The series of Technical Bulletin Pigments No. 3 No.

36
issued by the Inorganic Chemical Degussa Pigments for the Differencesbetween Natural Fillers
Products Division discusses fields of Coatings Industry*) and Synthetic Micro-Extenders
application in the lacquer and paint indus- in Emulsion Paints*)
try in the following editions: No. 15
Carbon Blacks for Coatings and Printing No. 37
Inks -A Survey Basic Characteristics and Applications of
Colour Black Parts 10 and 16,
No. 17 Coloristic Measurements of Jet-Black
Degussa Pigment Blacks and Pigment and Grey Coatings
Black Preparations for Coating Materials
No. 39
No. 21 Basic Characteristics and Applications of
Degussa Flatting Agents for the Coatings AEROSIL@Part 17,
Industry Reflection Measurements on Synthetic
Silica Products
No. 22
Basic Characteristics and Applications of No. 68
Colour Black Part 14, AEROSIL@for Lacquers and Paints
FloridaTest Results of Coatings Coloured
with Pigment Blacks

No. 34
Aluminium Silicate P 820
for Emulsion and Decorative Paints

Our cover shows:

demonstrationof typical effects attainable
with AEROSIL R 972: hydrophobic
behaviour, effectiveness as a free-flow
additive, application as an anti-settling
agent. *) not yet published in English
 Basic Characteristics and Applications
of AEROSIL@

Part 32: Following a brief descriptionof how the

The Use of Hydrophobic AEROSIL@ hydrophobic grades of AEROSIL@are pro-
in the Coatings Industry duced, the author goes into some detail to
describe ways of measuring this state of
Dr. Horst Ferch hydrophobicity. Possible applicationsin
Department of Applied Research and which hydrophobicAEROSlL is used in the
Technical Services, Silicas and Pigments, coatings industryare then describedand a
DegussaAG brief mention is made of further uses in
other branches of industry.

Based on lectures held bythe authorat the

47th Convention of the specialist group
“API” of the Gesellschaft Deutscher
Chemiker held in Hannover in 1979 and on
the occasion of the 13th EUROCOAT
Congress of AFTPV in Nice in 1987.

This edition of the Technical Bulletin Pig-

ments issued by the Inorganic Chemical
Products Division is printed using the
Degussa carbon black PRINTEX@55.

1
 Table of Contents

1 Introduction 3
2 Production and Properties of Hydrophobic AEROSIL 4
3 How to Measure HvdroDhobicitv 10
3.1 General Information 10
3.2 Measuring Methods 11
~

3.2.1 WaterVapourAdsorption 11
3.2.2 ContactAngle 12
3.2.3 Methanol Wettability 14
3.2.4 Infra-RedSpectroscopy 15
3.2.5 TotaEilanol Group Density 15
3.2.6 Carbon Content 15
3.2.7 Water-Soluble Part 16
3.2.8 Calorific Quantities 16
~~

3.2.9 “Residual Surface Area” 16

3.2.10 SAPPOK’s Degree of Hydrophilicity 16
3.3 Evaluation 17
4 Applications in the Coatings Industry 18
4.1 Rheology 18
4.1.1 Thickening Behaviour andThixotropy 19
4.1.2 Use as an Anti-Settling Agent 21
4.2 DisDersionAdditive 23
4.3 Coating Effect 25
4.4 Corrosion Protection 28
4.5 Adhesion 29
4.6 Uniformity 29
4.7 Free-Flow Properties 34
5 FurtherApplications 34
6 PracticalAdvice 35
7 Toxicological Information 35
8 Literature 37
Brief List of Technical Terms 39
Phvsico-Chemical Data of HvdroDhobicAEROSIL 43
Additional Degussa Products 44

2
1 by using the hydrophilic products, In this brochure, these newer products are
Introduction for example compared with the oldest of the hydro-
phobic silicas, AEROSIL R 972, which was
Overthe past 25 years synthetic hydro- - in the production Of free-flowing Pow- introduced in 1962 and is now produced on
phobic silicas have come to be used in ders for fire extinguishers (1); an industrial scale.The manufacturing pro-
cess was described in 1965 (6).Technical
numerous branches of industry. This new - in the development of highly-active
class of products offered the solution Bulletin Pigments No. 6 in this series deals
defoamers (2);
to problems which could not be solved with this product in more detail.
- in the reinforcement of special
fluoroelastomers (3);
- to achieve special effects in coating sys-
tems (4);
- to regulate the water balance of offset
printing inks (5).

Additional hydrophobic silicas have been

developed in order to increase the pos-
sibilities of application and to open up new
markets.

3
2
Production and Properties of
Hydrophobic AEROSIL

As mentioned before, the first industrially-

manufactured hydrophobic silica was
brought onto the market in 1962 and was
known as “Filler R 972”. After reports by
KLOSTERKOlTER in 1965 (7), based on a
one-year long-term inhalation test carried
out with laboratory animals, showed that
this new material did not cause silicosis,
the name was changed to “AEROSIL
R 972”. This hydrophobic special product
is convertedwith dimethyl dichlorosilane in
a fluid-bed reactor which is heated to
approximately 400°C. As a result of this,
around 70% of the previously existing
silanol groups react with the silane and
form Si-0-Si (CH& groups (6); the material
acquires a hydrophobiccharacter, see
Figure 1. When analysed, AEROSIL R 972 Figure 1: Schematic representation of the reaction of dimethyl dichlorosilane with the silica surface:
differsfrom the basic product as a result of conversion of “hydrophilic”to “hydrophobic”
its carbon content of approximately 1YO.
However,no difference can be observed as
regards the average primary particle size
when AEROSIL R 972 is compared with its was treated back in 1984 (10).Technical Due to the fact that all of the hydrophilic
hydrophiliccounterpart in electron micro- Bulletin Pigments No. 60 is dedicatedto grades of AEROSIL must be classified as
graphs. this subject. high-quality products from a point of view
of price, it was necessary to fall back on a
Figures 2 and 3 show a transmission elec- The properties of and special effects to be less expensive starting product as a basis.
tron micrograph (TEM) and a scanning attained with AEROSIL R 972 when applied For obvious reasons, the choice fell on a
electron micrograph (SEM) of this product. in coating systems were described in precipitatedsilica. An appropriate product
These pictures illustrate the tendency of 1979 (4) and further applicational pos- was brought onto the market in 1964 (12)
AEROS!L R 972 to aggregate and agglom- sibiiities oithis speciai siiica were reported and is now known as SiPERNAT@D 17.
erate, as is the case with the basic product on in 1980 (11).
AEROSIL 130.This statement is also valid
for all of the other hydrophobicgrades of Over the years it became apparent that
AEROSIL dealt with in this edition ofTech- AEROSIL R 972 was unable to fulfil all of
nical Bulletin Pigments.The question re- the demands placed on it by various
garding the existence of primary particles aspects of the different applications. What
in AEROSIL, as defined in DIN 53206, was wanted above all was a low-priced
hydrophobic version.
Figure 2: TEM of AEROSIL R 972

5
Figure 3 SEM of AEROSIL R 972
~~ ~

6
This hydrophobic special silica is used in
particular to improve the free flow be-
haviour of substances in powder form, e.g.
fire extinguishing powder based on sodium
bicarbonate (1).The commercial products
AEROSIL R 972 and SIPERNAT D 17 were
able to satisfy virtually all the market
demands for a period of nearly fifteen
years. SIPERNAT D 17 was unable to find
access to the coatings sector.

However, there are now several new com-

mercial products available on the market
which can be used for further applications,
and whose data are compiled in Table 1.
All of these hydrophobic grades of AEROSIL
are characterized by the additional letter
“R” in their name, which serves as a refer-
ence to the locationof the German produc-
tion plant in RheinfeldedBaden.Similar to
the productionof AEROSIL R 972, the new
AEROSIL grades are also manufactured
according to a technical process. The Figure 4 Infra-red spectra of hydrophilic AEROSIL 300 and hydrophobic AEROSIL R 812 (13)
nature of the chemical aftertreatment is
shown in Table 1 in the form of the chemi-
cal residues situated on the surface of the
silica; these can be easily detected by the same frequency range of this sample is
means of infra-red spectroscopy, e.g. shown on the right-handside following an
(4, 13), as demonstrated in Figure 4. The in situ treatment of the silica with the cor-
left-hand side of this figure depicts the responding silane. A reduction in the
range of the OH stretchingvibration bands number of both isolated and bridged
for the untreated basic product silanol groups can be observed here in the
right-handdiagram, and at the same time,
- at 3750 cm-1 (free SiOH groups) the CH stretching vibration bands of the
- between 3800 and 2800 cm-I newly-anchored methyl groups become
(bridged silanol groups); apparent at 237C cn-I.

