Kaushik 2010

Solvent Absorption Characteristics of
Epoxy-Colloidal Silica Nanocomposites
ANUPAMA KAUSHIK*
University Institute of Chemical Engineering & Technology
Panjab University, Chandigarh, India
JYOTI KAUSHIK
Department of Chemical Engineering, JMIT, Radaur
Yamunanagar, Haryana, India
ABSTRACT: The epoxy-colloidal silica nanocomposites were prepared by directly blending a two
pack system of Araldite (CY-230) and hardener (HY-951) with colloidal silica. As the colloidal silica
powder was considerably fine, the weight percent was kept quite low. The silica content was varied
from 1% to 3% by weight of the total matrix. These composites were then characterized for mor-
phology using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and absorp-
tion kinetics in various solvents including distilled water, ethanol, acetone, carbon tetrachloride, and
methylethylketone. Absorption kinetics was studied at two temperatures, that is, 30 C and 50 C.
The SEM micrographs indicated the uniform distribution at lower concentrations, that is, up to 2%
of colloidal silica. TGA results show improved thermal stability and increase in ash content with
increase in silica content. Swelling kinetics shows that for most of the solvents the nature of diffusion
is non-Fickian and as the silica content increases, deviation from Fickian behavior increases.
Moreover, diffusivity decreases with increase in silica content but increases with temperature.
Sorption values increases with silica content and also increase with temperature. Various reasons
for deviation from Fickian behavior were studied.
KEY WORDS: colloidal silica, epoxy composites, chemical absorption, morphology, barrier
properties, TGA.
INTRODUCTION
OLYMER COMPOSITES FEATURING both stiffness and strength have been of great
P commercial interest in the past decade. Conventional polymer composites are generally
directly formed through a simple blend of pristine polymer and inorganic filler. However,
phase separation on the order of a few microns often occurs because of a lack of substantial
interaction between the dispersed filler and the polymer matrix. Recently, an organic-
inorganic hybrid with a nanostructure (termed nanocomposite) has been developed through
nanotechnology. Nanocomposites have recently received much attention because of their
outstanding optical, electrical, and mechanical properties.
*Author to whom correspondence should be addressed. E-mail: anupamachem@gmail.com
Journal of REINFORCED PLASTICS AND COMPOSITES, Vol. 29, No. 18/2010 2821
0731-6844/10/18 282113 $10.00/0 DOI: 10.1177/0731684409360995
ß The Author(s), 2010. Reprints and permissions:
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2822 A. KAUSHIK AND J. KAUSHIK
Nanocomposites are a class of composite materials in which the dimensions of the

