16. - 18. 10.

2013, Brno, Czech Republic, EU

SYNTHESIS SUPPER HYDROPHOBIC NANO SILICA FOR APPLICATION ON COTTON

FABRIC
Laleh MALEKNIA, Ali BARZEGAR,Ramin KHAJAVI,Nahid ALIZADE GHAMSARI,Marzieh TAHERI
Islamic Azad University-South Tehran Branch, Tehran, Islamic Republic of Iran, Melika02@azad.ac.ir

Abstract
Cotton is extensively utilized in textile and clothing industry but since it is highly shrinkable because cellulose
chain as well as water absorption with hydroxyl group which exists in these chains, one can sometimes face
with hard ironing process and are not fixed at dimension; therefore, this paper deals with production, Nanosynthesis of the hydrophobic silica particles for making water proof and reduction of shrinkage of cotton
textiles. For this purpose, hydrophobic silica Nano-particles have simply and economically been produced
and then they have been dispersed in MT resin in different percents. Finally, the cotton goods turned to be
water proof through pad-dry-cure system. Scanning electron microscope was used to study the size of
synthesized Nano-particles and to study chemical structure of the Nano-particles FTIR test has been
employed. Image analyzer Software was utilized to measure the angle of a drop, also, to study shrinkage
rates, ASTM standard test has been employed. Micrographs resulted from SEM revealed that the average
size of the Nano-particles is 16nm.FTIR test also approved the existence of Methyl groups at hydrophobic
nanosilica structure. The results from experiments of contact angle of the drop and shrinkage rate revealed
that drop angle on cotton goods is 150 and the Nano-particles can extraordinarily make cotton goods water
proof and reduce the shrinkage rate remarkably.
Keywords: Silica nanoparticle aerogelcotton fabrichydrophobwrinkle
1.

INTRODUCTION

Silica aerogels are novel mesoporous materials with many intriguing properties such as low bulk density(~0.l
g/cm3), continuous porosities, high specific surface area (500-1000 m2/g) and extremely low thermal
conductivity (~0.02Wm1K1) [1-5]. These properties are derived from the nanoporous network of
interconnected primary particles. Because of their unique texture, silica aerogels are promising materials as
super-thermal insula tors, catalytic supports, adsorbents, host materials for drugdelivery systems [6-lo]. After
the pioneering contribution by Kistler in 1931 [11], it took nearly three decades for the aerogel to become
scientifically and industrially an interesting material. This is because of the tedious synthesis procedures
followed by Kistler which used to take several weeks to wash out the salts generated in hydrogel during the
process and supercritical drying of the wet-gel to get an aerogel. A decisive simplification and acceleration of
the aerogel synthesis was reported in 196os by Nicolaon and Teichner, who used expensive metal alkoxide
precursor such as TMOS and supercritical drying technique [12]. Further attempt to make the aerogels
commercially in intereting was made by brinker, who synthesized silica aerogel by drying a wet-gel at an
ambient pressure and thereby avoiding the risky supercritical drying method [13]. In principle, their process
involved a series of solvent exchanges and an organic modification of the inner surface of the wet-gel by
non-polar groups such as alkyl or aryl. The gel undergoes spring-back efficientduring the drying and thus
preserves the aerogel properties in the dried solid. However, the tedious solvent exchange and surface
modification steps prolong the processing with huge consumption of costly solvents [l4-l6]. Schwertfeger et
al. reported a process for the aerogel production using sodium silicate (SS), i.e. water-glass without solvent
exchange and supercritical drying [17]. In their process, they used silylating agents in bulk (e. g. for 100 g of
hydrogel, the quantities of HMDSO and TMCS used were minimum 50 g) which makes this process quite
expensive.Recently, we have focused our work on the development of silica aerogels using sodium silicate
precursor via ambient pressure drying (APD). Keeping in view the less processing time, low production cost

16. - 18. 10. 2013, Brno, Czech Republic, EU

and ease of production, we employed for the first time a co-precursor method for the organic modification of
hydrogels without solvent exchange as a pre-requisite [18,19]. In the present studies, our goal was to
develop a new approach which would allow for the cost-effective synthesis of silica aerogel powders. We
prepared hydrogels directly from sodium silicatewithout prior ion exchange (like Kistlers process) and
employed a co-precursor method (i.e. addition of the silylating agent directly to the sodium silicate) for the
organic modification of hydrogels in the aqueous phase using HMDS and nitric acid. The gels were then
immersed in n-hexane for one-step solvent exchange which essentially leads to the displacement of pore
water due to the organic modification in the aqueous phase and simultaneous intrusion of n-hexane into the
gel. During this process, the sodium ions present in the hydrogels were given out with the displaced pore
water. The novel aspect of this process is that all the three steps such as sodium ion removal, solvent
exchange and surface modification were accomplished simultaneously in one-step which makes this route a
very promising for the large scale production of powdered aerogels.
2.

