Journal of Sol-Gel Science and Technology 27, 43–52, 2003

c 2003 Kluwer Academic Publishers. Manufactured in The Netherlands.

Modified Silica Sol Coatings for Water-Repellent Textiles

B. MAHLTIG AND H. BÖTTCHER

Gesellschaft zur Förderung von Medizin-, Bio- und Umwelttechnologien e.V., GMBU, Postfach 520165,
D-01317 Dresden, Germany
dresden@gmbu.de

Received July 8, 2002; Accepted November 18, 2002

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.

Keywords: hydrophobicity, textiles, coating

1. Introduction recent years because of their high commercial and in-

The treatment of textiles with modified inorganic sols
opens numerous new possibilities for the improvement
of their applicative properties and for the functional-
ization of the fibre surface [1–8]. Some targets of the
actual research are shown in Fig. 1.
One of the topics is the realization of water-rellent
properties by coating with suitable sols. The equipment
of textiles with hydrophobic properties is of high inter-
est for textiles with water, oil or soil repellent proper-
ties, e.g. for special clothes, home textiles like carpets
or upholstered furniture and some out-door textiles. At
present the impregnation of textiles with fluorine con-
taining polymer dispersions or solutions is the most
applied technique. Now, the treatment with modified
inorganic sols could be an advantageous alternative.
Hydrophobic and water-repellent coatings on sol-gel
basis have been investigated for other purposes in the
dustrial importance [2, 9–12]. Because of the success of
hydrophobic sol-gel coatings for applications on differ-
ent types of materials, also such inorganic coatings on
organic materials like textile should be very promising.
Further, compared to commercially available organic
coating agents such inorganic, hydrophobic coatings
are expected to contain an increased stability at higher
temperature around 180◦ C [13]. Therefore, also new
applications for textiles with repellent properties used
under conditions of higher temperatures could be of-
fered by new inorganic silica coatings. The preparation
normally concerns a process which allows to enrich
alkyl- or perfluoroalkyl functional groups at the sur-
face. In contrast to the addition of simple alkyl groups,
the use of perfluorine alkyl groups leads beside of a
better hydrophobicity also to oleophobic abilities. To
attain hydrophobic and water repellent sol-gel coatings
usually hydrophobic additives were added to a metal
44 Mahltig and Böttcher
improved
abrasion
stability
dyeing
controlled release of
fragrant and repellent agents
Figure 1. Functionalization of textiles by coating with modified sols.
oxide sol. The most common experiments were re-
ported on the addition of the monomer perfluorooctyl-
triethoxysilane [14–20] but also the use of polymeric
fluorine compounds like nafion is reported in literature
[10, 21]. Main disadvantages of such fluoroalkyl com-
pounds are high expenses and a potential risk for human
health in case of skin contact and for the enviroment
in case of any emission of fluorine compounds during
and after the textile impregnation. Therefore, some pro-
ducers has stopped their production of water-repellent
clothes based on fluorine-containing compositions dur-
ing the last few years.
The aim of this study is to prepare water repel-
lent textiles via sol-gel coatings using non-fluorinated
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
examined:
– alkyltrialkoxysilanes with different alkyl chain
length,
– hydrophobic polysiloxane derivatives, and (for
comparison),
– a fluorinated compound.
These additives were added to a pure silica sol and a sec-
ond silica sol containing co-condensed crosslinkable
3-glycidoxypropyl triethoxysilane (GLYEO). Under
acidic conditions trialkoxy compounds perform at first
a hydrolysis to Si-OH groups and at second, a con-
densation with other Si-OH groups of the silica sol is
expected [22, 23]. GLYEO is a very common agent
used in sol-gel processes and is reported to perform
various reactions during the sol-gel process leading to
water and oil deceased
repelling inflammation
silica-sol coated UV protection
textiles
antimicrobial dermal and transdermal
properties properties
different functional groups in the sol like polyether,
ß-hydroxyether and diols [24–26]. Because of these
more hydrophilic groups a more hydrophilic sol-gel
coating could result and the addition of hydrophobic
additives to a hydrophilic sol can be investigated. Also
the reaction of GLYEO with functional groups on the
textile surface forming covalent bondings between the
inorganic coating and textile fibres was reported to en-
hance the wash fastness of sol-gel coatings on textiles
[5]. The resulting composite sols were dip-coated on
fabrics of polyamide and a polyester mixed with cotton.
To investigate those textile coatings under customary
conditions also the wash fastness of the coated textiles
was checked.
2. Experimental Section
2.1. Sample Preparation
Pure silica sol 1 was prepared via acidic hydrolysis
of tetraethoxysilane (TEOS) solved in a mixture
of ethanol and water. The hydrolysis was per-
formed via stirring of a mixture of 20 ml TEOS,
84 ml ethanol (96%) and 4 ml 0.01 N HCl for
24 hours at room temperature. The modified silica
sol 2 was prepared by stirring a mixture of 34 ml
TEOS, 50 ml ethanol (96%), 12 ml 0.01N HCl and
4 ml 3-glycidyloxypropyltriethoxysilane (GLYEO)
during 24 hours at room temperature. Both materials
TEOS and GLYEO were gained from Degussa-Hüls
(purity > 98%). After the preparation of both silica
sols the hydrophobic additives were added to the liq-
uid sol in concentrations from 0.1% up to 4 wt-% of
 Modified Silica Sol Coatings for Water-Repellent Textiles 45

