages resulting in a spherical particle [15]. Whether or
polymer adsorbs speci®cally to the cationic elongated not this mechanism is valid for the CaCO3 case could
surfaces, charge and ®eld shielding is obtained in a not be unambiguously elaborated as a result of the
tensorial manner as outlined in Fig. 2, mechanisms a and diculty to experimentally observe the primary rodlike
b. In any case, the selective adsorption generates an particle.
electrical quadrupole ®eld which increases with increas-
ing crystal size so that a self limitation of crystal growth Acknowledgements The authors would like to thank Th. Goldsch-
midt AG, Essen, Germany, for the supply of the PEG-b-PMAA
becomes operational and new nucleation events ®nally block copolymer and the Max Planck Society for ®nancial support.
become favoured. The quadrupole ®eld lines lead to a H.C. also acknowledges the Dr. Hermann Schnell Foundation for
positioning of the later nucleated and thus smaller ®nancial support.

References

1. Mann S, Webb J, Williams RJP (eds) 8. CoÈlfen H, Antonietti M (1998) Lang- 14. CoÈlfen H, Qi L (2001) Chem Eur
(1989) Biomineralization, chemical and muir 14:582 J 7:106
biochemical perspectives. VCH, Wein- 9. Marentette JM, Norwig J, Stockel- 15. Kniep R, Busch S (1996) Angew Chem
heim mann E, Meyer WH, Wegner G Int Ed Engl 35:22
2. Mann S (1993) Nature 365:499 (1997) Adv Mater 9:647 16. Busch S, Dolhaine H, DuChesne A,
3. Mann S (1995) Biomimetic materials 10. Antonietti M, Breulmann M, GoÈlt- Heinz S, Hochrein O, Laeri F,
chemistry. VCH, Weinheim ner CG, CoÈlfen H, Wong KK, Podebrad O, Vietze U, Weiland T,
4. Weiner S, Addadi L (1997) J Mater Walsh D, Mann S (1998) Chem Kniep R (1999) Eur J Inorg Chem
Chem 7:689 Eur J 4:2493 1643
5. Fritz M, Morse DE (1998) Curr Opin 11. Qi L, CoÈlfen H, Antonietti M (2000) 17. Sedlak M, CoÈlfen H (2001) Makromol
Colloid Interface Sci 3:55 Angew Chem Int Ed Engl 39:604 Chem Phys 202:587
6. Mann S, Ozin GA (1996) Nature 12. Qi L, CoÈlfen H, Antonietti M (2000) 18. Burchard U (1994) The P. Groth and
382:313 Chem Mater 12:2392 F. Krantz crystal model collection.
7. Sedlak M, Antonietti M, CoÈlfen H 13. OÈner M, Norwig J, Meyer WH, Weg- Freising
(1998) Macromol Chem Phys 199:247 ner G (1998) Chem Mater 10:460
Progr Colloid Polym Sci (2001) 117: 204±210
Ó Springer-Verlag 2001 DISPERSIONS

M. Benna Card-house microstructure of puri®ed

N. Kbir-Ariguib
C. Clinard sodium montmorillonite gels evidenced
F. Bergaya
by ®ltration properties at different pH

Abstract The e€ect of pH on the cakes obtained decreases as the pH

static ®ltration properties of puri®ed increases, which probably means the
sodium montmorillonite dispersions breakdown of the double-layer
depends on the applied pressure. At repulsion at natural pH and the
1.5 ´ 105 Pa, the double-layer re- breakdown of the ``repulsive net-
pulsion resists the applied pressure work'' at basic pH. The results also
at natural pH, which is close to show that the water retention is the
neutral pH, and at basic pH. At highest in the acidic cake and the
acidic pH, where the cake is the lowest in the neutral cake, which
thinnest and the least permeable, probably means that the edge-to-
the edge-to-face attractions act as face attractions in the acidic cake
hinges. At natural pH, the thickest resist the pressure more strongly
and the most permeable cake is than the face-to-face repulsions in
obtained. It retains less water than the cake at the natural pH. The
the acidic one because of the X-ray di€raction patterns of the
absence of edge-to-face contact acidic cake do not show a basal
between particles. These interpreta- re¯ection, whereas the other cakes
tions are con®rmed by transmission show interparticular distances rang-
M. Benna á C. Clinard á F. Bergaya (&) electron microscopy photographs. ing from about 13 to about 39 AÊ
CRMD CNRS-Universite d'OrleÂans 1b, At basic pH, the cake retains more (natural cake) and from about19 to
Rue de la FeÂrollerie 45071. water than at lower pH, but it has about 33 AÊ (basic cake).
OrleÂans CeÂdex 2, France
e-mail: [email protected] an intermediate permeability, possi-
bly because of adsorption of water
M. Benna á N. Kbir-Ariguib on the negatively charged edges of
Institut National de la Recherche
Scienti®que et Technique. BP 95, the clay mineral layers. At Key words Clays á pH and ®ltration
2050 Hammam-Lif, Tunisia 5.7 ´ 105 Pa, the permeability of the properties á Microtexture

Introduction ®ltration properties are thus dependent on the microtex-

ture of the clay, which depends on two main factors: the
The use of bentonite clays in drilling ¯uids is based on water content and pH. The e€ect of clay content was
their ability to present speci®c rheological and ®ltration studied by Benna et al. [1] and the e€ect of pH is the
properties (under dynamic and static conditions). During subject of the present article.
the drilling operation (even when it is stopped) a thin and The objective of this work is to determine the
impermeable cake is formed on the wall of the hole. Low in¯uence of the clay microtexture on the static
permeability and water loss are required macroscopic ®ltration properties of a puri®ed sodium montmorill-
parameters for the suitability of a clay to be used in onite. The ®ltration properties are followed, as a
drilling ¯uids. Some clays become suitable for use in function of pH variation, under two di€erent constant
drilling ¯uids after acidic or basic activation. The pressures.
 205

