Polymer Degradation and Stability 73 (2001) 363375

www.elsevier.nl/locate/polydegstab

Chemical modication of cassava starch for degradable

polyethylene sheets
Suda Kiatkamjornwonga,*, Prodepan Thakeowb, Manit Sonsukc
a

Department of Imaging and Printing Technology, Faculty of Science, Chulalongkorn University, 254 Phyathai Road, Bangkok 10330, Thailand
Multidisciplinary Program of Petrochemistry and Polymer Science, Chulalongkorn University, 254 Phyathai Road, Bangkok 10330, Thailand
c
The Oce of Atomic Energy for Peace, Ministry of Science, Technology and Environment, Vibhavadee Rugsit Road,
Chatchuchak Road, Bangkok 10900, Thailand

Received 20 February 2001; accepted 28 March 2001

Abstract
Cassava starch was chemically modied by radiation grafting with acrylic acid to obtain cassava starch graft poly(acrylic acid),
which was further modied by esterication and etherication with poly(ethylene glycol) 4000 and propylene oxide, respectively.
The modied product was characterized by NMR spectroscopy and contact angle measurement. The blends of LDPE with EBS
wax had properties similar to the LDPE blends with the modied starch in terms of surface wettability, tensile properties, and
hardness, but with a much better degradation in soil due to the much higher water absorption. This article describes the chemical
modications of hydrophilic cassava starch to become partially hydrophobic, which was then used for blending with LDPE sheets
for evaluations of mechanical, thermal and degradation properties. # 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Cassava starch; Radiation grafting; LDPE sheets; Esterication; Etherication; Ethylene-bis-stearamide; Contact angle; Degradation;
Mechanical and thermal properties

1. Introduction
Synthetic plastics have become the major new materials for everyday life. Much of this growth has taken place
at the expense of traditional materials, such as steel, aluminum, paper and glass. Synthetic polymers, such as
polystyrene (PS), polypropylene (PP), and polyethylene
(PE), are widely used for food packaging or food service
items, the biomedical eld, and agriculture. Because they
are easily produced, convenient, cheap, and long lasting
among other properties. It is almost inevitable that they
will continue to play an essential part in the distribution
of food and other commodities in spite of the concern
about their resistance to biodegradation. This situation
leads to the growing problem of pollution. Although these
inert polymers can be degraded by natural surroundings,
but the degradation process takes very long time. Therefore, there has been an increasing interest in the development of biodegradable polymers; for example, the

* Corresponding author. Tel.: +66-2218-557576; fax: +66-2546530; +66-225-3021.

E-mail address: ksuda@chula.ac.th (S. Kiatkamjornwong).

synthesis of biodegradable polymers such as poly(3hydroxy butyrate) or PHB and poly(3-hydroxy valerate)
or PHV [1] and the incorporation of natural products
such as starch into polymers [2].
Polyethylene is one of the most dominant packaging
materials, creating the real problems in the disposal of
one-trip packaging. There have been many attempts to
make polyethylene become easily degradable. A popular
method is the use of starch as natural ller in polyethylene. When exposed to a soil environment, the
starch component is consumed by microorganisms,
leading to increase porosity, void formation, and the
loss of integrity of the plastic matrix. The plastic matrix
will be broken down into smaller particles. However,
including such a component can lead to poor mechanical properties such as low tensile strength and low percentage of strain. These properties may result from
immiscibility between starch and polyethylene, because
of their dierence in hydrophobicity/hydrophilicity. We
attempt to modify the hydrophilic property of starch to
become more hydrophobic, and study the properties of
the plastic composite sheets from the modied starch with
low-density polyethylene (LDPE) in comparison with
LDPE blended with ethylene-bis-stearamide (EBS) wax.