7
Table 1: Specifications and further data on the hydrophobic AEROSIL grades. AEROSIL R 812 S differs from AEROSIL R 812 as a result of having a higher degree of
hydrophobicitywhich is achieved by means of an additional processing step

8
All of the hydrophobic grades of AEROSIL
listed in Table 1 are thermally stable as far
as applicationsin the coatings industryare
concerned, as Figures 5 and 6 confirm.
Figure 5 shows the weight loss of the
undried hydrophobicAEROSIL grades,
which was determined by means of thermo-
gravimetric analysis, as a function of the
temperature. On the basis of infra-red
measurements, Figure 6 confirms the fact
that both AEROSIL R 972 and AEROSIL
R 812 only undergo changes as a result of
oxidation at temperatures exceeding
400°C.

Asuggestion put forward in 1976 (15)

serves to classify the hydrophobic grades
of AEROSIL in the wide range of synthetic
silicas currently available on the market.

Figure 5: Weight loss of hydrophobic AEROSIL grades which were slowly heated in a nitrogen atmosphere
(14). (PERKIN-ELMER thermo-balance, model TGS-2)

Figure 6 Reduction in the IR absorption of the

methyl groups as a measure of the thermal stability
ofAEROSlLR972andAEROSlL R812(13). Measure-
ments were carried out on self-supporting discs
with a diameter of 13 mm and 6 mgIcm2 in weight

9
3 The use of hydrophobic substances in Although the term “hydrophobic” appears
How to Measure Hydrophobicity powder form has proved successful in to be easy to understand when taken to
numerous applications, with synthetic mean water-repellent, it is nevertheless dif-
3.1 silicas playing a particularly important role ficult to accurately define or to quantita-
General Information here. Products of this nature attain their tively determine this property. It is often the
hydrophobic characteristics as a result of case that the different methods do not lead
many different methods of surface treat- to the same conclusions (14). Aselection of
What exactly does the term “hydrophobic” ment, such as coating with wax or chemi- methods of determination are given below.
mean? Expressed simply, hydrophobic cal reaction of the surface groups with
means water-repellent. The plumage of appropriate silanes. It should be repeated
aquatic birds or the cuticles of leaves at this point, however, that all of the hydro-
on the plants are well-known natural phobic grades of AEROSIL mentioned in
examples of this. Further examples of this brochure are rendered hydrophobic by
hydrophobicity in daily use come from the means of a chemical reaction on the sur-
technical field: TEFLONa-coated frying face of the solid. The hydrophilic or hydro-
pans and top coats for automobiles. The phobic character of an amorphous silica
opposite of hydrophobic is “hydrophilic”. can be easily judged by shaking it together
In technology, use is often made of a with water in a test tube; hydrophobic
combination of hydrophobicand hydro- AEROSIL floats to the surface. All of the
philic properties. In the molecular range, hydrophobic AEROSIL grades react in the
the surfactants in household detergents same way during this test, Le. it is not
should be mentioned; the increasingly possibleto differentiate between them.
important offset printing process operates
with larger particles, and coarse pieces are
used in the flotation of ore.

10
 3.2
Measuring Methods

3.2.1
Water Vapour Adsorption

A method which is somewhat time-con-

suming, but definitely related to practice is
the intake of the water vapour adsorption
isotherms measured at varying levels of
relative moisture. Corresponding measure-
ments are generally made at room tempera-
ture, e.g. in the case of AEROSIL R 972 (4).
Figures 7-10 depict the corresponding
curves for the products AEROSIL R 202,
R 812, R 805, R 972 and R 974, each in
comparisonwith the respective hydrophilic
base silica.

It is understandable that the adsorption of

the latter is always higher.The numerical
values which are obtained with AEROSIL Figure 7: Water vapour adsorption isotherms at room temperature of AEROSIL 150 (basic hydrophilic
R 972 (Figure I O ) demonstrate an even substance) and the hydrophobic grade AEROSIL R 202, measured using small samples
lower adsorptionthan that shown in Figure
7 for AEROSIL R 202. If the shapes of the
curves shown in the four diagrams are
compared, it is possibleto observedefinite
and also characteristic differences which
occur independent of the size of the
specific surface area. When measured
according tothis method, the hydrophobic
character of the individual grades declines
in the following order: AEROSIL R 972 >
R 202 > R 812 > R 805 > R 974.

Figure 8 Water vapour adsorption isotherms at room temperature of AEROSIL 300 (basic hydrophilic
substance) and the hydrophobic grade AEROSIL R 812, measured using small samples
~

11
. "I
3.2.2
Contact Angle

The so-called contact angle method can

be used to determine the hydrophobicityor
“wettability” of smooth surfaces (16).This
method involves placing a droplet of water
of a certain volume under specified condi-
tions onto the surface to be examined.The
contact angle is then measured with the
aid of a horizontally-positionedmicro-
scope with a graduated scale. If the drop is
predominantly spherical in shape, the con-
tact angle is 8 > 90” and, according to
YOUNG’S equation, the interfacial energy
is Ewater/soiid > Ewater/air Wetting does not
take place, or only to a limitedextent. If the
drop resembles more of a hemisphere or
even spreads out (8 < go”), the expression
EwateVsolid < Ewater/air applies and wetting
takes place. This behaviour is illustrated in
Figure 11. Difficulties arising from the Figure 9 Water vapour adsorption isotherms at room temperature of AEROSIL 200 (basic hydrophilic
production of suitable moulded tablets substance) and the hydrophobic grades AEROSIL R 805 and AEROSIL R 974, measured using small samples
with “smooth” surfaces are experienced
when the contact angle method is used to
determine the wettability of hydrophobic
powder (17).

Figure 1 0 Water vapour adsorption isotherms at room temperature of AEROSIL 130 (basic hydrophilic
substance) and the hydrophobic grade AEROSIL R 972, measured using small samples

12
Of all the silica grades tested here, it is only
possible to produce a suitable moulded
disc withAEROSlL R972.Theother hydro-
phobic AEROSIL grades can be compres-
sed to mouldeddiscs under high pressure,
but these crumble on release without the
application of any external force. For this
reason, it is only possibleto give contact
angles for the Degussa silicas listed in
Table 2. Hence the contact angle method
is not suitable for the characterization of
hydrophobic silicas.

Contact angle given in degrees of

Water Glycerine Silicone oil Mineraloil
hydrophilic silica < 20" < 20* < 20* < 20*
SIPERNATD 17 144 113 < 20" c 20*
AEROSIL R 972 124 78 < 20" < 20"
* soaks into the moulded tablet after a short time
Table 2 Contact angles of different liquids on moulded discs (2 mm thick, 28 mm in diameter)made of some
Degussa silicas

13
3.2.3
Methanol Wettability

A suitableway of determining the wettabil-

ity of hydrophobic powders appears to be
with the aid of alcohol/water mixtures.
The higher the proportion of alcohol in the
liquid mixture in which wetting is taking
place, - Le. the immersion of the powder
into the liquid -, the “greater” the degree of
hydrophobicity (18). In principle, this
method can also be used to test the
homogeneity of the hydrophobicity.For
this purpose, samples are shaken with
various mixtures of methanol and water
and are then centrifuged.

If the height of the sediment is plotted

against the proportion of alcohol in the li-
quid, an ascending curve results. Agradual
rise denotes that the powder particles are
not uniformly hydrophobic.

On the other hand, a steep rise indicates a

uniform surface modification,see
Figure 12.