Literature review Experimental

Recent literature data on the static ®ltration properties of Materials

bentonite aqueous suspensions are very scarce [1], partic-
The Wyoming bentonite used in this study was provided by
ularly those on the e€ect of pH. In studies related to the Comptoir des MineÂraux et MatieÁres PremieÁres, France (ref. SPV)
petroleum industry, Loeber [2] and Li [3] reported results and was puri®ed by the classical NaCl exchange [4, 12].
for ®ltration properties of water/crude montmorillonite/ The granulometry and the method of preparation of the
electrolyte/polymer systems at the natural pH of the clay. suspensions have a great in¯uence on the degree of dispersity of
the clay and on the ®ltration properties. So, it is important to state
The static ®ltrations were done over 0.5 h in an ``API that all samples were prepared in the same way. The granulometry
standard ®lter press''. Scanning electron microscopy of the dry puri®ed sodium bentonite was controlled by sieving the
micrographs showed that the cake obtained from a 3% dry clay powder to 80 lm. During the sample preparations, it was
(w/w) crude bentonite aqueous suspension was homoge- particular care was taken to prevent attack of the clay mineral
structure by avoiding direct contact of acidic or basic compounds
neous and its permeability was of 4.6 ´ 10)18 m2 at with the dry bentonite powder. The clay content of 5.5% (w/w)
6 ´ 105 Pa [2]. For the water/clay system, this homoge- used corresponds to the lowest amount of this bentonite which
neity was con®rmed by the results of Li [3] which showed exhibits gel behaviour.
that the size, shape and mode of association of clay
particles have a great e€ect on the texture and the Preparation of the suspensions
permeability of the cake. For the same clay content (3%
The acidic (HCl) or basic (NaOH) solution (50% by weight of the
w/w) the permeability was 14.3 ´ 10)18 m2 at 2 ´ 105 Pa ®nal suspension) was added to the aqueous clay suspension, which
and 4.5 ´ 10)18 m2 at 7 ´ 105 Pa [3]. was shaken by hand for 5 min (5.5% clay and 44.5% bidistilled
The e€ect of clay content in aqueous clay suspensions water by weight of the ®nal suspension). The suspension was
on the ®ltration properties was recently studied at shaken on a roller shaker for 24 h, then left to rest for 24 h before
natural pH [1]; however, the time of ®ltration was not the experiments were carried out.
®xed and the ®ltration experiment was stopped when the
®ltrate did not ¯ow at all. The variation of permeability pH measurements
and/or thickness of the cakes obtained at two di€erent Three values of pH were chosen according to previous results [4]:
applied pressures allows the sol±gel transition to be the natural pH of the aqueous bentonite suspension (pH 7.50) and
detected and the importance of the clay texture to be pH 4.23 and 11.75 corresponding to the highest values of the yield
pointed out. stress in acidic and basic media. All pH values were measured with
The pH variation was correlated to the microtexture a high-precision Ingold combined glass electrode using a Bioblock
Scienti®c 93313 pH meter.
of the clay in many rheological studies (see Ref. [4] for
references). In the rheological investigations of aqueous
clay suspensions, the association of particles was the Filtration
subject of di€erent interpretations [5]. The major ques- The suspension was ®ltered in a stainless steel Millipore ®ltration
tion is the existence or the nonexistence of the edge-to- cell as already described [1]. The ®ltrate volume was measured as a
face interaction. It is very important to note that all function of time. The water retention, which is the complement of
authors who demonstrated the face-to-face association the water loss (water loss ˆ 100)water retention), was determined
by measuring the ®nal ®ltrate volume (Vf.f.). As the volume of
between clay particles by rheological investigation or water in the initial suspension (Vi.w.) is known, the water retention
textural studies [6±9] used montmorillonite suspensions is de®ned by
at the natural pH of the clay, without any variation of Water retention ˆ ‰ Vi:w: Vf:f: †=Vi:w: †Š  100 : 1†
pH. However, the existence of what is called a card-house
[10] microtexture between clay particles in aqueous The coecient of permeability (k), in square metres, is
calculated assuming that the microstructure of the cake is uniform,
suspensions owing to attractive edge-to-face associations which means that k is constant in all the bulk volume of the cake
in acidic media, or owing to repulsive interparticle during the ®ltration. This allows the use of the Darcy law:
interactions in basic media, has been discussed in our dVt:f: =dt ˆ kSP †= le† ; 2†
previous work [4].
The water loss and the permeability of crude benton- where Vt.f. is the ®ltrate volume at time t, S is the ®ltration surface
ite/cement slurries have been investigated in function of (S ˆ 13.2 ´ 10)4 m2), P is the experimental applied pressure, l is
the ®ltrate viscosity (in our experiments l ˆ 0.001 Pas ˆ viscosity of
high pH values, from 8.1 to 12.66, in the presence of water) and e is the thickness of the cake.
added calcium ions [11]. For the crude bentonite Integration of this equation assuming volume conservation
suspension (3% w/w) without added cement and at a gives the ®nal form of the Darcy law [1]:
Ca2+ concentration of 10)2 mol/l, the permeability is 2
Vt:f: ˆ 2kSP =le†Vf:f: t 3†
14.5 ´ 10)18 m2 at 6 ´ 105 Pa. The water loss remains Thus, the permeability coecient, k, can be determined
constant until pH 12, but at pH 12.66, the permeability 2
experimentally from Vt:f: ˆ f t† curves, where the linear slope is
increases and the water loss decreases. 2kSPVf.f./le.
206

For each pH value studied, the static ®ltration experiments were

carried out at 1.5 ´ 105 and 5.7 ´ 105. The ¯ow rate of ®ltration
was relatively high at the beginning and decreased near the end
when the ®ltrate did not ¯ow at all.
The cake removed from the ®ltration cell was immediately
divided into two parts: one part was immediately used to measure
the thickness of the cake; the second part of the cake, which was
obtained at 1.5 ´ 105 Pa, was prepared for transmission electron
microscopy (TEM) observation. When the applied pressure was
5.7 ´ 105 Pa, the second part of the cake was immediately used,
without grinding, in a Siemens D500 di€ractometer to obtain the
X-ray patterns.

Results

Filtering properties

Darcy law

The linear variation of the square of the ®ltrate volume is

shown in Fig. 1a and b as a function of time for all
the sodium montmorillonite suspensions, indicating the
validity of the Darcy law. At high applied pressure the
time required for ®ltration increases as the pH increases.
This behaviour was not observed at lower pressure.

Water retention

The water retention is probably the simplest macroscopic

parameter which gives an idea of the microtexture of the
cake; its variation with pH at 1.5 ´ 105 and 5.7 ´ 105 Pa
is shown in Fig. 2. The cakes retain more water at the
lower pressure. Whatever the applied pressure, the water
retention of the cake is the lowest at natural pH. At basic
pH, the water retention is higher than at acidic pH at the
lower pressure. At a higher pressure of 5.7 ´ 105 Pa, the Fig. 1a, b Darcy law. Linear variation of the square of the ®ltrate
volume with time
opposite behaviour is observed: the acidic cake retains
more water than the basic one.

Thickness and permeability

The variations of the thickness and the permeability with

pH depend on the applied pressure (Figs. 3, 4). At the
lower pressure, the thickness and the permeability are
highest at the natural pH and are higher at basic pH than
at acidic pH; however, at 5.7 ´ 105 Pa the thickness and
the permeability decrease as the pH increases and have
their highest values at acidic pH.

