IOSR Journal of Polymer and Textile Engineering (IOSR-JPTE)

e-ISSN: 2348-019X, p-ISSN: 2348-0181, Volume 3, Issue 2 (Mar. - Apr. 2016), PP 19-25
www.iosrjournals.org

One Bath Dyeing and Water Repellent Finishing Of Textile by

Sol-Gel Technique
Dr. Ravindra Kale1, Arunabh Agnihotri2, Priyanka Jagtap3, Mrs. Alka Ali4
1,2,3
(Department of Fibres and Textile Processing Technology, Institute of Chemical Technology, India)
4
(Department of Textile Chemistry, Uttar Pradesh Textile Technology Institute, India)

Abstract: Using sol–gel process, functional silica coatings can be deposited on textile materials which lead to
new textile properties and applications. In the present study combined dyeing and water repellent finish was
applied on cotton and polyester/cotton blend fabrics. Both the fabric samples were dyed with cheap basic dyes
by adding glycidoxypropyltrimethoxysilane as cross-linking agent. Hydrophobicity was imparted using long-
chained alkyltrialkoxysilanes like octyltriethoxysilane as water repellent agent which has properties quite
similar to hydrophobic fluorine-containing sol-gel coatings. The combined effect was obtained at the cost of
impairment in fastness properties of the dye and substantial decrease in tearing strength. There was marginal
decrease in both tensile strength and percentage of elongation of the fabrics.
Keywords: Basic Dyes, Nanotechnology, Silanes, Sol-gel coating, Water repellency

I. Introduction
Sol-gel process has had a history of more than 100 years as one of the modification and preparation
methods of materials since it was invented. Due to the resulting properties of high chemical homogeneity,
purity, lower processing temperature, easy shaping, and modification [1] sol-gel process has widely been
applied in areas such as ceramics, pharmacy, orthopedics, and it has been applied in functional finishing of
textiles in the last decade.
According to its purpose, silica gel can be divided into two categories. First, the functional gels
making the treated textiles obtain desired functions, such as anti-abrasion [2], wrinkle resistance [3], water or oil
repellence [4,5,6], antistatic [7], UV shielding [8,9], etc. Second the gels used as carriers to immobilize and/or
control functional ingredients, such as improving color fastness of dyed Textiles [10,11], preparing bioactive
textiles [12], flavor-releasing textiles [13] etc.
Using this process, functional silica coatings can be deposited on textile materials and can lead to
new textile properties and application [11, 6]. Also, dyes can be embedded into sol–gel coatings and deposited
on several types of materials leading to new possible application, e.g. optical devices or sensors [14, 15].
Mahltig & Böttcher [6] has reported a water repellent textile by coating with different modified silica
sols. For this, pure and with 3-glycidoxypropyltriethoxysilane co-condensed silica sols were modified by three
types of additives: alkyltrialkoxysilanes, polysiloxane derivatives and a fluorine-containing silane. Different
methods were used to evaluate the water repellent 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 coatings were gained
via addition of hydrophobic agents to commercial available silica sols. In case of the alkylsilane additives,
suitable water repellent properties can be only reached via addition of hexadecyltrimethoxysilane while the use
of additives containing a shorter alkyl chain length leads to insufficient water repellence [6].
The water repellence of sol-gel coating containing a polysiloxane with a polymerisation degree of
30 is quite similar to the one reached with hexadecyltrimethoxysilane modified coatings. Nevertheless, the water
repellence of those polysiloxane containing sol-gel layers show only sufficient washing fastness if an annealing
procedure follows the washing. Also suitable water repellent textiles with a sufficient washing fastness could be
prepared using fluorine-containing silica sol coatings. Altogether the addition of hexadecyltrimethoxysilane and
triethoxytridecafluorooctylsilane to sol-gel coatings offer the most suitable chance for preparation of water
repellent textiles by sol-gel coatings. By modification of silica sols with hexadecylsilane sol-gel coatings could
be prepared on textiles owning excellent water repellent properties without any addition of fluorine-containing
compounds [6].
Mahltig et al. reported hydrophobic silica sol coatings on textiles with respect to the influence of the
solvents and the concentration of the sol. For this purpose, two silica sols, prepared with the hydrophobic
additives octyltriethoxysilane and perfluoroctyltriethoxysilane, were diluted by different solvents: water, ethanol
and acetone. In case of using pure water for dilution, the hydrophobicity of coated textiles decreases drastically
with increasing dilution of the applied sol. For coatings on polyester fabrics or mixed fabrics made from
polyester and cotton, the use of the organic solvents ethanol or acetone leads to significant hydrophobicity even