0141-3910/01/$ - see front matter # 2001 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(01)00100-8

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2. Experimental

2.3. Etherication

2.1. Graft copolymerization

The esteried cassava starch-g-polyacrylate (50.0 g)

was later etheried by reacting with 50 ml of propylene
oxide (Analysis grade, Merck, Darmstadt, Germany) in
the presence of 1.5 g of sodium hydroxide (anhydrous
pallet, analysis grade, min assay 98%, Carlo Erba, Mailman, Italy), 4 g of distilled water, and 100 g of iso-propanol (analysis grade, min assay 99.9%, Carlo Erba, Milan,
Italy). The reaction mixture was agitated in a closed vessel
at 50 C for 48 h. After that, the suspension was neutralized with acetic acid (BDH, Poole, UK) and ltered on
a suction lter. The product was washed with an excess
amount of methanol and dried in a vacuum oven for 24 h.
This product was called the modied starch [4]. The
amount of hydroxypropyl groups on the modied
starch was determined spectrophotometrically via a
calibration curve, according to the Jones and Riddick
method [5] using an UVvis-NIR scanning spectrometer
(Model UV-3101PC, Shimadzu, Japan).
FTIR (Model 1760, Perkin-Elmer, USA) and 1H- and
13
C-NMR (Model DPX-300, Bruker, Switzerland) were
used to verify the reaction products. Thermal properties
and the contact angle were measured using a Thermal
Gravimetric Analyzer (Model TGA 7, Perkin-Elmer,
USA) and contact angle goniometer (FACE, Kyoto,
Japan), respectively.

Cassava starch used in this study was supplied from

Thai Wah Public Co., Ltd. (Bangkok, Thailand). Cassava starch-g-poly(acrylic acid) was prepared by -ray
irradiation graft copolymerization of gelatinized cassava
starch in the presence of acrylic acid monomer (Thai
Mitsui Chemical Co.). The gelatinization was conducted
by stirring 20 g of cassava starch in distilled water at
85 3 C for 1 h. After cooling, the gelatinized cassava
starch was mixed with acrylic acid solution [20 g of acrylic
acid and 2% w w 1 of maleic acid (Fluka, Buchs, Switzerland) in 50 ml of distilled water], stirred at room temperature for 45 min. Every step in this procedure was
performed under a dry nitrogen atmosphere. The mixture was then transferred to an aluminum tube and
purged with nitrogen gas again for 5 min. The tube was
tightly closed with a lid and paran lm and then irradiated by a gamma-ray irradiator (Gamma beam 650
Unit, Serial No.18R, Nordian International, Canada) at
a dose rate of 2 kGy h 1 to a total dose of 10 kGy. The
characterization of the obtained graft copolymer was
reported in terms of %homopolymer, %add-on,
%conversion, %grafting eciency, and %grafting ratio
after extraction of the homopolymer with methanol
(Merck, Darmstadt, Germany) in a Soxhlet extractor
for 24 h. Acid hydrolysis with 65% perchloric acid
(Carlo Erba, Milan, Italy) was carried out after the
copolymer was swollen in glacial acetic acid (BDH,
Poole, UK) for 1 h.
2.2. Esterication
Esterication of cassava starch-g-poly(acrylic acid)
was performed by a reaction of cassava starch-g-poly
(acrylic acid) (30.0 g) with poly(ethylene glycol) 4000
(PEG 4000, Fluka, Buchs, Switzerland) (41.75 g) in the
presence of p-toluene sulfonic acid (6.67 g, Fluka,
Buchs, Switzerland) for 8 h at 70 C. The reaction was
carried out in a ve-necked glass equipped with a stirrer,
thermometer, nitrogen gas inlet, condenser, and column
packed with a molecular sieve. The cassava starch-gpoly(acrylic acid) was rst dispersed in methanol, and
then the catalyst and the PEG 4000 were added in
sequence. After the time of reaction had elapsed, the
reaction mixture was left to cool. The mixture was then
ltered by a suction lter, washed with methanol
(analysis grade, Merck, Darmstadt, Germany), and
dried at 50 C in a vacuum oven for 24 h. The obtained
product was called esteried cassava starch-g-polyacrylate. The amount of PEG 4000 in esteried cassava
starch-g-polyacrylate was obtained after hydrolyzing
with 1 N HCl (37% RPE, Carlo Erba, Milan, Italy)
for 6 h [3].

