Polymer Degradation and Stability 56 (1997) 185-202

0 1997 Elsevier Science Limited

Printed in Northern Ireland. All rights resewed
ELSEVIER PII: SO141-3910(96)00212-1 0141-3910/97/$17.00

Biode ation of maleated linear low-density

polyethylene and starch blends

R. Chandra & Renu Rustgi

Department of Polymer Technology and Applied Chemistry, Delhi College of Engineering, Kashmere Gate,
Delhi 110006, India

(Received 16 July 1996; accepted 29 September 1996)

Environmental threats restrict the use of nondegradable polymers and

encourage the development and use of degradable plastics. In order to obtain
a cost-effective biodegradable plastic, starch-filled polyethylene (PE) is still the
best alternative. Starch and PE blend is incompatible at the molecular level
and often leads to poor performance. In order to overcome this drawback,
either PE or starch should be modified. The aim of this study was to modified
linear low-density polyethylene (LLDPE) and blend it with starch. Maleic
anhydride (MA) was grafted onto LLDPE in xylene using dicumyl peroxide
(DCP) as an initiator. Corn starch in varying concentrations (between 10 and
60%) was blended with MA-g-LLDPE in a torque rheometer. The same blend
compositions of nonfunctional LLDPE with the starch were prepared for
comparative studies. The torque and totalized torque generated during
blending are reported as a function of starch content. Torque decreased with
increasing starch content for the compositions from 10 to 50% and increased
for 60% starch content. Work energy decreased for all the compositions of
blends except for 60% starch content. Tensile strength and modulus increased
and percentage elongation decreased as the starch content increased in the
blends. Water absorption of the blends increased with an increase in starch
content. The biodegradability of MA-g-LLDPE/starch blends have been
studied in two biotic environments: (1) soil environment over a period of 6
months; (2) mixed fungi inoculum (Aspergillus niger, Penicillium funiculosum,
Chaetomium globosum, Gliocladium virens and Pullularia pullulans) for 28
days. The samples containing more than 30% starch content supported heavy
fungus growth. Blends exposed to a soil environment degraded more than in
fungi alone. Any changes in the various properties of the MA-g-
LLDPE/starch before and after degradation were monitored using FTIR
spectroscopy, weight loss, a scanning electron microscope (SEM) for surface
morphology, a differential scanning calorimeter (DSC) for crystallinity and a
thermogravimetric analyzer (TGA) for rapid determination of starch content.
Percentage crystallinity decreased as the starch content increased and biodeg-
radation resulted in an increase of crystallinity in MA-g-LLDPE/starch blends.
0 1997 Elsevier Science Limited