dispersed phase are nanometric. In some cases, nanocomposites exhibit greatly improved
properties with respect to conventional microcomposites loaded with the same amount of
reinforcing phase, thus allowing for a potential weight-saving design of many plastic
products [1]. Nanocomposites are a new class of materials showing better physical proper-
ties such as thermal, mechanical, and barrier properties than conventional composites,
because of much stronger interfacial forces between the nanometer-sized domains [24].
Although the mechanisms behind these improvements are not well understood at present,
it is evident that the altered properties of these materials are related to changes in polymer
molecular dynamics [5,6] and crystallinity [7], in addition to traditional filler
reinforcement.
Thermosetting epoxies are low-density polymers with excellent adhesive properties [8].
They are widely used in adhesives, coatings, and electrical and plumbing parts. The poly-
mers’ brittleness upon curing is one major drawback that prevents wider applications of
epoxies [9]. Adding reinforcements such as nanoplatelets, nanoparticles, and carbon nano-
tubes has attracted considerable attention as a means to enhance the properties and over-
come the limitations of epoxy resins. Nano-reinforcements, as opposed to traditional
reinforcements, have been shown to improve the mechanical and thermal properties at
much lower filler-loading levels. Due to the exceptionally high surface area of the nano-
fillers, the interphase region between the matrix and the filler comprises a considerable
portion of the composite. Thus particlematrix adhesion is crucial for proper stress trans-
fer from the matrix to the filler of the applied loads.
Silica particles can be obtained from precipitated silica, fumed silica, and colloidal silica,
but more and more research [1012] have been focused on colloidal silica due to its easily
homogeneous dispersion, tailorable surface property, etc. Owing to their low cost and ease
of surface modification for improved matrix adhesion, nanosilica particles comprise
important reinforcement for epoxy resins. Proper particle dispersion and separation are,
in general, essential in obtaining the best mechanical properties of the composite. Several
researchers have also found that interparticle distance contributes significantly to the
composite toughness [13]. In the past several years, silica particles were widely introduced
into polymers to improve the heat resistance, radiation resistance, mechanical and electri-
cal properties of polymer materials [1416]. Wu et al. [17] indicated that nanosilica par-
ticles could simultaneously provide PP with stiffening, strengthening, and toughening
effects at rather lower filler content (typically 0.5% by volume). Battistella et al. [18]
and Yao et al. [19] have studied the microscopic fracture behavior and characterization
of epoxy silica nanocomposites.
While there are several papers on the mechanical properties of silica reinforced nano-
composites, relatively little is available in the literature regarding other properties, apart
from some references to barrier properties [11]. In view of the enormous resistance of
inorganic oxides to swelling by solvents, there are obvious implications for improving
barrier properties of polymers through the production of organic-inorganic hybrids.
Substantial improvements in barrier properties have been reported for nanocomposites
produced from exfoliated clays where the filler content is relatively low, that is, up to
810%, and the filler has a plate-like structure with a high aspect ratio.
The scope of the present study is to explore the solvent absorption characteristics of
epoxy silica nanocomposites. In this, we will present some useful engineering data on
sorption, diffusivity, and permeability of a number of organic and inorganic solvents,
which have some relevance in industry and engineering.
Solvent Absorption Characteristics of Epoxy-Colloidal Silica Nanocomposites 2823
EXPERIMENTAL
Materials
Colloidal silica supplied by National Chemicalsof particle size 2030 nm, India was
reinforced mixed with epoxy resin (Araldite CY-230) supplied by CIBA GIEGY Ltd.
Bombay, India. The epoxy resin was cured with a suitable amount of hardener
(HY-951) (aliphatic amine); the ratio of hardener to resin used being 1 : 10. The mixture
was stirred continuously until a uniform blend of filler and resin was achieved. Colloidal
silica content was varied from 0.5% to 3% by weight of the total matrix. Data for com-
position of various samples is given in Table 1.
Specimen Preparation
The composites were prepared by mechanical mixing using a commercially available

laboratory mixing device. The filler particles were dried in an oven at 60 C for several
hours. After the fillers were compounded with the resin, the mixture was mechanically
dispersed for 30 min under a vacuum atmosphere to distribute the particles homoge-
neously and to remove entrapped air, which could significantly lower the mechanical
properties. Finally, the hardener was added to the suspension, followed by further stirring
for 5 min. The mixture was filled into molds and then cured for 24 h at room temperature,
and post-cured at 70 C for 910 h.
Characterization
MORPHOLOGY
Scanning electron micrographs (SEM) were obtained on a JSM 6100 CX (JEOL) elec-
tron microscope. The sample preparation technique used was based on Kato’s osmium
tetraoxide staining technique and Matsuo’s two-step sectioning method. The SEM of the
composite samples was done to observe the dispersion of clay in the composite.
THERMOGRAVIMETRIC ANALYSIS
Thermal stability of the epoxy silica nanocomposites was studied using thermogravimetric
analyzer (TGA) of type Perkin Elmer STA-6000. It has weighing capacity of 1500 mg with
resolution around 0.1 mg. Samples were taken in a considerably small quantity (in milligram)
Table 1. Sample identification depending on filler loading for various

samples of colloidal silica reinforced epoxy composites.
% age of resin % age of silica

Sample Amount of based on resin based on resin
identification silica (g) silica mixture (g) silica mixture (g)
S0 0 100 0
S1 0.89 99 1
S2 1.67 98.5 1.5
S3 2.25 98 2
S4 4.23 97.5 2.5
S5 5.10 97 3
Table 2. Solubility parameters, dipole moment, dielectric constant,

molar volume, and nature of solvent used in the study.
Solubility Molar volume

parameters Dipole Dielectric (cm3)
Solvents (cal/cm3)1/2 moment constant at 25 C Nature of solvent
Water 23.4 1.85 80 18 Polar protic solvent

