Synthesis and Characterization

of Hybrid Nanocomposites
Comprising Poly(vinyl Alcohol)
and Colloidal Silica
MOUSUMI DE SARKAR, PAROMITA DEB
Rubber Technology Center, Indian Institute of Technology, Kharagpur 721 302, India
Received: July 2, 2007
Accepted: February 20, 2009
ABSTRACT: Organicinorganic hybrid composite lms were developed using
poly(vinyl alcohol) (PVA) and an aqueous dispersion of colloidal silica of initial
particle size of 1530 nm. The hybrid lms, prepared with varied proportion of
colloidal silica (1090 phr), were found to be transparent, indicating the nanolevel
dispersion of the inorganic component over the polymer. Morphological studies
further revealed no signicant agglomeration of the silica domains embedded
into the polymer matrix. A depression in glass transition temperature of PVA is
observed with increasing proportion of silica. The degree of crystallinity also
showed a decreasing trend with increasing amount of silica. However, the
composite lms demonstrated superior mechanical performances, higher
resistances to dissolution in boiling water, and lower permeability compared with
virgin PVA, owing to the better interaction between PVA and silica as well as the
reinforcing action of nanosilica particles in the polymer matrix. C
2009 Wiley
Periodicals, Inc. Adv Polym Techn 27: 152162, 2008; Published online in Wiley
InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20129
KEY WORDS: Colloidal silica, Morphology, Nanocomposites,
Organicinorganic hybrid, Structureproperty relations
Correspondence to: Mousumi De Sarkar; e-mail: mouds22@
gmail.com.
Advances in Polymer Technology, Vol. 27, No. 3, 152162 (2008)
C
2009 Wiley Periodicals, Inc.
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
Introduction
O
rganicinorganic hybrid composites have at-
tracted considerable attention recently be-
cause of their distinctive physical and chemical
properties.
1
The hybrid composites inherit charac-
teristics such as exibility, easy processabilty, and
lightness from the organic components, whereas
properties such as strength, dimensional sta-
bility, chemical inertness, and thermal stabil-
ity are bestowed to them from the inorganic
scaffolds.
13
Because of their extraordinary perfor-
mances, organicinorganic hybrid composites nd
widespread applications in diverse high-technology
elds such as optics, electronics, sensors, and laser
technologies.
1
Hybrid composites consisting of a
wide variety of inorganic and organic components
developed so far are mostly prepared through sol
gel techniques at ambient temperature, in which the
starting materials are in solution phase.
47
The ma-
jor challenge associated with the solgel technique is
the sensitivity of the size of the in situ generated in-
organic scaffolds on the reaction conditions such as
temperature, pH, type of solvent used, andrate of re-
moval of solvent.
8
Agglomerations of the inorganic
components are often evidenced, particularly at
their higher concentrations, thereby preventing ho-
mogeneityandnanolevel dispersionandresultingin
the loss of optical transparency and deterioration of
mechanical performance of the composites.
9
More-
over, the solgel process often leads to signicant
shrinkage, causing internal stress and generation of
microvoids.
10
The use of preformed nanosized col-
loidal silica has proven to be successful while devel-
oping hybrid composites.
1116
The approach of us-
ing colloidal silica provides the advantage of precise
control on the size distribution of the inorganic do-
mains andthus results in their better dispersion over
the organic matrix, thereby giving rise to improved
properties. Athorough literature survey reveals that
the hybrid composites composed of nanosized col-
loidal silica were mostly synthesized through in situ
polymerization with acrylated monomers.
15,16
The
use of colloidal nanosilica with preformed polymer
for developing hybrid composites has not yet been
explored extensively. The reports published so far
are limitedtothe hybridcomposites containingacry-
late polymers or epoxies and colloidal silica.
17,18
In this study, poly(vinyl alcohol) (PVA) is utilized
as the organic component, and the colloidal silica in
the size range of 1530 nm is used as the inorganic
moiety. The interest in combining PVAand colloidal
silica is essentially boosted by the possibility of hy-
drogen bond formation among themselves involv-
ing the hydroxyl groups present in both the moi-
eties, thereby essentially eliminating the need for a
coupling agent. Strong interaction between the or-
ganic and inorganic phases is expected to improve
homogeneity and molecular-level mixing. Reports
are available depicting interaction between surface
hydroxyl groups of SiO
2
and PVA.
1921
Potential ap-
plications of PVAsilica hybrid lms may include
membranes for pervaporation, packaging, immobi-
lizations of enzymes for sensors, etc. This research
contribution is primarily directed to capture the in-
uence of colloidal silica nanoparticles on the prop-
erties of PVA/silica hybridcomposites. The morpho-
logical and structural features as well as the ther-
mal and mechanical characteristics of the hybrid
composite lms have been studied using different
instrumental techniques. The performances of the
composite lms have been evaluated on the basis of
their resistance toward dissolution in boiling water
as well as in terms of the extent of permeability of
oxygen gas through them.
Experimental
MATERIALS USED
The organic component, PVA (98 mole% hy-
drolyzed grade), used in this study, having degree
of polymerization of 1800, is procured from Loba
Chemie Pvt. Ltd., (Mumbai, India). The inorganic
component, colloidal silica, supplied by Sterling
Chemicals (Gujarat, India), is an aqueous dispersion
containing 30 wt% of silica of the average particle
size ranging from15 to 30 nm, with pH10. Both PVA
and colloidal silica utilized throughout this work are
used as received from the suppliers without further
purication.
PREPARATION OF PVACOLLOIDAL
SILICA HYBRID COMPOSITES
A 5 wt% homogeneous solution of PVA was rst
preparedbydissolvingPVApowder inboilingwater
and then continuously stirring for an hour. Requisite
amount of aqueous dispersion of colloidal silica was
added to the PVA solution and continuously stirred
for another hour at 27 2