1 INTRODUCTION there are three main classes of biodegradable

polymers. The first class of material is synthetic
Many of the physical and chemical properties of polymers, with vulnerable groups susceptible to
plastics make them ideal materials for a variety hydrolysis attack by microbes. A review has been
of products and applications. Most widely used published on backbone hydrolysis of polyesters,
alkane-derived plastics have poor biodeg- polyanhydrides, polyamides, polycarbonates,
radability and may have lifetimes of hundreds of polyurethanes, polyureas and polyacetals.’ The
years when buried in typical solid-waste sites. second class of materials is composed of naturally
Various approaches to render synthetic polymers occurring processible bacterial polymers, poly-
degradable have been considered. At present hydroxybutyrate (PHB) and polyhydoxyvalerate
18.5
186 R. Chandra, Renu Rustgi
(PHV). PHB and PHV are truly biodegradable,
being attacked by a wide variety of bacteria. A
review on these materials was made by Holmes et
al.= Although methods of fermentation and
extraction have recently been perfected, deter-
mination of processing parameters and high
production costs are problems to be solved. The
third class are blends of polymers and additives
that are readily consumed by microorganisms.
The classic example of this class of materials is
the use of starch blends with polyethylene (PE).
However, most of the synthetic polymers are
immiscible with starch at the molecular level.
This thermodynamic incompatibility often leads
to poor performance of these blends. The main
areas of research concentrate on determining
compatibility or coupling agents and repeatable
processing parameters. Corn starch is treated
with a siliane coupling agent to provide
compatibility with hydrocarbon polymers. The
presence of starch does not have any deter-
minable effect on the quality of the material, but
produces a textured product with improved
printing properties.’
Another approach is graft copolymerization of
a vinyl monomer on to the starch backbone.
Fanta and Bagley4 and Fanta’ have reviewed the
synthesis and discussed some applications of
starch graft copolymers. A review of the
literature indicates that although grafting of
synthetic polymers on starch is known to improve
some of the properties, very few processes have
led to full-scale commercialization.
An alternative approach is to bring about some
compatibility in starch and synthetic polymer by
blending starch with polymers containing polar
functional groups that can interact with starch.
Otey et al.&’ have demonstrated that aqueous
dispersion of starch and poly(ethylene-co-acrylic
acid) (EAA) can be processed to films,
containing more than 50% starch with clarity,
elasticity and water resistance by casting,
extrusion, blowing, milling and rolling. These
films are biodegradable and show potential for
packaging materials and for agricultural mulch.
The authors suggested that as internal bonding
within the starch molecules is reduced during
gelatinization and extrusion, new hydrogen bonds
are formed between the EAA carboxyl groups
and the starch hydroxyls. Increasing the level of
starch decreased the percentage elongation of the
film and increased the diffusion rate of water.
The authors also reported’ that low-density
polyethylene (LDPE) could be substituted for
EAA up to a level of 40% without adversely
affecting the physical properties of the blends.
A comparatively new method of producing
compatible thermoplastics blends is via reactive
blending, which relies on the in situ formation of
copolymers or interacting polymers. This differs
from other compatibilization routes where the
addition of a separate compatibilizer is required.
In reactive blending, the blend components
themselves are either chosen or modified so that
reaction occurs during melt blending, which
improves the compatibility and interfacial adhe-
sion of the two immiscible polymers. The small
amount of graft or block copolymers formed
during the blending process, due to reaction
between the two components, is generally
enough to stabilize the morphology and improve
the properties of the blends.
Jane et al.“‘.” reported that addition of high
molecular weight oxidized PE (OPE) improved
the tensile strength and elongation of starch/PE
composites with 15% starch content. The ratios
of OPE/starch ranged from 0.30 to 0.50. It was
suggested that ester formation and hydrogen
bonding between carboxyl and ketone groups in
the OPE and hydroxyl groups on the starch
granule surface were responsible for the im-
provement in the properties. They also reported
that as the percentage of starch in the blend is
increased, the tensile strength and the percentage
elongation decreases.
Synthetic polymers possessing functional
groups such as carboxylic acid, anhydride, epoxy
or urethane can react with the hydroxyl or
carboxyl group (in modified starch) to form a
blend with a stable morphology. The reactivity of
the functional groups is an important parameter
in reactive blending. The functional groups
should react to form the required concentration
of graft or block copolymers in the short
residence times typical of polymer processing.
From this point of view a cyclic anhydride group
may react more quickly than the carboxylic
groups; reaction of anhydride with hydroxyl to
form an ester is not an equilibrium reaction and
no water is produced during the reaction.
Anhydride functionality can be incorporated into
a polymer by copolymerization or grafting of an
anhydride such as maleic anhydride. Maleic
anhydride can be grafted with relative ease onto
many polymers in the presence of organic
peroxide, either at normal melt processing
 Biodegradation of polyethylene and starch blends
