Professional Documents
Culture Documents
Modified Silica Sol Coatings For Water-Repellent Textiles
Modified Silica Sol Coatings For Water-Repellent Textiles
c 2003 Kluwer Academic Publishers. Manufactured in The Netherlands.
Abstract. The preparation of water repellent textiles by coating with different modified silica sols has been
investigated. For this, pure and with 3-glycidoxypropyl triethoxysilane co-condensed silica sols were modified by
three types of additives: alkyltrialkoxysilanes, polysiloxane derivatives and a fluorine containing silane. Hydrophobic
properties of the coated fabrics of polyamide and of polyester mixed with cotton were determined using contact
angle measurements. The hydrophobicity increases with increasing concentration of the alkylsilane additive in the
silica sol and the length of the alkyl chain but with high additive concentrations plateau values in hydrophobicity
were reached. Analogously textile coatings with high hydrophobicity were gained using hydrophobic polysiloxane
or fluorine containing silicon compounds. The comparison of the different variants reveals that high wash-out
stabilities were reached only by silica sols containing fluorine compounds and hexadecylsilane additives. Therefore
long-chain alkyltrialkoxysilane compounds could be used as substitutes for fluorine compounds for the surface
modification of textiles in some practical applications.
oxide sol. The most common experiments were re- different functional groups in the sol like polyether,
ported on the addition of the monomer perfluorooctyl- ß-hydroxyether and diols [24–26]. Because of these
triethoxysilane [14–20] but also the use of polymeric more hydrophilic groups a more hydrophilic sol-gel
fluorine compounds like nafion is reported in literature coating could result and the addition of hydrophobic
[10, 21]. Main disadvantages of such fluoroalkyl com- additives to a hydrophilic sol can be investigated. Also
pounds are high expenses and a potential risk for human the reaction of GLYEO with functional groups on the
health in case of skin contact and for the enviroment textile surface forming covalent bondings between the
in case of any emission of fluorine compounds during inorganic coating and textile fibres was reported to en-
and after the textile impregnation. Therefore, some pro- hance the wash fastness of sol-gel coatings on textiles
ducers has stopped their production of water-repellent [5]. The resulting composite sols were dip-coated on
clothes based on fluorine-containing compositions dur- fabrics of polyamide and a polyester mixed with cotton.
ing the last few years. To investigate those textile coatings under customary
The aim of this study is to prepare water repel- conditions also the wash fastness of the coated textiles
lent textiles via sol-gel coatings using non-fluorinated was checked.
additives in order to attain a quite similar water re-
pellence like the use of fluorine compounds enables.
For this, three types of hydrophobic additives were 2. Experimental Section
examined:
2.1. Sample Preparation
– alkyltrialkoxysilanes with different alkyl chain
length, Pure silica sol 1 was prepared via acidic hydrolysis
– hydrophobic polysiloxane derivatives, and (for of tetraethoxysilane (TEOS) solved in a mixture
comparison), of ethanol and water. The hydrolysis was per-
– a fluorinated compound. formed via stirring of a mixture of 20 ml TEOS,
84 ml ethanol (96%) and 4 ml 0.01 N HCl for
These additives were added to a pure silica sol and a sec- 24 hours at room temperature. The modified silica
ond silica sol containing co-condensed crosslinkable sol 2 was prepared by stirring a mixture of 34 ml
3-glycidoxypropyl triethoxysilane (GLYEO). Under TEOS, 50 ml ethanol (96%), 12 ml 0.01N HCl and
acidic conditions trialkoxy compounds perform at first 4 ml 3-glycidyloxypropyltriethoxysilane (GLYEO)
a hydrolysis to Si-OH groups and at second, a con- during 24 hours at room temperature. Both materials
densation with other Si-OH groups of the silica sol is TEOS and GLYEO were gained from Degussa-Hüls
expected [22, 23]. GLYEO is a very common agent (purity > 98%). After the preparation of both silica
used in sol-gel processes and is reported to perform sols the hydrophobic additives were added to the liq-
various reactions during the sol-gel process leading to uid sol in concentrations from 0.1% up to 4 wt-% of
Modified Silica Sol Coatings for Water-Repellent Textiles 45
2.2.1. Contact Angle Measurements. For contact 2.2.3. Tests on Water Repellence Under Customary
angle measurements a commercial available device Conditions. To investigate the water repellence under
Surftens (OEG GmbH, Germany) was used. The con- customary conditions of the coated textiles two types
tact angle on coated glass was determined with water of tests were performed. First, the water uptake of the
(σW ) and methylene iodide (σMI ). The measurements textile under full contact with water was determined.