14
 Furthermore, it seems justified to infer that 3.2.4 3.2.6
an increased methanol requirement sig- Infra-Red Soectroscoov Carbon Content
nifies a higher degree of hydrophobicity.
A relatively simple method, which is attri- Two methods of characterizing synthetic An obvious way of characterizing a hydro-
buted to K. KLEIN (19),has proven effective hydrophobic silicas are available when phobic AEROSIL grade is to determine the
in practice with hydrophobic silicas. using infra-red spectroscopy: C content.Thisis the first step towards giv-
200 mg of the substance are added to ing an impression of the amount of organic
50 ml water in a separating funnel. As the - determination of the remaining silanol
groups that are present on the silica sur-
mixture is shaken, a burette-which is groups situated on the surface in iso-
face. However,this value does not seem to
immersed to the bottom of the water - is lated state,
tell us very much because
then used to slowly add methanol until all - determination of the relative methyl
of the silica has been wetted. The portion group density on the surface.
- the size of the specific surface area of
by weight of the methanol in the mixture the basic silica is not taken into account,
needed for this purpose is a measure for Numerical values for the relative methyl
group density are given in Table 1. Accord-
- in addition to a chemical fixing of the
the hydrophobicityof the silica. The values organic groups, a further adsorption of
attained in this way are recorded inTable 1. ing to both of these criteria, AEROSIL R 812
organic substances can also take place
However, it should be pointed out that, is more hydrophobic than, for instance,
on the silica.
within the meaning of an exact analysis, AEROSIL R 972.
this method yields very fluctuating values. Both the analytically-determined total car-
For comparative purposes, a measure- The infra-redtest method is time-consum-
bon content and the C content related to
ment of this nature must be carried out by ing and a spectrometer with good resolv-
the surface are included in Table 1. When
the same tester and if possiblein the same ing power (e.g. 2.5 cm-I) is needed. How-
the specific carbon distribution is taken as
laboratory. ever, once this method has been “mas-
a basis, the following sequence is obtained
tered”, it provides accurate comparative
in view of the increasing hydrophobicity:
values for characterization purposes.
AEROSIL R 974 < R 972 < R 812 or R 812 S
3.2.5 < R 202 or R 805.
Total Silanol Group Density
AEROSIL R 812 and AEROSIL R 812 S are
silicas which are also capable of firmly
The LiAIH4method can be employed to adsorbing organic substances by physical
determine the total silanol group density of means. This is not the case with AEROSIL
synthetic silicas (9,13). In accordance with R 972, R 974 and R 805.
Table 1, the increasing hydrophobicityis
given in the following order:
AEROSIL R 805 < R 812 S < R 972 < R 812
< R 202.
This method is not suitable for testing on an
occasional basis, as especially the drying
of the synthetic silica is of great signifi-
cance here.

15
3.2.7 3.2.9 3.2.10
Water-Soluble Part “ResidualSurface Area” SAPPOK’s Degree of Hydrophilicity

The proportion of hydrophobicsynthetic Aspecial feature of the pyrogenic silica The expression “degree of hydrophilicity
silica which is wetted by water is deter- AEROSIL is that the N2adsorptionaccord- according to SAPPOK may also be found
mined analytically. The lower this value is, ing to BET(23)reflectsthe surface chemis- in certain literature (53-55).This is the quo-
the higher the degree of hydrophobicity. try in the form of the concentration of iso- tient of the specific surface area according
However, this method is relatively inaccu- lated silanol groups (24). It seems logical, to BET measured with H20,and the same
rate and can only provide values which therefore, to use this specific surface area, value measuredwith N2.Thisdegreeof hy-
enable a differentiation of hydrophobic determined with N2according to the BET drophilicityaccording to SAPPOK is sup-
silicas in truly routine studies. method, and the “reduced” specific sur- posed to give indications as to the wettabil-
face following the chemical aftertreatment ity, dispersion and stability behaviour of
3.2.8 as a criterion for the surface coverage (13). pigments.
Calorific Quantities Numerical values for the “residual surface
area” related to the basic silica are given in On the basis of the BETtheory, it should not
Table 1. The following order is obtained be possibleto use this quotient to charac-
Another process which can be used to
when this method is applied: terize hydrophobic silicas, because this
characterize hydrophobic grades of
theory works on the principlethat all the
AEROSIL is the determination of the heats AEROSIL R 972 < R 812 < R 805 < R 812 S
values which are obtained are independent
of wetting in various liquids.The extent to < R 202.
of the properties of the solid surface.
which a method of this nature can be used
Nevertheless, it should be pointedout here However. this is not the case.
to explain the gradual applicational differ-
that this “residual surface area” method is
ences of finely-dividedhydrophobic mate-
somewhat inaccurate.This is due in par-
rials is uncertain at present. The method
ticular to the altered form of the BETad-
appears to be too expensive for purposes
sorption isotherms which arises during the
of quality control (20,21,22).
chemical surface modification.This makes
it difficult to evaluate the curves and re-
duces the value of the statement regarding
the degree of coverage.

16
3.3
Evaluation

Following a brief description of the various

ways of characterizing hydrophobicity, an
attempt will now be made to list the
AEROSIL R grades in the order of their
hydrophobicity. This is done in Table 3 by
compiling an “order of rank” based on the
methods permittingsuch statements to be
made; the smaller values signify the high-
est degree of hydrophobicity. Once the
mean value has been calculated, the grade
with the lowest value must represent the
product with the most pronouncedhydro-
phobic propertiesoverall. This results in
the following order:
Table 3 Procedure for drawing up a “hydrophobicorder of rank”with the hydrophobic grades of AEROSIL
AEROSIL R 202 > R 812 > R 805 > R 972
> R 974.
Acertain degree of randomness is also pre-
sent in this list, due to the fact that a com-
parisonof the individual methods does not
always result in the same order. Hence
it is not easy to give aclear-cut definitionof
the term “hydrophobicity” (14).
 ~

4
Applications in the Coatings Industry

Hydrophobic grades of AEROSIL may be

used in numerous ways to improve the ap-
plicational propertiesof paints and other
coatings, and to reduce the added amount
of silica in certain formulations. Effects of
this nature were compiled in a report back
in 1979 (4). Recently-acquired knowledge
relatingto these new special products
will be included in the familiar applications
dealt with in this section.

Now and again objectionsare raised to the

effect that the addition of AEROSIL re-
duces the gloss of top coats to such an ex-
tent that practicalapplication is rendered Table 4 Effects on the gloss of water-thinnable stoving enamels caused by additions of
impossible. Using as an example a black AEROSIL R 972 (4).
and a white stoving enamel based on a -
Composition: RESIMENE 5.5; CHEMPOL 10-0500 solution 65.0; TiOpRKB 2 27.8;
water-thinnable binder, Table 4 illustrates 2-ethyl hexanol 1.0; defoamer TROY 999 0.3; Fluorchemical FCI-430 0.4
that this argument is not valid if the
AEROSIL is sufficiently dispersed. Only
very slight reductions in gloss occur,
see Table 4.

4.1
Rheology

The influence on the rheologicalbehaviour

of liquid systems exerted by hydrophilic
AEROSIL was described way back in 1969
(25).Acompany publicationissued in 1986
also discusses the possible interaction
mechanisms of hydrophobic grades of
AEROSIL (26).

Figure 13: Viscosity behaviour of an ethanol-water

mixture 1:l following the addition of different
AEROSIL grades (14)

18
4.1.1
Thickeninn Behaviour and Thixotropy

In a large number of systems, higher in-

creases in viscosity can be attained with
hydrophobic silicas than with the same
added amount of hydrophilicsilicas.