temperature12-21 or in solid state22’23 or in
solution.24 Studies are available which indicate
that anhydride compounds improves the prop-
erties of composites made from cellulosic fillers.25
They reported that the properties of the
composites varied with the concentration of
maleic anhydride, type of wood used and pulping
technique. The tensile strength of the composite
of maleated high-density polyethylene (HDPE)
and wood flour increased with increasing filler
content.26
Studies involving the reactive blending of
starch with an anhydride functional polymer are
unavailable. The present work is presented in
three parts:
(1) solution grafting of linear low-density
polyethylene (LLDPE) with maleic anhydride
(MA);
(2) blending of functional and nonfunctional
LLDPE with varying starch content ranging
from 10 to 60%;
(3) biodegradation of MA-g-LLDPE/starch
blends in two biotic environments: soil and
mixed fungi inoculum.
In the first part, the synthesis and characterisa-
tion of MA-g-LLDPE is discussed. The second
part presents the preliminary findings on the
blends of starch and LLDPE containing the
anhydride functional group. A series of MA-g-
LLDPE/starch blends was prepared at starch
concentrations between 10 and 60% weight with
MA-g-LLDPE. The torque, totalized torque,
melt temperature and work energy during
mixing, water absorption, tensile strength, per-
centage elongation and modulus are reported and
discussed. The third part covers both the
biodegradafion methods performed on the
laboratory scale. The role of SEM, IR, DSC and
TGA in the assessment of degradation
elaborated. Finally, the results of the degradation
studies and conclusion are presented.
2 EXPERIMENTAL
2.1 Materials
The starch used in this study was unmodified
corn starch (CS) IP grade dried to a moisture
content of less than 1% before blending and
processing. Linear low-density polyethylene
187
(LLDPE) was supplied by M/S Reliance
Industries Ltd., a butene grade with a melt-flow
index of 1.7 g (10 mm-l at 190°C and a 2.16 kg
load. The density of the LLDPE was
0.918 gcmp3. The LLDPE had a peak melting
point of 13O”C, determined by a DuPont
differential scanning calorimeter 910. Maleic
anhydride (MA), AR grade (SD fine chemicals)
was recrystallized twice from chloroform. Di-
cumyl peroxide (DCP) was obtained from M/S
Hercules Inc., which was recrystallized twice by
dissolving in absolute ethanol, filtering the
solution while hot and chilling in ice water.
2.2 Graft copolymerization
The graft copolymerization was carried out in a
four-neck round bottom flask equipped with
overhead stirrer, condenser, thermometer and a
nitrogen gas inlet as described by Wang et ~1.~~
Sixty grams of LLDPE was dissolved in 700 ml of
xylene at 130°C. Nitrogen gas was purged
throughout the reaction to remove dissolved
oxygen at a flow rate of 25 cm3 min-‘. DCP
(0.9g) was added to this homogenized boiling
solution, followed by 30g of MA. The reaction
was carried out at 139 f 1°C for 90 min.
The reaction mixture was poured into 1.5 1 of
acetone under vigorous stirring. The precipitated
graft copolymer was isolated and washed several
times with acetone, and subsequently soxhlet-
extracted with acetone for 16 h to remove all
traces of xylene and unreacted maleic anhydride.
The product obtained was dried under vacuum at
80°C up to constant weight.
The degree of grafting (DG) in the grafted
LLDPE was analyzed by adding a standard
solution of ethanolic KOH to the xylene solution
of the samples and refluxing until it was
is
dissolved. Excess of KOH was back-titrated with
standard xylene solution of acetic acid. The DG
is calculated as the number of MA/100 LLDPE
units (MA/lOOPE), and was found to be 1.7
MA/lOOPE.
2.3 Blend preparation
Blending was carried out in a Haake Fisons
Rheomix-600 (equipped with a pair of roller
rotors) at 160°C. The rotor rate was maintained
at 60rpm, adding LLDPE and MA-g-LLDPE
first and slowly adding starch.
188 R. Chandra, Renu Rustgi
Torque, totalized torque and melting tempera-
ture were measured by Haake Rheocord 90
software with respect to the time of mixing. The
torque moment necessary to turn the mixer
blades2* was continuously recorded in SI units
(Nm) and obeys the following equation:
M=BN”
where M is the torque, m is the parameter of the
power law equation (r = KV), N is the rotor speed
(rpm) and B is a characteristic constant which is
determined experimentally.
The totalized torque (TTQ) is calculated as a
function of torque and time, and is a
continuously increasing function. It is defined as
the energy required to process a certain material
for a certain period of time under given
conditions; and it is simply the area under the
torque-time curve.
TTQ can be converted to work energy (W”) by
the following relationship:
TTQ
W, = 61.58 x N x
Mb x 9.807
where N is the rotor speed (rpm) and M,, is the
charged sample mass.
2.4 Molding
The blends were compression molded into sheets
2 mm thick using 20 X 20 cm window frame molds
in a Nuchem Hydraulic Press, Model CMP 30.
The platens of the press were heated to
160 f 5°C. The window was placed between two
glazed sheets, already sprayed with silicon mold
release agent on the contact surface and filled
with preweighed material. The assembly was then
placed in the hydraulic press and initially heated
for 6 min without applying any pressure to ensure
uniform heat flow through the material. The
temperature was maintained at 160 f 5°C for all
the compositions of blends for 10min at a
pressure of 25 t, which was applied gradually
during the first 5 min. The sheet thus obtained
was removed from the press after cooling to
room temperature.
2.5 Mechanical properties
Tensile specimens (ASTM D638) were cut from