Table 1. Composition of the investigated sols (the additive con- CH3

centration was varied in the range 0.1%–4.0 wt% in the basic sol).

Number Basic sol Additive

T1 [ Si O ]
O CH3 10 O
1 (From TEOS) —
2 (From TEOS/GLYEO) —
CH3
3 1 Methyltriethoxysilane C1
4 1 Iso-Butyltriethoxysilane C4 T2 [ Si O ]
O CH3 30 O
5 1 Octyltriethoxysilane C8
6 1 Hexadecyltrimethoxysilane C16
7 1 Phenyltriethoxysilane C6
CH3
3a 2 Methyltriethoxysilane C1
4a 2 Iso-Butyltriethoxysilane C4 T3 HO [CH2 ]
m
[ Si O ] [ CH2 ] OH
m
CH3 10
5a 2 Octyltriethoxysilane C8
6a 2 Hexadecyltrimethoxysilane C16
7a 2 Phenyltriethoxysilane C6
8 1 Polysiloxane T1 OC2H5
9 1 Polysiloxane T2 TF H5C2O Si CH2 CH2 (CF2 ) CF3
10 1 Polysiloxane T3 5
OC2H5
11 1 Triethoxytridecafluorooctylsilane
TF Figure 2. Schematical structures of the investigated polysiloxane
derivatives T1–T3 and of triethoxytridecafluorooctylsilane TF.

the sol. These mixtures of silica sol and hydrophobic

on textile substrates were performed 20 seconds after
additive were stirred for at least 30 minutes before
the water drop was placed on the textile substrate. On
the dip-coating process was performed. The types of
many textile samples containing a low water repellence
hydrophobic additives are listed in Table 1. The first
the water drop sink into the textile in short time less than
group of hydrophobic additives are alkyltrialkoxysi-
20 seconds, so in this case the contact angle was not
lanes (ABCR, Fluka) containing alkyl chains of 1 to
measurable.
16 C atoms or a phenyl group, respectively (Table 1).
The second group of additives consists of polysiloxane
2.2.2. Wash Fastness. Investigations on the leaching
derivatives T1–T3 (Degussa); the structures are shown
behaviour were performed at 40◦ C using a thermostatic
in Fig. 2. As fluorine containing additive triethoxytride-
dissolution tester PTWS3 (Pharma Test, Germany)
cafluorooctylsilane (TF) from Degussa-Hüls was used
equipped with a paddle stirrer. As washing solution an
(Fig. 2).
1% aqueous solution of sodium lauryl sulfate SDS with
Three types of substrates glass, polyamide (PA) and
pH 7 was used. After a leaching over 2 hours the tex-
a mixture of polyester and cotton (PES/CO) were dip-
tile samples were rinsed intensively with water, dried
coated (speed 30 cm/min) with the additive containing
at room temperature and afterwards again investigated
silica sols. After coating the samples were dried at room
using contact angle measurements. These first mea-
temperature for at least 2 hours and annealed during
surements are followed by a heating procedure. The
1 hour at 120◦ C.
once washed textiles were annealed at 120◦ C during
1 hour to simulate an iron procedure after washing and
2.2. Methods drying. Afterwards σw was determined again.