Ethanol 12.92 1.69 24.3 58.5 Polar protic solvent
CCl4 8.6 0 2.24 97.1 Non-polar solvent
Acetone 9.9 2.88 20.7 74.0 Dipolar aprotic solvent
Methylethylketone 9.33 2.78 18.5 90.1 Polar aprotic solvent
in a sample cup made of alumina with a maximum capacity of around 180 mL. All the tests
were performed in nitrogen environment and at heating rate of 10 C/min.
ABSORPTION KINETICS
The aim of chemical absorption studies was to test whether the composites were capable
of withstanding exposure to a variety of organic solvents. The initial weight of the polymer
samples was determined by weighing on a highly sensitive electronic balance with a least
count of 0.0001 g. To study the swelling kinetics, the so-called pat-and-technique was used
for liquid sorption. After taking the dry weight, square samples (size 25 25 mm2) of
definite thickness were placed in different solvents in a standard joint test tube, which
was maintained at a constant temperature of 30 and 50 ± 0.1 C (Julabo, VC-5, with
cooling as well as heating arrangement). Specimens were taken out at regular intervals
of time, solvent adhering to the surface was rubbed off, weighed immediately and replaced
in the solvent. This procedure was continued untill equilibrium swelling was achieved. This
was repeated for specimens with different styrene content ensuring the reproducibility of
results. The time taken for wiping out the solvent from sample surface and weighing was
kept small in order to minimize the error due to solvent evaporation. The solvents used for
chemical absorption study are given in Table 2.
RESULT AND DISCUSSION
Results of Scanning Electron Microscopy
The SEM of silica/epoxy composite had been done to analyze dispersion of filler and
fractured surface. Figure 1(a) and (b) shows the dispersion of colloidal silica in the resin
matrix containing 1% and 3% filler concentration. A good dispersion has been observed
at a lower concentration of the filler that is at 1%, except for some bright spots corre-
sponding to aggregates of colloidal silica. The epoxy-silica nanocomposites display typical
features of organic-inorganic hybrids, which consist of diffuse silica domains dispersed
within an organic matrix.
Thermogravimetric Analysis
TGA was carried out for pristine epoxy and silica nanocomposites in nitrogen atmo-
sphere and is illustrated in Figure 2. At a weight loss of 95%, the curve of pristine epoxy
Figure 1. (a) SEM micrograph of epoxy colloidal silica composite sample containing 1% silica, (b) SEM
photograph of epoxy colloidal silica composite sample containing 3% silica.
crosses over those of composites at roughly 330 C. There is not much difference in the
weight loss in this region. It seems that the initial temperature of weight loss does not
increase with increasing silica content. However, at a weight loss of 50%, silica tends to
increase the thermal resistance of the composites. The ash contents measured at 600 C
roughly correspond to theoretical amounts of silica. The first step with gradual weight loss
from room temperature to around 335 C is due to the evaporation of physically absorbed
solvent and residual monomers; the second weight loss in the range of 335470 C is
ascribed to the decomposition of the polymer; the third minor weight loss at 450600 C
may be caused by the part decomposition of silica bonded or entrapped polymeric seg-
ments. The higher the silica embedded content is, the more the residual mass is, that is, the
organic segment bonding or entrapping silica is more. The residual mass at 600 C slightly
increases with the increment of silica content, further demonstrating that considerably
little organic segment chemically bonded with silica.
100
80
Weight (%)
60
40
20 3
2
1
0
100 200 300 400 500 600
Temperature (°C)
Figure 2. TGA curves for neat resin and resin containing silica (1 neat resin, 2 1% silica, 3 2% silica).
Absorption Kinetics
The percent absorption was calculated using Equation (1):

mt mi
Percentage absorption ¼ , ð1Þ
mi
where mt is the mass of sample at time t and mi is the dry weight of sample.
The sorption of penetrant species into polymer matrix is quantified in terms of mole percent
uptake of solvent (Qt), which was calculated at each time interval using Equation (2) [11]:
me =mr
Mt ¼ 10, ð2Þ
mi
where me is the mass of solvent taken up at equilibrium, mr is the relative molecular mass
of the solvent, and mi, is the dry weight of sample.
At equilibrium, Mt is considered to be M1, mole percent uptake of solvent at infinite time.
To understand the mechanism of sorption, the values of Mt and M1 were substituted in
the general Equation (3) for transport phenomena [11]:
Mt
¼ Ktn , ð3Þ
M1
where Mt is the mole percent uptake at time t, M1 is the equilibrium mole percent uptake,
k is a constant, which depends on the structural characteristics of the polymer and its
interaction with solvent. The values of n determine the mode of transport.
The Fickian behavior can also be explained as below in Equation (4):

