Crosslinked Poly(vinyl alcohol) and Starch Composite

Films: Study of Their Physicomechanical, Thermal,

and Swelling Properties

B. Ramaraj
Central Institute of Plastics Engineering and Technology, 437/A, Hebbal Industrial area, Mysore 570 016, India

Received 14 June 2005; accepted 19 April 2006

DOI 10.1002/app.24612
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Crosslinked poly(vinyl alcohol) was blended water, 5% acetic acid, 50% ethanol, and sunflower oil
with 10, 20, 40, and 50 wt % starch by a solution-casting and their swelling characteristics in 50% ethanol and
process. The solution-cast films were dried, and then their sunflower oil. The prepared PVA/starch blends showed
physicomechanical properties including tensile strength, significant improvement in tensile modulus and in resist-
tensile elongation, tensile modulus, tear strength and den- ance to solubility in water, 5% acetic acid, and 50%
sity, and burst strength and density were tested. Thermal ethanol. Ó 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103:
analysis was performed by differential scanning calorime- 1127–1132, 2007
try. A moisture analysis of the PVA/starch films was
performed and their moisture content determined. Also Key words: composites; mechanical properties; differential
investigated were the films’resistance to solubility in scanning calorimetry (DSC); films; poly(vinyl alcohol)

INTRODUCTION size varies from source to source; rice starch granules

are roughly 3 mm in diameter, cornstarch has an
With the growing concern about environmental pol-
average granule size of 10 mm, whereas potato starch
lution from nondegradable synthetic plastics like
granules are about 35 mm in diameter. The use
polyethylene and polypropylene, the accumulation
of granular starch as a filler in plastics would be ad-
of plastic waste needs immediate resolution. Biode-
vantageous because (1) starch is an abundant, low-
gradable plastics have been intensively studied in
cost, and easily available renewable resource and (2)
recent years1–6 and have been used commercially in
starch is biodegradable and is useful in applications
various products such as garbage bags, composting
in which recovery or recycling would be difficult.14–22
yard bags, and grocery bags and for agricultural
Within the context of the ongoing research efforts
needs. Generally synthetic thermoplastics are blended
aimed at the preparation and evaluation of hydro-
with starch1–7 or natural fibers8–12 to make them
philic/biodegradable polymers,23–28 this article re-
environmentally friendly and degradable. Poly(vinyl
ports a study that has modified PVA films by cross-
alcohol) is one of the few degradable synthetic poly-
linking with glutaraldehyde and blending with starch.
mers13 available today. PVA is a water-processable
Various physicomechanical and thermal properties
polymer. The excellent chemical resistance and phys-
of the modified films were characterized. The aim of
ical properties of PVA have resulted in its broad
crosslinking PVA was to improve the mechanical
industrial use. But a limiting factor is the cost of
properties and water resistance of PVA films.
PVA, which has to compete with low-cost thermo-
plastic materials like polyethylene, polypropylene,
and poly(vinyl chloride) in packaging applications. EXPERIMENTAL
Hence, it is necessary to incorporate a low-cost, nat-
Materials
urally occurring filler or polymer like starch. Starch
is a polysaccharide produced by many plants as a The raw materials used in this study, poly(vinyl
storage polymer. It is composed of glucose mono- alcohol) (weight-average molecular weight of 125,000,
mers joined by 2-(1-4) linkages. The average granule degree of hydrolysis of 80%–90%, 0.75% ash) and
starch (potato starch, 0.55% ash, extrapure) were
supplied by M/S S. D. Fine Chem. Ltd. (Mumbai,
India). These polymers were kept in a dry environ-
Correspondence to: B. Ramaraj (ramaraj_rmrj@yahoo.co.in).
ment to prevent absorption of moisture prior to use.
Journal of Applied Polymer Science, Vol. 103, 1127–1132 (2007) Glutaraldehyde (25%) was supplied by M/S Rolex
V
C 2006 Wiley Periodicals, Inc. Chemicals (Mumbai, India).
1128 RAMARAJ

TABLE I TABLE II
Composition of Poly(vinyl alcohol) and Tensile Properties of PVA/Starch Composite Films
Starch Composite Films
Sample Tensile strength Elongation Elastic modulus
Sample Poly(vinyl Starch Glutaraldehyde code (Kg/cm2) (%) (Kg/cm2)
code alcohol) (g) (g) (mL)
Ax 136 500 42
A 20 — — Bx 133 207 46
Ax 20 — 4 CX 112 182 52
Bx 18 2 4 Dx 96 51 2040
Cx 16 4 4 Ex 89 13 3150
Dx 12 8 4
Ex 10 10 4