2.4. Blending
An LDPE resin with a melting index of 30.00 g (10
min) 1 from Thai Petrochemical (Public) Co., Ltd.,
Bangkok, Thailand was used for blending. The EBS wax
(Aromowax EBS SF1, Chemmin Corporation, Bangkok,
Thailand) was used as a dispersing agent. Mixing of the
components of LDPE, LDPE/modied starch (MS), and
LDPE/starch (ST) blends was accomplished using a tworoll mill (Model LRM 110, Lab Tech Engineer, Thailand)
at 165170 C for 20 min. LDPE was mixed with modied
starch (MS) of 1, 5, 10, or 20% ww 1, and 2% ww 1 of
EBS wax, respectively. The LDPE/ST blends used for
property comparisons were also prepared by the same
recipe. The plastic sheets obtained were then cut into small
pieces using a crushing machine (Bosco Engineering Co.,
Ltd., Thailand), which were later compressed in the mold
(150x150x2.5 mm3) using a compression molding machine
(Model LP 20, Lab Tech Engineer, Thailand) at 170 C for
5 min with a pressure of 6895 kN m 2.
2.5. Contact angle measurement
The contact angles between the water droplets and
polymer sheets were measured using the contact angle
goniometer, according to ASTM D5946-96. Cassava
starch, cassava starch-g-poly(acrylic acid), esteried
cassava starch-g-polyacrylate, and modied starch

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365

sheets were prepared to form a at pellet. LDPE and

LDPE composite sheets were prepared by hot press molding at 170 C with a pressure of 6895 kN m 2 for 5 min.

3. Results and discussion

2.6. Mechanical property testing

The gelatinized cassava starch and acrylic acid mixture was irradiated with -rays at a predetermined dose
rate of 2 kGy h 1 to a total dose of 10 kGy to avoid a
high amount of homopolymer and to achieve a high
grafting eciency. However, the obtained product was
subjected to extraction of homopolymer of poly(acrylic
acid). The graft copolymer of cassava starch-g-poly
(acrylic acid) was characterized using FTIR. It can be
seen in Fig. 1a and b that the presence of the carbonyl
peak at 1727 cm 1 in the FTIR spectrum veried the
grafting reaction of poly(acrylic acid) onto gelatinized
cassava starch. The graft copolymer was later hydrolyzed to characterize the graft copolymer, which gave
the following IR spectra in Fig. 1d, and chemical shifts
in 13C-NMR in Fig. 2a: 41 ppm (methylene carbon), 61,
72, 82 and 102 ppm (carbon of the anhydroglucose unit)

Tensile strength and percentage strain were measured,

in accordance with ASTM D638-96 using a tensile testing machine (Instron model 1011 tensile tester, USA). A
crosshead speed of 500 mm min 1 was used. Five specimens were tested for each blend.
2.7. Morphology property analysis
A scanning electron microscope (SEM, JSM-6400,
Japan) was used to observe the morphology of the
blends. The polymer blends were fractured in liquid
nitrogen and the fractured surfaces were sputter coated
with a thin layer of gold before observation.

3.1. Graft copolymerization

2.8. Thermal property analysis

Thermogravimetry analysis was performed on a thermogravimetric analyzer (Perkin-Elmer, USA) The samples were heated with a heating rate of 20 C min 1 in a
nitrogen atmosphere up to 500 and 700 C. The samples
were dried in a vacuum oven at 65 C for 24 h prior to
thermal analysis.
2.9. Water absorption test
The water absorption test was measured using a plastic sheet of 252525 mm3 dimensions according to
ASTM D570-98. The test specimens were rst dried in a
vacuum oven for 24 h at 50 C, then cooled in a desiccator, and immediately weighed. The conditioned specimens were entirely immersed in a container of distilled
water. Each sample was removed from the water container at a specied interval, wiped with a clean cloth,
and consequently weighed. The samples were placed
back in water after each measurement. The dierence
between the saturated weight and the dried weight was
calculated as the water absorption.
2.10. Soil burial degradation test
The soil burial test is an outdoor experiment, which
provides a realistic environment with seasonal changes,
less control of soil wetness and temperature, and the
presence of macro-organisms. The test was carried out in
soil of Saraburi Province, Thailand from JuneNovember 2000 or 5 months. The plastic sheets were buried at a
depth of 79 inches from the surface. After the plastic
sheets were removed, their surfaces were wiped with
water. They were then dried at 50 C for 24 h in a
vacuum oven and kept in dark before tensile testing.