EXPERIMENTAL

2.1.

Synthesis of silica aerogel powders

The chemicals used for the synthesis of silica aerogel powders were sodium silicat ( 33%Merck KGaA),
nitric acid (65 %Merck KGaA), hexamethyldisilazaneand n-hexane) Merck KGaA(. The sodium silicate (SS)
solution was diluted first with the deionized water so as to obtain 4.35 wt.% of silica in the starting material.
The silylated hydrogels were then prepared by a co-precursor method wherein the nitric acid and
hexamethyldisilazane (HMDS) were added to the sodium silicate (4.35 wt.%) under constant stirring. The sol
undergoes gelation in 5 min at room temperature (27 C). The silylated hydrogels prepared by the coprecursor method were immersed in n-hexane for one-step solvent exchange and sodium ion removal which
could be accomplished in 3 hr. The displaced pore water was then removed from the beakers and the
silylatedorgano-gels were centrifugewith distilled water and then dried the hydrogel at ambient pressure in a
furnace in two steps: firstly at 170 0C for 20 min and secondly at 200 0C for 20 min to obtain the aerogel
powder.
2.2.

Impregnate cotton fabrics by resin and aerogel silica powder

4-8 ml of MT resin was taken in a beaker and diluted it by 100 ml distilled water and then added diffrent
percentage of Silica aerogel powder to beaker over a magnetic stirrer with constant stirring for 3 hr till the
powder disperss well in resin. amountof aerogel powder were 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07 and
0.08gr. Fabric samples were prepared in 15*15cm and impregnated in different concentration of resin and
silica nano powders for 1hr and then dried and cured them at 1200C for 20 min.
2.3.

Methods and equipment of characterization

The microstructure of the aerogel powders was probed by a Field Emission Scanning Electron Microscope
(FE-SEM, JSM6700 F microscope, JEOL). The surface chemical modification of the aerogel powders was
confirmed by means of Fourier transform infrared spectroscopy (FT-IR, IFS 88, Bruker,Germany). The
contact angle ( ) measurements were done using a contact angle meter (Image analyzer ) to quantify the
degree of hydrophobicity. In order to Test the return of shrinkage in Cotton fabric impregnated by resin and
aerogel silica powder was used from the device wrinkle recovery tester AATCC 128(Shirley company
UK).Bending rigidity of fabrics measured by bending sensing device (SDL technology) M003B on the basis
of the standard ASTM D1388-96.

16. - 18. 10. 2013, Brno, Czech Republic, EU

3.

RESULTS AND DISCUSSION

3.1.

morphology

Microstructural studies were carried out for determine hydrophobic Silica nanoparticles by FESEM (FESEM, JSM6700 F microscope, JEOL). Fig.1 microscopic images show aerogel prepared with two different
magnifications. As the figures hows that nanoparticles have uniform distributionand the average particle size
is 31nm.

Fig 1 FESEM photogerafs of silica aerogel powder

3.2.

FTIR

FTIRwas used to study of surface modified aerogels produced using nonpolar solvents. The formulation of
hydrogel surface changes produced by themethyl groups of dimethylhexaSylazanis showns chematically in
following reactions:
Na2SiO3+ 2HNO3H2O [SiO2.xH2O]+ 2NaNO3
1
2)SiOH( + (CH3)3Si-NH-Si(CH3)3

HNO3 2(SiOSi(CH3)3) + NH3

Fig. 2 shows the FT-IR spectra of the aerogel powder synthesized with simultaneous surface modification,
solvent exchange and sodium ion removal. The peaks at 2963cm -1 correspond to the IR absorption with
exchanging OH in initial hydrogel by CH3 groups in Si bonds. [20,21] present in the aerogel powder which
confirms the surface modification and formation of hydrophobic Silica nanoparticles. During this process the
hydrogel was immersed in a water immiscible solvent such as n-hexane. As a consequence of water
displacement, n-hexane entered in the pore and eventually the hydrogel was transformed into
a silylatedorgano-gel and thus accomplished the solvent exchange.The solvent exchange in the present
studies is a one-step process and it is driven by the displacement of pore water from the hydrogel.

Fig. 2 FT-IR spectra of the aerogel powder

16. - 18. 10. 2013, Brno, Czech Republic, EU

3.3.