RESULTS AND DISCUSSION

Mechanical and thermal properties
Procedure for solution casting
From Table II, which shows the tensile properties
A series of PVA/starch blends were processed into of the films made of starch filler and poly(vinyl
films by solution casting through varying the starch alcohol) (PVA) matrix at different filler loadings, it is
content from 10% to 50%. The PVA powder was clear that the tensile strength of the films decreased
dissolved in hot water at 808C–908C. Then 4 mL of from 136 (sample Ax) to 89 (sample Ex) kg/cm2 and
25% glutaraldehyde solution was added as a cross- that the percentage of tensile elongation decreased
linking agent for PVA, and the starch powder made from 500% (sample Ax) to just 13% (sample Ex),
into paste was mixed according to the composition whereas the tensile modulus increased from 42
given in Table I and stirred well for about 30 min (sample Ax) to 3150 (sample Ex) kg/cm2 when starch
with constant stirring. Later the solution was filtered loading was increased from 10% to 50%. The addition
through cotton and cast into a glass plate mold of granular starch to PVA followed the general trend
(20
12 cm in size) lined with a polyethylene sheet. of the effects of filler on polymer properties. Tensile
The cast solution was evaporated at room temper- strength and elongation decreased as the amount of
ature (258C 6 38C) for 48 h. After evaporation, the starch added increased, and tensile modulus in-
films were removed from the glass plate and used creased because of the stiffening effect of the gran-
for further study. ules. The starch fillers increased the modulus, modi-
fied the shape, and induced a yield point in the
stress–strain diagram (Fig. 1) of ductile polymers
like PVA. The yielding phenomenon was really a
Testing methods
The tensile tests were carried out on cast films
according to ASTM D 882 in a Universal testing
machine (Lloyds UK, model LR 100K) with a cross-
head speed of 50 mm/min. Tear strength was mea-
sured according to ASTM D 1992 in a ATSFAAR
Elmendorf Tear Tester (ATS 100, Italy) using films
63
76 mm in size. Burst strength was measured
according to ASTM D 774-67 in a CIPET burst
strength tester (BST; A1 01) using films 6
6 cm in
size. Differential scanning calorimetry (DSC) mea-
surements were made using TA instruments (2010
DSC) from 408C to 2508C in a nitrogen atmosphere
at a heating rate of 108C/min. Moisture content
was measured for equilibrated samples in laboratory
conditions. The density of the modified films was
measured using a Mettler PM200 electronic weighing
balance according to the ASTM D 792 displacement
method. Moisture analysis was carried out with
dried samples in a humidity chamber made up of an
acrylic box (60
30
20 cm) containing a saturated
solution of sodium chloride. Solubility testing and
swelling analysis were carried out on dried film Figure 1 Stress–strain curves of PVA/starch composite
samples. films.

Journal of Applied Polymer Science DOI 10.1002/app

CROSSLINKED PVA AND STARCH COMPOSITE FILMS 1129

result of a crazing or a dewetting effect, in which

the adhesion of the filler with the matrix phase was
destroyed. The development of yield point at a high
concentration of filler is shown clearly in Figure 1
(sample Dx).
Several theories have been investigated about why
the composite properties depend on the filler-volume
fraction, F, and on geometry. Nicolais and Narkis29
developed a simple geometric model for the tensile
strength, s, of a composite with uniformly distrib-
uted spherical filler particles of equal radius

sc ¼ so ð1  1:21 F2=3 Þ (1)

where the subscripts c and o are the composite and

the matrix polymer, respectively. The experimental
and theoretical tensile values were calculated based
on eq. (1), and the tensile strength results are plotted
and shown in Figure 2. The data were slightly linear
with respect to F2/3 but had slopes that were less
negative than the value of 1.21 predicted by eq. (1).
This model was based on the assumption that there Figure 3 Relative tensile elongation of PVA/starch com-
was no adhesion between the matrix and the filler posite films.
particles. But the slope seen in Figure 2 suggests
some degree of adhesion between the PVA matrix
and starch filler, although not sufficient to prevent
the area reduction mechanism from reducing the ten- where ec is the elongation at break or yield of the
sile strength. composite and eo is the corresponding elongation of
Nielsen30,31 derived the following relationship be- the unfilled polymer. Tensile elongation was calcu-
tween elongation and volume fraction of the filler, F lated using eq. (2), and the experimental results are
plotted in Figure 3. It can be seen from the graph
ec ¼ eo ð1  F1=3 Þ (2) that the experimental results were more negative
than the predicted value of 1. The greater slope
seen in Figure 3 may reflect more adhesion of the
filler to the matrix than that assumed in eq. (2). Given
the hydrophilic nature of PVA and starch, a high
degree of adhesion would be expected.
Internal tear resistance is an important property
for films used in packaging. Tear strength of the
crosslinked PVA films and its blends containing
various amounts of starch in terms of gram force is
shown in Figure 4, from which it can be observed
that the tear resistance of crosslinked PVA (sample
Ax), 510 gf, decreased to 158 gf (sample Ex) with an
increase in starch content.
Another important mechanical property of the
film was burst strength, which is a measure of the
overall strength of a film. The effect of starch content
on the burst strength of PVA/starch films is shown
in Figure 5, which indicates the burst strength of the
films decreased from 5.976 kg/cm2 (sample Ax) to
4.991 kg/cm2 (sample Ex) with an increase in starch
content. The decreases in tear strength and burst
strength of the films with an increase in starch con-
tent may be attributed to the particular nature of
Figure 2 Relative tensile strength of PVA/starch compos- starch, which does not support the tear strength and
ite films. burst strength of crosslinked PVA films.