Mt 8 Dt
¼ 1 exp 2 2 , ð4Þ
M1 h
where D is the diffusion coefficient, t is the time, and h is the thickness of sample.
While the equilibrium content is almost independent of temperature, the diffusion rate,
which is given by the slope of the curve, is greatly influenced by temperature. The time
required to attain equilibrium water content is reduced as the immersion temperature
increase. The diffusivity, D, can be calculated from the initial linear portion of the absorp-
tion curve as:
1=2
Mt 4 D
¼ t1=2 : ð5Þ
M1 h
In Equation (3) for transport phenomenon, if n ¼ 0.5 diffusion obeys Fick’s law,
which occurs when segmental mobility of the polymer chains is faster than the rate of
diffusion of penetrant molecules. When n is deviating from 0.5, the diffusion is said to be
non-Fickian [20].
The diffusion coefficient, which is a measure of the ability of the penetrant molecules to
move among the polymer segment and the sorption coefficient, S, which gives an idea
about the equilibrium sorption, were calculated from Equations (6) and (7):

h 2
D¼ , ð6Þ
4M1
m1
S¼ , ð7Þ
mp
where h is the thickness of the sample, y is the slope of the linear portion of the sorption
curve, m1 represents the mass of the solvent taken up at the equilibrium, and mp repre-
sents the initial mass of the sample. The permeability coefficient (P), which gives a com-
bined effect of both D and S, was also calculated using the equation P ¼ D S.
One can consider the mass transport process to include three steps. Small solvent mole-
cules are first absorbed on the surface of the polymeric material. Then the molecules
diffuse through the polymer and finally, the solvent molecules desorb on the downstream
surface of the polymer. The duration and intensity of these steps is influenced by several
factors such as the polymer and permeant structures, temperature, mechanical deforma-
tion, solvent-polymer interaction, pre-contamination of the barrier material, presence of
fillers, etc. The transport of penetrant into the polymeric material can be explained in
terms of thermodynamics and kinetics [21]. The former is usually reffered as solubility and
latter as diffusion. The solubility is generally understood in terms of solubility parameter
as proposed by Hilderbrand. Hilderbrand parameters are divided into three parts: a dis-
persion component, a hydrogen bonding component, and a polar component. The molec-
ular dimensions of the permeant molecules must be small enough to enter the lattics
network of the polymer. As the network is swollen by the sorption of the solvent, the
network chains assumes an elongated configuration and elastic restritive forces develop in
opposition to the ongoing swelling. A state of equilibrium is reached when the elastic
restoring forces of the network chains exactly balances the osmotic pressure driving pene-
trant molecule into the network [22].
Tables 3 and 4 give k, n, M1, and diffusivity values of nanocomposites in distilled water
at 30 C and 50 C. As seen in the figures, moisture adsorption was more rapid in the initial
stages and declined with increasing time. Then, moisture content of the composite film
reached a plateau, indicating that it became equilibrated with each condition. The diffu-
sivity decreases with the increase in silica content. For neat polymer sample, diffusivity in
Table 3. Values of slope (n), intercept (k), diffusivity coefficient (D),

and equilibrium absorption (M1) for swelling curve of colloidal
silica/epoxy composites in distilled water at 30 C.
Distilled water
Sample D 108 P 108

S. No. identification K n M1 (cm2/s) S (g/g) (cm2/s)
1 S0 0.0974 0.4651 0.0933 3.00 0.017 0.05

2 S1 0.0880 0.4853 0.1155 2.73 0.021 0.06
3 S2 0.1372 0.4027 0.1388 2.64 0.025 0.07
4 S3 0.1977 0.3275 0.1540 2.28 0.028 0.06
5 S4 0.2334 0.2924 0.1671 1.84 0.030 0.06
6 S5 0.3139 0.2342 0.1842 1.72 0.033 0.06

silica/epoxy composites in distilled water at 50 C.
Distilled water
Sample D 108 P 108

