Effect of Wettability and Silicone Surface Modification on

the Self-Cleaning Functionalization of Wool

Wing Sze Tung, Walid A. Daoud

School of Applied Sciences and Engineering, Monash University, Churchill VIC 3842, Australia

Received 14 June 2008; accepted 29 September 2008

DOI 10.1002/app.29396
Published online 22 December 2008 in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Self-cleaning wool has been realized by the wettability of wool has been modified using different
treatment with a colloidal sol of anatase nanocrystals. nonionic wetting agents, in an attempt to shorten the wet-
However, the mechanical properties of wool have been ting time during dip-coating and the absorption rate was
significantly deteriorated following the self-cleaning func- compared. The effect of wetting agents on the functionali-
tionalization treatment. To minimize the undesirable side- zation process and the photocatalytic activity was exam-
effects induced by the nanocoating, a silicone surface mod- ined. The synchronized effect of wettability and silicone
ification post-treatment has been introduced. The change surface modification on the self-cleaning functionalization
in mechanical properties of TiO2-coated wool after modifi- of wool was also studied. V
C 2008 Wiley Periodicals, Inc. J Appl

cation with silicone was examined, and the effect of this Polym Sci 112: 235–243, 2009
process on the photocatalytic activity and its stability was
assessed by a degradation test of food stains. Moreover, Key words: nanotechnology; biopolymers; self-cleaning

INTRODUCTION investigated the potential application of nano-crys-

talline anatase TiO2, especially focusing on the func-
Since the discovery of photocatalytic water splitting
tions of self-cleaning, environmental purification of
on titanium dioxide (TiO2) electrodes in late 1960s,
air and water, sterilization, and deodorization.10–13
intensive studies have been carried out on photo-
TiO2 nanoparticles have been applied in low ther-
electrochemistry.1,2 With the advancement of the
mal resistant fiber materials using a low temperature
bottom-up nanotechnology, photocatalysis function
sol–gel method.4,14 These innovative self-cleaning
can now be imparted on materials to possess self-
fiber materials are currently in the stage of develop-
purification property and become capable of decom-
ment and optimization.3,15,16 The self-cleaning coat-
posing their contaminants such as dirt, stains, and
ing technology has mostly been applied to cellulosic
harmful microorganisms via a powerful oxidation
fibers in the concurrent research effort. However,
effect triggered by incident light.3,4 Owing to its fas-
transferring the application technology to protein
cinating potential in various applications, this novel
fibers has been hindered because of the relatively
concept has attracted great scientific interest univer-
low chemical and thermal resistance of protein mate-
sally in recent decades.5–8 Among all photosensitive
rials.17–20 Nevertheless, there has been a break-
semiconductors, titanium dioxide, particularly in the
through when self-cleaning keratin fibers have been
anatase nano-crystalline form, has been regarded as
successfully realized by our research group,21 where
the most promising photocatalyst because of its spe-
the natural protein fibers possess self-purification
cial physical and chemical attributes, such as effi-
properties after imparting nano-crystalline anatase
cient photocatalytic activities, facilitated by its
TiO2 on their surface.22,23 Unfortunately, the intrinsic
particle size to diffuse the excited electrons and
properties of wool fibers, such as mechanical and
holes toward the surface before recombination, high
physical properties, have been deteriorated after the
stability, high oxidizing ability, nontoxicity, and
self-cleaning coating treatment, which hampered the
low-cost.2,9 Therefore, many research groups have
practicability of self-cleaning wool fibers and limited
their utilization. Moreover, the poor wettability of
Correspondence to: W. A. Daoud (walid.daoud@sci. wool fibers in TiO2 colloids causes a difficulty in the
monash.edu.au). implementation of this technology in a large-scale
Contract grant sponsors: Monash Research Graduate industrial production. Therefore, it is necessary to
School, School of Applied Sciences and Engineering, modify the coating treatment to achieve maximum
Monash University; Australian Wool Innovations.
maintenance of the intrinsic properties of wool
Journal of Applied Polymer Science, Vol. 112, 235–243 (2009) fibers and improving the industrial feasibility of the
V
C 2008 Wiley Periodicals, Inc. self-cleaning treatment. In this contribution, the
236 TUNG AND DAOUD