DOI: 10.9790/019X-03021925 www.iosrjournals.org 19 | Page

 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

in case of strong dilution down to a sol concentration <1%. The hydrophobic effect of coated polyamide textile
is less. The use of a combination of water with less inflammable organic solvents such as di (propylene glycol)
n-propylether in hydrophobic silica sols yields textile coatings with good hydrophobicity, even in case of low
sol concentration [16].
In this research work, attempt has been made to incorporate basic dyes and water repellent compound
in the sol-gel coating of cotton and polyester/cotton blend.

II. Experimental
Ready for dyeing plain weave cotton (110 g/m2, 17 picks/cm, 12 ends/cm) woven fabric was obtained
from Tata Mill, Mumbai. Plain weave polyester/cotton (P/C) (160 g/m2) fabric was obtained from Piyush
Syndicate, Mumbai. Tetraethylorthosilicate (TEOS) was obtained Evonik Degussa Pvt. Ltd. Mumbai.
Glycidoxypropyltrimethoxysilane (GPTMS) and Octyltri ethoxysilane (OTES) were obtained from Dow
Corning India Pvt. Ltd. Mumbai. Sodium Lauryl Sulphate was obtained from S.d Fine Pvt. Ltd. Mumbai.
Ethanol (98% pure) and Hydrochloride acid (HCl) used were of laboratory reagent grade. Coracryl Violet C3R
was obtained from Colourtex Pvt. Ltd. Surat, Gujarat.

1.1 Preparation of sols

Sols were prepared by taking 50 ml ethanol, 34.20 ml TEOS, 3.8 ml GPTMS and 12 ml 0.01N HCl in a
beaker. Modification of the silica sols were performed by substitution of TEOS by OTES in various proportions
to make total volume 100ml. The mixture was stirred with magnetic stirrer for 24 hours at room temperature by
covering the beaker with polyethylene sheet.

2.2 Application of Sol on fabrics

Coracryl Violet C3R dye (10 gpl) was added to this sol just prior to padding and then the fabrics were
padded through this sol using 2 dip 2 nip method for 70% expression for cotton and 60% for P/C. The samples
were then dried in air and cured in oven at 120 0C for 1 hour. It was then soaped at 40 0C for 2 hours by 10 gpl
Sodium Lauryl Sulphate at neutral pH. The sample was then rinsed with water and air dried.

2.3 Color value by reflectance method

The samples were evaluated for colour depth in terms of Kubelka Munk function (K/S) using computer
Color Matching System (SpectraScan 5100+) of Premier Colorscan Instruments Pvt. Ltd. Mumbai.
Kubelka Munk (K/S) function is given by:
K (1- R)2
=
S 2R (1)
. Where,
"R" is the reflectance at complete opacity,
"K" is the absorption coefficient,
"S" is the scattering coefficient

2.4 Fastness testing of dyed fabric

For washing fastness, light fastness and rubbing fastness, ISO 105 C10, ISO 105-A02 and ISO 105 X-
12 test methods were used respectively.

2.5 Tests for Water Repellency

2.5.1 Contact angle measurements
The contact angles were measured using a drop shape analysis apparatus of DSA100, Kruss Company,
Germany. The measurements were performed 20 seconds after the water drop was placed on the textile
substrate. Contact angle was measured at five different spots on the fabric and reported value is the average of
these five readings.

2.5.2 Spray Rating (Rain Test)

The resistance of fabrics to the penetration of water by impact is measured by AATCC 35-2006 test method.

2.5.3 Water uptake test

In this test, fabric sample of 10 ×10 cm was placed in 300 ml distilled water for 1 minute. The water uptake by
the textile during placement under water was determined using a balance [6].

2.6 Scanning electron microscopy

Surface morphology of the fabrics was characterized using SEM of JEOL JSM 6380LA, JEOL ltd. Japan.
DOI: 10.9790/019X-03021925 www.iosrjournals.org 20 | Page
 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

2.7 Physical Characteristics of the sol-gel applied fabric

For tensile strength & percentage of elongation ASTM D 5034-95 method was used whereas for tearing strength
and stiffness, ASTM D1424-96R04 and ASTM D1388-08(2012) test methods were used respectively.