C to obtain a perfectly
homogeneous solution. The amount of aqueous
Advances in Polymer Technology DOI 10.1002/adv 153
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
TABLE I
Composition of Hybrid Composites
Amount of Silica (wt%)
Sample Aqueous Colloidal
Designation PVA (phr) Silica Dispersions (phr) Calculated Amount (W
c
) Actual Amount
a
(W
a
)
P0 100 0 0 0
P10 100 10 3 2.9
P20 100 20 6 5.8
P30 100 30 9 8.7
P40 100 40 12 11.4
P50 100 50 15 14.1
P60 100 60 18 16.5
P70 100 70 21 18.3
P80 100 80 24 20.6
P90 100 90 27 21.8
a
As obtained from the residue at 700

C in an air atmosphere through TGA.

dispersion of colloidal silica was varied from 0 to
90 phr (parts per hundred parts resin) with respect
to PVA. The compositions of all the reactionmixtures
are presented in Table I. The reaction mixtures con-
taining PVA and colloidal silica solution were then
casted onto thoroughly cleaned stainless steel plates
and left undisturbed at room temperature for 48 h
to remove water. The resultant lms were then kept
at 50

C for further drying for 24 hours to eliminate

the residual moisture. Thicknesses of the resultant
dried lms, measured with a high-precision thick-
ness gauge, were about 0.05 to 0.07 mm. Since PVA
is substantially hygroscopic in nature, the lms were
stored inside desiccators lled with anhydrous silica
gels before proceeding for characterizations.
CHARACTERIZATION OF THE HYBRID
COMPOSITES
The transmittance of the hybrid composite lms
was quantiedwitha UVvisible spectrophotometer
(UV 1600 Shimadzu) in the wavelength range of 200
to 800 cm
1
at room temperature.
The size, shape, and distribution of silica par-
ticles over the polymer matrix were precisely de-
termined with a transmission electron microscope
(Model C12, Philips). Very dilute solutions of the
precursor mixtures of the hybrid composites were
casted directly on copper grids of 300-mesh size and
allowed to dry completely. With the resultant very
thin lms (<0.5 m thickness) of the composites,
transmission electron microscopic (TEM) studies
were performed. The acceleration voltage used was
80 kV, and magnication was 13,500. A scan-
ning electron microscope (JOEL SEM 5800) with an
integrated energy-dispersive spectroscopic (EDAX)
system was used to map the location of silicon
atoms in the hybrid lms at a magnication of
2000.
The wide-angle x-ray diffraction studies of the
hybrid composite lms were carried out with a PW
1710 x-ray diffractometer. Nickel-ltered Cu K ra-
diation with =1.54