1 S0 0.2369 0.2930 0.1643 3.45 0.030 0.10

2 S1 0.2086 0.3163 0.2096 2.86 0.038 0.11
3 S2 0.2026 0.3173 0.2451 2.72 0.044 0.12
4 S3 0.1906 0.3369 0.2770 2.70 0.050 0.15
5 S4 0.1550 0.3790 0.2869 2.68 0.054 0.15
6 S5 0.2259 0.3005 0.3235 2.33 0.058 0.14
distilled water is 3.0 cm2/s and it decreases to 1.72 cm2/s. Sorption increases with the
increase in silica content. Diffusivity and sorption at 50 C is higher than that at 30 C.
The value of n is 0.46 for neat resin and 0.48 for composite containing 1% silica, that is,
the diffusion is close to Fickian behavior for these two samples. But as the silica content
increases, deviation from Fickian behavior increases. But at 50 C, deviation from Fickian
behavior is prominent. Deviation from Fickian behaviour at 50 C than at room temper-
ature can be explained on the basis that temperature increases rate of diffusion and might
change relative rate of diffusion through low density and high density phases thus causing
more pronounced non-Fickian anomalies at 50 C in comparison to room temperature.
Tables 5 and 6 give k, n, M1, and diffusivity values of nanocomposites in ethanol at
30 C and 50 C. The diffusivity decreases with the increase in silica content. For neat
polymer sample diffusivity in ethanol is 4.25 cm2/s and it decreases to 1.75 cm2/s. For
ethanol, diffusivity at higher temperature 50 C is lower than that at 30 C, but sorption
is higher at 50 C. The value of n is 0.23 for neat resin showing deviation from Fickian
behavior. But at higher temperature of 50 C, n is 0.48 for neat resin but deviates from 0.5
as silica content increases.
Tables 7 and 8 give k, n, M1, and diffusivity values of nanocomposites in carbon
tetrachloride at 30 C and 50 C. The diffusivity decreases with the increase in silica content.
For neat polymer sample diffusivity in CCl4 is 2.60 cm2/s and it decreases to 2.03 cm2/s.

silica/epoxy composites in ethanol at 30 C.
Ethanol
Sample D 108 P 108

1 S0 0.2504 0.2319 0.0528 4.25 0.024 0.10

2 S1 0.1763 0.3472 0.0642 3.51 0.030 0.10
3 S2 0.7247 0.2604 0.0758 2.79 0.037 0.10
4 S3 0.2730 0.2616 0.0837 2.31 0.039 0.09
5 S4 0.3109 0.2342 0.0893 2.19 0.041 0.09
6 S5 0.3877 0.1919 0.1017 1.75 0.047 0.08

silica/epoxy composites in ethanol at 50 C.
Ethanol
Sample D 108 P 108

1 S0 0.0985 0.4832 0.1264 3.28 0.058 0.19

2 S1 0.2758 0.2664 0.1598 3.27 0.074 0.24
3 S2 0.1860 0.3542 0.1754 3.21 0.081 0.26
4 S3 0.3316 0.2254 0.1863 3.14 0.086 0.27
5 S4 0.3019 0.2474 0.2230 2.99 0.103 0.31
6 S5 0.4226 0.1758 0.2448 2.27 0.113 0.26
For CCl4, diffusivity at higher temperature 50 C is higher than that at 30 C and sorption is
also higher at 50 C. If the value of n is seen at both the temperatures, there is significant
deviation from Fickian diffusion. The reason can be attributed to the nature of solvent.
Epoxy is a highly polar secondly polymer because of the presence of tertiary amine cross-
links while CCl4 is a non-polar solvent. Moreover, solubility parameter of CCl4 is quite
different from that of epoxy resin which lies between 9.7 and 10.91(cal/cm3)1/2.
Tables 9 and 10 give k, n, M1, and diffusivity values of nanocomposites in acetone at
30 C and 50 C. The diffusivity follows the same trend, that is, decreases with the increase
in silica content. For neat polymer sample diffusivity in acetone is 3.67 cm2/s and it
decreases to 3.07 cm2/s. For acetone, diffusivity at higher temperature 50 C is higher
than that at 30 C and sorption is also higher at 50 C. The value of n for acetone is far
from 0.5 displaying non-Fickian behavior. The sorption values in acetone are quite high as
compared to other solvents because the value of solubility parameter of acetone is close to
that of epoxy.
Tables 11 and 12 give k, n, M1, and diffusivity values of nanocomposites in methyl ethyl
ketone at 30 C and 50 C. The diffusivity follows the same trend, that is, decreases with the
increase in silica content. For neat polymer sample diffusivity in MEK is 3.49 cm2/s and it
decreases to 2.24 cm2/s. For MEK there is little difference between diffusivity at 50 C and
at 30 C but sorption values are higher at 50 C. For neat resin, the value of n is 0.38 at 30 C
and 0.39 at 50 C, but deviates as the concentration of silica increases.