Microstructure of the cakes

X ray di€raction of cakes obtained at 5.7 ´ 105 Pa

The X-ray di€raction patterns (Fig. 5) show a broad

distribution of peaks between 13 and 39 AÊ for the cake at Fig. 2 Water retention of the cakes as a function of pH
 207

Fig. 3 Thickness of the cakes as a function of pH

Fig. 5a±c X-ray di€ractograms of the cakes obtained at 5.7 ´ 105 Pa

Fig. 4 Permeability of the cakes as a function of pH zones that are very dense. The porosity essentially
consists of closed pores with broad size distribution.
± The basic cake (Fig. 6b) is less disoriented than the
natural pH and between 19 and 33 AÊ for the cake at basic acidic one. There is a preferential orientation which
pH. The X-ray di€raction pattern of the acidic cake does gives a majority of open pores. There are some zones
not show signi®cant peaks in the region of small that are denser than the others.
distances and shows only a relatively weak peak at about ± The natural cake (Fig. 6c) is the most-oriented
38 AÊ. sample. A few zones are denser than the others. We
have already observed this phenomenon in the initial
natural gel. The porosity essentially is related to open
TEM of cakes obtained at 1.5 ´ 105 Pa
pores.
Observations at low magni®cation give an idea of the Observations at high magni®cation are shown in
texture (homogeneity, orientation and porosity) of the Fig. 7.
cakes obtained.
± The acidic cake (Fig. 7a) is the most disoriented and
± In the acidic cake (Fig. 6a) a pronounced disorienta- the densest cake; however, a preferential orientation
tion of the particles is observed, and there are many of the long particles is detectable. The smaller
208

Fig. 6a±c Transmission electron microscopy (TEM) photographs of Fig. 7a±c TEM photographs of the cakes obtained at 1.5 ´ 105 Pa at
the cakes obtained at 1.5 ´ 105 Pa at low magni®cation. a: pH 4.23, high magni®cation. a pH 4.23, b pH 11.75 and c pH 7.50
b pH 11.75 and c pH 7.50

particles are very disoriented, with many edge-to-face ed, while the long particles, because of their size,
contacts. This is explained by the fact that particles cannot be easily rearranged. The edge-to-face attrac-
with a small lateral extension can be easily disorient- tions, which are well built-up at this relatively low
 209

pressure, are clearly shown on the TEM photograph.

The distribution of the number of layers per particle is
between 2 and 9 with many isolated layers.
± The right side of the photograph in Fig. 7b illustrates
the tendency of the orientation and the anisotropy
of the porosity in the basic cake. On the left side, we
see the disorientation of particles; thus, the resistance
of the ``repulsive network'' to the low applied pres-
sure. The distribution of the number of layers per
particle is mainly from 2 to 9 as in the acidic cake, but
in this case the isolated layers are very scarce.
± The preferential orientation of particles of the natural
sample (Fig. 7c) is clearly shown and there is, as
expected, only one type of interparticular interaction,
the face-to-face aggregation. The open porosity is also
con®rmed at this scale, and the density of the particles
is the lowest. Isolated layers are scarce and the
stacking of three layers per particle is most frequent
and representative, but stackings of up to ten layers
per particle are also observed.

Discussion

According to our previous work [4] on the rheological

and electrokinetic properties of bentonite as a function of
pH, the three values of the pH chosen correspond to the
maximum of face-to-edge attraction (pH 4.23), the
isoelectric point of the edges (pH 7.50), which corre-
sponds to zero charge on the edges and there is only the
face-to-face double-layer repulsion, and all the contri-
bution of edge-to-face, face-to-face and edge-to-face
repulsion (pH 11.75) when all edges are negatively
charged. Fig. 8 Summary of the results of cake properties (thickness, e, water
The variation of the ®ltration properties with pH is retention, WR, and permeability, k) as a function of pH and applied
pressure
summarised in Fig. 8.
± At the relatively low applied pressure (1.5 ´ 105 Pa)
media. As the particles in the initial basic gel are in all
the acidic cake is less permeable and retains more
directions, the basic cake traps more water than the
water but it is thinner than the natural one. The edge-
natural one, in which the particles are parallel; therefore,
to-face attractions (as hinges) attract the layers. At
the basic cake is less permeable and thinner than the
the natural pH, the di€use double-layer repulsion
natural one.
prevents the aggregation of the clay mineral layers at
At the acidic pH, the cake is the most permeable and
this relatively low pressure. The basic cake is more
its water retention is the highest, which proves that it is
permeable than the acidic one but it contains more
the most porous. This highest porosity is con®rmed by
water. In basic media, all faces and edges are
the fact that the acidic cake is the thickest one. This
negatively charged and water is probably adsorbed
displays once again the existence of edge-to-face attrac-
on faces and edges. In acidic media, the existence of
tions at acidic pH, which allow more water to be trapped
edge-to-face connections prevents adsorption of water
between particles.
on these localised sites and consequently the basic
To summarise, the e€ect of pH on the ®ltration
cake contains more water than the acidic one.
properties is explained in terms of interparticular inter-
At 5.7 ´ 105 Pa the applied pressure is probably actions. If the edge-to-face attraction did not exist in
suciently high to overcome the double-layer repulsion acidic media and if the edge-to-face, face-to-face and
at natural pH and the natural cake retains less water than edge-to-edge repulsions did not exist in basic media,
the other two. Also this pressure is sucient to break otherwise if there was only face-to-face repulsion what-
down the three-dimensional ``repulsive network'' in basic ever the pH, there would be no variation of the ®ltration
210

properties with pH. The experiments show clearly that literature data on the interactions between particles in
permeability, thickness and water retention of the cakes the montmorillonite gels. Comparison of the ®ltration
vary with pH. Also, the ®ltration parameters change with and textural properties of the bentonite studied allows
applied pressure, which means that the interparticular the interparticular interactions between clay particles at
interactions change when the pH is varied. di€erent pH to be revealed. The existence of edge-to-face
attraction was con®rmed in acidic media. In highly basic
media, a network based on edge-to-edge, edge-to-face
Conclusion and face-to-face repulsion instead of attraction was also
con®rmed.
The microtexture of the cakes depends on the interpar-
ticular interactions in the initial suspension. The results Acknowledgements The authors wish to thank M. Crespin for the
obtained by di€erent techniques (®ltration, TEM and X-ray di€raction experiments and T. Cacciaguerra for the TEM
X-ray di€raction) are in good agreement with the sample preparation.

References

1. Benna M, Kbir-Ariguib N, Clinard C, 5. Norrish K (1954) Discuss Faraday Soc 9. Gaboriau H (1991) Thesis. University
Bergaya F (2001) Appl Clay Sci 18:120±134 of OrleÂans
19:103±120 6. Pons CH, Rousseau F, Tchoubar D 10. Van Olphen H (1977) Introduction to
2. Loeber L (1992) Thesis. University of (1981) Clay Miner 16:23±42 clay colloid chemistry, 2nd edn. Wiley,
OrleÂans 7. Tessier D (1984) Doctoral thesis. Uni- New York
3. Li Y (1996) Thesis. University of versity of Paris VII 11. PleÂe D, Lebedenko F, Obrecht F,
OrleÂans 8. Tessier D (1991) In: De Boodt M, Letellier M, Van Damme H (1990)
4. Benna M, Kbir-Ariguib N, Magnin A, Hayes M, Herbillon A (eds) Soils and Cem Concr Res 20:45±61
Bergaya F (1999) J Colloid Interface their association in aggregates. Plenum, 12. Annabi-Bergaya F (1978) Doctoral
Sci 218:442±455 New York, pp 387±415 thesis. University of OrleÂans
Progr Colloid Polym Sci (2001) 117: 211±216
Ó Springer-Verlag 2001 DISPERSIONS