each sheet. Tensile tests were performed on a
Zwick Universal Testing Machine of 5 kN
capacity. Five samples of each compositions were
strained at a rate of 28mm min-’ at room
temperature, and average values of elongation at
break, tensile strength and modulus were
determined.
2.6 Water absorption
The three molded specimens (7.5 X 2.5 cm) of
each composition were dried in an oven under a
vacuum for 6 h at 50 f 3°C cooled in a desiccator
and immediately weighed to the nearest 0.001 g.
The conditioned samples were placed in a
container of distilled water maintained at
23 f 1°C. The samples were then removed
weekly from the water once at a time, gently
blotted with tissue paper to remove the excess of
water on the surface, weighed to the nearest
0.001 g immediately, and replaced in the water.
The weighings were repeated at the end of the
every week for 4 weeks and the average of three
values was recorded. Percentage increase in
weight during immersion was calculated to the
nearest 0.01% as follows:
o/
0
w_J-wC
f x 100
WC
where Wf is the final increased weight percentage,
W, the wet weight and W, the conditioned weight
of the testing samples.
2.7 Biodegradation studies
The biodegradation of the samples was studied in
two biotic environments: soil, and a mixed fungi
inoculum system, according to ASTM G21-70.
2.8 Exposure to soft environment
Samples of 25 X 25 X 3 mm size were buried in
alluvial type of soil. Soil was obtained from
farmland topsoil in March before planting. It was
sifted to remove large clumps and plant debris.
The procedure used for soil burial was as
described by Cole.‘” Soil was maintained at
approximately 20% moisture weight. The square
samples were buried at a depth of 10cm. A
control box contained only samples and no soil
was also maintained for comparative studies.
 Biodegradation of polyethylene and starch blends
Samples were removed every month. After
removal, samples were washed in distilled water
and dried at 50 f 3°C in a vacuum oven for 24 h.
Samples were then allowed to equilibrate in a
desiccator at least 24 h before testing. The weight
of each sample was measured before and after
degradation.
2.9 Exposure to Fungi environment
Degradation was determined according to ASTM
test method G21-70. ASTM G21-70 describes a
method to evaluate the resistance of polymeric
materials to fungi. Polymer samples were placed
in sterile petri dishes containing solidified
nutrient salt agar. A mixed fungus spore solution
was prepared from spores of Aspergillus niger,
Penicilliurn funiculosum, Chaetomium globosum,
Gliocladiurn virens and Pullularia pullulans as
described by the ASTM method. The surfaces
including the surface of the test specimens were
inoculated with the composite spore suspension
by spraying the suspension from a sterilized
atomizer with 110 kPa (16 psi) of the air pressure
so that the entire surface was moistened with the
spore suspension. Covered petri dishes were
incubated at 28-30°C (82-86°F) and 85-90%
relative humidity for a minimum of 28 days. Petri
dish covers were sealed by wax to avoid any kind
of contamination. The only carbon source for the
growth of the fungi was from the samples. The
fungus growth was followed by visual observa-
tion. The specimens after 28 days were washed
free of growth, immersed in an aqueous solution
of mercuric chloride for 5 min, rinse in tap water
and air-dried overnight at room temperature.
2.10 Infrared spectroscopy
Fourier transform infrared (FTIR) spectra of
MA-g-LLDPE and its blends (films) were
obtained in Perkin Elmer spectrometer (model
1750) in the spectral region between 4000 and
400 cm-‘.
2.11 Opacity
Opacity of the blends was tested before and after
the degradation using the PSI opacity test
apparatus consisting of a digital galvanometer,
189
electronic calibrating unit, a photocell unit, light
source and a fixture for holding the samples.
2.12 Scanning electron microscopy (SEM)
The surface morphology of the MA-g-LLDPE
and their blends before and after biodegradation
was observed by means of a Jeol scanning
microscope 840. Thin 500 8, gold coatings were
applied to the samples using Jeol fine coat ion
sputter JFC-1100 at 1 kV current for 5 min. The
electron gun voltage was set at 10 kV. The
micrographs of the samples were taken at
different magnifications to identify cracks, holes
and other changes on the surface of the samples
during degradation.
2.13 Differential scanning calorimetry
Crystallinity studies were conducted using a
DuPont-9900 thermal analyzer with a DSC-910
module under nitrogen atmosphere. The instru-
ment was calibrated using indium. Samples of
5-10mg were sealed in aluminium pans and
subjected to heating-cooling cycles. Previous
thermal effects were minimized by initially
heating the samples until melting. The samples
were then cooled to room temperature at a
constant heating rate 5°C min-’ to favor crystalli-
zation. Subsequently, the second heating was
recorded at 10°C min-’ in the temperature range
of 25-170°C resulting in endothermic curves.
The heat of fusion was calculated by
integrating the areas under the endothermic
curve using DuPont General 2.2 software. The
degree of crystallinity was obtained from the
ratio between the fusion heats of the samples
(HT) and 100% crystalline LLDPE (H;).
%Crystallinity = 5 X 100
2.14 Thermogravimetric analysis
Thermogravimetric analysis (TGA) was carried
out on a DuPont-9900 thermal analyzer which
contained a TGA-951 module under a nitrogen
atmosphere. The samples were heated from room
temperature to 600°C at a heating rate of
10”Cmin’ and a nitrogen gas flow rate of
40-50 cm3 min-‘. Sample size/weight varied from
5 to 10mg. The derivative of TGA thermograms
were obtained using DuPont analysis software,
190 R. Chandra, Rem Rust@