and equilibrium absorption (M1) for swelling curve of
colloidal silica/epoxy composites in CCl4 at 30 C.
Carbon tetrachloride
Sample D 108 P 108

1 S0 0.1933 0.3266 0.0155 2.60 0.024 0.06

2 S1 0.2333 0.2926 0.0164 2.59 0.026 0.07
3 S2 0.2352 0.2909 0.0202 2.37 0.031 0.07
4 S3 0.2951 0.2413 0.0222 2.32 0.034 0.08
5 S4 0.1719 0.3510 0.0251 2.24 0.039 0.09
6 S5 0.3407 0.2154 0.0299 2.03 0.046 0.09

silica/epoxy composites in CCl4 at 50 C.
Carbon tetrachloride
Sample D 108 P 108

1 S0 0.3215 0.2255 0.0268 2.75 0.035 0.10

2 S1 0.2405 0.2895 0.0295 2.60 0.045 0.12
3 S2 0.3119 0.2333 0.0373 2.56 0.057 0.15
4 S3 0.3142 0.2327 0.0417 2.39 0.063 0.15
5 S4 0.3977 0.1610 0.0480 2.33 0.073 0.17
6 S5 0.2181 0.3108 0.0524 2.31 0.079 0.18

silica/epoxy composites in acetone at 30 C.
Acetone
Sample D 108 P 108

1 S0 0.2735 0.2645 0.0968 3.67 0.056 0.21

2 S1 0.2712 0.2682 0.1074 3.42 0.062 0.21
3 S2 0.2938 0.2497 0.1397 3.39 0.081 0.27
4 S3 0.2819 0.2611 0.1575 3.36 0.091 0.31
5 S4 0.3255 0.2297 0.1632 3.14 0.095 0.30
6 S5 0.3317 0.2290 0.1696 3.06 0.098 0.30
If the comparison is withdrawn for diffusivity values the acetone has the highest values
than all other solvents, this is due to the fact that acetone has the solubility parameter close
to the solubility parameter of epoxy resin, which lies between 9.7 and 10.91(cal/cm3)1/2.
The large deviation from Fickian behavior for nanocomposite samples with increasing
silica content can be explained on the basis of solvent crazing and swelling fracture; solvent
crazing has been observed at quite high penetrant activities and can lead to non-Fickian
and Equilibrium absorption (M1) for swelling curve of colloidal
silica/epoxy composites in acetone at 50 C.
Acetone
Sample D 108 P 108

1 S0 0.3736 0.1987 0.1028 5.22 0.060 0.31

2 S1 0.4315 0.1619 0.1518 4.86 0.088 0.43
3 S2 0.6115 0.1000 0.2237 4.39 0.130 0.57
4 S3 0.4440 0.1653 0.2993 3.83 0.174 0.67
5 S4 0.3908 0.1947 0.3432 3.67 0.199 0.73
6 S5 0.4602 0.1611 0.3932 2.78 0.231 0.64
silica/epoxy composites in MEK at 30 C.
Methylethylketone
Sample D 108 P 108

1 S0 0.1490 0.3820 0.0586 3.49 0.042 0.15

2 S1 0.3764 0.1974 0.0792 3.43 0.057 0.20
3 S2 0.4231 0.1732 0.0973 3.13 0.070 0.22
4 S3 0.4135 0.1724 0.1085 3.11 0.078 0.24
5 S4 0.6525 0.0840 0.1139 3.01 0.082 0.25
6 S5 0.7042 0.1029 0.1311 2.24 0.095 0.21
silica/epoxy composites in MEK at 50 C.
Methylethylketone
Sample D 108 P 108