application process of self-cleaning coating treatment

has been modified using wetting agents and silicone
to overcome the aforementioned shortfalls. In this
study, the post-treatment with amino-modified sili-
cone has been introduced to investigate its effect on
the recovery of the mechanical properties as well as
on the purification performance. To improve the
wettability of wool, different nonionic surfactants Figure 2 Molecular structure of TweenV 80.
R

have been used as wetting agents and their effect on

the self-cleaning properties has also been studied. siloxane)-(dimethylsiloxane)] copolymer (BD-10076-
80A, Bald Silicone Technology, China), was
EXPERIMENTAL employed as a softening agent in the chemical post-
treatment process for recovering the deteriorated
Preparation of titanium dioxide colloid mechanical properties after the anatase coating treat-
The titanium dioxide sol was prepared by hydrolysis ment. The chemical structure of the amino-modified
and condensation of 97% titanium tetraisopropoxide silicone polymer is shown in Figure 1. The silicone
(Yizheng City Tianyang Chemical Plant, China) in polymer was diluted at concentrations 20 g/L (2%)
acidic aqueous containing glacial acetic acid (Lab- and 40 g/L (4%) with 45
C warm water in different
Scan, Thailand) and 37% hydrochloric acid (Lab-Scan, concentration ratios of 10 mL : 1 g and 30 mL : 1 g.
Thailand). The concentration ratio of titanium tetraiso- The self-cleaning coated samples were subjected
propoxide, acetic acid, and hydrochloric was 1 : 1 : 0.28 to the silicone solutions at 45
C for 30 min. After
as previously reported.22,23 The mixed solution was that, the samples were dried at room temperature
then heated at 60
C under vigorous agitation for 16 h. prior to evaluation. The anatase coated sample with-
out post-treatment is termed S0, coated and post-
treated with 2 and 4% silicone in concentration ratio
Self-cleaning surface coating of 10 : 1 are termed S1 and S2; and coated and post-
Pure commercial white worsted wool with twill treated with 2 and 4% silicone in concentration ratio
weaving structure was used in this experiment. Sam- of 30 : 1 are termed S3 and S4, respectively.
ples were firstly precleaned by nonionic detergent
(Kieralon OL) in a volume-to-weight ratio of 50 : 1 Effect of surfactants on self-cleaning coating
at 45
C for 30 min to remove all impurities prior to
Two commercial nonionic surfactants, TweenV 80
R

self-cleaning coating. The dried samples were then

(T80) and TritonV X-100 (X100), were used as wet-
R

dipped in the titanium dioxide sol for 1 min and

pressed with an automatic horizontal press (Rapid ting agent to improve the wettability of the fibers.
N. 413, Rapid Labortex Co., Taiwan) at a nip pres- The chemical structures of T80 and X100 are shown
sure of 2.75 kg cm2 with a roller rotation speed of in Figures 2 and 3. The wetting agent, in an appro-
7.5 rpm. After drying in a preheated oven at 60
C priate concentration, was either mixed into the tita-
for 5 min, the samples were cured in a curing oven nium dioxide sol prior to the dip-coating process or
(Mathis Labdryer, Werner Mathis AG Co., Switzer- added in situ during the formulation preparation.
land) at 120
C for 3 min. The sols prepared with 0.1 and 0.4% T80 prior to
dip-coating are termed T80A and T80B, respectively.
The sol prepared with 0.1% X100 prior to dip-coat-
Silicone surface modification ing is termed X100A, and the sol prepared with
0.1% X100 in situ is termed X100S.
A commercial cationic surfactant, amino-modified
silicone emulsion, [(aminoethylaminopropylmethyl-
Mechanical properties
The mechanical properties were evaluated before
and after the silicone surface modification. The tear-
ing strength of the samples was measured using

Figure 1 Molecular structure of amino-modified silicone

Figure 3 Molecular structure of TritonV X-100.
R
polymer.