46 Mahltig and Böttcher
140 A polyamide
100
glass
80
60
40
0 1 2 3 4
polyester/cotton
100
glass
80
60
40
0 1 2 3 4
octyltriethoxysilane in silica sol 2 [wt-%]
Figure 4. Contact angles of water σW after the coating procedure Figure 5. Contact angle of water σW of sol 1 (above) and 2 (below)
based on silica sol 2 on glass substrates. with added octyltriethoxysilane after coating on glass and textiles.
In summary, this first evaluation leads to the re- C8 to a coating based on sol 1 leads to textiles own-
sult that sufficient hydrophobic coatings are only ing water repellent properties and the measured σW on
available by addition of C16 or added C8 at higher those textile materials were determined to be between
concentrations. To produce water repellent textiles, the 112◦ up to 135◦ (Fig. 5). Those contact angles on tex-
contact angle measurements on coated glass substrates tiles are quite higher compared to values measured on
are important for a first evaluation of the additives but glass and are also less influenced by the additive con-
in a second step also the properties of coated textiles centration. Such increasing of contact angles could be
have to be investigated. easily explained by a rougher textile surface compared
Figure 5 represents σW on the coated textile sub- to the smoother glass substrate [28]. In this case, high
strates polyamide and polyester/cotton in comparison contact angles on coated textiles for their own are only
with σW measured on coated glass. Contact angle mea- a weak argument to evaluate water repellent proper-
surements on textiles coated with the silica sols 1 and ties of textiles. A different behaviour is observed after
2 without any further hydrophobic additives cannot be coating of textiles based on sol 2 containing added C8
performed because those coated textiles show less wa- (Fig. 5). In this case, on polyamide textile PA only
ter repellent properties, and a water drop placed on the smaller σW values between 108◦ and 124◦ could be
textile sinks completely into the textile during a few observed. On coated polyester/cotton textile PES/CO
seconds which is faster than the duration of the con- substrates only after the use of the highest C8 concen-
tact angle measurement itself. Only small addition of tration a contact angle of 116◦ was measurable. The use
48 Mahltig and Böttcher
of lower C8 concentrations leads to less water repellent be determined and σW was not measurable on this type
textiles. of coated textile.
In contrast to the pure silica sol 1, the addition of the In general, water repellent textiles should be more
epoxy compound GLYEO in 2 should result in more suitable prepared by using silica sols based on the more
hydrophilic coatings. This could be one reason for the hydrophobic sol 1 instead of 2, so further experiments
lower contact angles of modified 2 on PA compared with polysiloxane or fluorine containing additives were
to similar coatings based on sol 1 on the same textile. performed with the sol 1. With addition of 4 wt%
In case of PES/CO textiles, the textile substrates them- polysiloxane additives T1, T2 and T3 to sol 1 coatings
selves contain higher hydrophilic properties caused by on glass with high contact angles of water between 91◦
the cotton. Compared to coatings on PA, coatings with for T2 and 102◦ for T1 can be prepared. This values are
a higher hydrophobicity are necessary to gain water quite similar to the contact angles reached by addition
repellent PES/CO textiles. Therefore this study is fo- of C8 or C16. Also on textiles, water repellent prop-
cused especially on the contact angle measurements on erties can be reached by polysiloxane containing silica
coatings prepared from silica sols containing a higher sols (Table 2). A similar behaviour was observed with
amount of hydrophobic additives (4 wt% of the additive the silica sol 1 modified with the fluorine containing
in the sol) (Table 2). compound TF. In this case, σW on coated glass of 104◦
As shown in Fig. 6, in case of sol 1 the contact angles and on coated PES/CO of 138◦ was determined.
on coated textile are significantly increased compared The contact angle of methylene iodide CH2 I2 on
to the ones measured on coated glass. Also an increase coated glass indicates the oleophobic properties of the
of σW with increasing length of the alkyl group was sol-gel coatings. σMI on the unmodified coatings with
observed while the type of textile does not influence sol 1 and 2 on glass is 46◦ and 41◦ , respectively. With
σW significantly. The use of the silica sol 2 leads to such small values no oleophobic properties of the coat-
a stronger increase of σW on coated glass as function ing should be expected. After modification of the silica
of the alkyl length. In comparison to this, the increase sols with the most hydrophobic additives, values of σMI
of σW on coated textile is less influenced by the size of were reached in the range of 38◦ to 53◦ which is quite
the alkyl group. Although with use of the additive C1 similar to the values determined for the silica coatings
in sol 2 on PES/CO less water repellent properties can without any further additive (Table 2). Only with use of
140
to prepare water repellent textiles via a sol-gel coat-
polyamide ing. To investigate those water repellent textiles under
120
conditions of common use, washing tests and the de-
100
termination of water uptake under different conditions
glass were performed on the coated textiles.