Otto HorvaÂth Light-induced reduction of heavy-metal ions

J. Hegyi
on titanium dioxide dispersions

Abstract Photoactive semiconduc- as demonstrated by the examples of

tors such as TiO2 can be applied for Hg(II), Bi(III), and Pb(II). The
wastewater treatment; not only for relatively lower eciency for the
degradation of organic pollutants, deposition of Cu may be attributed
but also for removal of heavy-metal to a short-circuiting e€ect. Surfac-
ions. Photoassisted reduction of dif- tants of di€erent type also function
ferent, mostly toxic metal ions, such as potential electron donors in these
as Hg(II), Pb(II), Bi(III), and Cu(II), systems. Negatively charged dodecyl
has been realized in aqueous systems sulfate proved to be much more
containing ethanol as a sacri®cial ecient than ethanol, while cationic
O. HorvaÂth (&) á J. Hegyi
University of VeszpreÂm, electron donor. The eciency of the cetyltrimethylammonium is rather
Department of General and Inorganic photoreduction carried out under weak in this respect.
Chemistry, 8201 VeszpreÂm, the same circumstances is primarily
P.O. Box 158, Hungary determined by the standard reduc- Key words Photocatalysis á
e-mail: [email protected]
Tel.: +36-88-427915 tion potential of the species con- Semiconductor á Heavy metal á
Fax: +36-88-427915 taining the metal ion to be removed Decontamination á Titanium dioxide

Introduction sacri®cial electron donor, the irradiation time, and the pH

of the system. In this article, we present work on the
Semiconductor catalysis has received considerable atten- photoassisted reduction of Hg(II), Pb(II), Bi(III), and
tion in the past two decades as an alternative for treating Cu(II) on TiO2. We show how the application of an
water polluted with hazardous organic chemicals [1±10]. added sacri®cial electron donor (ethanol) can make the
To a lesser extent, it has also been studied for application overall reaction catalytic, how the concentration of this
to water containing metals (for decontamination and reductant in¯uences the eciency of the process. The
metal recovery) [11±15]. The utilization of semiconductor e€ects of commercial surfactants as potential electron
photocatalysis as a means of decontaminating heavy- donors were also studied for the purpose of simultaneous
metal (Hg, Pb) polluted water has several advantages removal of heavy-metal ions and detergent contaminants
compared to other methods. Toxic metals in their from wastewater.
oxidation states can neither be biodegraded nor can they
be chemically removed. However, under appropriate
Experimental
conditions quantitative removal of heavy-metal ions
becomes possible with irradiated TiO2 semiconductor Reagents
particles [16±18]. Mostly, the metal ions are deposited on
the surface of the semiconductor particles in a reduced, The following metal salts (reagent grade) were used: HgCl2,
elemental form. The eciency of this process depends on CuSO4 á 5 H2O, Pb(NO3)2, BiCl3 (Aldrich). TiO2 (Fluka, predom-
inantly in rutile form) was utilized as a photocatalyst. Triply
the standard reduction potentials of the metal ions, the distilled water was used for the preparation of solutions containing
Gibbs free-energy change of the overall reaction, the 1 ´ 10)3 M metal ion to be reduced and 0.1 wt % TiO2 suspended.
presence or absence of oxygen, the concentration of the Analytical grade ethanol, sodium dodecyl sulfate(SDS), and
212

cetyltrimethylammonium bromide (CTAB) (Aldrich) were applied particle suspended in water causes electronic transitions
as electron donors in various concentration. No pH adjustment of from the valence band to the conduction band, leaving
the solutions to be irradiated was done.
holes in the former. These electrons and holes then either
Instruments migrate to the particle surface and become involved in
redox reactions or they recombine and simply liberate
A 150-W high-pressure mercury lamp was utilized as a light source. A heat.
10-cm cylindrical glass cuvette ®lled with circulating cooling water
was used to absorb the IR emission toward the photoreactor, which
Conduction band electrons are consumed in reactions
was a 1-cm cuvette with 3-cm3 volume. It was open on top, and that reduce oxidants (Ox1®Red1), while holes are ®lled
1.2 cm2 of its front surface was illuminated. Using a spectroradiom- via oxidation reactions (Red2®Ox2).
eter, the integral lamp output between 310 and 390 nm was found to The photogenerated hole (h+) can oxidize H2O as an
be 62 mW/cm2 at the front surface of the reactor cuvette. A GBC initial step.
UV±vis 911A spectrophotometer was applied for the analysis.
TiO2
2H2 O + 4h‡ ! O2 ‡ 4H‡ 1†
Procedure hm

Photolyses of the reaction mixtures were carried out for various Oxygen molecule, however, can function as an electron
time intervals up to 40 min. Oxygen-free experiments were carried acceptor to chemically reverse this process.
out by bubbling nitrogen through the reaction solution for 15 min
TiO2
prior to and throughout the experiment. The contents of the O2 +4H‡ ‡ 4e ! 2H2 O 2†
reactor were magnetically stirred and thermostated (at 20 °C) by hm
using an aluminum block with circulating water.
If the carrier ¯uxes owing to the reactions in Eqs. (1) and
Analysis (2) are exactly balanced, there is no net chemistry, and O2
has functioned as a chemical surface state for mediating
After the irradiation the suspension was centrifuged and the the e))h+ recombination process. Net chemistry can
supernatant solution was analyzed for metal ions spectrophoto-
metrically by using halide ions as complexing agents. A 0.5 cm3 only occur at the TiO2 surface if either reaction is
aliquot of the clear part of the sample was taken and introduced intercepted at an intermediate stage. Alternatively, the
into 2.5 cm3 4 M NaCl solution in a 1-cm quartz cuvette. The e)and h+ at the TiO2 surface must react with di€erent
absorbance of the chlorometallate complexes formed was measured redox couples in the contacting medium as illustrated in
at a wavelength appropriate for the metal ion studied. Only rather
dilute halide solution could be used for the systems containing
Scheme 1.
surfactants because of their precipitation at higher ionic strenghts. In pollutant destruction, either Eq. (1) or Eq. (2)
In these cases, 2 cm3 clear sample was mixed with 1 cm3 0.01 M constitutes half the conjugate reaction pair; the other half
NaI solution to form iodometallates. Absorbances of the halomet- of the pair or partner comprises the pollutant molecule,
allates obeyed the BLB law for each metal ion in the concentration ion, or microorganism.
range studied (0 ) 7 ´ 10)4 M).
TiO2
4OH ‡ 4h‡ ! 4OH ; 3†


hm
Results and discussion
TiO2
O2 +2H2 O + 4e ! 4OH 4†
Theory hm
Hydroxyl radicals are generated by the oxidation of
The energetics and charge-transfer processes involved in water at the valence band of TiO2 [1, 4, 6, 7]. This occurs
a typical photocatalytic process are illustrated in at a standard potential of 2.8 V [19], which decreases
Scheme 1. Bandgap illumination (hm) of a semiconductor with increasing pH. The very reactive OH radicals
interact with the organic substrates, promoting their
oxidation and, ®nally, mineralization.
During typical photocatalytic oxidation of organic
components, oxygen is reduced to become superoxide
()0.56 V) and/or perhydroxyl ()0.13 V) radicals [19],
depending on the pH. These radicals eventually form
hydroxyl radicals, which enter into the oxidation cycle
[1, 4, 6, 7].
Besides oxygen, any dissolved species with a reduction
potential more positive than the conduction band of the
photocatalyst can, in principle, consume electrons and
complete the redox cycle. For example, with a toxic metal
ion, M2+:
TiO2
2M 2‡ + 4e ! 2M 5†
hm
 213