Journal of Applied Polymer Science DOI 10.1002/app

SELF-CLEANING FUNCTIONALIZATION OF WOOL 237

TABLE I
Tearing Strength of Pristine and Coated Wool with
and Without Silicone Modification
Pristine fibers S0 S1 S2 S3 S4

Warp (gf) 2816 1728 2368 2187 2165 2112

Weft (gf) 1184 800 1067 1067 1056 1013
Average (gf) 2000 1264 1717 1627 1611 1563
Overall change (%) 36.80 14.13 18.67 19.47 21.87

Elmendorf Tearing Tester (Thwing-Albert Instru- soaking the sample into the titanium dioxide sol.
ment Co., USA) with a standard capacity of 6400 g The wetting time reported is the average of five
in accordance with ASTM D 1242-96. The bending measurements for each test sample.
rigidity of the samples was obtained on Kawabata
Pure Bending Tester—KES-FB2 (KATO Tech. Co.,
Japan) according to the Kawabata Evaluation System RESULTS AND DISCUSSION
for Fabrics (KES-F). Silicone surface modification
Mechanical properties
Photocatalytic purification performance From our previous work, it was found that the self-
The photocatalytic degradation of food stains, such cleaning coating treatment causes damage to fibers,
as concentrated coffee and red wine stains, was eval- which is probably attributed to the acid content in
uated using Suntest solar simulator—XenotestV
R the titanium dioxide sol and to the alteration of the
Alpha LM Light Exposure and Weathering Test fiber surface after the deposition of titanium dioxide
Instrument (Atlas Material Testing Technology LLC, nanoparticles. Hence, the tearing strength and bend-
Germany) with the irradiance of 45–95 mWcm2 for ing rigidity of coated fibers were measured before
8, 20, and 40 h. and after a surface modification post-treatment with
silicone. The tearing strength of pristine, coated and
coated and silicone-modified wool fibers are shown
Reproducibility of photocatalytic in Table I. Compared with pristine wool fibers, S0
purification performance showed the greatest deterioration in tearing strength
of 37% after self-cleaning coating treatment. On the
A stability test was performed to study the effect of other hand, the lost tearing strength was signifi-
different treatment processes on the reproducibility cantly recovered after the post-treatment. Of the four
of the self-cleaning performance. The stain degrada- treated samples, S1 showed the least drop in tearing
tion activity of modified self-cleaning fibers were strength (14%) followed by S2, S3, and S4, indicating
compared before and after repeated solvent washing that S1 had the best recuperation of tearing strength.
according to ISO 105-D01 using petroleum ether as The recovery of the lost tearing strength is probably
solvent. attributed to the change of frictions. Because surface
friction of wool fibers can be altered by silicone
treatments,24 silicone-based polymers may act as
Wettability and absorption rate
lubricant to ease the interfiber and interyarn frictions
The samples absorption rate of sols prepared with leading to an improvement in tearing strength.
and without wetting agents was observed. The wet- The change of bending rigidity of coated fibers
ting time required by a sample to thoroughly absorb before and after post-treatment with silicone is
the sol was recorded by stopwatch instantly after shown in Table II. The pliability is directly affected

TABLE II
Bending Rigidity of Pristine and Coated Wool with
and Without Silicone Modification
Pristine fibers S0 S1 S2 S3 S4
2
Warp (g cm /cm) 0.143 0.383 0.167 0.171 0.171 0.167
Weft (g cm2/cm) 0.092 0.142 0.110 0.108 0.109 0.108
Average (g cm2/cm) 0.118 0.263 0.139 0.140 0.140 0.138
Overall change (%) 123.40 17.87 18.72 19.15 17.02

Journal of Applied Polymer Science DOI 10.1002/app

238 TUNG AND DAOUD

Photocatalytic purification performance

Degradation of food stains was conducted to analyze
the effect of silicone surface modification on the pho-
tocatalytic activity of self-cleaning functionalized
wool fibers. Stain degradation of pristine, TiO2-
coated, silicone-modified TiO2-coated wool fibers are
illustrated in Figures 4 and 5, respectively. Consist-
ent with our previous studies, stains on pristine
fibers remained intact after solar-simulated irradia-
tion, whereas the self-cleaning functionalized fibers
(S0) were able to completely discolor both concen-
trated coffee and red wine stains upon irradiation.
After the silicone post-treatment, all modified and
TiO2-coated fibers were able to possess significant
purification performance. However, when compared
to S0, a slight change was observed on fibers treated
with different silicone concentrations. S1 and S2
showed very similar degradation ability on both
concentrated coffee and red wine stains, and they
were able to completely discolor the stains within
40 h of solar-simulated irradiation; however, the
photocatalytic ability of S3 and S4 was reduced