2.2.1. Contact Angle Measurements. For contact
angle measurements a commercial available device
Surftens (OEG GmbH, Germany) was used. The con-
tact angle on coated glass was determined with water
(σW ) and methylene iodide (σMI ). The measurements
2.2.3. Tests on Water Repellence Under Customary
Conditions. To investigate the water repellence under
customary conditions of the coated textiles two types
of tests were performed. First, the water uptake of the
textile under full contact with water was determined.
46 Mahltig and Böttcher

In this case, a textile sample of 10 cm × 10 cm was

placed in 300 ml destilled water for 1 minute. The wa-
ter uptake by the textile during placement under water
was determined using a balance. As second method to
investigate the water repellence under practical condi-
tions, the common “rain test” was used. For this, water
was sprayed against the coated textile surface under
controlled and specified conditions. The textile sample
(20 cm × 20 cm) was fixed in an angle of 45◦ under
a spray nozzle (distance 16 cm). Then 250 ml water
were sprayed on the textile during 30 seconds. The
uptake of water by the textile sample during this pro-
cedure was determined using a commercial balance.
The increase in weight caused by the uptaken water
was set in comparison to the unwetted textile sample.
To gain a comparison with commercially available hy-
drophobic textiles, materials from Acordis (Germany)
and Ploucquet (Germany) were investigated using the
same methods. The Acordis material contains a fluoro-
carbon coating on polyacryl textile, while the Ploucquet
fabric contains a fluorocarbon coating on polyester.

3. Results and Discussion

3.1. Contact Angle Measurements

Hydrophobic and water-repellent sol-gel coatings on

textiles were prepared by dip-coating of the silica sols
1 and 2 modified by three types of hydrophobic addi-
tives: alkyltrialkoxysilanes with alkyl chain lengths of
1, 4, 8 and 16 C-atoms, differently modified polysilox-
anes and a fluorine containing compound (Table 1 and
Fig. 2).
To evaluate the hydrophobic properties of such sol-
gel coatings first investigations were performed using
contact angle measurements on coated glass substrates.
The contact angle of water σW on a pure silica layer
from 1 on glass is 66◦ . The changements of σW by
addition of different alkyltrialkoxysilanes is shown in
Fig. 3 as function of the additive concentration in the
sol 1 and as function of the number of C-atoms in the
alkyl chain of the additives. Using the additives C1,
C4 and C6, no significant increase in the contact angle
can be observed even at high additive concentration.
Also, the addition up to a concentration of 1% octyl-
triethoxysilane C8 leads to no effect, but with further
increasing concentration σW increases up to values of
94◦ . Beside this, the addition of the long-chained C16
leads to high values of σW around 100◦ , even in case of
using small concentrations of the additive. Therefore
Figure 3. Contact angles of water σW after the coating procedure
based on silica sol 1 on glass substrates.
it can be stated that coatings with silica sols contain-
ing long-chained alkylsilane additives show increased
hydrophobic properties. The increasing hydrophobic-
ity as function of chainlength could be explained by
an increased shielding of the hydrophilic silica by the
larger alkylchains [27]. In comparison with the pure
silica sol 1 the GLYEO containing sol 2 contains an in-
creased hydrophilicity (σW 51◦ after coating of glass)
and a different behaviour after adding the hydrophobic
additives. The addition of the hydrophobic alkylsilane
additives to sol 2 leads to a significant increase in σW
with exception of the addition of C1 (Fig. 4). The be-
haviour in case of addition of C8 and C16 to sol 2 is
quite similar to the situation with sol 1, so hydrophobic
coatings on glass can be even prepared, if the used start-
ing silica sol contains more hydrophilic abilities. High
σW values on coatings containing C16 were observed
even at low additive concentration.
 Modified Silica Sol Coatings for Water-Repellent Textiles 47

