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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
and 60
/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 to 150
C at a heating rate
of 10
, 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
) Loss Modulus (E
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. 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 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 to 200
C and 210
C
to 380
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 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 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
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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