80 The tests of water uptake were performed on coated
PES/CO and the increase of weight of the textile ma-
60 terial after water treatment is given in Fig 7. The ad-
ditive concentration was set to 4 wt% in the sol. After
40 placement under water the uncoated PES/CO material
obtains an increase in weight of 157%. A simple sol-gel
0 2 4 6 8 10 12 14 16
number of C-atoms
coating using the silica sols 1 and 2 leads to a reduced
water uptake of 109% and 92%, respectively. With in-
160
creasing alkyl chain length of the additive up to C16
σ W [°] on glass and textile materials
160
140
increase of weight [%]
120
100
80
60
40
20
0
1 2 3 4 5 6 7 3a 4a 5a 6a 7a 8 9 10 11 without
sol
90
80
increase of weight [%]
70
60
50
40
30
20
10
0
1 2 3 4 5 6 7 3a 4a 5a 6a 7a 8 9 10 11 without
sol
products can be prepared but there are also commercial on PES/CO materials coated with silica sols contain-
products with better properties. ing 4 wt% of hydrophobic additive. After leaching with
SDS solution at 40◦ C and drying at room temperature
only coatings containing C8, C16 and TF contain still
3.3. Washing Fastness of Water Repellent Properties water repellent properties and σW in range of 127◦ to
131◦ were determined on the coated PES/CO. With
For practical use of water repellent textiles also the other coatings no contact angle measurements were
washing fastness of the hydrophobic properties have to possible due to the less water repellence after wash-
be investigated. These investigations were performed ing. In case of using C16 no significant difference in
Modified Silica Sol Coatings for Water-Repellent Textiles 51
wash fastness was determinable, whether silica sol 1 alkyl chainlength leads to insufficient water repellence.
or sol 2 was used. Therefore, it can be concluded that The water repellence of sol-gel coating containing a
the wash fastness of hydrophobic properties depends polysiloxane with a polymerisation degree of 30 is quite
mainly on the type of hydrophobic additive than on the similar to the one reached with hexadecyltrimethoxysi-
type of used silica sol and the use of GLYEO as cou- lane modified coatings. Nevertheless, the water repel-
pling agent. Nevertheless, also coatings containing C8, lence of those polysiloxane containing sol-gel layers
C16 and TF show decreased σW values after washing. show only sufficient washing fastness if an anneal-
To simulate the ironing procedure after the washing, ing procedure follows the washing. Also suitable wa-
the washed textile materials were annealed at 120◦ C ter repellent textiles with a sufficient washing fastness
during 1 hour. This annealing improved the water re- could be prepared using fluorine containing silica sol
pellent properties of the washed textiles coated with coatings.
sols containing C8, C16, T1, T2 and TF in such a way Altogether the addition of hexadecyltrimethoxysi-
that contact angles quite similar to the values before lane and triethoxytridecafluorooctylsilane to sol-gel
washing were determined. Such a bring back of hy- coatings offer the most suitable chance for prepara-
drophobic properties via annealing of the once washed tion of water repellent textiles by sol-gel coatings. By
textile is well known in literature [29]. In this case, modification of silica sols with hexadecylsilane sol-gel
ironing is an appropriate method to preserve water re- coatings could be prepared on textiles owning excel-
pellent properties of the coated textile but for common lent water repellent properties without any addition of
use it is often claimed that the water repellent proper- fluorine containing compounds.
ties should be own high wash fastness without any fol-
lowing annealing. Therefore after complete evaluation
of the coated water repellent textiles using the three Acknowledgments
methods contact angle measurements, spray test and
washing test only silica sols modified with hexadecyl- For financial support we owe many thanks to the AiF
silane C16, the polysiloxane T2 and TF gives suitable (Forschungsvorhaben: FKZ 16IN006—Keratex).
results for customary use. The polysiloxane additive
T2 leads to quite good results in the spray test but the
water repellent abilities of those coatings are only resis- References
tant against washing, if an annealing procedure follows
the washing. Therefore, especially long-chained alkyl- 1. B. Mahltig and H. Böttcher, Melliand Textilber. 83, 251 (2002).
trialkoxysilanes like hexadecyltrimethoxysilane could 2. Y. Akamatsu, K. Makita, H. Inaba, and T. Minami, Thin Solid
Films 389, 138 (2001).
be used to prepare water repellent textiles via sol-gel 3. T. Textor, T. Bahners, and E. Schollmeyer, Melliand Textilber.
coatings with properties quite similar to hydrophobic 80, 847 (1999).
fluorine containing sol-gel coatings. 4. D. Knittel, T. Bahners, and E. Schollmeyer, Nachrichten aus der
Chemie 49, 1405 (2001).