Fig. 1. IR spectra of cassava starch and chemically modied products:

(a) cassava starch; (b) cassava starch-g-poly(acrylic acid); (c) esteried
cassava starch-g-polyacrylate; (d) side chain of esteried cassava
starch-g-polyacrylate; (e) esteried/etheried cassava starch-g-polyacrylate (MS, modied starch).

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Table 1
Characterization of cassava starch-g-poly(acrylic acid)
Propertya

Value (%)

Homopolymer content
Add-on
Conversion
Grafting eciency
Grafting ratio

2.7 0.2
24.9 1.0
40.0 0.8
90.0 0.2
33.2 1.8

a
Prepared by a dose rate of 2 kGy h
with a starch-to-acrylic acid ratio of 1:1.

Fig. 2. 13C-NMR spectra of (a) cassava starch-g-poly(acrylic acid); (b)

esteried cassava-starch-g-polyacrylate; (c) esteried/etheried cassava
starch-g-polyacrylate.

and 178 ppm (carbonyl carbon of poly(acrylic acid)).

According to Table 1, a high eciency of grafting is
needed for further chemical modications. Basically, the
total dose and dose rate irradiation are important
parameters in any radiation grafting systems. In the
direct irradiation method, the total dose determines the
number of grafting sites, while the dose rate determines
the length of the grafted branches. The length of the
branches is also controlled by other factors such as the
presence of chain transfer reactions, the concentration
of the monomer, the reaction temperature, the viscosity
of the reaction medium, diusion phenomena and so
on. Too high a dose rate would aect the amount of
esterication and the subsequent etherication. The
grafting reaction of acrylic acid gives a pure graft
copolymer since there is no residual initiator that might
interfere the subsequent reactions and blending [6].
3.2. Esterication
After esterication, the appearance of esteried cassava starch-g-polyacrylate was changed from that of a
rigid, non-sticky, and clear, white powder to the nonrigid, sticky and opaque-white powder. The evidence of
esterication was veried by utilizing FTIR, showing

to a total dose of 10 kGy

the shift of the carbonyl of carboxylic acid groups to the

carbonyl of ester groups from 1727 to 1738 cm 1
(Fig. 1c and d). Moreover, the solid state 13C-NMR
spectra shown in Fig. 2b conrm the esterication. The
chemical shift of the carbonyl carbon from 177.9 to
175.6 ppm also indicated the conversion of carboxylic
groups into ester groups. The peak at 52 ppm indicates
the carbon of C O on PEG 4000 chains. The other
chemical shifts are similar to those of the grafted cassava starch. In addition, the side chain of the esteried
cassava starch-g-polyacrylate was separated and determined using 1H-NMR as shown in Fig. 3. The peaks
found in 1H-NMR spectra are as follows. The chemical
shifts in cassava starch in D2O: at 3.34.2 ppm (protons
of the anhydroglucose units of starch), 4.64.9 ppm
(protons of water molecules), 5.25.6 ppm (equatorial
protons of anhydroglucose units of starch as shown in
Fig. 3a). The chemical shifts in the side chain of starch-gpoly(acrylic acid) in CDCl3 (Fig. 3b): 1.5 ppm (methylene protons), 4.3 ppm (protons of methylene groups
having their carbon atoms bonded with the oxygen
atom), 7.2 ppm (protons of the impurity in CDCl3). The
chemical shifts in the side chain of esteried starch-gpolyacrylate in CDCl3 (Fig. 3c): 1.22.8 ppm (methylene
protons), 3.43.8 ppm (protons of PEG 4000), 7.27.3
ppm (protons of the impurity of CDCl3). The amount of
PEG 4000 on the esteried cassava starch-g-polyacrylate,
determined by a gravimetric method of acid hydrolysis,
was 15.2 1.8%. The formation of a carboxylic acid ester
can be prepared by treatment of carboxylic acid with an
alcohol in the presence of an acid catalyst. Although
p-toluenesulfonic acid was used as an external catalyst,
the percentage esterication is relatively low, because
esterication is a reversible reaction and appreciable
concentrations of both the carboxylic acid and ester are
present at equilibrium. To obtain a good yield, it is
necessary to force the reaction to completion either by
removing the water formed or using excess reactants. In
addition, this starch graft poly(acrylic acid) is a macromolecule with steric hindrance. The yield of the reaction
products of the starch graft poly(acrylic acid) and
poly(ethylene glycol) 4000 is thus the optimum result
under the specied conditions.