Awas used as the x-ray source.
The x-ray generator was run at 40 kV and 20 mA.
Measurements were performedat 2 values between
10

and 60

, with a scanning speed of 2

/min. The
samples of almost equal thickness and area were ex-
posed. In the wide-angle x-ray diffraction plots, the
crystalline andamorphous segments were separated
by curve tting by nonlinear least-square method
under the assumption that the intensity peak pro-
les could be approximated by the Lorentzian func-
tion. The degree of crystallinity (x
c
) was calculated
using the following equation
22
:
x
c
(%) =

I
c
I
c
+ I
a

100 (1)
where I
c
is the area under crystalline peak and I
a
the
area under amorphous peak.
The interplanar distance (d), the interchain dis-
tance (r), and the size of the crystallites were deter-
mined by the following equations
22
:
d =

2 sin
(2)
r = 1.22 d (3)
154 Advances in Polymer Technology DOI 10.1002/adv
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
Dynamic mechanical thermal analysis was carried
out with a DMTA IV analyzer (Rheometric Scien-
tic) under tension mode at a frequency of 1 Hz
with a heating rate of 2

C/min to record the storage

modulus, loss modulus, and loss tangent within the
temperature range of 0

C to 150

C. The glass tran-

sition temperatures of the composites correspond to
the maxima of the loss tangent (tan ) peaks or the
ination points in tan plot.
Thermogravimetric analysis (TGA) was per-
formed with a Pyris Diamond TG/DTA thermo-
gravimeter in both nitrogen and air atmospheres.
For the TGA studies, approximately 20 mg of the
sample was placed in the platinum pan and heated
from room temperature to 700

C at a heating rate
of 10

C/min. The residual weights of the samples

found at 700

C in an air atmosphere were consid-

ered to be the exact amount of silica incorporated in
the hybrid composites.
The mechanical performance of the composite
lms was studiedthroughthe testing of tensile prop-
erties as well as hardness. For the tensile testing,
dumbbell-shaped specimens were rst punched out
from the prepared composite lms. Tensile prop-
erties of the specimens were performed with a
UTM tensiometer, Honseld, at room temperature
(27 2

C) at a strain rate of 500 mm/min follow-

ing the ASTM D412 method. The values of ultimate
tensile strength and elongation at break reported
here were based on the average of at least three
measurements fromeach specimen. Hardness of the
prepared hybrid lms was determined by static in-
dentation tests with a Shore-Ddurometer. Hardness
values of ve specimens were tested for each com-
position and the average readings were noted.
Boiling water resistance of the composite lms
was measured in terms of the time taken by the
lms to get completely dissolved (without any vis-
ible trace) in boiling water. For this experiment,
small pieces of approximately identical dimensions
and weights were cut from the hybrid compos-
ite lms. Each piece was then immersed indi-
vidually into test tubes containing boiling water.
The dissolution time taken for each specimen was
recorded. The values of the dissolutiontime reported
here are based on the average of ve consecutive
experiments.
Permeability tests were carried out with hybrid
composite lms with thickness of about 0.06 mm.
Oxygen transmission rates (OTRs) were evaluated
at room temperature (27

C) according to the ASTM

D1434 method.
Results and Discussion
SILICA CONTENT OF THE
HYBRID COMPOSITES
The aqueous dispersion of colloidal silica solu-
tion used in this study contains 30 wt% of silica.
Therefore, the amount of silica practically added for
the preparation of the hybrid samples can easily be
calculated from the initial loading of aqueous dis-
persion of colloidal silica solution and is displayed
in Table I. The actual amount of silica retained in the
hybrid composites is determined from the amount
of residue obtained through TGA, carried out in an
air atmosphere at 700

C. The actual amount of silica

retained in the composite lms is also given in the
table. It is apparent from the table that the actual sil-
ica content of the composite lms is less than that of
their theoretically added amount, which is probably
associated to their loss during the preparation and
processing of the composite lms.
OPTICAL TRANSPARENCY OF THE
HYBRID COMPOSITES
The visual inspections of the hybrid lms of
thickness of about 0.06 mm reveal that the opti-
cal transparency is retained even with the signi-
cantly high loading of silica of 22 wt% (P90). It
is well known that any particle with size greater
than 100 nm diffracts light.
3
Since the composite
lms prepared here show reasonably good optical
transparency, it can be logically concluded that the
inorganic domains present in the composites are
of less than 100-nm size and therefore the com-
posites developed here can be technically termed
nanocomposites. Since initial size of the colloidal
silica added was in the range of 1530 nm, it can
also be inferred that agglomeration of the silica
was not pronounced in those composites. Had there
been signicant agglomeration of the colloidal silica,
the transparency would have been much hindered
and the lms would have appeared to be translu-
cent/nearly opaque.
To quantify the optical transparency of the PVA
colloidal silica composite lms, UVvisible spec-
troscopic studies were performed. Figure 1 shows
the percentage transmittance of the composite lms
prepared with various loading of colloidal silica
against wavelength as observed through UVvisible
spectroscopy. From the gure, it is evident that
Advances in Polymer Technology DOI 10.1002/adv 155
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
150 300 450 600 750 900
0
25
50
75
100
T
r
a
n
s
m
i
t
t
a
n
c
e