III. Results And Discussion

3.1 Dyeing Property of the fabrics
Fig 1 shows the plot of Color strength of the fabric samples dyed by Coracryl Violet C3R for Cotton
and P/C respectively. It can be seen that addition of OTES results in marginal increase in the color strength. The
reason for this behavior is that the dye gets immobilized inside the 3D network created by sol-gel network.
TABLE 1 shows the fastness data of cotton and P/C blend samples. We can observe that the wash and
light fastness gets impaired but rubbing gets affected marginally in presence of OTES. The wash fastness of the
fabric gets affected because the dye gets hydrolyzed in alkaline medium as isoelectric point of silica coating is
between pHIEP 1.5 to 4.5 [17]. The reason of poor light fastness is that the cationic dyes are inherently sensitive
to the light energy. Since sol-gel being a coating, the rubbing fastness is not expected to be of excellent quality.
However, one of the most important factors that influence fastness is the electrical net charge of the dye. It is
known that silica sol coatings have an isoelectric point around pH 4, so at neutral pH they are negatively
charged. For this reason positively charged dyes can interact with the surrounding silica matrix. Therefore their
fastness is better than that of uncharged or negatively charged dyestuffs. Hence basic dyes are more suitable for
incorporating into silica sols.

3.2 Water Repellent property of fabrics

The values of contact angles and spray ratings for addition of increasing concentrations of OTES on
cotton and P/C samples are shown in TABLE 2 and Fig 2 and 3.
It was found that only for TEOS/GPTMS coated samples shows water absorbency as when we put a
water drop on it, the drop sunk immediately. But with increase in concentration of OTES in the silane mixture
the contact angle goes on increasing reaching up to 137 0 for 40% replacement of TEOS with OTES. Also from
the spray rating values we can conclude that water absorbent cotton fabric has become water repellent. We can
observe similar trend for P/C blend samples as well. However the hydrophobicity is more pronounced for cotton
than P/C blend due to more effective bonding of silanes to the easily available hydroxyl groups of cotton fabric.
The results obtained from gain in weight of cotton samples are shown in TABLE 3. We can see that
for both the samples as the amount of OTES goes on increasing on the fabric sample the water absorbing
tendency of the fabric goes on decreasing.
It can be concluded that coatings with silica sols containing long-chained alkylsilane additives show
increased hydrophobic properties. The increasing hydrophobicity could be explained by an increased shielding
of the hydrophilic silica by the larger hydrophobic alkyl chains of OTES. The presence of coating can be further
corroborated by the SEM photographs of the samples as shown in Fig 4 and 5.
TABLE 4 and 5 shows the results obtained for tensile strength testing of cotton and P/C fabrics coated
with Sol-gel containing OTES compound.
It is observed that for untreated cotton and P/C samples the tensile strength was high which got reduced
when treated with TEOS and GPTMS but after addition of OTES it went on increasing with increase in
concentrations of OTES for both in warp and weft direction whereas the percentage of elongation for control
samples it was low and then got increased when only TEOS and GPTMS was applied but again started
decreasing with the addition of OTES. However this change in tensile strength and percentage of elongation was
marginal in nature. This is happening because all the silane samples cross-link with the hydroxyl groups of
cotton fabrics making it stiffer. This fact is supported by increase in bending length of the samples.
We also studied the tearing strength of sol-gel coated samples and found that the tearing strength got
substantially reduced for silane treated samples. These changes in mechanical properties can be attributed to the
thick gel film formation on the fiber surface and the adhesion of net-like gel between fibers, which can be
obviously observed from SEM in Fig 4 and 5.
Thus it is possible to simultaneously dye and give water repellent and stiff finish to the cotton and P/C
blend by sol-gel technique.

IV. Conclusion
Cotton and P/C blend can be dyed with cheap basic dyes using sol-gel method by adding GPTMS as
cross-linking agent. Long-chained alkyltrialkoxysilanes like OTES could be used to prepare water repellent
textiles via sol-gel coatings with properties quite similar to hydrophobic fluorine-containing sol-gel coatings.
Simultaneous dyeing and water repellent finishing is possible by this sol-gel technique. The combined effect is
obtained at the cost of impairment in fastness properties of the dye. There is a marginal decrease in both tensile

DOI: 10.9790/019X-03021925 www.iosrjournals.org 21 | Page

 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

strength and percentage of elongation of the fabrics for the lower concentration of the OTES which finally came
at par with the control sample.