In this instance, Eqs. (1) and (5) form a conjugate pair, carried out under similar circumstances but in a deox-
giving the overall reaction ygenated system with continuous purging with nitrogen
resulted in 40% eciency of reduction after 20 min
2M 2‡ ‡ 2H2 O ! 2M ‡ O2 ‡ 4H ‡ 6†
(Fig. 1). Addition of 5 ´ 10)4 M ethanol (as a hole
Considering the energetics of this reaction (Eq. 6), it is scavenger) dramatically accelerated the photoinduced
photocatalytic if its Gibbs free-energy change is negative deposition of mercury. More than 85% of the initial
(DG0<0) [20]. In this case, the reaction is driven in the amount of Hg(II) was reduced within 10 min (Fig. 1). It
spontaneous direction by the light, and the radiant clearly indicates that the overall reaction
energy simply serves to overcome the activation barrier TiO2
for the process. If Eq. (6) involves a positive DG0, the HgCl2 ‡ CH3 CH2 OH ! Hg + 2HCl + CH3 CHO
hm
reaction is photosynthetic, the light drives the system in
the thermodynamically uphill direction. Photoassisted 7†
reduction of metal ions is photosynthetic in most cases, is photocatalytic. A sharp decrease in the reduction rate
except for those with very positive potentials, i.e., when can be noticed in the reduction eciency versus irradi-
they have standard reduction potentials that are more ation time plot after 10-min irradiation. This phenom-
positive relative to the O2/H2O redox couple. Also these enon can be attributed to the limiting e€ect of the low
reactions can be made photocatalytic with the addition initial concentration of ethanol and the decrease in the
of appropriate hole scavengers, resulting in a negative actual reduction potential of Hg(II). Theoretically,
free-energy change for the overall process. according to Eq. (7), 5 ´ 10)4 M ethanol stoichiometri-
cally correponds to 1 ´ 10)3 M HgCl2. At about 90%
deposition, however, the reduction potential of Hg(II) in
Photocatalytic reduction of Hg(II) this system is about 0.6 V lower than its value at the
beginning of the photolysis. Besides, most of the electron
Hg(II) is the only one of the metal ions studied for which donor ethanol is used up by that time. These simulta-
the standard reduction potential is more positive than neous e€ects decrease the rate of the photoinduced
that of the O2/H2O pair at pH 7 (0.85 V versus 1.229± reduction by more than 1 order of magnitude. Of course,
0.059pH ˆ 0.816 V [21]). The di€erence between the at higher ethanol concentration (above 0.03 M) no
redox potentials, however, is not signi®cant. Besides, similar e€ect can be experienced, and photoreduction
this reduction potential (0.85 V) is valid only for Hg2+. and elimination of mercury from the solution is more
In aqueous solutions and natural pH, HgCl2 dissolves than 99% complete in under 20 min of illumination, even
undissociated; about 1% HgCl2 exists as Hg2+ [19]. The in the air-saturated system.
redox potential for the HgCl2/Hg couple is 0.41 V [22],
which is too low for a catalytic reaction. Owing to this
fact, photolysis of an air-saturated solution did not lead Photocatalytic reduction of Bi(III)
to an appreciable deposition of mercury on TiO2, i.e., less
than 10% of the initial concentration (1 ´ 10)3 M) of The standard reduction potential of the Bi(III)/Bi couple
Hg(II) was reduced after 20-min irradiation. Photolysis is 0.317 V [23], which is more negative than that of the
O2/H2O pair in neutral and, especially, in acidic solution.

Fig. 1 Eciency of Hg(II) reduction versus irradiation time in the Fig. 2 Eciency of Bi(III) reduction versus irradiation time. The
absence (n) and in the presence (r) of (5 ´ 10)4 M) ethanol concentration of added ethanol is 5 ´ 10)4 M
214

Thus, the reduction of Bi(III) can only be photocatalytic Photocatalytic reduction of Pb(II)
in the presence of ethanol as a sacri®cial electron donor.
With the use of this hole scavenger, Bi(III) is also reduced Besides Hg, one of the most toxic heavy metals is Pb, so
and deposited on the surface of TiO2 particles. The its removal from wastewater is of basic importance. The
reduction eciency is over 90% after 30-min irradiation standard reduction potential of Pb(II) is )0.125 V [23];
in a deaerated system initially containing 5 ´ 10)4 M however, it is partly removable with the use of ethanol. In
ethanol (Fig. 2); hence, Bi(III) is quantitatively remov- this case, however, an extremely high ethanol concentra-
able if the concentration of the ethanol added is tion is necessary (40 v/v%»7 M). Even so, a maximum
increased. eciency of 84% could be reached (Fig. 4). It is worth
mentioning that in earlier experiments Pb(II) was
deposited in the form of PbO2 as a result of photoin-
E€ect of ethanol concentration duced oxidation on Pt-loaded TiO2 particles [24]. Metal-
free TiO2, however, was not e€ective in this respect.
As mentioned for the photoreduction of Hg(II), an
increase in the concentration of the sacri®cial electron
donor added enhances the rate of the photoinduced E€ects of anionic and cationic surfactants
reduction and, thus, the eciency of the deposition after
a certain period of irradiation time. The eciency of the SDS is one of the most frequently used detergents in
photoreduction of Hg(II), Bi(III), and Cu(II) was domestic and industrial laundry operations. As a primary
measured after 10-min illumination at various ethanol pollutant in municipal wastewater, SDS has attracted
concentrations. As can be seen in Fig. 3, the eciency environmental concerns [25]. Since it is toxic to aquatic
versus concentration of ethanol functions are in accor- and animal life, and is rather resistant to biodegradation,
dance with the relation of the standard reduction its photocatalytic destruction, which proved to be feasible
potentials in the case of Hg(II) (0.41 V for HgCl2/Hg) and reasonable, has become of practical importance. The
and Bi(III) (0.317 V). At cethanol>5 ´ 10)4 M the plots degradation of SDS on TiO2 is an oxidation reaction [10];
for these metal ions are close to each other, correspond- hence, this process must promote the photoreduction of
ing to similar redox potentials. Although the standard Hg(II). This conclusion is also supported by the pho-
reduction potential of the Cu(II)/Cu pair (0.34 V) is tolysis of the HgCl2/TiO2 system containing 0.03 M SDS.
between those of Hg(II) and Bi(III), a higher concentra- As it can be seen in Fig. 5, practically a quantitative
tion of hole scavengers than in the case of Bi(III) was deposition of Hg could be achieved after 10-min illumi-
needed to reach the same eciency. Moreover, only an nation. If ethanol is added to the initial solution, the
eciency of about 60% was reached even at 0.1 M eciency of the reduction decreases with the increase in
ethanol concentration. (For a quantitative deposition of the ethanol concentration (Fig. 6); it is higher, however,
Cu, 1 M ethanol had to be applied.) Such deviating than the eciency with ethanol alone. This phenomenon
behavior of Cu may be interpreted by its short-circuiting clearly indicates that SDS as a hole scavenger is signi®-
e€ect on the surface of the TiO2 particles [20], which cantly better than ethanol. This synergic e€ect suggests
promotes the electron±hole recombination. the simultaneous removal of toxic metals and anionic
surfactants from wastewater by photocatalytic processes.