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367

Fig. 3. 1H-NMR spectra of (a) cassava starch; (b) side chain of starch-g-poly(acrylic acid); (c) side chain of esteried cassava starch-g-polyacrylate;
(d) esteried/etheried cassava starch-g-polyacrylate.

3.3. Etherication
The hydroxypropyl groups on cassava starch were
etheried with propylene oxide in the presence of sodium
as a catalyst. After etherication, the white powder of
esteried cassava starch-g-polyacrylate became yellowish
pale. The puried, modied starch was analyzed by IR
(Fig. 1e), 13C-NMR (Fig. 2c) and 1H-NMR (Fig. 3d)
spectrometry. The presence of a peak at a chemical shift
of 19.96 ppm is indicative of the presence of hydroxypropyl groups on the modied starch. The chemical
shift at 52 ppm indicates the presence of C O on PEG
4000 chains. Furthermore, the occurrence of a distinct
peak at 1.2 ppm in the 1H-NMR spectrum (Fig. 3d) is
attributed to protons of hydroxypropyl groups on the
modied starch.
The amount of hydroxypropyl groups was determined
spectrophotometrically, which includes hydrolysis of the
hydroxypropyl group to propylene glycol, which in turn
is dehydrated to propionaldehyde and to an enolic form
of allyl alcohol. These products are measured spectrophotometrically after they are reacted with ninhydrin to

form a product having a purple color. The value of the

hydroxypropyl equivalent groups on the modied starch
is found to be 1.30%.
When the esteried starch reacts with propylene
oxide, two dierent starch ethers may result depending
on whether the nucleophilic attack takes place at the
primary or the secondary carbon atom as shown in Eqs.
(1) and (2). The major and usual product is the one that
results from the nucleophilic attack at the least hindered
(primary) carbon atom. This relatively low content
(1.30%) could be the result of the steric hindrance of
esteried cassava starch-g-polyacrylate, which limits the
accessibility of sodium hydroxide and propylene oxide.
Structures I, II, and III show the starch products of
starch-g-poly(acrylic acid), esteried starch-g-polyacrylate, and esteried/etheried starch-g-polyacrylate,
respectively, resulted from the three modication reactions of starch, which represent the possible sites of
esterication and etherication reactions.

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Table 2
Contact angles of cassava starch, esteried starch-g-polyacrylate,
etheried modied starch, EBS wax, and low density polyethylene and
its blends, and the calculated work of adhesion
Sample

Contact anglea
( )

Wadb
(mN m 1)

Cassava starch

Dissolve,
hydrophilic (0 )
77.5 0.5
80 0.3
82 0.8
93 1.2
96.4 0.9
94 1.4
94.8 1.2
94.9 1.2
94.8 0.6
94.4 0.4
95.9 1.7

145.6

Cassava starch-g-poly(acrylic acid)

Esteried starch-g-polyacrylate
Etheried modied starch
EBS wax
LDPE (without EBS wax)
LDPE (with EBS wax)
LDPE/MS1 (with EBS wax)
LDPE/MS5 (with EBS wax)
LDPE/MS10 (with EBS wax)
LDPE/MS20 (with EBS wax)
LDPE/MS10 (without EBS wax)

88.6
85.4
82.9
68.5
64.7
68.0
66.7
66.6
66.7
67.2
65.3

Contact angles of methylene diiodide on the modied starch and

blends were approximately 0 .
b
Work of adhesion, Wad= LV(1+cos), where LV is the surface
tension of water (72.8 mN m 1).