Journal of Applied Polymer Science DOI 10.1002/app

1130 RAMARAJ

Figure 4 Tear strength of PVA/starch composite films.

Figure 6 DSC thermograms of PVA/starch composite
films.

From the DSC thermograms of PVA and PVA/

starch blends shown in Figure 6, it is clear that PVA
enhanced Tg. The DSC thermogram of PVA/starch
(sample A) showed a broad Tg at 101.588C and a Tm
blend with 10% starch content (sample BX) showed
at 189.788C. When PVA was crosslinked with glutar-
Tg and Tm at 110.568C and 183.178C, respectively.
aldehyde (sample Ax), the Tg and Tm peak maxi-
Poly(vinyl alcohol) is a linear aliphatic hydroxyl
mums increased to 106.178C and 191.268C, respec-
polymer containing secondary hydroxyl groups in
tively. As a general rule, any structural features that
every alternate carbon, and the concentration of hy-
reduce segmental mobility or free volume will in-
droxyl groups has a significant impact on Tg and Tm.
crease the Tg. The crosslinking of the PVA matrix
The incorporation of starch (10%) powder (sample
introduced restrictions on segmental mobility and
Bx) increased the Tg peak maximum from 106.178C
to 110.568C. In this case the incorporation of starch
into the PVA matrix introduced more hydroxyl
groups and enhanced hydrogen bonding, which
increased the Tg peak maximum because both PVA
and starch are polar polymers with hydroxyl groups.
However, at 50% starch loading, because too many
starch particles were confined between PVA polymer
chains, the Tg decreased to 108.158C and the Tm
increased to 188.448C compared with those in the Bx
film.

Moisture content and density

The moisture content of the PVA/starch films is
reported in Table III, from which it can be observed
that the moisture content of PVA (12.07) decreased
slightly (11.05) because of crosslinking with glutaral-
dehyde. The addition of starch to the crosslinked
PVA did not produce much variation in moisture
content. This may be because both PVA and starch
are polar polymers containing hydroxyl groups.
From Table III, which also shows the density of
Figure 5 Burst strength of PVA/starch composite films. the different PVA/starch films, it can be observed

Journal of Applied Polymer Science DOI 10.1002/app

CROSSLINKED PVA AND STARCH COMPOSITE FILMS 1131

TABLE III
Effect of Starch on Moisture Content and Density
of PVA/Starch Composite Films
Sample code Moisture content (%) Density (g/cm3)
A 12.07 1.26
Ax 11.05 1.24
Bx 11.85 1.26
Cx 11.84 1.29
Dx 11.80 1.34
Ex 11.78 1.37

that the density of PVA (1.26) decreased slightly

(1.24) because of crosslinking with glutaraldehyde.
This may be because crosslinking reduced the num-
ber of hydroxyl groups per unit mass of the sample
and hence decreased hydrogen bonding interaction,
which led to a decrease in density. The addition of
starch to the crosslinked PVA network increased the
density from 1.24 g/cm3 (sample Ax) to 1.37 g/cm3
(sample Ex). This may have been because both PVA
and starch are polar polymers containing hydroxyl Figure 7 Moisture analysis of PVA/starch composite
groups that make strong hydrogen bonds between films.
them.

The swelling analyses of PVA/starch blends in

Solubility resistance and swelling analysis 50% ethanol and sunflower oil are shown in Figures 8
The solubility resistance of PVA and PVA/starch and 9, respectively. As can be seen from the graph,
composites in water, 5% acetic acid, 50% ethanol, the swelling rate of PVA matrix was higher than
and sunflower oil as model food stimulants is shown that of the starch-filled composites in 50% ethanol,
in Table IV. In water and in 5% acetic acid, solubility whereas in sunflower oil, the maximum swelling
resistance, measured in terms of dissolution time, was found to be in the reverse order one of that
increased with an increase in starch content. Even
though the difference was only marginal, the resist-
ance to water and aqueous solutions would be bene-
ficial in a variety of applications of the polymer as a
degradable plastic material.
The sensitivity of both PVA and starch, being
hydrophilic polymers, to moisture was analyzed in a
humidity chamber at 90% RH (Fig. 7). As can be
seen in Figure 7, the starch films had a faster and
higher moisture transmission rate than that of the
unfilled PVA matrix.

TABLE IV
Effect of Starch on Solubility of
PVA/Starch Composite Films
Dissolution time (min)
Sample 5% 50% Sunflower
code Water Acetic acid Ethanol oil
A 10 30 Not soluble Not soluble
Ax 30 60 Not soluble Not soluble
Bx 15 45 Not soluble Not soluble
Cx 25 50 Not soluble Not soluble
Dx 45 165 Not soluble Not soluble
Ex 75 190 Not soluble Not soluble Figure 8 Swelling analysis of PVA/starch composite
films in 50% ethanol.

Journal of Applied Polymer Science DOI 10.1002/app

1132 RAMARAJ

The author is grateful to Dr. Sushil K. Verma, director gen-

eral, CIPET, for his constant encouragement and necessary
support.

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Journal of Applied Polymer Science DOI 10.1002/app