Fig. 3 Eciency of Hg(II) (r), Bi(III) (n), and Cu(II) (m) reduction
versus the logarithm of the concentration of ethanol. The irradiation Fig. 4 Eciency of Pb(II) reduction versus ethanol concentration.
time is 10 min The irradiation time is 10 min
 215

Fig. 7 Eciency of Hg(II) reduction versus irradiation time in the

presence of 0.01 M cetyltrimethylammonium bromide
Fig. 5 Eciency of Hg(II) reduction versus reaction time in the
presence of 0.03 M sodium dodecyl sulfate (SDS)
sacri®cial electron donors and the surface charge of the
TiO2 particles and, thus, the adsorption of charged
reactants, such as detergents. In order to explore the pH
e€ects in the presence of surfactants, further experiments
are in progress.

Conclusion

Light-induced reduction of most of the toxic heavy-metal

ions on TiO2 particles can be made photocatalytic by the
application of a sacri®cial electron donor at an appro-
priate concentration. Ethanol proved to be suitable for
this purpose. In the case of originally photocatalytic
systems, addition of electron donors enhance the rate of
Fig. 6 Eciency of Hg(II) reduction versus ethanol concentration in
the presence of 0.03 M SDS the reduction. The presence of oxygen diminishes the
photoinduced deposition of metals, because of the com-
petitive scavenging of conductance band electrons and
CTAB as a cationic surfactant was also tested as reoxidation of the metals deposited. The eciency of the
potential electron donor for the photoreduction of photoreduction carried out under the same circumstanc-
Hg(II). Deviating from SDS, CTAB (0.01 M) only es is primarily determined by the standard reduction
slightly promotes the photoreduction of Hg(II) (Fig. 7). potential of the species containing the metal ion to be
If 0.01 M CTAB and ethanol are used together, the removed. It has been demonstrated by the examples of
reduction eciency is higher than in the presence of Hg(II), Bi(III), and Pb(II). Cu(II) showed deviating
CTAB alone, but lower than in the presence of ethanol behavior; the relatively lower eciency of its deposition
alone; about 40% after 20-min irradiation even with 1 M may be attributed to a short-circuiting e€ect. Commer-
ethanol (and 0.01 M CTAB). This phenomenon indi- cially used surfactants also proved to be potential hole
cates that cetyltrimethylammonium ions compete with scavengers. Negatively charged dodecyl sulfate is much
ethanol for the holes on the surface of the TiO2 particles, more ecient than ethanol, while cationic cetyltrimethy-
but the positive charge of the surfactant hinders its lammonium is rather weak in this respect.
ecient reaction. As mentioned, the pH was not adjusted
in the solutions studied in this work; however, the pH can Acknowledgement Support of this work by the Hungarian Minis-
considerably in¯uence both the redox reactions of the try of Education (FKFP 0082/1999) is gratefully acknowledged.

References

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Progr Colloid Polym Sci (2001) 117: 217±222
Ó Springer-Verlag 2001 DISPERSIONS

GyoÈrgy Fetter In situ structural investigations of the

TamaÂs HoraÂnyi
Attila BoÂta Synperonic(A7)±water system under shear

Abstract A sample holder was Bragg pro®les do not return to the

constructed for small-angle X-ray starting position but drastic changes
scattering(SAXS) measurements can be detected in their shapes
that can be used as a shear cell. The which indicate signi®cant changes in
lamellar structure of a nonionic the lamellar arrangements. These
G. Fetter surfactant (Synperonic A7)±water structural changes also explain the
Department of Chemical Information
Technology, system was investigated in this cell. tixotropic behaviour of the system
Budapest University of Technology and The SAXS curves of the sample which was observed in rheological
Economics, were detected in the steady state tests.
1521 Budapest, Hungary and under shear for a certain time,
T. HoraÂnyi á A. BoÂta (&) and ®nally in the steady state once
Institute of Physical Chemistry, again. The Bragg pro®les of the
Budapest University of Technology and SAXS curves shift to smaller char- Key words Small-angle X-ray
Economics, 1521 Budapest,
Hungary acteristic periodic distances under scattering á Lamellar systems á
e-mail: [email protected] the shear stress. After shear the Shear á Tixotropy á Surfactant

Introduction rheological test revealed that the system was tixotropic.

This rheological behaviour shows that the shear stress
The association of colloid systems containing amphi- may a€ect the lamellar structure. The change in the
philic molecules (among them the surfactants, also lamellar structure can be attributed to two reasons: the
called tensides, which are of great practical importance) destruction of the lamellar arrangement and the forma-
form nanometre-sized structures in di€erent arrange- tion of new structures.
ments (micelles, lamellar, hexagonal, or inverse hexag- Simultaneous structural and rheological investiga-
onal) depending on the concentration. They are the tions permit in situ examinations to reveal and feature
so-called lyotropic systems, having a wide range of of the structure which are connected with the in¯uence
application in industry and the household. They can be of the shearing stress [9]. Small-angle X-ray scattering
produced, for example, from mixtures of fatty alcohols (SAXS) and small-angle neutron scattering are
and water [1]. powerful methods to study lamellar arrangement.
The concentration of the tenside and the temperature Synchrotron rays are especially useful because of the
have a major in¯uence on the rheological characteristics, high-power radiation, which allows the identi®cation
which are very important in practical applications [2]. A of structural changes with short lifetimes (seconds or
nonionic surfactant (Synperonic A7)±water system was milliseconds) [10]. We have constructed a shear cell
studied intensively by Tadros and coworkers [3±5]. They which allows in situ SAXS measurements. Scanning
reported that this system exhibits lamellar structure in the structural changes of the Synperonic A7±water
the concentration range between 55 and 80% (w/w). lamellar system under shear stress in our cell allows
NeÂmeth et al. [6±8] characterized the structural beha- essential information for the interpretation of the
viour by rheological measurements and the experimental rheological characteristics and properties of the system
data were interpreted by using a slip-plane model. The to be obtained.
218