This is the case, for instance, in a 1:1

ethanol-water mixture, as illustrated in Fi-
gure 13, where AEROSIL R 972 serves as
an example. It is also possibleto recognize
from this example how the likewise hydro-
phobic AEROSIL R 812 does not display
this behaviour to anywhere near such an
extent. It is not possibleto predict which
hydrophobic silica will demonstrate the
best behaviour in a particularcase, and for
this reason, practical tests are unavoid-
able. This statement is valid for pure
solventsand mixtures of such as well as for
binder systems. Figure 1 4 Increase in the viscosity and thixotropy of epoxy ester-based zinc dust paints from different
manufacturers after the addition of hydrophobic AEROSIL (14). Dissolver dispersion at 4000 r.p.m.
Three epoxy esters of the same composi- Peripheral velocity = 8.4 m/s
tion but from different manufacturers are
shown in Figure 14, which depicts the
increases in the viscosity and the corres-
ponding thixotropic index values of these
three systems, induced by the addition of
hydrophobic silicas. The thixotropic index
was calculatedfrom the viscosity values
attained at a shear rate ratio of 1:I 0.

Figure 14 shows that

- the three binders used display different
behaviour although the initial viscosity
was comparable;
- AEROSIL R 812 provides the best result
in each of the cases;
- the difference in the thixotropy is greater
than that of the viscosity.

Figure 1 5 Viscosity behaviour of epoxy resin solutions thickened with 3% by weight of AEROSIL during
12 weeks of storage at room temperature (14)

19
Afurther example will be used to de-
monstrate how, in addition to the level of
viscosity and a possiblethixotropic effect,
the time-dependentviscosity behaviour
can also be changed to advantage.

Figure 15 illustrates the viscosity be-

haviour of 50% epoxy resin solutions con-
taining different grades of AEROSIL.

3 % by weight of silica was added in each

case. The thickeningeffect of AEROSIL
R 972 is very slight; the hydrophilicgrade
AEROSIL 200 only demonstrates a high
initial viscosity; good long-termviscosity
behaviour is attained solely with AEROSIL
R 805.