3.4. Contact angle measurement

The contact angle measurement gave the results
shown in Table 2. The contact angle increases in every
step of modication, because of more carbon atoms on
the modied starches. This result indicates that the
modied starch (MS) becomes more hydrophobic. After
blending with LDPE, the contact angles of all plastic
composite sheets were not signicantly dierent. One
interesting point is that the modied cassava starches (the

esteried starch and the esteried/etheried starch) are

still relatively polar since their contact angles are still
smaller than 90 . The EBS wax, which is ethylene-bisstearamide with an amine content of 3.0% and water
content of 0.20% max, has a similar polarity to the
esteried/etheried starch, which has 15.25 and 1.30% of
poly(ethylene glycol) and hydroxypropyl groups, respectively. Both the hydroxyl groups of the glycol and propylene oxide are polar like that of the amide, while the
ethylene moiety in EBS wax is similar to the ethylene

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369

Fig. 4. TGA and DGA thermograms of (a) cassava starch; (b) cassava
starch-g-poly(acrylic acid); (c) esteried cassava starch-g-polyacrylate;
(d) esteried/etheried cassava starch-g-polyacrylate (modied starch).

moiety in the acrylate chains grafted on the starch

backbones.
Therefore, LDPE without EBS wax (96.4 ), LDPE
with EBS wax (94 ), and LDPE/MS 10 without EBS
wax (95.9 ) have close contact angles and work of
adhesion. The EBS wax and MS are anticipated to perform similarly in the LDPE blends.
3.5. Thermal property analysis
The thermogravimetric curves are shown in Figs. 4
and 5. Cassava starch was stable up to 275 C (Fig. 4a).
The maximum decomposition rate appeared at 375 C.
The free water bound with starch molecules was present,
although the starch was heated before the analysis. For
the modied cassava starch (Fig. 4bd), there were two
stages of decomposition. The rst was starch moiety
decomposition, and the second was poly(acrylic acid)
moiety decomposition. Then second decomposition stage
started above 400 C and ended at about 550 C, giving an
ash residue. For LDPE (Fig. 5), the curve was stable up

Fig. 5. TGA and DTA thermograms of (a) LDPE; (b) LDPE/MS1;

(c) LDPE/MS5; (d) LDPE/MS10; (e) LDPE/MS [LDPE, low density
polyethylene; MS, modied starch (esteried/etheried starch)].

to 350 C and reached maximum decomposition at

505 C. After blending with various contents of modied
starch, the decomposition onset temperature of plastic
composite sheets was lower than for LDPE sheets (at
about 300 C). This was attributed to the decomposition
of the modied starch composition. This observation
suggests that the starch or modied starch blended
LDPE plastics consume less thermal energy to start a
decomposition process. It also implies that this type of
blended material degrades easily in modied starch or
starch.
3.6. Morphology of the blended samples
The plastic sheets of LDPE (Fig. 6a), LDPE/ST10
(Fig. 6b), and LDPS/MS10 (Fig. 6c) were selected for
observation of the fractured surface, and their morpholo-

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Fig. 7. Tensile strength and %strain of LDPE composite sheets.

3.7. Mechanical property analysis

Fig. 6. Morphology of blended samples (a) LDPE; (b) LDPE/ST10;

(c) LDPE/MS10.

gies were compared and illustrated in Fig. 6. Small particles were observed in the starch-lled polyethylene sheet
(Fig. 6b). These particles could be the ruptured grains,
which were immiscible with LDPE. Fewer particles were
observed in the modied starch-lled LDPE composite
sheets (Fig. 6c). These results indicated that the modied starch improved the compatibility with the LDPE
matrix.

The eects of the starch and modied starch contents

on mechanical properties of LDPE composite sheets are
demonstrated for the tensile strength and %strain,
respectively, as shown in Fig. 7. For cassava starch- and
modied starch-lled LDPE composite sheets, the same
conclusion regarding tensile strength properties can be
reached. The tensile strength of the LDPE composite
sheets increased with increasing starch content and
decreased with low modied starch content. Furthermore,
the tensile strengths of starch-lled LDPE composite
sheets became even higher than LDPE sheets (without
starch) when the contents of starch were higher than
1%. The starch phase possibly enhances the tensile
strength of LDPE composite sheets containing starch
and modied starch. Because the tensile strength of the
unlled-LDPE was found to be lower than that for
either MS-lled or starch-lled LDPE sheets. However,
it tended to be higher when the starch or modied
starch concentration was up to 20%. The percentage of
strain decreased with increasing starch and modied
starch contents in the blends. The addition of starch and
modied starch to LDPE markedly reduced the percentage of strain, and a signicant dierence was observed
between LDPE/ST and LDPE/MS blends. This is because
starch and modied starch mixed incompatibly with
LDPE, leading the LDPE composite sheets to become
brittle, with low tensile strength and %strain. When comparing LDPE/MS10 blends with and without EBS wax,
their tensile strengths were not signicantly dierent, but
the %strain values were drastically dierent. The decrease
in the %strain of LDPE/MS10 that contains EBS wax
may be the result of EBS wax distributed throughout
LDPE matrix, leading to a discontinued phase of LDPE.
On the other hand, the modied starch may be acting like
a plasticizer.