(
%
)
Wavelength (cm )
P0 (0%)
P30 (8.7%)
P50 (14.1%)
P70 (18.3%)
P90 (21.8%)
P0
P90
FIGURE 1. UVvisible spectroscopic results of
PVAcolloidal silica hybrid composite lms with various
amounts of silica. (The values in the parenthesis signify
the actual silica loading in wt%.)
transmittance drops marginally with increasing col-
loidal silica loading. The slight decrease in optical
transparencies of the composites with high loading
of silica may be attributed to the alteration of refrac-
tive indices of the polymer lms with embedded
silica. However, all the composite lms show rea-
sonably high transparency of more than 70% in the
visible wavelength range irrespective of their col-
loidal silica content.
MORPHOLOGY OF THE
HYBRID COMPOSITES
Figure 2 shows the representative TEM micro-
graphof the PVAcolloidal silica composite lmcon-
600 nm
FIGURE 2. Transmission electron micrograph of
PVAcolloidal silica hybrid composite (P80) with
20.6 wt% of silica.
taining about 21 wt% of silica (P80). The black spots
in the TEMmicrograph indicate the position of silica
domains over the continuous polymer matrix. It is
apparent from the TEM micrograph that silica do-
mains are dispersed well over the PVA matrix. The
average size of the silica domains was subsequently
measuredthroughstandardimage analysis software
and was found to be in the range of 2025 nm, which
is about the same as that of the colloidal dispersion
of nanosilica particles initially used to develop the
PVA-based hybrid composite.
The distribution of silica over the polymer ma-
trix in the hybrid composites was further elucidated
by the EDAX silica mapping technique. The EDAX
mapping of the composites with two different sil-
ica contents of 14 wt% (P50) and 21 wt% (P80)
are shown in Figs. 3a and 3b, respectively. The loca-
tion of silica is designated here as white dots, over
the polymer matrix (the dark background). From
the gures, it is apparent that the silica particles are
uniformly distributed over the matrix, without any
evidence of agglomeration even with high loading
of silica. As is obvious, the number of silica parti-
cles per unit area is more in P80 than in P50 (Fig. 3b
vs. 3a). In the hybrid composites, the homogeneous
distribution of colloidal silica in the PVA matrix is
(a)
(b)
2 m
2 m
FIGURE 3. EDAX silicon mappings for hybrid
composites: (a) P50 and (b) P80, comprising 14.1 and
20.6 wt% of silica, respectively.
156 Advances in Polymer Technology DOI 10.1002/adv
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
probably due to the plausible intermolecular hydro-
gen bonding between the two components involv-
ing hydroxyl groups present in both the moieties.
The formation of intramolecular hydrogen bonding
among the colloidal silica particles themselves lead-
ing to their aggregations is improbable owing to the
electrically charged layers over the silica nanoparti-
cles in the colloidal suspension.
X-RAY DIFFRACTION STUDIES OF THE
HYBRID COMPOSITES
The x-ray diffraction results of the hybrid com-
posite lms with different amounts of silica are
shown in Fig. 4. Pure PVA (P0) displays a strong
diffraction peak at 2 =19.35