140 A polyamide

σW [°] on glass and textile materials

120 polyester/cotton

100

glass
80

60

40

0 1 2 3 4

octyltriethoxysilane in silica sol 1 [wt-%]

σW [°] on glass and textile materials 140 B

polyamide
120

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-
sult that sufficient hydrophobic coatings are only
available by addition of C16 or added C8 at higher
concentrations. To produce water repellent textiles, the
contact angle measurements on coated glass substrates
are important for a first evaluation of the additives but
in a second step also the properties of coated textiles
have to be investigated.
Figure 5 represents σW on the coated textile sub-
strates polyamide and polyester/cotton in comparison
with σW measured on coated glass. Contact angle mea-
surements on textiles coated with the silica sols 1 and
2 without any further hydrophobic additives cannot be
performed because those coated textiles show less wa-
ter repellent properties, and a water drop placed on the
textile sinks completely into the textile during a few
seconds which is faster than the duration of the con-
tact angle measurement itself. Only small addition of
C8 to a coating based on sol 1 leads to textiles own-
ing water repellent properties and the measured σW on
those textile materials were determined to be between
112◦ up to 135◦ (Fig. 5). Those contact angles on tex-
tiles are quite higher compared to values measured on
glass and are also less influenced by the additive con-
centration. Such increasing of contact angles could be
easily explained by a rougher textile surface compared
to the smoother glass substrate [28]. In this case, high
contact angles on coated textiles for their own are only
a weak argument to evaluate water repellent proper-
ties of textiles. A different behaviour is observed after
coating of textiles based on sol 2 containing added C8
(Fig. 5). In this case, on polyamide textile PA only
smaller σW values between 108◦ and 124◦ could be
observed. On coated polyester/cotton textile PES/CO
substrates only after the use of the highest C8 concen-
tration a contact angle of 116◦ was measurable. The use
48 Mahltig and Böttcher

of lower C8 concentrations leads to less water repellent
textiles.
In contrast to the pure silica sol 1, the addition of the
epoxy compound GLYEO in 2 should result in more
hydrophilic coatings. This could be one reason for the
lower contact angles of modified 2 on PA compared
to similar coatings based on sol 1 on the same textile.
In case of PES/CO textiles, the textile substrates them-
selves contain higher hydrophilic properties caused by
the cotton. Compared to coatings on PA, coatings with
a higher hydrophobicity are necessary to gain water
repellent PES/CO textiles. Therefore this study is fo-
cused especially on the contact angle measurements on
coatings prepared from silica sols containing a higher
amount of hydrophobic additives (4 wt% of the additive
in the sol) (Table 2).
As shown in Fig. 6, in case of sol 1 the contact angles
on coated textile are significantly increased compared
to the ones measured on coated glass. Also an increase
of σW with increasing length of the alkyl group was
observed while the type of textile does not influence
σW significantly. The use of the silica sol 2 leads to
a stronger increase of σW on coated glass as function
of the alkyl length. In comparison to this, the increase
of σW on coated textile is less influenced by the size of
the alkyl group. Although with use of the additive C1
in sol 2 on PES/CO less water repellent properties can
be determined and σW was not measurable on this type
of coated textile.
In general, water repellent textiles should be more
suitable prepared by using silica sols based on the more
hydrophobic sol 1 instead of 2, so further experiments
with polysiloxane or fluorine containing additives were
performed with the sol 1. With addition of 4 wt%
polysiloxane additives T1, T2 and T3 to sol 1 coatings
on glass with high contact angles of water between 91◦
for T2 and 102◦ for T1 can be prepared. This values are
quite similar to the contact angles reached by addition
of C8 or C16. Also on textiles, water repellent prop-
erties can be reached by polysiloxane containing silica
sols (Table 2). A similar behaviour was observed with
the silica sol 1 modified with the fluorine containing
compound TF. In this case, σW on coated glass of 104◦
and on coated PES/CO of 138◦ was determined.
The contact angle of methylene iodide CH2 I2 on
coated glass indicates the oleophobic properties of the
sol-gel coatings. σMI on the unmodified coatings with
sol 1 and 2 on glass is 46◦ and 41◦ , respectively. With
such small values no oleophobic properties of the coat-
ing should be expected. After modification of the silica
sols with the most hydrophobic additives, values of σMI
were reached in the range of 38◦ to 53◦ which is quite
similar to the values determined for the silica coatings
without any further additive (Table 2). Only with use of