Some results in a white high solids coating

will now bediscussed. Figure 16 illustrates
the increases in viscosity attainable with
additions of 0.3% of hydrophobic silica
and also the calculatedthixotropic index. without the addition of AEROSIL at room temperature (14). Composition: BAYER-TITAN RKB 3 28.00;
AEROSIL R 805 also provided the most AEROSIL in each case 0.28; ALKYDAL F 261 hs 43.90; RESIMENE 740 13.00; ethyl glycol acetate 5.22;
favourable result as regards the gloss at- ethyl glycol 5.00; butyl glycol 2.30; xylene 2.50.48 hours in the ball mill KU 1 using porcelain balls
tained (87%) and the sagging behaviour.
The latter was measured by coating plates
of glass with a 150 pm film applicator over Special mention should be made at this In a company publication issued back in
a length of 16 cm and then placing the point about the orange peel effect which 1986 (27), it was pointed out that AEROSIL
plates in a vertical position.The only occurred on the surface of the coatings R 202 can cause:
system which demonstrated no sagging containing AEROSIL R 202. This effect can
only occur with AEROSIL R 202 and not
- levelling problems, e.g. the orange peel
was that containing AEROSlL R 805.
effect,
with any other grades of AEROSIL referred
to in this publication. AEROSIL R 202 - adhesion problems, e.g. with multi-layer
is produced with the aid of polydimethyl systems, etc.
siloxanes, which are known to cause such
an effect. If the best rheological results are obtained
with AEROSIL R 202, tests must be carried
out prior to application in practice in order
-
to determine whether or not side-effects
~~~ ~

occur.

20
4.1.2
Use as an Anti-Settling Agent

The use of AEROSIL as a suspending

agent for pigments and fillers in the coat-
ings industry is the oldest field of applica-
tion for this class of products (29). In
general, the addition of small amounts is
sufficientto obtain the desired anti-settling
effect which is accompanied, as a rule, by
a certain increase in the viscosity.

It is importantto establish that the improve-

ment in the suspension behaviour cannot
be explained entirely by the increase in the
viscosity. Parallel tests served to demon-
strate how a subsequent adjustment of
the viscosity up to the same level of the
samples in the controltest only produced a
gradual improvement and not the positive
effect of improving the suspension
behaviour, such as is shown in Figure 17. Figure 17: Comparison of the sedimentation tendency of epoxy ester-based zinc dust paints after four
weeks of storage at room temperature. Left: control paint, right: paint produced with an addition of 2 % of
The advantage of all of the hydrophobic AEROSIL R 972 (4).
grades over AEROSIL 200 is that - due to Composition: JAGALYD ED 4,50% in xylene 19.6; zinc dust super-fine 72.5; butanol 1.0; SHELLSOL A9.4;
Co octoate, 6% Co 0.2
their having a lower silanol group density
(seeTable1)-agglomeration is not so
great and they may therefore be dispersed
more easily, see Figure 23.If the cost-
benefit ratio is considered, all of the argu-
ments speak in favour of the use of
AEROSIL R 972.

JAGALYD ED 4

Figure 1 8 Sediment consistency measurements

carried out on zinc dust paints (composition see
sub-title to Figure 17) after three months of storage
at room temperature (4)

21
The optimum addition of AEROSIL can be
readily determined in practicewith the aid
of a DYNOMETER (30,31).Using zinc
dust paints as an example, Figure 18
demonstrates the effect which may be
obtained with AEROSIL R 972.

It is of significancethat the control sample,

which contained no addition of AEROSIL,
had become so hard after only four weeks
of storage that it was no longer possible
to carry out a measurement with the
DYNOMETER. - If 2% by weight of
AEROSIL R 972 is added to these paints,
the power input in the DYNOMETER
requiredto reach the bottom of the test
apparatus is nil. This value corresponds to
the added amount of AEROSIL R 972
determined in practice (4).

Like AEROSIL 200, AEROSIL R 972 has

also been used as a thixotrope in special
effect coatings for many years (28).This
statement is still valid today. By preventing
the occurrence of sagging, it is possible to
produce a well-defined special effect in
this application, which is naturally based
on the use of an appropriate silicone oil.

This statement is illustrated clearly in

Figure 19. Finally, special mention should
be made of the fact that hammer finish
coatings containing AEROSIL show no
sign of greying even after storage.

Figure 19: Sagging behaviour of hammer finish coatings.Above: control coating, below: containing0.8% of
AEROSIL R 972 (4). Composition:ALKYDAL R 40 50.0; PLASTOPAL EBS 200,6O% in butanol3.6; MAPRENAL
MF 750,55% in isobutanol 18.0; EFWEKO NC 18/2,20% in ethyl acetate 5.0; butanol 13.5; SHELLSOL A 4.0;
ethyl glycol acetate 2.0; STAPA POLYCHROM 3 3.6; silicone hammer finish solutionTRS 0.3

22
An improvement in the long-term suspen-
sion behaviour cannot only be achieved
with specificallyheavy pigments. Products
with a low specific density, such as SiOn-
based flatting agents with a density of
1.9 g/cm3, can also be held effectively in
suspension, as demonstrated in
Figure 20.

The results shown in Figures 17 and 20 are

representative of the findings of numerous
other tests, in which AEROSIL grades lead
to the real solution of problems in other
systems.

AEROSIL R 972, for example, is effective

as an anti-settlingagent, improving impor-
tant properties, even after application
of a coating onto the respective substrate,
see Figures34 and 35.

4.2
Figure 2 0 Improvement in the suspension behaviour of Flatting AgentTS 100 in a coating resultingfrom the
DispersionAdditive addition of 0.5% of AEROSIL R 972

The state of dispersion of mainly high qual-

ity pigments can be greatly improved by
slight additions of hydrophobicAEROSIL.
This is demonstratedwith a pigment black
in Figure21where the jetness and blue un-
dertone attainable serve as an example.

Figure 21: Black value MYand blue component M, of stoving enamels containing 5% of Pigment Black
FW 200 and 0.6% of AEROSIL as a function of the dispersion time in the ball mill (14).
Composition: MAPRENAL MF 800,55% in isobutanol13.3; butanol 0.6; Colour Black FW 200 2.2; AEROSIL
0.264; ALKYDAL F 310,6O% in MAPRENAL MF 800,55% in isobutanollO.7; solvent mixture RL 938/9 21.9

23
Figure 22: Increase in the degree of gloss of alkyd/
melamine-basedstoving enamels containing col- time. Peripheral velocity of the stirrer: 8.4 m/s. Both grades of AEROSIL had already been predispersed.
oured pigments resulting from the addition of 0.1 YO Composition: see sub-title to Figure 17
and 0.5% of AEROSIL R 972 (14).
Composition: ALFTALATAS 502,6O% in xylene 46.6;
MAPRENAL MF 800,55% in isobutanol21.8; diluent
15.8; Paliotolyellow 1770 or Heliogen blue NFB or
cobalt blue 5002 12.0; Bayertitan R-KB 3 10.0 with
Paliotol yellow, otherwise 1.5

This mode of action is demonstrated in The grindometer values of zinc dust paints All of the findings discussed in this section
Figure22 by an increaseingloss with tints which may be obtained as a function of the are always dependent on the dispersing
of inorganic and organic coloured dispersion time are recorded in Figure 23. conditions. It is by no means the case that
pigments. This diagram illustrates how much more the presence of one of the AEROSIL
easily hydrophobic silica may be dis- grades necessarily leads to an increase in
persed. For practical purposes, no more gloss or improvement in the optimum
differences can be detected between the efficiency in every application, seeTable4.
hydrophobic grade and the control sample
after 20 minutes of dispersion.

24
 .

4.3
Coating Effect

If zinc dust is mixed in a household blender

with 0.5% of AEROSIL R 972 in the dry
stage, the hydrophobicsilica completely
envelops the Zn particles, as demon-
strated in Figure 24. The same effect is
also observed in the corresponding zinc
dust paints (4), see Figure 25. This coating
effect of solids has been known for quite a
long time (32), and is also used as a basis
for the prevention of the “gassing” of zinc
dust paints during storage, which is shown
in Figure26.The envelopment of zinc dust
with AEROSIL R 972 can possibly be
attributed to purely electrical interactions,
because synthetic silicas are always
negatively charged (33) and metals are
always charged positively.

AEROSIL R 972 (right) (4)

-
-

Figure 2 5 SEMs of etched zinc dust paints, l e k control, right: containing 2 % of AEROSIL R 972 related to
zinc dust (4).
Composition: JAGALYD ED 4,50% in xylene 19.6; zinc dust sups-fine 72.5; butanol 1.0; SHELLSOL A9.4;
Co-octoate, 6% Co 0.2

25
However, non-metallicanti-corrosive pig-
ments can also be coated, as illustrated in
Figure 27 by using zinc phosphate as an
example. The theory of electrostatic in-
teractions cannot be used to explain this
particular phenomenon. It is also possible
to attribute this coating effect to the better
dispersibility, discussed in 4.2, which
brings about an improvement in the optical
effectiveness of the different pigments.

Figure 2 6 Prevention of gassing of a zinc dust paint on a basis of epoxy ester following storage at
room temperature for four weeks. Left no addition; right: containing 2% of AEROSIL R 972 related to zinc
dust (14).
Composition: JAGALYD ED 4,50% in xylene 19.6; zinc dust super-fine 72.5; butanol 1.0; SHELLSOLA9.4;
Co-octoate, 6% Co 0.2

Figure 27: SEMs of zinc phosphate (left) and zinc

phosphate together with 1YOof AEROSIL R 972
(right) (14)

26
Hydrophobic silica may also be used to