, corresponding to

101
reection.
23
From the gure, it is evident that the
intensity of this crystalline peak of PVA decreases
in the composites upon the introduction of colloidal
silica. The degree of crystallinity, interplanar spac-
ing, and interchain distances of the PVA segments
in the composite lms are calculated from the x-ray
diffraction results and are given in Table II. It is ev-
ident from the table that the degree of crystallinity
monotonically decreases, whereas interplanar and
interchain distances increase with increase in silica
content.
It is well knownthat the crystallinityof PVAarises
fromthe stronghydrogenbondingbetweenthe adja-
cent polymer chains involving the hydroxyl groups
( OH) present in the PVA backbone.
3
On the basis
10 20 30 40 50 60
2 ()
(a)
(b)
(c)
(d)
(e)
(f)
FIGURE 4. X-ray diffraction results of (a) pure PVA and
PVAcolloidal silica hybrid composites: (b) P10, (c) P30,
(d) P50, (e) P70, and (f) P90 with 2.9, 8.7, 14.1, 18.3, and
21.8 wt% of silica, respectively.
TABLE II
Results from X-Ray Diffraction Studies
Degree of Interplanar Interchain
Sample Crystallinity (%) Spacing (d,

A) spacing (r,

A)
P0 55 4.54 5.54
P10 53 4.54 5.54
P30 50 4.54 5.54
P50 44 4.57 5.58
P70 39 4.59 5.60
P90 35 4.59 5.69
of the x-ray diffraction results obtained here, it can
be concluded that the colloidal silica interacts with
the PVA chains, resulting in an increase in the in-
terplanar and interchain spacings, and thereby dis-
turbing the crystalline arrangement of PVA in the
composite lms. Moreover, since the colloidal silica
gels are amorphous in nature, they do not construc-
tively contribute to the crystallinity of the compos-
ites. Colloidal silica particles practically act as de-
fects in the crystalline arrangement of the PVA. As a
result, the degree of crystallinity decreases linearly
with increase in colloidal silica loading.
DYNAMIC MECHANICAL THERMAL
ANALYSIS OF THE HYBRID COMPOSITES
The inuence of silica loadingonthe storage mod-
ulus andloss modulus values of PVAcolloidal silica
composite lms, observed through DMTA at room
temperature (25

C), are given in Table III. It can be

noted that the storage modulus values increase ap-
preciably with increase in colloidal silica loading
compared with pure PVA. The storage modulus of
virgin PVA increases from 0.54 10
8
MPa to 22.2
10
8
MPa with 90 phr (22 wt%) of silicaan
increase of more than 40 times. As apparent from
the table, the silica content follows a nonlinear rela-
tionship with storage modulus of PVAsilica com-
posites. The increment in storage modulus becomes
suddenly more pronounced with the addition of
50 phr or higher amount of silica. It can be con-
cluded that inorganic colloidal silica may be act-
ing as physical reinforcement, thereby increasing the
storage modulus of the resultant composites. Arela-
tively minor increase in loss modulus values is also
observed with increasing amount of silica. The in-
uence of colloidal nanosilica content on the loss
tangent peak (tan ) of the composites is shown
in Fig. 5. It can be observed that the temperature
Advances in Polymer Technology DOI 10.1002/adv 157
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
TABLE III
Dynamic Mechanical and Mechanical Properties of Hybrid Composites
Dynamic Mechanical Properties Mechanical Properties
Storage Modulus (E

) Loss Modulus (E

) Glass Transition Tensile Elongation Hardnesss

Sample at 25

C (10
8
, MPa) at 25

C (10
8
, MPa) Temperature (T
g
,

C) Strength (MPa) at Break (%) (Shore D)
P0 0.54 0.10 71 32.9 80 45
P10 1.02 0.19 76 34.0 72 51
P20 0.93 0.14 71 36.8 70 55
P30 1.94 0.31 52 36.3 65 57
P40 2.08 0.32 50 35.8 74 60
P50 4.55 0.86 38 37.1 80 62
P60 6.83 0.86 23 38.4 62 63
P70 10.50 1.17 27 45.2 89 65
P80 15.31 1.75 25 46.3 84 67
P90 22.20 2.44 24 48.1 90 69
corresponding to tan peak maxima of the com-
posites, representing the glass transition tempera-
ture, shifts to lower values upon incorporation of
silica. As observed in the gure, tan peaks were
not well dened for certain composites such as P50
and P70. Artifacts, in terms of multiple peaks, are
seen with those compositions. For them, the tem-
perature corresponding to the most prominent tan
peak is considered as T
g
. The inuence of silica
content on the glass transition temperatures (T
g
) of
the composites lms is captured in Table III. The
glass transition temperature of pure PVA has been
found here to be 71