Table 2. Contact angles of sols coated on different materials (additive concentrations

of 4 wt% in the sol).

Sol Additive σW on glass σMI on glass σW on PA σW on PES/CO

1 — 66◦ 46◦ Not measurable Not measurable
2 — 51◦ 41◦ Not measurable Not measurable
3 C1 70◦ 46◦ 112◦ 121◦
4 C4 74◦ 48◦ 117◦ 123◦
5 C8 94◦ 43◦ 131◦ 135◦
6 C16 100◦ 53◦ 135◦ 142◦
7 C6 71◦ 43◦ 121◦ 120◦
3a C1 54◦ 38◦ 115◦ Not measurable
4a C4 66◦ 42◦ 109◦ 108◦
5a C8 98◦ 49◦ 124◦ 116◦
6a C16 101◦ 44◦ 130◦ 131◦
7a C6 72◦ 46◦ 96◦ 108◦
8 T1 102◦ 29◦ 122◦ 118◦
9 T2 91◦ 44◦ 122◦ 128◦
10 T3 99◦ 52◦ 126◦ 120◦
11 TF 104◦ 62◦ 128◦ 138◦
 Modified Silica Sol Coatings for Water-Repellent Textiles 49

160 alkylsilanes C8 and C16, the polysiloxane derivatives

polyester/cotton and the fluorine compound TF are suitable additives
σW [°] on glass and textile materials

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

the water uptake is significantly decreased to 17% in

140
120
100
80
60
40
0 2
Figure 6. Contact angle of water σW of sol 1 (above) and 2 (below)
with added. 4 wt% alkylsilanes of different number of C atoms after
coating on glass and textiles.
the polysiloxane additive T1 a significantly decreased
value of 29◦ was obtained and a significantly increased
value of 62◦ was observed in case of using the flu-
orine compound TF. Therefore the oleophobic prop-
erties of the investigated sol-gel coatings are mainly
not effected by addition of the investigated hydropho-
bic additives. Only in case of using the fluorine con-
taining compound TF a significantly increased σMI can
be reached, so in this case an increased oleophobicity
should be expected.
3.2. Water Repellent Properties
The contact angle measurements on coated glass and
textiles allows a first evaluation of hydrophobic coat-
ings to reach water repellent textiles. Altogether, the
polyester/cotton case of sol 6 and to 12% in case of sol 6a. Also textile
samples coated with sol 9 containing the polysiloxane
polyamide
T2 and with the fluorine containing sol 11 show low
values for water uptake of 30% and 27%, respectively.
glass To evaluate the water repellent properties under more
customary conditions like rain, a spray test was per-
formed on coated PES/CO material (Fig. 7). In case of
non coated PES/CO material, the uptake of water dur-
ing the spraying leads to a weight increase of the textile
of 99%. A simple coating with the silica sols 1 or 2 with-
4 6 8 10 12 14 16
out any further hydrophobic additive leads already to a
number of C-atoms significant reduction in water uptake and the increase in
weight is reduced to 18% in case of 2 and 20% in case
of sol 1. Further addition of alkyltrialkoxysilane addi-
tives in a concentration of 4 wt% leads to a decrease
in water uptake during spraying but only via addition
of C16 a significant decrease to a water uptake under
5% was reached. Similar values are also reached with
the polysiloxane T2 containing the highest polymerisa-
tion degree of the investigated polysiloxanes and with
the fluorine compound TF. Therefore for practical use
of water repellent textiles for rain protection clothes
coatings with the additives C16, T2 and TF are most
suitable. The also investigated commercially available
hydrophobic polyacryl material (Acordis) contains a
water uptake of 22% after placement under water and
1% after the spray test. These values are in the range of
the ones gained with C16 containing silica sol coatings.
In contrast to this the commercial polyester material
from Ploucquet shows no water uptake even after place-
ment under water or after spray test. Therefore with
hydrophobic silica coatings textiles with hydropho-
bic properties similar to some commercially available
50 Mahltig and Böttcher