Experimental of Ni-®ltered Cu Ka radiation (1.542 AÊ) was recorded in the 10)3±

10)1 AÊ)1 range of the scattering variable, de®ned as s ˆ (2sinh)/k,
where 2h is the scattering angle. The primary beam was slit-
Material
collimated. The intensity curves were corrected by considering the
geometry of the beam pro®le in order to obtain point-focused
The sample was prepared from a surfactant Synperonic (ICI
product, Brussels, B) and water. The surfactant was used as curves. The sample was ®lled into thin-walled quartz capillaries
(Hilgenberg, Germany) with a diameter of 1 mm for the prelim-
supplied. Synperonic was made by ethoxylation of Synperonic
alcohol (consisting of 66% C13 and 34 % C15 alkyl chains). The inary SAXS investigations or directly into the shear cell for the
``in situ'' SAXS measurements.
ethoxylation process yields a wide distribution of poly(ethylene
oxide) chains; therefore, only the average ethoxylation number can
be given, which in the case of A7 is 7. The sample which was Rheology
investigated contained 80% (w/w) surfactant and 20% (w/w) water.
Before homogenization the sample must be heated to about 60 °C Rheological measurements were made with a Haake RS 100
because its viscosity decreases, and the higher-temperature sample oscillatory rheometer. A stainless steel cone±plate sensor was used
was easily homogenized with water. Of course, the sample must be (diameter of 20 mm and cone angle of 4°) and the sample thickness
bubble-free; therefore, it was stirred intensively for 30 min. Then, was 0.134 mm in the top of the sensor. The sample was inserted
the mixture was left to cool to room temperature and was stored into the centre of the plate of the sensor, then the plate of the sensor
for a 1-week period before any measurement. was slowly elevated with constant velocity to the measurement
position. The sample were kept under saturated water vapour for
Equipment the whole time of the measurements, because the structure and the
rheological properties of the lamellar system are highly dependent
The shear cell developed for the SAXS equipment is presented in on the water concentration. Before the measurements, the sample
Fig. 1. It consists of three main parts: the sample holder bordered was thermostated for 10 min; this was also a relaxation±saturation
partly by moveable X-ray windows made of Plexiglass (without period. The maximum allowed deviation in the temperature during
characteristic SAXS pattern), the electromechanical mover fas- the measurements was ‹0.2 °C.
tened to the sample holder, and the digital control unit connected
by wires to the mover.
In the sample holder one of the Plexiglass windows can be Results
moved perpendicularly to the X-ray source to induce stress in the
sample. The thickness of sample layer is adjustable between 0 and
1 mm. The width of the window is 16 mm and its height is 6 mm. The lamellar structure of the system was investigated at
The sample holder can be thermostated. di€erent temperatures. The sample has a centrosymmet-
The most important parts of the electromechanical mover are ric two-dimensional SAXS pattern because of its macro-
two solenoids in di€erent positions. One of the solenoids is ®xed,
the other is displaceable in the direction of the vibration of the scopical nonoriented arrangements. The shapes of the
Plexiglass window. The possible amplitude of the vibration is 0± scattering curves di€er strongly, depending on the
5 mm. The resolution of the amplitude adjustment is 0.05 mm. temperature as can be seen in Fig. 2. In the SAXS
There is a soft steel sheet between the solenoids which is caused to curves, a single Bragg re¯ection peak can be observed
vibrate by the alternating magnetic ®eld and which transmits the
motion towards the Plexiglass window.
which is characteristic of the lamellar structure. At 20 °C
The digital control unit switches a voltage to the solenoids for 0± the Bragg di€raction peak is very sharp, re¯ecting a
100 s. The resolution of the time adjustment is 0.001 s. The working highly ordered lamellar arrangement. This structural
times of the solenoids need not be the same; they can be adjusted arrangement changes drastically when the sample is
separately. The control unit is directed by a crystal oscillator. heated to 60 °C. The broadening of the Bragg pro®le
reveals a signi®cantly less ordered structure than that
SAXS apparatus
formed at 20 °C. The change of the lamellar structure is
The SAXS measurements were performed by a Kratky camera and in agreement with the thermotropic behaviour of the
a proportional counter (Anton Paar, Graz, Austria). The intensity system [6]. The existence of the lamellar structure at

Fig. 1 Shearing cell for the small-

angle X-ray scattering (SAXS)
equipment
 219

the layer structures. Micrographs of two di€erent parts

of the sample showing typical large multilamellar bodies
consisting of closely packed parallel layers with smooth
surfaces are shown in Figs. 3 and 4. The parallel layers
form large sheets (Fig. 3); however, the planes of some
stacks are crumpled and some stacks show di€erent
irregular shapes (Fig. 4). The latter morphology was
already present and embedded in the large sheets.
The sample was ®lled into the shearing cell and
incubated at 20 °C. The characteristic Bragg pro®les of
the lamellar arrangement were detected as a function of
time at 20 °C. These di€ractograms are shown in Fig. 5.
In the steady state, the Bragg pro®le has the same
position and the same full width at half maximum as
detected with the sample ®lled in a quartz capillary,
indicating that the regularity of the lamellar arrangement
does not depend on the surface character of the sample
holder. After starting the shear process, the Bragg pro®le
was measured four times. The time of data collection in
each measurement was extended to 5 min. The time of
the measurement of the maximum of each Bragg peak is
de®ned as the shear time and is marked on each curve in
Fig. 5. The lamellar arrangement is a€ected by the shear
process as the Bragg pro®le is shifted. During the process
Fig. 2 SAXS patterns of the 80% (w/w) Synperonic A7±water the periodicity is changed from 48.3 to 46.8 AÊ. During
lamellar system at 20 and 60 °C (measured A, desmeared B) the shear process the widths of the pro®les do not change,
which means that the average layer number of the stacks
remains constant. After the shear ended, broadening of
20 °C can be proved by the freeze±fracture method, the Bragg pro®le was observed. After 1 h the shape of the
which is an excellent tool for direct visualization of Bragg pro®le changed entirely and the peak was split into
colloid structures. The freeze±fracture electron micro- two di€use peaks. The positions of the peaks correspond
graphs of the sample give unambiguous information on to layer distances of about 50 and 45 AÊ, the ®rst longer

Fig. 3 Freeze±fracture electron

micrograph of the 80% (w/w)
Synperonic A7±water lamellar
system
220

Fig. 4 Freeze±fracture electron

micrograph of the 80% (w/w)
Synperonic A7±water lamellar
system

and from the presence of two types of alkyl chains (C13

and C15).
Another series of measurements was made at 60 °C.
The Bragg pro®les obtained are presented in Fig. 6. The
di€use peak was observed to broaden after a short shear
process. After a long time of shear the Bragg peak
disappeared entirely, indicating that the lamellar struc-
ture ceased to exist. When the shear ended the Bragg
peak did not appear again, which means the layer
structure was not restored.
For the characterization of the structural changes
measured during the shear process, the layer distance and
a control parameter are plotted as function of the shear
time in Fig. 7. The reciprocal value of the full width at
half maximum of the Bragg peak was de®ned as a control
parameter because this value is related to the number of
layers of each domain. The changes in the layer distance
and the control parameter are a€ected by the tempera-
ture very signi®cantly. In the temperature domain of the
layer structure around 20 °C, the control parameter
remains nearly constant and the layer distance diminish-
es only in a narrow range. At 60 °C, the destroyed
lamellar structure may be metastable because it disap-
pears after a short shear. At this high temperature the
Fig. 5 Change in the pro®les in the ®rst Bragg re¯exion of the SAXS
curve at 20 °C with shearing time existence of the layer structure can be explained by the
thermal prehistory. Namely, after preparation at room
temperature followed by heating, domains with de-
and the second shorter than the distance in the starting stroyed layer structures can remain in the metastable
state. Presumably, phase separation occurs and two types form which built up after short shear.
of domain form, which have di€erent compositions The rheological test carried out at 20 °C reveals
originating from the inhomogeneity of the sample, more signi®cant tixotropic behaviour as can be seen in Fig. 8.
exactly from the wide distribution of ethoxylate chains The viscosity of the samples decreases and at the same
 221

time the stress increases with an increase in the shear rate.