General 2.2. The initial decomposition tempera-
ture (IDT), the temperature where the TG plot
deviates markedly from the base line, and final
decomposition temperature (FDT) of TG plots
were obtained.
3 RESULTS AND DISCUSSION
The reaction between MA and LLDPE was
carried out in the presence of DCP in xylene
solution at 139°C for 90min.*’ Gel was noticed in
the samples at a high concentration of DCP. In
view of the knowledge of the influence of the
MA groups on the chain thermodynamics, it may
be assumed that degradation of the PE chain had
not occurred to an observable extent. This is in
strong contrast to the case of maleation of
polypropylene under comparable conditions.3”
Therefore MA-g-LLDPE with maximum DC
(1.7 MA/100 PE) was chosen for blending and
other experimental studies.
The FTIR spectra of purified MA-g-LLDPE
showed two bands at 1846 and 1779cm-’
assigned to the presence of anhydride groups.
3.1 Studies on reactive and nonreactive
blending using torque rheometer
The properties associated with blending of starch
onto the functional and nonfunctional LLDPE
were studied by Haake Rheocord 90. The final
mixing torque (TQ), totalized torque (TTQ) and
work energy for the MA-g-LLDPE/starch blends
are shown in Table 1. The TTQ were used for the
calculation of work energy using the thermoplas-
tic analysis software provided with the system.
The LLDPE/starch and MA-g-LLDPE/starch
blends were made with various starch contents
ranging from 10 to 60% at 60rpm and 160°C.
The LLDPE/starch blends were rigid, whereas
the MA-g-LLDPE/starch blends were flexible
and tough.
All the compositions of MA-g-LLDPE/starch
blends exhibited higher final mixing torque, final
mixing temperature and totalized torque com-
pared to the nonfunctional LLDPE/starch blends
prepared under the same conditions (i.e. rpm and
temperature). This could be attributed to the
increase in the viscosity of MA-g-LLDPE/starch
blends due to the reaction and/or the association
between starch and MA-g-LLDPE molecules.
The possible reaction between MA-g-LLDPE
and starch during the blending is given in Fig. 1.
During the reactive blending of MA-g-
LLDPE/starch, the anhydride groups of the
polymer can react with the hydroxyls of the
starch to form ester linkages. The carboxylic
groups, arising from the hydrolyzed anhydride,
can also form hydrogen bonds with the hydroxyl
groups. These factors contribute to the
differences in the magnitude of torque between
the reactive and nonreactive blends of the same
starch content. Figure 2 shows the comparison of
torque-time curves for LLDPE and MA-g-
LLDPE blends containing 10% starch content,
where the corresponding torques were 32.3 and
10.3 Nm, respectively. The difference in torque
between MA-g-LLDPE and LLDPE is 18.2Nm
which increased to 22 Nm for their corresponding
blends with 10% starch content, indicating some
possible interaction or reaction between MA-g-
LLDPE and starch.
Torque is proportional to the melt viscosity.
Assuming no interaction between nonfunctional
LLDPE and starch, the torque contribution (due
to the starch component in the blend) can be
calculated. For incompatible polymer blends