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

number of sol-gel system

100

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

number of sol-gel system

Figure 7. Water uptake after placement under water (above) and after spray test (below) on coated polyester/cotton textile. The composition
of the investigated sols is presented in Table 1.

products can be prepared but there are also commercial
products with better properties.
3.3. Washing Fastness of Water Repellent Properties
For practical use of water repellent textiles also the
washing fastness of the hydrophobic properties have to
be investigated. These investigations were performed
on PES/CO materials coated with silica sols contain-
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
water repellent properties and σW in range of 127◦ to
131◦ were determined on the coated PES/CO. With
other coatings no contact angle measurements were
possible due to the less water repellence after wash-
ing. In case of using C16 no significant difference in
 Modified Silica Sol Coatings for Water-Repellent Textiles
wash fastness was determinable, whether silica sol 1
or sol 2 was used. Therefore, it can be concluded that
the wash fastness of hydrophobic properties depends
mainly on the type of hydrophobic additive than on the
type of used silica sol and the use of GLYEO as cou-
pling agent. Nevertheless, also coatings containing C8,
C16 and TF show decreased σW values after washing.
To simulate the ironing procedure after the washing,
the washed textile materials were annealed at 120◦ C
during 1 hour. This annealing improved the water re-
pellent properties of the washed textiles coated with
sols containing C8, C16, T1, T2 and TF in such a way
that contact angles quite similar to the values before
washing were determined. Such a bring back of hy-
drophobic properties via annealing of the once washed
textile is well known in literature [29]. In this case,
ironing is an appropriate method to preserve water re-
pellent properties of the coated textile but for common
use it is often claimed that the water repellent proper-
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
methods contact angle measurements, spray test and
washing test only silica sols modified with hexadecyl-
silane C16, the polysiloxane T2 and TF gives suitable
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-
tant against washing, if an annealing procedure follows
the washing. Therefore, especially long-chained alkyl-
trialkoxysilanes like hexadecyltrimethoxysilane could
be used to prepare water repellent textiles via sol-gel
coatings with properties quite similar to hydrophobic
fluorine containing sol-gel coatings.
4. Conclusions
This study concerns the preparation of water repellent
textiles via coating with various modified silica sols.
Different methods were used to evaluate the water re-
pellent properties of such coatings. First investigations
were performed by contact angle measurements on
coated glass and textiles. For investigations on more
customary conditions a spray test and a washing test
were performed. Hydrophobic properties of the coat-
ings were gained via addition of hydrophobic agents to
commercial available silica sols. In case of the alkyl-
silane additives suitable water repellent properties can
be only reached via addition of hexadecyltrimethoxysi-