5. J. Trepte and H. Böttcher, J. Sol-Gel Sci. Techn. 19, 691 (2000).
4. Conclusions 6. R.Z. Domingues, A.E. Clark, and A.B. Brennan, J. Biomed.
Mater. Res. 55, 468 (2001).
7. R.L. Oréfice, L.L. Hench, A.E. Clark, and A.B. Brennan,
This study concerns the preparation of water repellent J. Biomed. Mater. Res. 55, 460 (2001).
textiles via coating with various modified silica sols. 8. T. Peltola, M. Jokinen, S. Veittola, J. Simola, and A. Yli-Urpo,
Different methods were used to evaluate the water re- J. Biomed. Mater. Res. 54, 579 (2001).
pellent properties of such coatings. First investigations 9. S. Shibuichi, T. Yamamoto, T. Onda, and K. Tsujii, J. Colloid
were performed by contact angle measurements on Interf. Sci. 208, 287 (1998).
10. S.K. Young and K.A. Mauritz, J. Polym. Sci. B 39, 1282 (2001).
coated glass and textiles. For investigations on more 11. A.F. Thünemann, Polym. Int. 49, 636 (2000).
customary conditions a spray test and a washing test 12. Y. Wu, H. Sugimura, Y. Inoue, and O. Takai, Chem. Vap.
were performed. Hydrophobic properties of the coat- Deposition 8, 47 (2002).
ings were gained via addition of hydrophobic agents to 13. H.-J. Imminger, BWF-Textil (Germany), private communica-
commercial available silica sols. In case of the alkyl- tions.
14. K. Makita, Y. Akamatsu, S. Yamazaki, Y. Kai, and Y. Abe,
silane additives suitable water repellent properties can J. Ceram. Soc. Jpn. 105, 1093 (1997).
be only reached via addition of hexadecyltrimethoxysi- 15. B.S. Hong, J.H. Han, S.T. Kim, Y.J. Cho, M.S. Park,
lane while the use of additives containing a shorter T. Dolukhanyan, and C. Sung, Thin Solid Films 351, 274 (1999).
52 Mahltig and Böttcher
16. Y. Akamatsu, K. Makita, H. Inaba, and T. Minami, Thin Solid 23. M.W. Daniels, J. Sefcik, L.F. Francis, and A.V. McCormick,
Films 389, 138 (2001). J. Colloid Interface Sci. 219, 351 (1999).
17. H.-J. Jeong, D.-K. Kim, S.-B. Lee, S.-H. Kwon, and K. Kadono, 24. G. Schottner, Chem. Mater. 13, 3422 (2001).
J. Colloid Interf. Sci. 235, 130 (2001). 25. Z. Gao, Z. Zhao, Y. Ou, Z. Qi, and F. Wang, Polym. Int. 40, 187
18. H. Miyafuji and S. Saka, Materials Sci. Res. Int. 5, 270 (1996).
(1999). 26. B. Riegel, W. Kiefer, S. Hofacker, and G. Schottner, J. Sol-Gel
19. A. Nakjima, K. Abe, K. Hashimoto, and T. Watanabe, Thin Solid Sci. Technol. 13, 385 (1998).
Films, 376, 140 (2000). 27. K. Grundke, S. Zschoche, K. Pöschel, T. Gietzelt, S. Michel,
20. J. Kron, G. Schottner, and K.-J. Deichmann, Thin Solid Films P. Friedel, D. Jehnichen, and A.W. Neumann, Macromolecules
392, 236 (2001). 34, 6768 (2001).
21. Q. Deng, R.B. Moore, and K.A. Mauritz, J. Appl. Polym. Sci. 28. S. Palzer, C. Hiebl, K. Sommer, and H. Lechner, Chem. Ing.
68, 747 (1998). Tech 73, 1032 (2001).
22. K. Izawa, T. Ogasawara, H. Masuda, H. Okabayashi, and 29. W. Naßl, L. Schreiber, and F. Dirschl, Melliand Textilber. 83,
I. Noda, Macromolecules 35, 92 (2002). 243 (2002).