CzH, CA
Table 1. Torque, totaliied torque and work energy profile
of MA-g-LLDPE/starch blends +CHz>
n

) CH-CH,
Blend Final torque Totalized Work energy o-
I I
composition (Nm) torque (J K’) oc co OH
cl0 &OH
MA-g-LLDPE/ (Nm min) \ /
0
starch ”

I
MA-Q-LLDPE
C”,
100/o 30.0 316 1184.96
90110 32.3 343 1889.99
SO/20 32.0 329 1767.58 o-

70130 31.3 314 1672.12 OH

60140 30.8 312 1376.31 MAg-LLDPUStarch
Blend
50150 28.7 248 744.86
40160 33.1 282 1013.07 Fig. 1. Possible reaction for reactive blending of MA-g-
LLDPE and starch.
 Biodegradation of polyethylene and starch blends 191

33

0 2 4 6 8 10

Time (min)
Fig. 2. Comparison of torque-time curve of (- ) MA-g-LLDPE/starch (90/10) and (--) LLDPE/starch (90/10) blends.

using the logarithmic mixing rule,31 the melt starch and LLDPE (10.3 Nm) are known. The
viscosity (q) is given by appraisal torque value for starch content was
used to calculate the torque of MA-g-
In 77= i WiIn 77i LLDPE/starch blends containing the same
i=l
amount of starch. The calculated value was found
Hence the expression for torque is (r) is
n to underpredict the observed torque for the
In r = 2 oj In r, blend by 21%. Although somewhat indirect,
i=l these calculation support the view that there is
where wi and ri are the mass fraction and torque, some physical and/or chemical interaction
respectively, of component i in the blend. between MA-g-LLDPE and starch.
As an example, the contribution of torque, due In case of reactive blending, it was found that,
to 10% starch, can be calculated if the values of as the content of starch increased from 10 to
torque for LLDPE (11.8 Nm) and the blend of 50%, the torque value decreased. Figure 3 shows

40

30

5,
r
10

Fig. 3. Comparison of final mixing torques of MA-g-LLDPE/starch blends.