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3.8. Morphology of the failure samples

Fig. 8 elucidates the failure mechanisms of plastic
composite sheets: the failure surface morphology of the
sample subjected to tensile strength at break is used as a
helpful indicator. The LDPE, LDPE/ST10, and LDPE/
MS10 sheets were chosen for the tensile property test.
For LDPE and LDPE/ST10 sheets (Fig. 8ad), the failure surface morphology of the tensile test at break
seemed to be similar. The surfaces after the tensile failure test showed the presence of cavities in the form of

371

ridges and valleys. A ridge is present on one fracture

surface and a corresponding valley on the other. The
failure mode appeared to be shear tearing, which is an
accepted mode of failure in metals and polymers [7].
The observed bril bundles were the result of slow crack
growth. It was also found that the bril bundle of the
LDPE/ST10 blend was shorter than that of the LDPE
sheet. For LDPE/MS10 blend (Fig. 8e and f ), there
were fewer valleys that indicated that materials snapped
at the point of stress. The presence of the rough surface
indicated that the failure surface was similar to a planar

Fig. 8. Failure of starch-lled LDPE sheets under tensile testing at break: (a) LDPE sheet (500); (b) LDPE sheet (3500); (c) LDPE/ST10 (500);
(d) LDPE/ST10 (3500); (e) LDPE/MS10 (500); (f) LDPE/MS10 (3500).

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S. Kiatkamjornwong et al. / Polymer Degradation and Stability 73 (2001) 363375

Fig. 9. Tensile strengths of LDPE, LDPE/ST and LDPE/MS blends.

fracture surface. The phenomena were evidence of no

severe interfacial failure between starch and LDPE
resulting from a faster crack growth.
3.9. Soil burial degradation test
In order to evaluate the degradation of LDPE composite sheets in a realistic environment, a soil burial
experiment was carried out. After removal, dark spots of
mold growth were observed on the surface of LDPE
composite sheets. Mechanical property measurement and
surface morphology of the samples were then performed.
3.10. Mechanical property measurement of soil burial
degradation test
Figs. 9 and 10 present the tensile strength and the
percentage strain of LDPE, LDPE/ST, and LDPE/MS
blends, respectively, after the soil burial test. The results
show that both the tensile strength and the percentage of
strain decreased at a slow rate. This indicates that the soil
burial had a weak eect on tensile properties of LDPE
sheets. The decline of the tensile strength and %strain was
an indicator of soil burial eciency, especially where large
amounts of starch and modied starch were used. The

Fig. 10. Percentages of strain of LDPE, LDPE/ST and LDPE/MS

blends after the soil burial test.

presence of the modied moieties of ester and ether groups

led to a decrease in mechanical properties, because
they could absorb moisture from the surroundings,
which could then be attacked by microorganisms such as
fungi and bacteria, and resulting in porosity and voids.
Then the loss of integrity of the plastic matrix enhances
the breakdown of the matrix polymer into smaller particles, which could be attacked by other degradation
routes.
3.11. Surface morphology of samples
The surface morphologies of LDPE, LDPE/ST10,
and LDPE/MS10 sheets were studied in order to follow
the changes after soil burial for 2 months. It can be seen
in Fig. 11 that the surface of LDPE sheets (Fig. 11b, d
and f ) after the soil burial test became rougher, with
more cavities than the control sheet (Fig. 11a, b and e).
For LDPE/ST10 and LDPE/MS10 plastic sheets, many
holes throughout the plastic sheets were observed. This
occurrence may be caused by microorganisms in the soil
that utilized the carbon sources in starch and modied
starch as a food source or by the external inuence of
rainfall and underground water leading to leaching of
the destroyed surface.