1 S0 0.1433 0.3949 0.0787 3.47 0.057 0.20

2 S1 0.5388 0.2439 0.0859 3.22 0.062 0.20
3 S2 0.4369 0.2755 0.1173 3.06 0.084 0.26
4 S3 0.3106 0.2321 0.1296 2.99 0.093 0.28
5 S4 0.3668 0.2023 0.14856 2.90 0.103 0.30
6 S5 0.4633 0.1572 0.1569 2.66 0.113 0.30
diffusion for which the swelling stresses are sufficient to cause local polymer failure.
The swelling stresses set up in the polymer by diffusion of solvent causes crazes and
sometimes ultimately fracture the polymer specimen during sorption experiment and mois-
ture induced swelling stresses increased with increase in moisture content.
Several researchers have observed non-Fickian diffusion in epoxies [23]. They have
proposed different theories behind such behavior. The non-Fickian behavior may occur
due to swelling of the polymer matrix, which increases the number of active sites available
for sorption [24]; and by chemical degradation of epoxy resins and/or epoxy/filler interface
[25,26]. In the latter case, the water diffusion initially follows the Fickian model, but then
the deviations from the ideal behavior are explained by the flow of water molecules along
the fillermatrix interface followed by diffusion into the bulk resin and transport of water
by microcracks [27]. Deviations from Fickian diffusion also arise as a consequence of the
finite rates by which changes in polymer structure occur in response to the stresses imposed
upon the material before and during the sorption process. If the polymer is partially
crystalline or contains fillers, the transport process is dependent upon the degree of crystal-
linity and the properties of the filler [21]. The presence of filler may be expected to cause a
decrease in permeability due to increase in crystalline region and also formation of tortu-
ous path for diffusing molecules.
CONCLUSIONS
The following conclusions can be made:

. SEMs show uniform dispersion at lower concentrations of silica but formation of
agglomerates as silica content increases.
. TGA results show improved thermal stability and increase in ash content with increase
in silica content.
. Swelling kinetics shows that for most of the solvents the nature of diffusion is
non-Fickian and as the silica content increases, deviation from Fickian behavior
increases. Moreover diffusivity decreases with increase in silica content but increases
with temperature. Sorption values increases with silica content and also increase with
temperature.
ACKNOWLEDGMENTS
We gratefully acknowledge the funding provided by All India Council of Technical

Education, New Delhi, India for their financial support under Career Award for Young
Teachers (CAYT) to Dr Anupama Kaushik.
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Solvent Absorption Characteristics of

Epoxy-Colloidal Silica Nanocomposites

*Author to whom correspondence should be addressed. E-mail: anupamachem@gmail.com

Nanocomposites are a class of composite materials in which the dimensions of the

The composites were prepared by mechanical mixing using a commercially available

Table 1. Sample identification depending on filler loading for various

% age of resin % age of silica

Table 2. Solubility parameters, dipole moment, dielectric constant,

Solubility Molar volume

Water 23.4 1.85 80 18 Polar protic solvent

RESULT AND DISCUSSION

Results of Scanning Electron Microscopy

The percent absorption was calculated using Equation (1):

Table 3. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.0974 0.4651 0.0933 3.00 0.017 0.05

Table 4. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.2369 0.2930 0.1643 3.45 0.030 0.10

Table 5. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.2504 0.2319 0.0528 4.25 0.024 0.10

Table 6. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.0985 0.4832 0.1264 3.28 0.058 0.19

Table 7. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.1933 0.3266 0.0155 2.60 0.024 0.06

Table 8. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.3215 0.2255 0.0268 2.75 0.035 0.10

Table 9. Values of slope (n), intercept (k), diffusivity coefficient (D),

Sample D 108 P 108

1 S0 0.2735 0.2645 0.0968 3.67 0.056 0.21

Sample D 108 P 108

1 S0 0.3736 0.1987 0.1028 5.22 0.060 0.31

Sample D 108 P 108

1 S0 0.1490 0.3820 0.0586 3.49 0.042 0.15

Sample D 108 P 108

1 S0 0.1433 0.3949 0.0787 3.47 0.057 0.20

The following conclusions can be made:

We gratefully acknowledge the funding provided by All India Council of Technical

1. Preghenella, M., Pegoretti, A. and Migliaresi, C. (2005). Thermo-Mechanical Characterization of Fumed

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