SYNTHESIS, CHARACTERISATION AND SWELLING STUDIES ON Poly- vinyl alcohol (PVA)

-STARCH BIODEGRADABLE COMPOSITE FILMS

Abhinav Mahajan
Dr SS BHATNAGAR U.I.C.E.T.
PANJAB UNIVERSITY
Chandigarh, INDIA
abhinav.mahajan9@gmail.com

Ritu Gupta
Dr SS BHATNAGAR U.I.C.E.T.
PANJAB UNIVERSITY
Chandigarh, INDIA
rit_gupta@yahoo.com

R.K.Wanchoo
Dr SS BHATNAGAR U.I.C.E.T.
PANJAB UNIVERSITY
Chandigarh, INDIA
wanchoo@pu.ac.in
Abstract Biodegradable films of polyvinyl alcohol (PVA)
and starch, 60-40 (wt%/ wt%) have been prepared by solution
casting method. Effect of different cross-linking agents, i.e.
glutaraldehyde and formaldehyde with different concentration
on the swelling behaviour, porosity and mesh size on these
PVA-starch biodegradable films has been studied. The
crosslinked films have also been characterised using SEM and
FTIR techniques.
Keywords- polyvinyl
formaldehyde , swelling.

I.

alcohol

glutaraldehyde

INTRODUCTION

Hydrogels have gained a great deal of attention and significant

progress has been made in designing, synthesizing and using
these materials, for many biological, tissue engineering and
biomedical applications. Hydrogels are crosslinked polymeric
network, hydrophilic in nature, which can absorb large
amounts of water or biological fluids but are insoluble. The
hydrophilicity is due to the presence of hydrophilic groups
such as alcohols, carboxyls and sulphonic acids. In the swollen
state, the mass fraction of water in a hydrogel is much higher
than the mass fraction of polymer. Depending on the
properties of the polymers used as well as on the nature and
density of the network joints, such structures in equilibrium
can contain various amounts of water. Hydrogels are
highly absorbent (they can contain over 99.9% water) natural
or synthetic polymers. Hydrogels also possess a degree of
flexibility very similar to natural tissue, due to their significant
water content.
This paper reviews the preparation methods of hydrogels from
hydrophilic polymers of natural and synthetic origin crosslinked with different crosslinkers.
II.

PVA-STARCH HYDROGEL

PVA is a polymer with many industrial applications because of

its biodegradability, biocompatibility, chemical resistance and
excellent physical properties. However, the degradation of
pure PVA is quite slow and another shortcoming of PVA is its

high cost. Hence the solution to enhance the biodegradation

rate and to reduce the cost of PVA lies in preparing composites
with biodegradable, cheaper polymers like starch. In the PVAstarch hydrogel, starch is only partially compatible with PVA.
The addition of starch to PVA does not improve its physical
properties. Thus the mechanical properties and water
resistance of PVA-starch hydrogel needs to be improved for it
to be used in the environment and biomedical fields. This can
be done by adding glutaraldehyde (GA) or formaldehyde
(HCHO) to PVA-starch hydrogel as a cross-linker which
forms a strong network with the hydrogel by covalent bonds
or molecular interactions between the molecules.
III.

PREPARATION

Two fifty ml of 10% (w/v) PVA and starch solution were

prepared. To the two fifty ml of PVA solution, 167ml of starch
dispersion in water prepared by heating at 100C, was added
with constant stirring to get a homogeneous mixture. The
PVA-starch membranes were crosslinked using 1, 2 and 3mL
of GA and HCHO solution. Care was taken to eliminate
entrapment of air bubbles during mixing and the mixture was
used to obtain a membrane by the conventional solution
casting method. After drying the membranes at room
temperature, the films were allowed to dry in a vacuum hot-air
oven at 40C for 48 h and dried starch/PVA films were
removed from the mold. The dried films were stored in a
desiccator having anhydrous calcium chloride.
IV. APPLICATION OF HYDROGELS
1.

Poly(vinyl alcohol) -Starch has been widely used in

various field. For instance, their composition is used as
adhesives, sizing agents for fibers or textiles, or formed
into molded articles such as films or sheets.

2.

It has been reported that the poly(vinyl alcohol)-Starch

film is decomposed by microorganisms in the soil.
Accordingly, if the polyvinyl alcohol-starch film can be
used as the materials suitable for agricultural uses, the
environmental pollution is not caused, that is, it can be
said that such a film is industrially remarkably useful.

3.

environmentally sensitive hydrogels which are also

known as 'Smart Gels' or 'Intelligent Gels'. These
hydrogels have the ability to sense changes of pH,
temperature, or the concentration of metabolite and
release their load as result of such a change.

4.

as sustained-release drug delivery systems.

V. CHARACTERISATION
A. FTIR
FTIR (Fourier Transform Infrared Spectroscopy) is a useful
technique for identifying chemical structure of a substance. It
is based on the principle that the basic components of a
substance, i.e. chemical bonds, usually can be excited and
absorb infrared light at frequencies that are typical of the types
of the chemical bonds. The resulting IR absorption spectrum
represents a fingerprint of measured sample. This technique is
widely used to investigate the structural arrangement in
hydrogel by comparison with the starting materials.
B. Scanning Electron Microscopy (SEM)
SEM can be used to provide information about the sample's
surface topography, composition, and other properties such as
electrical conductivity. Magnification in SEM can be
controlled over a range of up to 6 orders of magnitude from
about 10 to 500,000 times. This is a powerful technique
widely used to capture the characteristic network structure in
hydrogels .
C.