lane while the use of additives containing a shorter
51
alkyl chainlength leads to insufficient water repellence.
The water repellence of sol-gel coating containing a
polysiloxane with a polymerisation degree of 30 is quite
similar to the one reached with hexadecyltrimethoxysi-
lane modified coatings. Nevertheless, the water repel-
lence of those polysiloxane containing sol-gel layers
show only sufficient washing fastness if an anneal-
ing procedure follows the washing. Also suitable wa-
ter repellent textiles with a sufficient washing fastness
could be prepared using fluorine containing silica sol
coatings.
Altogether the addition of hexadecyltrimethoxysi-
lane and triethoxytridecafluorooctylsilane to sol-gel
coatings offer the most suitable chance for prepara-
tion of water repellent textiles by sol-gel coatings. By
modification of silica sols with hexadecylsilane sol-gel
coatings could be prepared on textiles owning excel-
lent water repellent properties without any addition of
fluorine containing compounds.
Acknowledgments
For financial support we owe many thanks to the AiF
(Forschungsvorhaben: FKZ 16IN006—Keratex).
References
1. B. Mahltig and H. Böttcher, Melliand Textilber. 83, 251 (2002).
2. Y. Akamatsu, K. Makita, H. Inaba, and T. Minami, Thin Solid
Films 389, 138 (2001).
3. T. Textor, T. Bahners, and E. Schollmeyer, Melliand Textilber.
80, 847 (1999).
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).
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,
J. Biomed. Mater. Res. 55, 460 (2001).
8. T. Peltola, M. Jokinen, S. Veittola, J. Simola, and A. Yli-Urpo,
J. Biomed. Mater. Res. 54, 579 (2001).
9. S. Shibuichi, T. Yamamoto, T. Onda, and K. Tsujii, J. Colloid
Interf. Sci. 208, 287 (1998).
10. S.K. Young and K.A. Mauritz, J. Polym. Sci. B 39, 1282 (2001).
11. A.F. Thünemann, Polym. Int. 49, 636 (2000).
12. Y. Wu, H. Sugimura, Y. Inoue, and O. Takai, Chem. Vap.
Deposition 8, 47 (2002).
13. H.-J. Imminger, BWF-Textil (Germany), private communica-
tions.
14. K. Makita, Y. Akamatsu, S. Yamazaki, Y. Kai, and Y. Abe,
J. Ceram. Soc. Jpn. 105, 1093 (1997).
15. B.S. Hong, J.H. Han, S.T. Kim, Y.J. Cho, M.S. Park,
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
Films 389, 138 (2001).
17. H.-J. Jeong, D.-K. Kim, S.-B. Lee, S.-H. Kwon, and K. Kadono,
J. Colloid Interf. Sci. 235, 130 (2001).
18. H. Miyafuji and S. Saka, Materials Sci. Res. Int. 5, 270
(1999).
19. A. Nakjima, K. Abe, K. Hashimoto, and T. Watanabe, Thin Solid
Films, 376, 140 (2000).
20. J. Kron, G. Schottner, and K.-J. Deichmann, Thin Solid Films
392, 236 (2001).
21. Q. Deng, R.B. Moore, and K.A. Mauritz, J. Appl. Polym. Sci.
68, 747 (1998).
22. K. Izawa, T. Ogasawara, H. Masuda, H. Okabayashi, and
I. Noda, Macromolecules 35, 92 (2002).
23. M.W. Daniels, J. Sefcik, L.F. Francis, and A.V. McCormick,
J. Colloid Interface Sci. 219, 351 (1999).
24. G. Schottner, Chem. Mater. 13, 3422 (2001).
25. Z. Gao, Z. Zhao, Y. Ou, Z. Qi, and F. Wang, Polym. Int. 40, 187
(1996).
26. B. Riegel, W. Kiefer, S. Hofacker, and G. Schottner, J. Sol-Gel
Sci. Technol. 13, 385 (1998).
27. K. Grundke, S. Zschoche, K. Pöschel, T. Gietzelt, S. Michel,
P. Friedel, D. Jehnichen, and A.W. Neumann, Macromolecules
34, 6768 (2001).
28. S. Palzer, C. Hiebl, K. Sommer, and H. Lechner, Chem. Ing.
Tech 73, 1032 (2001).
29. W. Naßl, L. Schreiber, and F. Dirschl, Melliand Textilber. 83,
243 (2002).