Paliogenred AEROSIL AEROSIL
stabilize a particular state reached during
L3885 R 972 R 805
dispersion. Table 5 gives evidence of a
more stable distributionof the red pigment viscosity of mill base mPas at Dm 4% s-1 3711 8834 8162
frequently used in top coats for auto- (Haslke RV 11, SV I) mPas at Dm433 s-’ 1352 1785 1406
mobiles after 48 hours of dispersion in a Thixotropic index 2.9 5.4 6.3
laboratory ball mill. In additionto the trans- I

parency, which is higher than that of the Transparency(red high solids stoving enamel) 105.6 141.5 140
control sample, and which indicates a bet- (Lange KMVLt 12 / grey filter 2)
ter pigment distribution,Table 5 also in- Table 5 Increase in the viscosity and thixotropic index of a mill base based on Paliogen red” L 3885
cludes the changed rheological measuring and in the transparency of a high solids stoving enamel following the addition of AEROSIL (14)
data of the mill base brought about by the
addition of AEROSIL.

Not only solids can be coated with

AEROSIL.The use of hydrophobic silicas
also enables water to be enveloped. News AEFFOSIL
about this world sensation was published R202 R805 R812 R812S R972
in 1966 under the motto “Degussa
chemists invent dry water” (34).Attempts Formulationpossible no nQ Yes Yes no
were made at this time to mix 10% of Shearing stability in min - - 0.5 5 -
AEROSIL R 972 into water with the aid of a Table 6 Practical test to determine which hydrohobic grades of AEROSIL are suitable for producing “dry
high-shear powder mixer. water” using 5 % by weight (35). The shearing stability was tested in a household blender. The formation
of a clearly compacted, “smearable” mass was considered as signifying a collapse of the formulation
This resulted in a free-flowing white pow-
der. Whilst 10% of AEROSIL R 972 were
required in those days, smaller quantities
are now sufficient to produce “dry water”.
The results compiled in Table 6 are ob-
tained with 5% of hydrophobicAEROSIL.

If this test had been included in theevalua-

tion described in 3.3, the order of hydro-
phobicity determined would not have been
changed, but there would have been less
difference between AEROSIL R 202 and
AEROSIL R 812.

27
4.4
Corrosion Protection

The use ofAEROSlL R 972 as an additive to

increase the resistance to corrosion was
described in 1974 (29).The positive effects
which may be obtained with AEROSIL
R 972 are illustrated in Figures 28 and 29
using zinc dust paints and zinc chromate
priming coats as examples.

However,AEROSIL R 972 can also improve

formulationswhich do not contain anti-cor-
rosive pigments. For example, Figure 30
depicts an industrial coating based on a
water-thinnable, oil-free alkyd resin
(s. Table 4 for formulation), which de-
monstrated a greatly improved resistance Figure 2 8 Zinc dust paints based on an epoxy ester Figure 29: Zinc chromate primers after a 168-hour
after a 168-hour salt spray test in accordance with salt spray test in accordance with DIN 50021 and
following stresses imposed during the
DIN 50021 and ASTM B 117-64. Left: control paint, ASTM B 117-64. Left control paint, right: containing
accelerated durability test (dew cycle) right: containing 2 % of AEROSIL R 972 related to 1.3% of AEROSIL R 972 related to pigment (14).
according to DIN 50018. -Results of this zinc dust (14). Composition: LAROFLEX MP 35 19.5; zinc white,
nature are confirmed by independent Composition: JAGALYD 4,50% in xylene 19.6; zinc red seal 2.9; zinc phosphate ZIN P 1.4; zinc chro-
dust super-fine 72.5; butanol 1.0; SHELLSOL A 9.4; mate 1 W6.8; iron oxide red 130 M 6.8; talc AT1 13.5;
laboratories, such as the Transportation
Co-octoate, 6 % Co 0.2. Compare Figure31 SHELLSOLA 11.6; xylene 32.6; ethyl glycol acetate
Laboratoryof the Californian Department 2.4; chlorinated paraffin 40 2.0; castor oil derivate
of Transportation (38). - 0.6. Compare Figure 32

Figure 3 0 Stoving enamel based on a water-thinn-

able binder following 7 dew cycles, to conform with
DIN 50018 (14). Left control sample, right: contain-
ing 0.5% of AEROSIL R 972 related to the total for-
mulation

28
4.5
Adhesion

An addition ofAEROSlL is known to im-

prove the applicational propertiesof stov-
ing enamels, e.g. during the performance
of the mandrel bend test, as defined in DIN
53 152 (36). Figure 31 demonstrates the
improved adhesion of epoxy ester which
was applied onto a steel plate. It is interest-
ing to note that the hydrophobic grades
of AEROSIL bring about an improvement in
the adhesion of the epoxy resins by an
average of 13%.

4.6
Uniformity

The results of numerous tests have de-

monstrated a tremendous improvement in
the uniformity or homogeneity of coating
Systems that include hydrophilic or hydro- Figure 31: Increase in the adhesive strength of epoxy esters on steel plates by the addition of 1.5%of
phobic grades of AEROSJL.This section hydrophobic silica. Measured following two days Of storage at room temperature (14). See Figure28
includes several representativeexamples
of applications containing hydrophobic
AEROSIL grades.

To begin with, these claims are supported

by surface representationsof priming
coats depicted in Figures 32 and 33. For
this purpose,we returned to examples
which were already used for a different
representation in section 4.4.

Figure 32: Scanning electron micrographs of an etched zinc chromate primer (4). Left control paint, right:
containing 1.3% of AEROSIL R 972 related to pigment content. See Figure29

29
Figure 32 depicts a zinc chromate primer
and Figure 33 a zinc dust paint. The left-
hand side of this picture is not out of focus;
the blurred effect is due to the fact that the
upper layers of the control paint not con-
tainingAEROSlLarevirtuallyfreefrom zinc
dust, see Figure 34.The depth of focus of
the scanning electron microscope is not
sufficient to obtain a more sharply defined
photograph,such as theoneshown on the
right-hand side of Figure 33.Even a top
view of this sample, which contains 2% of
AEROSIL R972, shows the completely uni-
form distribution in the zinc dust coating
film. This fact is clearly confirmed in Figure
34 which depicts photographsof micro-
tome sections. The upper half of Figure 34
also illustrates clearly how sedimentation
has occurred in the relatively short time be-
tween applicationof the coating and dry-
ing.Thiscan be prevented by an addition of
2% of AEROSIL R 972.
Figure 3 3 SEMs of etched zinc dust paints (4). Left: control paint, right: containing 2% of AEROSIL R 972
related to zinc dust. See Figure 26
The more uniform distribution of the zinc
dust can definitely be used to explain the
improvement in the anti-corrosive effect
(4).This statement is valid regardless of
which theories are drawn upon as a basis
to explain the protection mechanism of
zinc dust paints.

This goes for both the “sealing theory” and

the “cathodic protection mechanism
theory” which were compared in 1964 (40).

30
Figure 34: Optical micrographs of cry0 microtome sections of zinc dust paint samples (14). Paint was applied to a PVC film, the surface was vapour-blastedwith
gold. Above: control paint, below: containing 2% of AEROSIL R 972 related to zinc dust

31
Figure 3 5 SEMs depicting microtome sections of wood glazes on absorbent wood. Left: control paint, right: containing 1.5%
of AEROSIL R 972 related to the total coating (37). Basis: 8% of ALFTALAT AF 641 and 9 % of Flatting Agent OK 412

A more uniform distribution can also bring

about definite improvements in the case of
applicationscontaining flatting agents
(37). Figure35 likewise depicts microtome
sections of wood glazes on a porous
wooden substrate. The coating on the left-
hand side of the picture has penetrated
into the substrate to such an extent that the
SiOn-basedflatting agent particlesare now
lying on the coating surface without any
binder to envelop them. This produces an
extremely poor optical effect, compare the
left-hand side of Figure 36.

32
Figure 36: Photographs of the wood finishes shown in Figure 35

The addition ofkEROSli R 972 prevents

an excessive penetration of the binder
solution into the surface of the wood. This
means that adequate binder remains in
the coating to completely embed even the
flatting agent particleslying on the surface.
Aperfect optical effect is obtained, com-
pare the right-handside of Figure 36.
4.7
Free-Flow Properties

Synthetic silicas, especially the various

AEROSIL grades, are used in many
branches of industry to improve the free-
flow behaviour of substances in powder
form (32, 39). Hydrophobic silicas are
particularly effective here (4).The free-flow
properties of powder coatings can also
be considerably improved, as shown in
Table 7. In addition to this, small amounts
of AEROSIL R 972 can also be used to
reduce the unwanted electrostatic charge
of coating materials in powder form.
This occurs regardless of whether the Table 7: Free-flow cone height and electrostatic charge of commercial powder coatings before and after
basic substance has a positive or a nega- the addition of AEROSIL R 972 (4).The measurement of the electrostatic charge is described in (33)
tive charge. The very slight additions of
AEROSIL R 972 used to improve the flow
properties of ready-ground powder coat-
ings have little or no effect on the levelling
properties of the powder coating during
the film forming and curing processes. 5 The application of hydrophobic silicas in
Further Applications the production of powdered rubber mix-
tures (45) is also conceivable.This possible
application and the above-mentioned use
Hydrophobic AEROSIL grades are also
in deodorants are based on the conception