Swelling Behaviour

Hydrogels have ability to swell when put in contact with a

compatible solvent, the latter attacks the hydrogel surface and
penetrates into the polymeric network. The unsolvated glassy
phase is separated from rubbery hydrogel region with a
moving boundary. Regularly the meshes of the network in the
rubbery phase will start expanding, allowing other solvent
molecules to penetrate within the hydrogel network. Achilleos
et al. have developed a technique for the real-time
visualisation of dynamic deformation profiles during gel
swelling processes (figure:-1).

Figure 1. Swelling of an acrylate gel in an aqueous solution

with simultaneous visualization of a material grid; the
snapshots were recorded at t = (a) 0, (b) 1.25, (c) 2.25, (d)
6, (e) 8.5 and (f) 24 h, respectively.[Reference 1]
D. Swelling Studies-

Degree of S welling

3.5
3
2.5
2
1.5
1
0.5
0

10

15

20

25

30

35

Time (min)

Fig2:- Degree of Swelling v/s time for PVA/Starch

hydrogel crosslinked with 1ml GA.

Degree of Swelling

5
4
3
2
1
0

10 20 30 40 50 60 70
Time (min)

Fig3:- Degree of Swelling v/s time for PVA/Starch hydrogel

crosslinked with 2ml GA.

VI. RESULTS

Degree of Swelling

Table 1-

0
0

500 1000 1500

Time (min)

Fig4:- Degree of Swelling v/s time for PVA/Starch

hydrogel crosslinked with 3 ml GA.
6

0.2083

0.8581

0.1711

0.8587

0.0908

0.8501

10

20

30

40

50

60

Time (min)

Vol( ml)

0.6497

0.7164

0.2136

0.9504

0.3707

0.905

S
D
=4
t
2
So
l

Fig5:- Degree of Swelling v/s time for PVA/Starch

hydrogel crosslinked with 1ml HCHO.
6

Where , S is the difference of the weight of membrane at time

t to the intial weight of membrane.S o is the intial weight of
membrane.l is the thickness of membrane

4
Degree of Swelling

2
0

Power law parameters for PVA-Starch hydrogel with

formaldehyde as a cross-linker-

Table 2-

2
0

Vol( ml)

4
Degree of Swelling

Power law parameters for PVA-Starch hydrogel with

glutaraldehyde as a cross-linker-

First 60% of the data given in the graphs is taken and slope is
calculated by using above equation.

0 10 20 30 40 50 60 70 80

Glutaraldehyde-

Time (min)

Table 3Fig6:- Degree of Swelling v/s time for PVA/Starch

hydrogel crosslinked with 2ml HCHO.
8
6
Degree of Swelling

Slope

Diffusion coeff (cm2/sec)

0.2734

3.67*10-7

0.2503

2.17*10-7

0.1005

2.86*10-8

Formaldehyde-

2
0

Vol( ml)

Table 40

20

40

60

80

Time (min)

Fig7:- Degree of Swelling v/s time for PVA/Starch hydrogel

crosslinked with 3ml HCHO.

100

Vol( ml)

Slope

Diffusion coeff (cm2/sec)

0.6338

2.02*10-7

0.2908

6.64*10-8

0.1792

1.24*10-8

VII.

CONCLUSION

The composition of raw materials used in this experiment was

selected in such a manner so as to provide a membrane of
suitable flexibility and mechanical properties. Membrane
obtained by the above method was colorless, transparent and
showed sufficient strength. Glutaraldehyde act as a strong
cross-linker as compared to Formaldehyde. As the value of n
(Table 1and 2 ) is greater than 0.5 . Therefore, the transport is
non-fickian. The absorbency and permeability of the
starch/PVA blend films crosslinked by HCHO or GA
decreased as the increase of HCHO or GA (when its content is
above 10 wt%) since it can lead the intermolecular and
intramolecular linkage of -OH between starch and PVA
molecules and therefore the hydrophilic groups were reduced.
GlutaraldehydeTable 5Vol(ml)

Time Of Swelling (min)

1
2
3

30
60
1320

FormaldehydeTable 6Vol(ml)

Time Of Swelling (min)

1
2
3

50
75
90

PVA-starch membrane crosslinked with 3 ml glutaraldehyde

has more stability , that is, of 22 hours as compared to other
membranes.

VIII.

REFERENCES

1) Gemeinhart RA, Park H, Park K, Pore structure of

superporous hydrogels, Polym Adv Technol, 11, 617625, 2000.
2) Widiarto,S., Effect of Borax on Mechanical
properties and Biodegradability of Sago-starchPoly(vinyl alcohol) Blend Films, J.Sains Tek., 3
(2005), 151-157.
3) Varshosaz,J.
and
Koopaie,N.,
Cross-linked
poly(vinyl alcohol) Hydrogel: Study of Swelling and
Drug Release Behaviour, Iranian polymer Jl., 2
(2002),123-131.
4) Lawton,J.W. and Fanta,G.F., Glycerol-plasticised
films prepared from starch-poly(vinyl alcohol)
mixtures: Effect of poly(ethylene-co-acrylic acid),
Carbohydrate Polymers, 23 (1994), 275-280.
5) N.A. Peppas (Ed.), Hydrogels in medicine and
pharmacy , vol . 1 , CRC press, Raton ,FL, 1986.
6) Syed K. H. Gulrez, Saphwan Al-Assafand Glyn O
Phillips, Hydrogels: Methods of Preparation,
Characterisation and Applications, Progress in
Molecular and Environmental Bioengineering From
Analysis and Modeling to Technology Applications.
7) Xiaozhao Han, Sensen Chen, Xianguo Hu ,
Controlled-release
fertilizer
encapsulated
by
starch/polyvinyl alcohol coating ; Desalination 240
(2009) 21_26