C. With increasing amount of

colloidal silica, the glass transition temperature de-
creases. The composite lms with about 22 wt% of
25 0 25 50 75 100 125 150 175
0.05
0.10
0.15
0.20
0.25

Temperature (
o
C)
P0 (0%)
P50 (14.1%)
P70 (18.3%)
P90 (21.8%)
FIGURE 5. Variation of tan values with silica loading in
PVAcolloidal silica hybrid composites. (The values in the
parenthesis signify the actual amount of silica in wt%.)
colloidal silica (P90) demonstrate a T
g
of 24

C. It is
worth mentioning here that precise and unambigu-
ous determination of T
g
basedon the tan peak max-
ima was not possible through this study for most of
the compositions. The error in determining T
g
val-
ues has been found to be as high as 6

C. However,
it is certain through the DMTA results that T
g
de-
creases with increasing silica content in the hybrid
composites. The decrease in T
g
upon incorporation
of silica in polymer composites was documented
previously. Preghenella et al.
24
reported reduction in
T
g
with increasing loading of fumed silica in epoxy
nanocomposites. Sun and coworkers
25
also noticed
that a reduction in T
g
of the silica-lledcompositions
resultedbecause of the presence of residual moisture
and organic materials in the silica surface. In case of
PVAcolloidal silica hybridcomposites, the decrease
in T
g
can also be correlated to the presence of en-
trapped moisture in the colloidal silica surface. The
TGAresults shown in a later section also provide ev-
idence of entrapped water in the hybrid composites.
In addition to entrapped moisture, there could be
other factors contributing to the reduction of T
g
in
silica-lled composites, as well. In pure PVA, intra-
and intermolecular hydrogen bonds are present, in-
volving the hydroxyl groups in polymer backbone.
With increasing amount of colloidal silica, it is likely
that more and more PVA chains become attached
to silica through hydrogen bonds. In other words,
the hydrogen bonds involving only PVA chains
are getting replaced by the hydrogen bonds be-
tween PVA and colloidal silica, which implies that
the polymerpolymer interaction initially present
in pure PVA may be changing to polymerller
(nanosilica) interactions in the composites. It has
158 Advances in Polymer Technology DOI 10.1002/adv
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
been revealed from x-ray diffraction results shown
earlier that upon incorporation of colloidal silica,
the crystallinity of the PVA chains gets disrupted
owing to lesser extent of hydrogen bonds involving
exclusively the PVA chains. The decrease in crys-
tallinity in PVAsilica composites upon the addition
of silica may lead to relatively easier movement of
polymer chains, thus resulting in the depression of
glass transition temperature. At this time, the ac-
tual cause of depression of glass transition temper-
ature upon the addition of silica is debatable. Ex-
haustive research is required to reach a coherent
conclusion.
MECHANICAL PROPERTIES OF THE
HYBRID COMPOSITES
Figure 6 displays the stressstrain curves of the
PVAsilica compositions with different levels of sil-
ica. It is apparent that the nature of the tensile curve
does not alter appreciably with changing silica load-
ing. Table III elucidates the inuence of silica on
the ultimate tensile strength values for the hybrid
composites. An increase in tensile strength has been
noticed with increasing amount of silica. The pure
PVA lm demonstrates the ultimate tensile strength
of 32.9 MPa, whereas the composite lm prepared
with 90 phr of colloidal silica dispersion (P90) con-
taining about 22 wt%of silica shows tensile strength
of 48.1 MPa. These observations can be explained by
considering the fact that the colloidal silica may be
acting as physical reinforcement in the PVA matrix,
causing a decrease in the tensile strength. The elon-
0 20 40 60 80 100
0
10
20
30
40
50
S
t
r
e
s
s

(
M
P
a
)
Strain (%)
P0 (0%)
P30 (8.7%)
P50 (14.1%)
P70 (18.3%)
P90 (21.8%)
FIGURE 6. Tensile stressstrain curves of
PVAcolloidal silica hybrid composites. (The values in the
parenthesis signify the actual silica loading in wt%.)
gation at break values, on the other hand, does not
follow a denitive trend, as shown in Table III.
The change in Shore-D hardness of the PVA
colloidal silica composite lms with change in silica
content is also displayed in Table III. It is apparent
from the data that hardness increases signicantly
with increase in silica loading. With the addition of
colloidal silica to the PVA matrix, hydrogen bonds
are probably formed between colloidal silica and
PVA chains. Moreover, the inorganic colloidal silica
may impart mechanical reinforcement in the PVA
matrix. As a result, hardness of the composite lms
increases with increase in silica content.
THERMAL PROPERTIES OF THE
HYBRID COMPOSITES
Figure 7a shows the TGAcurves of pure PVA(P0)
and composite lms comprising different levels of
colloidal silica in N
2
atmosphere. It is clear that the
temperature at whichthe initial weight loss occurred
remainedalmost the same with increasing silica con-
tent. However, the amount of residue (as shown in
Table IV) at 700