S. Kiatkamjornwong et al. / Polymer Degradation and Stability 73 (2001) 363375

3.12. Water absorption test

The water permeability of modied starch is another
cause of degradation. The synthetic component appeared
to be biodegraded by surface absorption of moisture and
microorganisms, such as fungi and bacteria, because
water absorption on the material allows the microorganisms to grow and utilize the material as a carbon source.
Figs. 12 and 13 reveal the results for the %water absorption and water absorption rate. For LDPE, the percentage

373

of water absorption is less than 0.5%, indicating the

hydrophobicity of LDPE. The water absorption of
starch- and modied starch-lled LDPE composite
sheets increased with increasing modied moiety content. However, the water absorption of the samples of
this work is still low. It can be observed that the water
absorption of the modied starch-lled LDPE sheets was
higher than that of the unmodied ones. This result
implied that the former could absorb more water and
microorganisms in soil water, and thus leading to a greater

Fig. 11. SEM micrographs of (a) control LDPE sheets; (b) LDPE sheet after 2-month soil burial test; (c) control LDPE/ST10 sheet; (d) LDPE/ST10
sheet after two-month soil burial test; (e) control LDPE/MS10 sheet; (f) LDPE/MS10 sheet after 2-month soil burial test.

374

S. Kiatkamjornwong et al. / Polymer Degradation and Stability 73 (2001) 363375

Fig. 12. Water absorption of LDPE, LDPE/ST and LDPE/MS blends

after exposure to distilled water.

weight increase (with water) and more biodegradation of

the lled LDPE sheets. The highest water absorption rate
was on the rst day of exposure. After that the water
absorption rate decreased slowly. This result implied that
the blends became saturated with water.

4. Conclusions
Cassava starch-g-poly(acrylic acid) copolymers were
prepared by a simultaneous irradiation technique with
-ray irradiation from a 60Co source. The graft copolymers obtained were later modied from being hydrophilic to hydrophobic, and were mixed with LDPE. The
physical and mechanical properties of the blends were
studied. The graft copolymer was prepared using -ray
irradiation at a dose rate of 2 kGy h 1 to a total dose of
10 kGy, and a ratio of acrylic acid to cassava starch of
1:1. The resulting graft copolymer contained 2.7%
homopolymer, 24.9% add-on, 40% conversion, 90%
grafting eciency, and a 33.2% grafting ratio.
The chemical modications were carried out by esterication and etherication with poly(ethylene glycol)
4000 and propylene oxide, respectively, onto the grafted
starch. The amounts of the poly(ethylene glycol) 4000
and the hydroxypropyl group on the modied starch

Fig. 13. Water absorption rate of LDPE, LDPE/ST and LDPE/MS

blends after exposure to distilled water.

were found to be 15.25 and 1.30%, respectively. Fourier

transform infrared spectroscopy, 13C-NMR and 1HNMR spectrometry, and ultraviolet spectroscopy were
used for analysis. This modied starch was mixed with
LDPE at various proportions in a two-roll mill. Mechanical and hardness properties, thermal properties, degradation in soil, and water absorption were investigated. It
was found that the tensile strength of LDPE composite
sheets decreased, compared with the unmodied LDPE
sheet, but they showed a positive tendency to increase
with an increasing amount of the modied cassava starch.
The hardness increased with an increasing amount of the
modied cassava starch, but the resistance to thermal
degradation decreased from 350 C (for LDPE) to
300 C. The degradation of plastic sheets in a soil burial
test took place slowly according to the low water absorption of 2.5%. This work shows that incorporation of the
modied starch to LDPE did not signicantly improve the
mechanical properties of the LDPE composite sheets.
Interestingly, this modied starch did not absorb too
much moisture in the air, but could slightly absorb water
in direct contact by not more than 2.5% by weight,
helping to enhance the biodegradability of LDPE plastic sheets. The modied starch disperses favorably in the
LDPE matrix, which is similar to the dispersing property of EBS wax.

S. Kiatkamjornwong et al. / Polymer Degradation and Stability 73 (2001) 363375

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