References
[1]. J. Zarzycki, Past and present of sol-gel science and technology, Journal of Sol-Gel Science and Technology, 10, 1997, 17–22.
[2]. M. Lee & N. Jo, Coating of methyltriethoxysilane-modified colloidal silica on polymer substrates for abrasion resistance, Journal of
Sol-Gel Science and Technology, 24, 2002, 175 -180.
[3]. C. Schramm, W. Binder & I. Tessadr, Durable press finishing of cotton fabric with 1,2,3,4-butanetetracarboxylic acid and
TEOS/GPTMS, Journal of Sol-Gel Science and Technology, 29, 2004, 155–165.
[4]. W. Daoud, J. Xin, & X. Tao. Super-hydrophobic silica nanocomposite coating by a low-temperature process, Journal of American
Ceramic Society, 87, 2004, 782–1784.
[5]. B. Mahltig, D. Fiedler, & P. Simon, Silver containing sol-gel coatings on textiles: Antimicrobial effect as function of curing
treatment, The Journal of the Textile Institute, 102, 2002, 739–745.
[6]. [6] B. Mathltig, & H. Böttcher, Modified silica sol coatings for water-repellent textiles, Journal of Sol-Gel Science and Technology,
27, 2003, 43–52.
[7]. P. Xu, W. Wang, & S. Chen, Application of nanosol on the antistatic property of polyester, Melliand International, 11, 2005, 56–
59.
[8]. J. Xin, W. Daoud, & Y. Kong, A new approach to UV-blocking treatment for cotton fabrics, Textile Research Journal, 74, 2004,
97–100.
[9]. Y. Xing, & X. Ding, UV photo-stabilization of tetrabutyltitanate for aramid fibers via sol-gel surface modification, Journal of
Applied Polymer Science, 103, 2007, 3113–3119.
[10]. J. Du, L. Zhan, & S. Chen, Wash fastness of dyed fabric treated by the sol-gel process, Coloration Technology, 121, 2005, 29–36.
[11]. B. Mahltig & T. Textor, Combination of silica sol and dyes on textiles, Journal of Sol-Gel Science and Technology, 39, 2006, 111–
118.
[12]. Karout, C. Chopar & A. Pierre, Nanostructures for enzyme stabilization, Journal of Molecular Catalysis B: Enzymatic, 44, 2007,
117–126.
[13]. S. Veith, M. Perren & S. Pratsinis, Encapsulation and retention of decanoic acid in sol-gel-made silicas, Journal of Colloid and
Interface Science, 283, 2005, 495– 502.
[14]. D. Avnir D, Organic Chemistry within Ceramic Matrices: Doped Sol-Gel Materials, Accounts of Chemical Research, 28, 1995,
328–334.
[15]. M. Noire, C. Bouzon, L. Couston, J. Gontier, P. Marty & D. Pouyat D, Optical Sensing of high acidity using a sol-gel entrapped
indicator, Sensors and Actuators B-Chem, 51, 1998, 214-219.
[16]. B. Mahltig, F. Audenaert & H. Böttcher, Hydrophobic Silica Sol Coatings on Textiles—the Influence of Solvent and Sol
Concentration, Journal of Sol-Gel Science and Technology. 34, 2005, 103–109.
[17]. C. Brinker & G. Scherer, Sol–Gel Science: The Physics and Chemistry of Sol-gel-Processing, Academic Press Inc., Boston, 1990.

TABLES
Table 1: Fastness properties for dyed and finished Cotton and P/C fabric for different
TEOS/GPTMS/OTES ratio
TEOS/GPTMS/OTES Cotton P/C
Ratio Rubbing Wash Fastness Light Rubbing Wash Fastness Light Fastness
Fastness Fastness Fastness
Dry Wet Staining Colour Dry Wet Staining Colour
Change Change
90/10/0 (Control) 4-5 4 4-5 2 3-4 3-4 4 2 2 3-4
87.5/10/2.5 3 3-4 1-2 2-3 3-4 3 3-4 1-2 2-3 3-4
85/10/5 3 3-4 1-2 2-3 3-4 3 3-4 1-2 2-3 3-4
80/10/10 3 3-4 1-2 2-3 3 3 3-4 1-2 2-3 3
70/10/20 3 3-4 1-2 2-3 3 3 3-4 1-2 2-3 3
60/10/30 3 3-4 1-2 2-3 3 3 3-4 1-2 2-3 3
50/10/40 3 3-4 1-2 2-3 3 3 3-4 1-2 2-3 3