192 R. Chandra, Rem Rust@

a comparison of final mixing torques of blends
containing 10, 30 and 50% starch. The factor
responsible for the decrease in torque value is
not the amount of starch, but rather the decrease
in the polymer reactive sites (maleic anhydride
groups) as the polymer content decreases.
However, at 60% starch content the torque
increased suddenly, which may be due to the fact
that at this stage the increase in starch content
plays the dominant role rather than the polymer
reactive site.
3.2 Melt temperature
The melt temperature of the mixing chamber was
set at 160°C; however, due to frictional effects the
melt temperature increased to NO-185°C for the
LLDPE/starch blends and 200-205°C for MA-g-
LLDPE/starch blends. The lower temperature
displayed in LLDPE/starch blends was due to
lower viscosity and absence of the reaction
compared to the corresponding MA-g-
LLDPE/starch blends. The increase in the
temperature was proportional to the starch
content of the blends. The greater the viscosity,
the higher the increase in the melt temperature.
It should be noted that the torque measurements
could not be made at the same melt temperatures
for different blends (due to viscous dissipation
rise). Because a small increase in the temperature
lowers the viscosity, the actual torques for the
MA-g-LLDPE/starch blends would be higher
than the nonreactive blends at a given tempera-
ture. The presence of LLDPE and MA-g-LLDPE
melt prevented discoloration or burning of the
starch at such high temperatures, except for the
blends which were made at very high rpm and/or
mixing times.
less than the MA-g-LLDPE and its blends.
Although the loading peak for LLDPE and its
blends have higher values than MA-g-LLDPE
and its blends, torque values reach very low
stable values in the case of the former. The
higher stable torques for maleated LLDPE and
its blends increase the area under the torque-
time curves, resulting in higher work energies.
The comparison of the work energies of
MA-g-LLDPE and its 10% starch content blend
show a notable increase in work energy, which
can be assigned to the reaction between starch
and maleated LLDPE. As the starch content in
the blends increases, the material requires more
time to fuse, which results in a shifting of the
fusion peak towards a higher time scale.
However, as one moves from 10 to 50% starch
content blends, the shifting of the fusion peak to
the higher time-scale and a decrease in the
minimum torque values result in a decrease of
the area under the torque-time curve, which
subsequently results in a decrease of work
energy. At 60% starch content the work energy
increased, which suggested that in this composi-
tion a large portion of the starch remains
unreacted.
3.4 Mechanical properties
Average values of elongation at break, tensile
strength and modulus for MA-g-LLDPE/starch
blends are tabulated in Table 2. In the case of
LLDPE/starch blends, as the starch content in
the blends was increased, the tensile strength and
elongation at break were found to decrease. For
MA-g-LLDPE the presence of starch increased
the tensile strength and decreased elongation at
break of the blends. The results are in direct