C increases with increasing silica

content, suggesting successful incorporation of the
silica moiety into the hybrid materials. The black
color of the residues found with the hybrid compos-
ites after the TGA runs at 700

C provides evidence
of some amount of organic moiety being trapped
in the silica. Virgin PVA showed a residue of about
1.8%, which may be due to its incomplete decompo-
sition in an inert atmosphere (N
2
) or due to a trace
of impurity present in the TGA pan.
To understand the decomposition behavior of the
hybrid composites lucidly, derivative plots of TGA
results were evaluated. Figure 7b shows the plot of
differential TGA of pure PVA, as well as the hybrid
composites. Virgin PVA demonstrates two distinct
steps of thermal decomposition ranging between
35

C200

C and 210

C380

C. A not-so-signicant
step of decomposition is also observed in pure PVA
in the range of 400

C to 500

C. On the other hand,

the hybrid composites demonstrate three distinct
steps of thermal decomposition. In addition to the
two similar decomposition steps as observed in
pure PVA in the ranges of 35

C to 200

C and 210

C
to 380

C, the hybrid composites featured prominent

decomposition in the range of 400

C to 500

C. This
decomposition step, distinctly found in hybrid com-
posites, becomes more prominent with increasing
loading of colloidal silica. The decomposition peaks
were deconvoluted through curve tting and the
area under each peak was subsequently evaluated
Advances in Polymer Technology DOI 10.1002/adv 159
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
0 100 200 300 400 500 600 700 800
0
20
40
60
80
100
W
e
i
g
h
t

l
o
s
s

(
%
)
Temperature (
o
C)
P0
P10
P30
P50
P70
P90
P0
P90
(a)
0 150 300 450 600 750
Temperature (
o
C)
P0
P10
P30
P50
P70
P90
(b)
FIGURE 7. (a) TGA curves of pure PVA (P0) and
different PVAcolloidal silica hybrid composites.
(b) Derivation plots of TGA results for pure PVA (P0) and
different PVAcolloidal silica hybrid composites.
and their relative proportions are given in Table IV.
The rst step of decomposition, found in pure PVA
and the hybrid composites in the range of 35

C to
200

C, can be related to the loss of entrapped water

molecules. It is a well-known fact that PVA is a hy-
groscopic material. The humidity of the atmosphere
causes PVA to absorb some moisture on account
of the hydrophilic nature of the hydroxyl groups.
Moreover, the test lms were prepared through
casting from the aqueous solutions. Therefore, the
presence of some amount of entrapped water is
inevitable. It is interesting to notice from the table
that in the temperature range of 35

C to 200

C, the
decomposition peak area for virgin PVA is almost
identical with those for composites with different
silica loadings. Therefore, it can be concluded
that, since the amount of PVA is the same in all
the composites, the extent of rst decomposition
due to the elimination of water is comparable
for the entire compositional range. At elevated
temperature (>100

C), in virgin PVA, the intra- or

interchain hydrogen bonding can be converted to
covalent bonding with the elimination of water. The
crosslinking involving the hydroxyl groups of PVA
and colloidal silica with the elimination of water is
also possible for the hybrid composites.
The second step between 210

C and 380

C signi-
es the decomposition of the main chain PVA moi-
ety. It can be noticed that the maxima of the decom-
position peaks shift to lower temperatures in the
hybrid composites with increasing silica content as
compared with the virgin PVA. The third decompo-
sition step observed in the composites in the range
of 400