used in numerous other applications, for
of “dry water” which was published in (46).
example outside the coatings sector in:
- toners, to stabilize the triboelectric This list is by no means complete and is
characteristics (41,42) intended to give some examples which
- deodorants (43),to convert the aqueous could encourage ideas for further applica-
tions.
phase containing the active substances
into 8 !oose, sprz!yable powder;
- silicone-based sealing compounds;
- protective cable fillers for light-conduc-
tive cables as a water-repellent thicken-
ing agent (44) (so-called “cable gels”);
- waterproof gel greases;
- special greasesfor packaging machines
used in the food industry.

34
6 7 Known data are compiled in Table 8. The
Practical Advice Toxicological Information “PatchTest” and the test for irritating ef-
fects on the mucous membranes proved
Which grades of AEROSlLshould the paint All of the hydrophobic silicas mentioned in negative in all cases, i.e. were without find-
chemist use in practice? It is easy to this brochure are X-ray amorphous. Like ings. It should be pointed out that the
answer this question (14): the basic hydrophilic products,they do not numerical values given for the acute oral
cause silicosis (47-49). AEROSIL R 972 LD50depend to a large extent on the bulk
The most significant product is density of the material being examined and
and AEROSIL R 974 are known to be
AEROSIL 200. on the testing laboratory. It was not possi-
expelled from the lungs of rats soon after
If the results obtained with this standard intake (7,50). The occurrence of fibrosis ble under the test conditionsto apply more
grade are not satisfactory, AEROSIL in animal experiments was only observed silica in any of the cases.
R 972 should be applied, particularlyfor following high doses of the substance.This
anti-corrosionpurposes. cannot occur if a low dust concentration All of the recommended hydrophobic
at the place of work is ensured.The general silicas are delivered in paper sacks. Inten-
Only in cases where even AEROSIL sive handling tests have been carried out
R 972 is unable to produce the desired dust limit value of 4 mg/m3has been valid
in the Federal Republic of Germany since with synthetic silicas in order to avoid any
effect should one resort to other grades in-plant dust problems that a customer
of AEROSIL, e.g. in the following order: 1989. Similar values are also in force in
other western industrial states. might experience. Most of these results
- AEROSIL R 805 have been published(51,52) and include:
- AEROSIL R 812. Up until now there has been no evidenceto - the manual or fully-automaticemptying
For example, these grades may be show that hydrophobic silicas damage the of sacks;
used to advantage in certain vinyl skin in any way. Due to a certain water - the transportationof the hydrophobic
ester resinsfor casting resins or adhe- adsorption capacity, hydrophobic silicas
can withdraw water from the human skin. silicas within the works, which is easiest
sives. in this case by means of a suction con-
The “dry feeling” which is experienced
AEROSIL R 202 should only be used in veyor;
during direct contact with the product is
the coatings industry if extensive tests based on this effect. The normal state can - the automatic weighing and dosing;
by the consumer have proved that no be restored by simply washing one’s
applicational problems occur as regards
- the dust-freetransferof the silica to mix-
hands.
levelling, recoating or adhesion. ing and dispersing appliances.
AEROSIL R 202 is recommended for use
in epoxy systems (27),and especially for
casting resins.

35
Table 8 Toxicological data of hydrophobic grades of AEROSIL according to (49)
8 10) H. FERCH, K. SEIBOLD, farbe + lack 20) J. J. CHESSICK, A. C. ZETTLE-
Literature 90,88 (1984) MOYER,Adv. Cat. 11,263 (1959)

1) Technical Bulletin Pigments No. 31, 11) Technical Bulletin Pigments No. 67 21) B. MARCINIEC,A. KRYSTAFKIE-
DegussaAG, FrankfurVM.,4th edition DegussaAG, Frankfurt/M., 3rd edition WIECZ, L. DOMKA, Coll. Polym. Sci.
(1981) (1981) 261,366 (1983)

2) H. FERCH, M. LAMBERMONT, 12) G. KALLRATH: DE-PS 1.229.504 22) 0. J. SCHMITZ, F. J. SELL,

R. OELMULLER,Adhasion 29,21 (1962), DE-PS 1.172.245 (1963), both K. HAMANN, farbe + lack 79,1049
(1985) DegussaAG, FrankfurUM. (1979)

H. FERCH, A. REISERT, R. BODE, 13) J. MATHIAS, G. WANNEMACHER, 23) S. BRUNAUER, P. H. EMMETT,

Kautsch. + Gummi. Kunststoffe 39, J. Coll. Interf. Sci. 125,61 (1988) E.TELLER, J. Am. Chem. SOC.60,
1084 (1986) 309 (1938)
14) H. FERCH, 17.AFTPVCongressBook
H. FERCH, farbe + lack 85,651 (1979) p. 128 (1987) 24) E. KOBERSTEIN, M. VOLL, Z. Physik.
Chem. NF 71,275 (1970)
Technical Bulletin Pigments No. 26, 15) H. FERCH, Chem. Ing. Techn. 48,11
DegussaAG, FrankfurVM., 3rd edition (1976) 25) H. FRATZSCHER, farbe + lack 75,6
(1980) (1969)
16) I.A. LICHTMAN, J.V. SINKA, D. W.
H. BRUNNER,D. SCHUTTE, EVANS,Ass. Mex.Tec. Ind. Cell. Paper 26) M. ETTLINGER, H. FERCH, J. MATHIAS
Chem.-Z. 89,437 (1965) (Bol) 15,26 (1975) in Technical Bulletin Pigments No. 23,
DegussaAG, Frankfurt/M., 5th edition
W. KLOSTERKOlTER,Arch. Hyg. 17) W.T.YENI, R. S. CHAHAL,T. SALMAN, (1986)
Bakt. 149, 577 (1965) Canad. Met. Quart. 12,231 (1973)
27) Technical Bulletin Pigments No. 27,
E. WAGNER, H. BRUNNER, Angew. 18) S. GARHSVA, S. CONTRERAS, Degussa AG, Frankfurt/M., 4th edition
Chem. 72,744 (1960) J. GOLDFARB, Coll. Polym. Sci. 256, (1989)
241 (1978)
R. BODE, H. FERCH, H. FRATZ- 28) Technical Bulletin Pigments No. 42,
19) K. KLEIN, DegussaAG, personal Degussa AG, FrankfurVM.(1968)
SCHER, Kautsch. + Gummi . Kunst-
stoffe 20,578 (1967) report (1970)

37
29) H. FERCH in H. KIlTEL: Lehrbuch der 38) Report FHWA-CA-TL-78-21, obtainable 48) H. FERCH, S. HABERSANG, Seifen,
Lacke und Beschichtungen,Bd. 2, from US-NationalTechnical Informa- Ole, Fette, Wachse 108,487 (1982)
Verlag W. A. Colomb, Schwandorf tion Service, Springfield, VA22 161
(1974) 49) H. FERCH, H. GEROFKE, H. ITZEL,
39) K. KLEIN, Seifen, Ole, Fette, Wachse H. KLEBE, Sozialmed. Praventivmed.
30) U. VEIEL, W. PAPENROTH, 94, 12 (1968) Arbeitsmed. 22,6 and 33 (1987)
IX. FATIPEC Congress Book, Sect. 3,
19 (1968) 40) K. M. OESTERLE, Deutsche FarbenZ. 50) P. I. REUZEL, ClVO Inst.TNO,
18, 151 (1964) NL-ZEIST, pers. Mitt. (1985)
31) W. PAPENROTH, XI. FATIPEC
Congress Book 595 (1972) 41) Xerox Corp. US-PS 3.819.367 (1974) 51) Technical Bulletin Pigments No. 70
DegussaAG, Frankfurt/M. (1978)
32) Technical Bulletin Pigments No. 31, 42) Kodak DE-PS 2.821.565 A 1 (1978)
DegussaAG, Frankfurt/M., 1st edition 52) H. FERCH, W. SCHMITZ, J. Chem.
(1969),2nd edition (1978) 43) S. PRUSSIN, EU-PS 18.137 (1980) Techn. Biotechn. 30,699 (1980)

33) H. FERCH, Seifen, Ole, Fette, Wachse 44) Raychem Corp. EU-PS 67.009 (1981) 53) ,,EinfluO physikalischer Eigenschaften
101, 17 (1975) and 101,51 (1975) organischer Pigmente auf ihr an-
45) R. CASPARY, I. HESKE, J.Appl. wendungstechnischesVerhalten".
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35) J. Mathias, lecture held at Colloid

Chemistry Symposium VCV-STI,
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DegussaAG, Frankfurt/M., 2nd edition
(1985)

37) H. FERCH,25th Meeting OCCA.New

Zealand, Rotorua, (1987), Congress
Book.

38
Brief List of Technical Terms

AEROSILB Binder Cry0 Microtome Section

Trade mark used by Degussa AG, is the non-volatile part of acoating material is made using a piece of equipment called
FrankfurVM. for a -+ submicron synthetic excluding +pigment and 4 filler, but in- a microtome. The sample is cooled and
silica which is produced according to the cluding plasticizers, +surface driers and then cut with a diamond knife.
process of high-temperature hydrolysis. other non-volatile additives. The binder
connects the individual pigment particles Defoamers
Aaalomerates and the substrate thus combiningto make Name given to substances which are
up the finished coating (DIN 55945). added to frothy liquid systems in order to
Are defined in DIN 53206 as loose clusters
of +aggregates which may be broken reduce or inhibit the formation of foam.
down during dispersion. Bridged Silanol Groups
Here: shorter expression used for+ silanol Dispersion
Aggregates groups which have entered into a hydrogen is the uniform distributionof- pigments in
bridge linkage. +binders or powdered formulation
Interwoven union of particlesjoined at the
interfaceswhose surface area is less than components with the aid of dispersing
the sum of the surface areas of the- BS equipment.
primary particles (DIN 53206). As a rule, Abbreviation for British Standard.
aggregates are not broken down during the Drying Agents, better: Surface Driers
-+dispersion of +pigments. Coating are organic, soluble metallic compounds
Collectiveterm for one or more connecting which are added to oils in order to consid-
Anti-Settling Agent layers on a substrate, which are manufac- erably shorten the drying time.
Product designed to keep -+ pigments tured from coating materials.
which are prone to settling in suspension in
a coating system. Corrosion Protection Dynometer
Measures taken in order to prevent corro- Combined measuring apparatus which
Application sive damage. can be used to determine the surface ten-
Here -+ coating. sion of liquid systems and the depth and
consistency of sediment. Manufacturer:
ASTM Byk Labotron MeOtechnikAG, D-8192
Geretsried.
Abbreviation for the American Society for
Testing and Materials.

39
Elastomers Film Formation Gloss
are wide-meshed, cross-linked macro- is the transition of an applied coating mate- is the sensory impression for the more or