Table 2: Contact angle and Spray test rating for dyed and finished, cotton and P/C fabric for different
TEOS/GPTMS/OTES ratio.
TEOS/GPTMS/OTES Ratio Cotton P/C
Contact Angle(0) Spray Rating Contact Angle(0) Spray Rating
90/10/0 (Control) - 0 - 0
87.5/10/2.5 100 50 90 60
85/10/5 103 55 95 75
80/10/10 110 60 98 80
70/10/20 125 65 100 85
60/10/30 130 70 101 90
50/10/40 137 70 103 90

DOI: 10.9790/019X-03021925 www.iosrjournals.org 22 | Page

 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

Table 3: Water Uptake for dyed and finished, cotton and P/C fabric for different TEOS/GPTMS/OTES
ratio
TEOS/GPTMS/OTES Ratio Gain in Weight (%)
Cotton P/C
90/10/0 (Control) 61 42
87.5/10/2.5 19 25
85/10/5 15 18
80/10/10 13 12
70/10/20 11 10
60/10/30 9 9
50/10/40 5 8

Table 4: Mechanical properties of dyed and finished cotton fabric for different TEOS/GPTMS/OTES
ratio
TEOS/GPTMS/OTES Ratio Cotton
Tensile Strength (kgf) Elongation (%) Tearing Strength(kgf) Bending Length
Warp Weft Warp Weft Warp Weft (cm)
Untreated 63.90 33.36 11.46 17.07 1.22 1.41 2.41
90/10/0 (Control) 57.70 30.55 14.21 19.03 0.68 0.74 2.81
87.5/10/2.5 57.93 31.27 14.02 19.00 0.59 0.58 3.39
85/10/5 58.30 31.87 13.87 18.76 0.57 0.52 3.80
80/10/10 58.97 32.26 13.43 18.32 0.55 0.50 3.89
70/10/20 60.32 33.42 12.21 17.49 0.48 0.48 3.95
60/10/30 61.56 34.65 11.87 17.12 0.45 0.47 4.03
50/10/40 63.95 34.85 11.21 17.05 0.43 0.45 4.15

Table 5: Mechanical properties of dyed and finished P/C fabric for different TEOS/GPTMS/OTES ratio
TEOS/GPTMS/OTES Polyester/Cotton
Ratio Tensile Strength (kgf) Elongation (%) Bending Length (cm)
Warp Weft Warp Weft
Untreated 137.7 63.30 51.7 31.5 1.53
90/10/0 (Control) 117.8 52.80 55.24 36.47 1.03
87.5/10/2.5 120.2 53.40 54.23 35.78 1.29
85/10/5 126.3 54.30 53.04 34.84 1.38
80/10/10 130.6 55.32 52.54 33.19 1.48
70/10/20 134.3 57.45 51.39 32.39 1.53
50/10/40 135.3 59.30 51.49 31.32 1.57

FIGURES

Figure 1: Plot of Color Strength (K/S) for dyed and finished cotton and P/C fabric for different
TEOS/GPTMS/OTES ratio

DOI: 10.9790/019X-03021925 www.iosrjournals.org 23 | Page

 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

Figure 2: Contact angles for dyed and finished cottondfabric for different TEOS/GPTMS/OTES ratio
a: 87.5/10/2.5 b: 85/10/5 c: 80/10/10 d: 70/10/20 e: 50/10/40

Figure 3: Contact angles for dyed and finished P/C fabric for different TEOS/GPTMS/OTES ratio a: 87.5/10/2.5
b: 85/10/5 c: 80/10/10 d: 70/10/20 e: 5/100/40

a b
Figure 4: SEM of a: Untreated cotton b: 80/10/10 TEOS/GPTMS/OTES treated cotton

DOI: 10.9790/019X-03021925 www.iosrjournals.org 24 | Page

 One Bath Dyeing and Water Repellent Finishing Of Textile by Sol-Gel Technique

a b
Figure 5: SEM of a: Untreated P/C b: 80/10/10 TEOS/GPTMS/OTES treated P/C

DOI: 10.9790/019X-03021925 www.iosrjournals.org 25 | Page