Finally, neither the viscosity nor the stress returns to the
starting values after the end of the measurement. The
same test measurement cannot be done at temperatures
higher than 50 °C because the sample is in the ¯uid state
and it cannot be ®lled into the cell of the rheometer;
however, a drastically destroyed lamellar arrangement
was detected by SAXS even at 60 °C.

Conclusion

The lamellar arrangement is inhomogeneous as can be

seen in the freeze±fracture pictures. The thickness of the
layer stacks can be estimated to be more than 102 nm and
in the lateral direction the extension of the homogeneous
domain is 1 or 2 orders of magnitude larger. The freeze±
fracture pictures throw light on the fact that a great
number of structural defects are present, which can
in¯uence the rheological behaviour of the system.
Without doubt the conditions of the two shear processes
(in the shear cell and the rheometer) are di€erent, but the
application of the shear cell constructed reveals that the
Fig. 6 Change in the pro®les in the ®rst Bragg re¯exion of the SAXS tixotropic behaviour of the Synperonic A7±water system
curve at 60 °C with shearing time is connected to only small changes in the lamellar
structure. The changes that are connected to the

Fig. 7 Changes in the layer distance and the control parameter

(reciprocal value of the full width at half maximum of the Bragg Fig. 8 Rheological test of the 80% (w/w) Synperonic A7±water
pro®le) during the time of the stress lamellar system at 20 °C
222

rheological behaviour may occur in larger dimensions cant changes in the lamellar arrangements; formation of
and cannot be observed by the SAXS method in the new domain structures. We can assume that these
range of the scattering variable applied (10)3±10)1 AÊ)1). structural changes may be in progress in the shear test
The shear results in changes with long relaxation times in at some level and result in the tixotropic behaviour of the
both the layer arrangement and the domain formation. the Synperonic A7±water system.
One hour after the ending of the shear process the Bragg
pro®les do not return to the starting position detected in Acknowledgements This work was supported by the Hungarian
the starting steady state but drastic changes appear in Scienti®c Funds OTKA (T 014396, T 21781) and a bilateral
their shapes, indicating simultaneous processes: signi®- German-Hungarian Program TEÂT (D-42/1998).

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Progr Colloid Polym Sci (2001) 1 17 : 225
O Springer-Verlag2001

Activated carbon 1, 5 Glasses 172 Polymerisation 101, 182

Adsorption 32, 37, 47. 51. 63. 70 Gocthite 32 Polymer-surfactant complex 136
Adsorption from binary liquid 13 Group contribution 1 Polystyrene latices 37
Aggregation 172, 200 Potentiometry 18
Aggregation number 136 Heavy metal 2 11 Probing interactions in swollen gels 153
y-AI2O3 27 Hematite 27 Protein adsorption 42
Alcohol cluster 13 Herbicide 47 Protein separation 189
Aminobenzoic acid 32 High-performance liquid chromatogra-
Amph~philicdiblock copolymer 195 phy 47 Radiotracer technique 27
Amphoteric surface 5 Hydrophobe 101 Reduction 80
Anions 27 Hydrohobic clays 63 Rehlogy 159
Atomic force microscopy 42 Hydrophobic hydration 56 Rheological properties 104
Rheology of bovine serum albumin and
Binding isotherm 141 Intercalation 88, 94 ovalbumin gels 189
Biodegradable polymers 167 Ion exchange 153
Block copolymers 200 Ions in macromolecular systems 153 Salivary pellicle 42
Boltzmann theory 136 IR spectroscopy 117 Scanning electron microscopy 117
Scattering 126
Kaolinite 94 Selectivitv 153
CaC03 200
Calcium montmorillonite 117 Self-organization 126
Lactide/glycolide copolymers 167 Senliconductor 2 11
Calorimetry 18 Lamellar structure 159
Captation 51 Shear 217
Lamellar systems 21 7 Silica surface 13
Carbon black 110 Layer structure 51
Cationic surfactant monomer 182 Small-angle X-ray scattering 217
Lead ion 117 Small-angle X-ray diffraction 145
Chemical composition 104 Liposome 145
Chloroacetanilide 47 Sodium dodecyl sulphate 136
Liquid structure 37 Soil 47
Clays 204 Liquid-phase adsorption 1
Coagulation 37 Specific adsorption 27
Lyotropic phase 182 Stratification 195
Colloids 113, 126
Colloidal stability 104, 131 Macrogcl 141 Strength 120
Conventional pollutants 70 Magnetic fluids (ferrofluids) 104 Surface charging 18
Cosonication 110 Magnetorheological properties 104 Surface complexation model 18
Critical stability 101 Microgel 56, 141 Surface energy 76
Crystal design 200 Microparticlcs 117 Surface force 13
Microtexture 204 Surface structure 37
Decontamination 21 1 Miniemulsion 101 Surface-excess isotherms 1
Delamination 120 Miniemulsion polymerization 110 Surfactant 141, 217
Dendrimers 80 Montmorillonite 88 Surfactant self-assembly 159
Differential scanning calorimetry 145 Morphogenesis 200
Diffusion 126 Thermodynamics 141
Multilamellar structure 145 Three-phase partitioning 189
Disjoining pressure 195
Drug carrier 167 Nanocomposite 120 TiOz 88
Dye adsorption 56 Noble metal nanoparticles 80 Titaniumdioxide 21 1
Dynamic light scattering 113 Tixotropy 217
Organic pollutants 63 Trends and perspectives 70
Electrokinetics 32 Organically modified ceramic 76
Emulsion gel 189 Organoclay 120 Universality 172
Enamel 42 Osrnotic pressure 101 Water structure 56
Encapsulation 110 Oxides 18 Wear resistance 76
Encapsulation of nanoparticles 80 Weld line 120
Ensemble structure 172 "P NMR Spectroscopy 153
Palladium nanoparticles 94 Wettability 167
Environmental adsorbents 70
Environmental protection 70 pH and filtration properties 204 X-ray diffraction 63
Excess isotherm 5 1 pH effect 5 X-ray photoelectron spectroscopy surface
Phase separation 131 analysis 167
Ferrofluids 131 Phase transition 131, 145 X-ray photoelectron spectroscopy 5
Fluctuation 172 Phosphonic acid 153
Foam film 195 Photocatalysis 21 1 ZnO nanoparticles 88
Fourier transform 1R attenuated total Photooxidation 88
reflection 13 Poisson Poly(ethy1ene oxide) 136
Fullerencs 126 Polar monomers 110
Functional groups 5 Poly(ethy1cne terephthalate) 76
Polymer brushes 195
Glass fibre 76 Polymer colloids 56
Glass transition 113 Polymer stabilization 94