C to 500

C may involve the decomposition

of polymer chains directly associated or entrapped
in the colloidal silica systems. In virgin PVA, this
step is not prominent and may involve breaking of
C O covalent bonds in the PVA network. It is
evident from Fig. 7b and Table IV that with the in-
crease in silica loading, the third step of decomposi-
tion becomes prominent and the peak maxima shifts
to higher temperatures.
BOILING WATER RESISTANCE OF THE
HYBRID COMPOSITES
Figure 8 captures the inuence of colloidal
silica on the resistance to dissolution of the hybrid
composites in boiling water. The tendency of the
hybrid composite samples comprising PVA and
colloidal silica to get dissolved in boiling water
decreases with the increasing amount of silica, as
shown in Fig. 8. It has been observed that pure
PVA lms dissolve almost instantly in boiling
water. However, in composites, the resistance to
solvation in boiling water increases with the gradual
increase in silica loading. Composite lms with
about 22% silica remain undissolved even after 2 h.
It is interesting to notice that with the composites
containing more than 14 wt% of silica (P50), the
resistance to solvation in boiling water increases
quite drastically, which is in line with the trend
observed in the storage modulus values (Table III).
160 Advances in Polymer Technology DOI 10.1002/adv
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
TABLE IV
Results from the Derivatives of Thermogravimetric Analysis
First Decomposition Step Second Decomposition Step Third Decomposition Step
Peak Maxima Area Under Peak Area Under Peak Area Under Residue
a
at
Sample (

C) the Peak (a.u.) Maxima (

C) the Peak (a.u.) Maxima (

C) the Peak (a.u.) 700

C (wt%)
P0 92 10.0 302 84.9 421 5.1 1.8
P10 92 9.6 298 78.7 430 11.7 8.5
P30 102 9.9 292 73.9 432 16.2 15.1
P50 112 10.1 291 70.8 432 19.1 16.9
P70 122 9.6 282 69.2 434 21.2 21.8
P90 122 9.5 272 63.4 436 27.1 27.5
a
In nitrogen atmosphere.
0 5 10 15 20 25
0
40
80
120
160
200
D
i
s
s
o
l
u
t
i
o
n

t
i
m
e

(
m
i
n
)
Actual silica content (wt%)
FIGURE 8. Changes in boiling water resistance of
PVAcolloidal silica hybrid composites with silica content.
PERMEABILITY STUDIES WITH
PVACOLLOIDAL SILICA
HYBRID COMPOSITES
The change in oxygen transmission rates (OTRs)
of the composite lms upon the incorporation of
colloidal silica is shown in Fig. 9. There is an ap-
preciable reduction in OTR observed through the
composite lms with increase in silica loading. Pure
PVAdemonstrates OTR of 2.3 10
6
cm
3
/(m
2
day),
whereas P90 with about 22 wt%of silica shows OTR
of 0.32 10
6
cm
3
/(m
2
day)a reduction of about
seven times. The reduction in OTR may be a con-
sequence of more obstacles created by the silica do-
mains over the polymer matrix, causing difculty
for the gas molecules to penetrate and pass through
the composite lms.
0 5 10 15 20 25
0.0
0.5
1.0
1.5
2.0
2.5
3.0
O
T
R


1

0
6
(
c
m
3
m
2
d
a
y
)
Actual silica content (wt%)
FIGURE 9. Changes in oxygen transmission rates
(OTRs) through PVAcolloidal silica hybrid composite
lms with silica content.
Conclusion
PVA and colloidal silica hybrid composite lms
demonstrated high optical transparencies, indicat-
ing nanolevel dispersion of inorganic silica moieties
over the PVA matrix. Microstructure analysis re-
vealed that the hybrid composites were capable of
sustaining high silica loading without agglomera-
tion. TEM studies showed that the dimension of the
silica domains lie within the range of 2025 nm, irre-
spective of the loadingof silica. EDAXmapof the hy-
brid composites showed homogeneous nanometer-
level dispersion of silica particles, even with their
high loading. The hybrid composites showed sub-
stantial mechanical reinforcements, however, at the
Advances in Polymer Technology DOI 10.1002/adv 161
HYBRID NANOCOMPOSITES OF POLY(VINYL ALCOHOL) AND COLLOIDAL SILICA
expense of crystallinity, which showed a decreas-
ing trend with increasing silica loading. The ten-
sile strength and hardness values increased with
increasing amounts of colloidal silica. Hybrid com-
posites demonstrated better resistance to solvation
in boiling water and lesser permeability than those
of virgin PVA. On the basis of the experimental ob-
servations, it can be inferred that the signicant in-
teraction took place at the interfaces of PVA and
inorganic silica moieties, probably involving the hy-
drogen bonds.
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