Figure 4 Stain degradation of concentrated coffee (a)

pristine wool, (b) S0, (c) S1, (d) S2, (e) S3, and (f) S4. [Color
figure can be viewed in the online issue, which is available
at www.interscience.wiley.com.].

by the stiffness of the fibers, which corresponds to

the bending rigidity. The higher the bending rigid-
ity, the stiffer the fiber, and the less the pliancy. Af-
ter the TiO2-coating treatment, the bending rigidity
of S0 was significantly increased by 123.4%, whereas
the bending rigidity of all post-treated TiO2-coated
fibers was almost seven times lower when compared
with S0. The bending rigidity of different post-
treated fibers increased in the ascending order of S4
(17.02%), S1 (17.87%), S2 (18.72%), and S3 (19.15%),
signifying that S4 possessed the greatest ability to
restore the deteriorated pliability of wool, followed
by S1, S2, and S3. In agreement with the observa-
tions from the tearing strength, it is believed that the
modification of wool surface with silicone improved
the bending rigidity as a result of friction diminution
between fibers.
The above results confirm the ability of the sili-
cone treatment to offset the drop of mechanical
Figure 5 Stain degradation of red wine (a) pristine wool,
properties induced by the TiO2 coating, where S1 (b) S0, (c) S1, (d) S2, (e) S3, and (f) S4. [Color figure can be
showed the best performance among all post-treated viewed in the online issue, which is available at www.
TiO2-coated fibers. interscience.wiley.com.].

Journal of Applied Polymer Science DOI 10.1002/app

SELF-CLEANING FUNCTIONALIZATION OF WOOL 239

TABLE III
Absorption Time of Pristine and Coated Wool with and
Without Silicone Modification
Pristine fibers T80A T80B X100A X100S

Time (sec) 60þ 55–56 2–3 2–3 2–3

oxygen atoms of titanium dioxide and amino groups

of silicone. These results showed that the photocata-
lytic purification performance was adversely affected
if high concentration of silicone is used.

Reproducibility of photocatalytic
Figure 6 Stain degradation of concentrated coffee on S1 purification performance
(a) before stability test and (b) after stability test. [Color
figure can be viewed in the online issue, which is available Considering the results discussed in sections Me-
at www.interscience.wiley.com.]. chanical Properties and Photocatalytic Purification
Performance, S1 showed the best improvement in
especially on red wine stain. This signifies that the mechanical properties with no significant adverse
photocatalytic efficiency is affected by the level of effect on the purification performance. Therefore, the
silicone concentration used in the post-treatment. It stability testing was conducted on S1 only. The
was found that a concentration ratio of 10 : 1 is reproducibility of the photocatalytic ability of S1 is
more favorable for TiO2-coated fibers. Of the two demonstrated in Figures 6 and 7. In contrast to S1
coated fibers treated with 10 : 1 ratio, both S1 and S2 before washing, the shape of the stains on S1 after
possessed similar self-cleaning performance as S0 washing was unevenly spread on the fiber surface,
did; nevertheless, S1 is more favorable because of and the stain area was smaller. This denotes that the
the lower silicone concentration applied. Moreover, hydrophilicity of the titanium dioxide coating
the shape and size of the stains varied between
TiO2-coated and silicone-treated TiO2-coated wool.
Stains on S0 were spread in a circular shape over a
large area on fibers surface, whereas the area and
shape of stains in S1, S2, S3, and S4 were smaller
and irregular. This implies that the silicone-treated
TiO2-coated wool is comparatively more hydropho-
bic than TiO2-coated wool. This change in surface
wettability after treatment with silicone is attributed
to the hydrophobic nature of silicone. It is believed
that the hydrophobic alkyl groups of silicone altered
the chemical structure through H-bonding between

Figure 7 Stain degradation of red wine on S1 (a) before Figure 8 Stain degradation of concentrated coffee (a)
stability test and (b) after stability test. [Color figure can T80A, (b) T80B, (c) X100A, and (d) X100S. [Color figure
be viewed in the online issue, which is available at can be viewed in the online issue, which is available at
www.interscience.wiley.com.]. www.interscience.wiley.com.].