Super hydrophobicity of the aerogel powders

Fig. 3 show the micrographs of obtain result from water droplets placed in the surface of cotton fabric coated
with different concentrations hydrophobic silica aerogel powder. The drop maintained spheroidshape with
contact angle of 1400 on the fabric coated with 0.03gr aerogel powder. The result shows increasing the
contact angle by increasing amount of aerogel in a exact concentration of REZIN but surface gradually
becomes undesirable.
Table 1.duration of the shelf-life drops on the cotton fabric
Duration of
the shelflife drops
on the
goods
50min
70min
70min
110min
105min
85min
85min
65min

Mount of
aerogel
powders

0.01gr
0.015gr
0.02gr
0.03gr
0.04gr
0.05gr
0.06gr
0.07gr

Sample1
Sample2
Sample3
Sample4
Sample5
Sample6
Sample7
Sample8
Fig 3 duration of the shelf-life drops on the cotton fabric

Table 2 duration of the shelf-life drops on the cotton fabric after steam iron
duration of
the shelflife drops
on the
goods after
steam iron
0.5min
7min
10min
20min
12min
11min
5min
2min

mount of
aerogel
powders

0.01gr
0.015gr
0.02gr
0.03gr
0.04gr
0.05gr
0.06gr
0.07gr

Sample1
Sample2
Sample3
Sample4
Sample5
Sample6
Sample7
Sample8

Fig 4 duration of the shelf-life drops on the cotton fabric

after steam iron

Fig 3 micrographs of obtain result from water droplets placed in the surface of cottonfabric

16. - 18. 10. 2013, Brno, Czech Republic, EU

3.4.

wrinkle recovery test

result of fabrics wrinkle recovery test, determined that the silica aerogel powder have a salienteffect on the
decreasing of cotton fiber crimping.Cotton fabrics absorb moisture and it cause wrinkling the fabrics. the
water molecule cause the gliding cellulose chain on each other and then the side hydrogen bond of the chain
can make new graft in presence of water molecule in new places that be the reason of the
wrinkling.WrinkleRecovery Test shows that the superhydrophobic SiO2 nano particle on the cellulose chain
prevent moisture absorption so ase a result the chaingliding on each other and make new bonding and at
last it prevent to wrinkle the fabrics.
Table 3 angle of the wrinkles
mount
of
aerogel
powders

angle of
the
wrinkles
in the
direction
ofthe
weft end

0gr

85

angle of
the
wrinkles
in the
direction
of the
warp
yarn
90

0.01gr
0.02gr
0.03gr
0.04gr
0.05gr
0.06gr
0.07gr

99
109
118
96
108
119
97

105
123
132
118
115
119
115

Raw
sample
Sample1
Sample2
Sample3
Sample4
Sample5
Sample6
Sample7

3.5.

Fig 5 angle of the wrinkles in the directionof the warp yarn

and weft enddirection of the warp yarn and weft end

bending rigidity

Table 4 shows the results obtained for impregnated fabrics with difrrent percentages resin and Silica
aerogel.for investigation the bonding rigidity of coated cotton fabrics, SDLmtechnology M003B for measuring
bending rigidity was used. In this study different percentages of resin were analyzed on cotton fabrics.
According to the result increasing amount of rezin cause increasing the bending rigidity but as respect that
the bending rigidity affects on final operation and ZIR DAST the optimum mount af resin was 7 ml.
Table 4 bonding rigidity of coated cotton
bending
rigidity of
fabrics
Rawsample
Sample1
Sample2

0.01gf/cm2
0.017gf/cm2
0.019gf/cm2

the amount
of resin
impregnated
to goods
0ml
4ml
5ml

Sample3

0.025gf/cm2

6ml

Sample4

0.032gf/cm2

7ml

Sample5

0.035gf/cm2

8ml

Fig 6 bending rigidity of coated cotton fabrics

16. - 18. 10. 2013, Brno, Czech Republic, EU

4.

CONCLUSIONS

This method forsynthesising Silicaaergelpowder wasan easyand economicalwayby using cheap materials ,
such assodium silicate and reduce synthesis time.the total processing time of the aerogel powders could be
restricted to 4 hr. according to this parameters this method was more affordable than the previous synthesis
methods sodium silicate and HMDS and nitric acid were mixed for the organic modification of hydrogels in
the aqueous phase . The gels were then immersed in a nonpolar solvent such as, n-hexane for solvent
exchange . During this process, the sodium ions present in the hydrogels were given out with the displaced
pore water.Thepropertiesofthe aerogelpowder obtainedand usingitonthecotton textile for makeithydrophob
was an important step intheresearch processtobring other productshyrophob. The contact angle for the
sample which was impregnated by aerogel powder, was about 1400. According to wonderful proprties of this
nanoparticles, by using other resins on cottonsubstrate to reach contact angel up to 150 0. If the contact angle
being more than 1500, that substrate will be a super hydrophobic.Use of this nanoparticles on cotton fabric
perevent wrinkles on fabrics as well.
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