molecular substances with reversible rial from liquid to solid state.Thefilm forma- less directed reflection of beams of light on
expansibility. tion results from drying or curing. Both a surface.
processes can take place simultaneously
Electron Microscope or one after another (DIN 55945). Hammer Finish Coating
Microscope using electron beams to de- is one of the special effect coatings, which
Gas Black can be used to achieve intentional, visible
pict very small objects.
Carbon black whose manufacture is and uniformly-distributed irregularitieson
Epoxy Resins characterized by the evaporation by heat- the surface of a coating film.
ing of the hydrocarbons serving as raw
are reaction resins with an adequate
materials, followed by combustion of the Highly Dispersed
number of epoxy groups for curing
gas with the aid of a burnable carrier gas. Finely divided.
purposes.
Gassing Hydrophilic
Fibrosis
Term used to describe the development of Having an affinity to water; wettable by
Increase in connective tissue.
hydrogen occurring in zinc dust paints, water.
which is caused by the reaction of water
Filler
with the zinc dust. Hydrophobic
is a substance which is practically insolu-
ble in the applied medium.The refractive General Dust Limit Value Water-repellent; not wettable by water.
index of white fillers is generally < 1.7.
is the maximum permissible dust concen- lanition Loss
In certain media, a filler can also serve as
tration for “non-hazardous substances” ~

a-pigment (DIN 55943). is the term given in DIN 55921 forthe differ-
at the place of work, valid in the Federal
Republic of Germany. ence in weight between the dry weight and
the weight of the ignition residue. Values
given as a percentage.

40
Infra-Red Spectroscopy Mill Base Pigment
~~

Modern optical process in which the infra- Concentrated mixture of --f pigments, is defined in DIN 55945, BS 2015 and
red range of absorption spectra of mainly +fillers (and dispersion additives) in a ASTM D 16 as an organic or inorganic col-
organic compounds in solid, liquid or -+binder: solvent ratio chosen to suit the ourant which can be chromatic or achro-
gaseous form are used for qualitative and respective method of dispersion. matic and is insoluble in solvents.
quantitativeanalysis and for determining
the structure. Monomolecular Powder Coatings
Monomolecular layers are made up of a are paints in powder form which produce a
in situ single moleculethickness of the substance coating on a substrate following applica-
means the formation of a substance at the concerned; they play a significant role in tion and melting.
time when it is required. corrosion and in many interfacial
phenomena. PreciDitatedSilicas
JIS
are virtually non-porous synthetic silicas
Abbreviation for Offset Printing Inks which are formed during the conversion of
Japanese IndustrialStandard. or flat-bed printinginks, are paste-like sys- water glass and sulphuric acid.
tems which dry as a result of oxidative and/
LD 50 or physical processes.The water stability Primary Particles
Lethal Dose = dose leading to death. of these systems is particularly good as a according to DIN 53206, are the smallest
In experiments on animals, this is usually result of the printing process, which is particleswhich make up powdered solids.
fixed at LD 50, which is the dose that leads based on an interactionbetweenthe water
Recognizable as individual particlesby
to the death of 50% of the animals within and the ink.
means-ofelectron microscopy.
a certain period of time.
Oranae Peel Effects Priming Coat (Primer)
Levelling is a term used in IS0 4618 to describe
The primer is made up of coating layers
The term denotes the ability of a coating irregularities in the surface of a coating designed to connect the substrate and the
that is still in the liquid state, to self- film which give the latter the crinkled
coating layers applied to the priming coat.
regulate the irregularities which occurred appearance of orange peel. It may also fulfil other special functions,
during application (DIN 55945). e.g. +corrosion protection.
Patch Test
MAK Value Tolerance test carried out by observing the
(German: Maximale Arbeitsplatz-Konzen- local effect of substances on the conjuncti-
tration) is the highest permissible concen- val sac of New Zealand White rabbits.
tration in the air of a material being used at
the place of work which, accordingto the
present level of knowledge, must not be
exceeded even as a result of repeated or
long-term effects.+General Dust Limit
Value.

41
Residual Surface Area Silicosis ThermogravimetricAnalysis
Mathematical quantity which is deter- Progressivepneumoconiosis as a result of Term used to describe a thermoanalytical
mined as the difference between the+ inhaling dust containing quartz: occupa- process which makes use of the changes
specific surface of the basic hydrophilic tional disease. in weight that occur as a result of the
silica and that of the hydrophobic conversion of substances caused by
(= aftertreated)silica. SIPERNAT@ heating.
Registeredtrade mark used by Degussa
Scanning Electron Microscope Thixotropic Index
AG, Frankfurt/Main for +precipitated
Analytical appliancewhich scans an object silicas and silicates. Viscosity quotient establishedby using the
line for line with an electron beam, resulting measuring equipment at two different
in impulses which are converted into SDecific Surface shear rates and rotational speeds.
scanner dots to give the finished picture. If possible, the rotationalspeeds should
is the surface area of a solid, relativeto its
be in a ratio of 1:lo.
mass, given in mVg. Generally determined
Sediment according to the BET method (DIN 66 131).
Thixotropy
Matter that settles to the bottom of a liquid
system if not held in suspension. Substrate Time-dependent gel-sol-gel conversion
which is reversible under isothermal condi-
is an insoluble, generally achromatic
SEM tions.
substancewhich is involved in thecompo-
Scanning Electron Microscopy. sition of certain coloured coatings
Toner
(DIN 55945).
Silanol Group Density Pigmented resin powder. The particle size
Suspending Agent is approximately 10-20 pm. Toner is the
Density of the- silanol groups situated on
Anti-Settling Agent. colouringsubstance used in photocopying
the silica surface. -t
processes.
Silanol Groups TEM
Toxicology
= Si-OH groups situated on the silica Transmission Electron Microscopy.
The science of harmful, in some cases
surface.
fatal, effects of substances in excessive
amounts.

Triboelectric Effect
occurs when different materials are
brought into contact with one another
(non-conductors e.g. polymer glass).
Friction causes electrons to be removed
from or conveyed to the surface.

42
Physico-Chemical Data of
Hydrophobic AEROSlL

acc. to DIN 66131 10) contains approx. 1% of chemically bound carbon

acc. to DIN IS0 787/Xl oder JIS K 5101/18 (not sieved) 11) contains approx. 3.5-5.0% of chemicallybound carbon
acc. to DIN IS0 787/11, ASTM D 280, JIS K 5101/21 12) contains approx. 4.5-6.5% of chemically bound carbon
acc. to DIN 55921,ASTM D 1208, JIS K 5101/23 13) contains approx. 2.0-3.0% of chemically bound carbon
acc. to DIN IS0 787/1X, ASTM D 1208, JIS K 5101/24 14) contains approx. 3.0-4.0% of chemically bound carbon
acc. to DIN IS0 787/XVlll, JIS K5101/20 15) contains approx. 0.6-1.2% of chemicallybound carbon
The sieve residue acc. to Mocker cannot be determined 16) contains approx. 0.7-1.3% of chemicallybound carbon
with water in the case of hydrophobic AEROSIL grades
relatedto material ignited for 2 hours at 1000 "C
relatedto material dried for 2 hours at 105 "C
HCI content is a part of the ignition loss

43
 Additional Degussa Products

Active oxygen compounds Copper compounds Silanes

~

Adhesives Flattina aaents Silica dispersions

Barium compounds Highly dispersed metallic oxides Silicates
Blue pigments Hvdrocvanic acid and its derivatives Strontium compounds
~~

Carbon blacks and pigment black Lead compounds Titanium compounds

preparations Methacrylic acid and its derivatives Toner resins
Catalvsts Powder cellulose Zeolites
Ceramic colours PreciDitatedsilicas Zinc compounds
Coloured pigments Selenium compounds
Semi-finished plastic products

The Industrial and Fine Chemical DEGALAN@LP DEGACUFtE@

Products Divisionof DegussaAG supplies Thermoplastic methacrylic resin in solid Cyclo-aliphatic epoxides and Photo-
the Coatings Industry with: form used in the manufactureof protective initiator KJ 85 for use in cationic radiation
coatings for concrete, road marking paint curing.
and marine paint; heat-seal coatings for
aluminiumfoils, imitation leather top coat-
ings, etc.

DEGADUW
Cold curing, low-viscosity methacrylic-
resin for floor and wall coatings.

DEGARQUTE@
Cold curing, low-viscosity methacrylic
resin used in the manufactureof 2-com-
ponent cold plastics for lane markings on
city streets and country roads, and for
coloured markings on cycle paths.

44
The product range of DegussaAG’s
Inorganic Chemical Products Division
includesthe following registered
trademarks:

The informationand statements contained

herein are provided free of charge.
They are believedto be accurate at the time
of publication, but Degussa makes no
warranty with respect thereto, including
but not limitedto any results to be obtained
or the infringement of any proprietaryrights.
Use or application of such information
or statements is at user’s sole discretion,
without any liability on the part of Degussa.
Nothing herein shall be construed as a
license of or recommendation for use
which infringes upon any proprietary rights.
All sales are subject to Degussa’s General
Conditions of Sale and Delivery.