Journal of Applied Polymer Science DOI 10.1002/app

240 TUNG AND DAOUD

time permitted is generally less than 5 s; however,

pristine fibers could not get thoroughly wetted even
after 60 s of dipping. To facilitate the industrial
implementation of the self-cleaning coating treat-
ment, it is necessary to shorten the time required for
a thorough wetting. In this experiment, T80B,
X100A, and X100S revealed close absorption rates,
which were almost 20 times faster than that of pris-
tine fibers and T80A. It is believed that the improve-
ment in wettability is attributed to the hydrophilic
oxyethylene groups in T80 and X100. The introduc-
tion of extra hydrophilic groups onto the nonpolar
surface of wool fiber increased the absorption rate of
fibers. From Table III, a thorough wetting was
obtained after 3 s of dipping for T80B, X100A, and
X100S, whereas T80A required 55–56 s. The results
denote that T80B, X100A, and X100S effectively dis-
persed the titanium dioxide nanoparticles in the sol
and shortened the absorption time during TiO2 coat-
ing. The effectiveness of a wetting agent depends
highly on the nature of functional groups of sub-
strate, polarity of substrate surface, conditions of the
aqueous solution (e.g., temperature, solution compo-
sition, and duration), and molecular structure of the
wetting agent.25 In this view, owing to the fact that
the fiber substrate and solution conditions are fixed,
Figure 9 Stain degradation of red wine (a) T80A, (b)
T80B, (c) X100A, and (d) X100S. [Color figure can be
viewed in the online issue, which is available at www.
interscience.wiley.com.].

surface decreases after repeated washing. Although

the hydrophilicity changed, there was no significant
change observed in the discoloration of concentrated
coffee and red wine stains of silicone-modified TiO2-
coated fibers (S1) before and after the stability test,
which could possibly be attributed to the silicone
bonding with the titanium dioxide which acts as a
protective shield, thus preventing titanium dioxide
from being washed off during the stability test.
From these results, it can be concluded that S1 pos-
sessed remarkably reproducible photocatalytic abil-
ity even after severe stability testing and that the
surface modification of TiO2-coated wool with 2%
silicone in a 10 : 1 concentration ratio can offset the
loss of wool mechanical properties while not
adversely affecting the photocatalytic performance
or its reproducibility.

Effect of surfactants on self-cleaning coating

Wettability and absorption rate
The time required for wool fibers to thoroughly
absorb the titanium dioxide nano-sol colloid during
Figure 10 Stain degradation of concentrated coffee after
dip-coating was recorded with and without two stability test (a) T80A, (b) T80B, (c) X100A, and (d) X100S.
common wetting agents, TweenV 80 (T80) and
R
[Color figure can be viewed in the online issue, which is
TritonV X-100 (X100). In the industry, the contact
R
available at www.interscience.wiley.com.].

Journal of Applied Polymer Science DOI 10.1002/app

SELF-CLEANING FUNCTIONALIZATION OF WOOL 241

exhibited outstanding stability, where the stain deg-

radation ability was retained after repeated washing
(Figs. 10 and 11). It is believed that T80 and X100
assisted the dispersion and stabilization of TiO2 par-
ticles on fibers during the dip-coating due to the fact
that they consist of both hydrophilic and hydropho-
bic groups.25,26 Hence, both types of nonionic wet-
ting agents led to improvement of the photocatalytic
activity of TiO2-coated wool.
The synchronized effect of wettability control and
silicone surface modification on the self-cleaning
properties of wool fibers was also studied by means
of stain degradation and stability test. After the sili-
cone treatment, the discoloration of stains was
slightly reduced. Figures 12 and 13 show that both
concentrated coffee and red wine stains were nota-
bly degraded after 8 h of solar-simulated irradiation;
however, an insignificant amount of stain can still be
observed after 20 h of irradiation. From the shape of
the stains, all wettability-modified and silicone-
modified TiO2-coated fibers became more hydropho-
bic, which is in agreement with the results shown in
section Photocatalytic Purification Performance.
Although wettability-modified TiO2-coated fibers
displayed similar purification property after the sta-
bility test (Figs. 10 and 11) and silicone treatment
Figure 11 Stain degradation of red wine after stability
test (a) T80A, (b) T80B, (c) X100A, and (d) X100S. [Color
figure can be viewed in the online issue, which is available
at www.interscience.wiley.com.].

the molecular structure of the wetting agent becomes

the major factor in affecting the wettability perform-
ance. Compared to X100, T80 appeared less efficient
in improving the fiber wettability because of its
long-chain molecular structure, and hence its inabil-
ity to efficiently disperse titanium dioxide nanopar-
ticles. However, the absorption rate can be
facilitated by increasing the concentration of the sur-
factant,25 which explained why T80B led to shorter
wetting time than T80A.

Photocatalytic purification performance

and reproducibility
The stain degradation on fibers coated with and
without wetting agents is illustrated in Figures 8
and 9. Fibers coated with TiO2 in presence of T80A,
T80B, X100A, and X100S possessed excellent stain
degradation ability. Both concentrated coffee and
red wine stains were almost completely discolored
within 8 h and totally removed within 20 h of solar-
simulated irradiation. The photocatalytic activity
was substantially enhanced, where the time required
Figure 12 Stain degradation of concentrated coffee after
to completely degrade the stains decreased from 40 silicone modification (a) T80A, (b) T80B, (c) X100A, and
to 20 h of irradiation when compared with S0. (d) X100S. [Color figure can be viewed in the online issue,
Besides, all wettability-modified TiO2-coated fibers which is available at www.interscience.wiley.com.].

Journal of Applied Polymer Science DOI 10.1002/app

242 TUNG AND DAOUD

it was unable to promote a strong binding between

the nanoparticles and wool to be able to withstand
the silicone treatment and stability test. Whereas
TritonV X-100 was able to expedite the absorption
R

rate effectively and promoted good binding between

titanium dioxide and wool, and thus reproducible
photocatalytic properties could be obtained after the
silicone post-treatment and stability test. Moreover,
the results further verify that X100S TiO2-coated
fibers prepared with TritonV X-100 in situ possessed
R

significant self-cleaning property with good stability.

CONCLUSIONS
The self-cleaning functionalization of wool via tita-
nium dioxide coating has been modified by wettabil-
ity promotion using nonionic surfactants and surface
modification with silicone. The TiO2-coating-induced
drop of wool mechanical properties can be substan-
tially recovered with minimal adverse effect on the
self-cleaning performance. The initial deterioration
on tearing strength and bending rigidity caused by
TiO2-coating has notably been offset, particularly
when 2% amino-modified silicone emulsion was
used in a concentration ratio of 10 : 1. Although the
Figure 13 Stain degradation of red wine after silicone
modification (a) T80A, (b) T80B, (c) X100A, and (d) X100S.
[Color figure can be viewed in the online issue, which is
available at www.interscience.wiley.com.].

(Figs. 12 and 13), they were significantly different in

their self-cleaning ability after having undergone
both silicone treatment and stability test. For concen-
trated coffee stain in Figure 14, all wettability-modi-
fied TiO2-coated and silicone-modified fibers
showed similar photocatalytic activity before and af-
ter stability test. On the other hand, they reacted
very differently on red wine stain (Fig. 15). Silicone-
treated T80A no longer possessed photocatalytic
properties after stability test; where red wine stain
remained intact on the fiber surface after solar-simu-
lated irradiation. The photocatalytic ability of sili-
cone-treated T80B was significantly reduced after
stability test, where the red wine stain was observ-
able even after 20 h of solar-simulated irradiation.
On the other hand, fibers treated with X100 dis-
played better photocatalytic reproducibility after
washing. The photocatalytic activity of both silicone-
treated X100A and X100S was completely reproduci-
ble after the stability test, where red wine stains
were almost completely discolored after 20 h of irra-
diation. When comparing TiO2-coated X100, silicone-
modified X100S demonstrated comparatively better Figure 14 Stain degradation of concentrated coffee after
silicone modification and stability test (a) T80A, (b) T80B,
reproducibility than silicone-modified X100A. The (c) X100A, and (d) X100S. [Color figure can be viewed in
results imply that, although TweenV 80 successfully
R
the online issue, which is available at www.interscience.
dispersed titanium dioxide nanoparticles in the sol, wiley.com.].

Journal of Applied Polymer Science DOI 10.1002/app

SELF-CLEANING FUNCTIONALIZATION OF WOOL 243

amino-modified silicone show great potential in the

practical self-cleaning functionalization of wool
materials.

The authors are grateful to Dr. S. K. Leung for her experimen-

tal assistance and fruitful discussions and to Mr. X. Wang for
his help with the silicone modification study.

References
1. Fujishima, A.; Honda, K. Nature 1972, 238, 37.
2. Fujishima, A.; Zhang, X. C R Chim 2006, 9, 750.
3. Daoud, W. A.; Xin, J. H. J Am Ceram Soc 2004, 87, 953.
4. Daoud, W. A.; Xin, J. H. Chem Commun 2005, 2110.
5. Fujishima, A.; Rao, T. N.; Tryk, D. A. J Photochem Photobiol
C-Photochem Rev 2000, 1, 1.
6. Mills, A.; Lee, S. K. J Photochem Photobiol A-Chem 2002, 152,
233.
7. Yang, H.; Zhu, S.; Pan, N. J Appl Polym Sci 2004, 92, 3201.
8. Daoud, W. A.; Xin, J. H.; Zhang, Y. H. Surf Sci 2005, 599, 69.
9. Anpo, M.; Shima, T.; Kodama, S.; Kubokawa, Y. J Phys Chem
1987, 91, 4305.
10. Oppenläender, T. Photochemical Purification of Water and
Air; Wiley-VCH: Germany, 2003.
11. Kaneko, M.; Okura, I. Photocatalysis: Science and Technology;
Kodasha-Springer: Tokyo, 2002.
12. Rincón, A. G.; Pulgarin, C. Appl Catal B-Environ 2004, 49, 99.
13. Daoud, W. A.; Xin, J. H.; Zhang, Y. H.; Qi, K. H. J Non-Cryst
Solids 2005, 351, 1486.
Figure 15 Stain degradation of red wine after silicone 14. Daoud, W. A.; Xin, J. H. J Sol-Gel Sci Technol 2004, 29, 25.
modification and stability test (a) T80A, (b) T80B, (c) 15. Bozzi, A.; Yuranova, T.; Guasaquillo, I.; Laub, D.; Kiwi, J. J
X100A, and (d) X100S. [Color figure can be viewed in the Photochem Photobiol A-Chem 2005, 174, 156.
online issue, which is available at www.interscience. 16. Langlet, M.; Kim, A.; Audier, M.; Herrmann, J. M. J Sol-Gel
wiley.com.]. Sci Technol 2002, 25, 223.
17. Meilert, K. T.; Laub, D.; Kiwi, J. J Mol Catal A-Chem 2005,
237, 101.
18. Yuranova, T.; Mosteo, R.; Bandara, J.; Laub, D.; Kiwi, J. J Mol
self-cleaning ability toward both concentrated coffee Catal A-Chem 2006, 244, 160.
and red wine stains remained unchanged, its repro- 19. Bozzi, A.; Yuranova, T.; Kiwi, J. J Photochem Photobiol A-
ducibility after stability test was slightly impaired. Chem 2005, 172, 27.
20. Qi, K. H.; Daoud, W. A.; Xin, J. H.; Mak, C. L.; Tang, W. S.;
Moreover, the absorption rate of TiO2 sol by fibers Cheung, W. P. J Mater Chem 2006, 16, 4567.
was greatly increased with good photocatalytic self- 21. Daoud, W. A.; Leung, S. K.; Tung, W. S.; Xin, J. H.; Cheuk, K.;
cleaning activity by using different wetting agents. Qi, K. Chem Mater 2008, 20, 1242.
However, only TritonVX-100 modified TiO2-coated
R
22. Tung, W. S.; Daoud, W. A. J Colloid Interface Sci 2008, 326,
possesses good and reproducible photocatalytic ac- 283.
23. Tung, W. S.; Daoud, W. A. Acta Biomater 2009, 5, 50.
tivity. This study demonstrates that improving fibers 24. Kim, M. S.; Kang, T. J Textile Res J 2002, 72, 113.
wettability during TiO2 coating and the ability to 25. Simončič, B.; Rozman, V. Colloid Surf A 2007, 292, 236.
recover fibers mechanical properties following TiO2- 26. Alexeev, V. L.; Ilekti, P.; Persello, J.; Lambard, J.; Gulik, T.; Ca-
coating using a surface modification treatment with bane, B. Langmuir 1996, 12, 2392.

Journal of Applied Polymer Science DOI 10.1002/app