3.3 Work energy

Table 2. Mechanical properties of MA-g-LLDPE/starch
Work energy, the energy required to process a blends
certain material for a certain period of time at
Blend Tensile % Modulus
given conditions, is the area under the torque- composition strength Elongation at WW
time curve. The area between the fusion peak MA-g-LLDPE/ (MPa) break
and minimum stable torque is used for the starch
calculation of work energy by the instrument
100/o 13.65 533.49 300.12
thermoplastic analysis software. As is seen from 90/10 14.36 277.56 342.19
the above definition the greater the torque or 80120 14.72 237.36 352.22
longer the time taken to reach the stable torque, 70130 14.84 162.36 371.27
60140 15.01 139.80 417.36
the higher the value of work energy. The values 50150 15.64 124.84 489.21
of the work energy calculated for the nonfunc- 40160 16.34 104.27 520.16
tional LLDPE and its blends were found to be
 Biodegradation of polyethylene and starch blends
contrast to those present by Willetg and Jane et
al.” The increase in tensile strength of
MA-g-LLDPE/starch blends could be due to
increased interfacial adhesion resulting from the
reaction between starch and MA-g-LLDPE.
Modulus increased due to the stiffening effect
of the starch granules, as the starch is stiffer than
LLDPE. Since the starch contains both amor-
phous and crystalline regions,32 the calculated
starch moduli are averages which reflect the
contribution of each phase. There is considerable
evidence that in native starch the chains are
arranged in double helices in the crystalline
regions of the starch. 32 The hydrogen bonding in
the starch gives it much higher modulus than
semicrystalline polymers such as LLDPE, which
has no hydrogen bonding. Therefore, there is a
direct relation between the amount of starch in
the blends and the increase of the modulus value.
In the case of MA-g-LLDPE/starch blends,
moduli increased greater in comparison to the
LLDPE/starch blends due to the reaction
between maleated LLDPE and starch which
improves adhesion, or reduces slippage at the
matrix-filler interface.
3.5 Water absorption
MA-g-LLDPE/starch blends exhibited reason-
ably good water resistance compared to
LLDPE/starch blends. The clarity of the water
during the water absorption test indicated
negligible extraction of the solids in the case of
the former. In the first 7 days, the reactive blends
containing 50% starch absorbed only 2.8% of
water; however, the LLDPE/starch blend ab-
sorbed 22% of water in the first week. The water
absorption slowly increased over a period of the
28 days, by which time the blends containing 10,
20, 30, 40, 50 and 60% starch absorbed 2.5, 3.8,
5.4, 7.2, 8.9 and 10.1% of water, respectively.
The per cent weight gained by the MA-g-
LLDPE/starch samples over a period of 28 days
when immersed in the water is shown in Fig. 4.
3.6 Biodegradation
Two methods were selected for assessing the
polymer biodegradability.
3.7 Exposure to soil environment
Figure 5 shows the change in the weight ratio
(degraded/initial sample weight) as a function of
193
0 7 14 21 28
Davs
Fig. 4. Percentage weight gain of MA-g-LLDPElstarch
blends during water absorption.
time for the MA-g-LLDPE/starch blends buried
in the alluvial soil. In the soil, water diffuses into
the polymer sample, causing swelling and
enhancing biodegradation. The blends containing
a higher percentage of starch (50 and 60% starch
content) degraded rapidly in first 30 days, during
which the maximum starch content was accessed.
Over the next 5 months a gradual decrease of
starch occurred.
In both the series of blends (LLDPE/starch
and MA-g-LLDPE/starch) containing lo-30%
starch content, less than 10% of the starch was
degraded. This result shows close agreement with
the percolation analysis performed by Peanasky
et a1.33 According to these authors, microbial
invasion took place from the top and bottom
surfaces of the polymer films by computer
simulation. Starch is not efficiently removed from
the blends at concentration below 30 vol.%.
Above this threshold, starch is very efficiently
removed from the blends. This suggests that the
starch granules in the PE/starch blends cluster in
a manner consistent with a percolation phenome-
non. Wool et a1.34 described the invasion of
polymer/starch matrix by microorganisms and/or
extracellular enzymes in terms of a scalar
percolation theory. The minimum level of starch
needed to achieve connectivity between starch
domains, and therefore accessibility of the starch
to biodegradation, is the percolation threshold.
From simulation experiments, this level was
found to be about 31% starch by volume. Below
this level the theoretical analysis, as well as acid
194 R. Chandra, Rem Rust@

b
5 0.85 --
0
E

E 0.8 --
.F
f!
0.75 --

0.7 -I I I
0 30 60 so 120 150 180
Time(in days)

-•*--9o/lO -+--80/m -A-70/30-j(--60/40+50150-O-40160

Fig. 5. Change in the weight ratio (degraded/initial sample weight) in MA-g-LLDPE/starch blends exposed to soil
environment.

hydrolysis studies, showed less than 10% of the
starch was accessible to hydrolysis. Similar results
were also obtained by Goheen and Wool”“*“”for a
PE/starch blend burial in soil.
The LLDPE and MA-g-LLDPE samples
buried in soil also lost weight when compared to
the control sample. This may be due to
degradation of some low molecular weight
species in the materia13’
3.8 Exposure to fungi environment
The samples containing a higher percentage of
starch supported fungal growth. The fungal
growth could be seen with visual observations
after 1 week and kept growing rapidly with time.
As seen from the photographs in Fig. 6(a)-(d)
the rate of fungal growth increased with the
amount of starch in the blends. Starch, being a
natural polymer, could be readily used as a
carbon source by the fungus. As the starch
content is increased, the starch becomes a
continuous phase in the blend and can be easily
accessed by the organisms. In low starch
contents, the starch may remain encapsulated in
the synthetic polymer matrix due to the reaction,
thereby making it difficult for the organisms to
access and use it as a source of carbon. In such a
case the fungal growth will be slow/negligible.
On the other hand, a synthetic polymer does not
serve as an efficient carbon source. Therefore, in
a blend of the two, the starch component is
degraded more readily by the fungus, leaving
MA-g-LLDPE almost unaffected. The samples
made from pure LLDPE and MA-g-LLDPE did
not show any fungus growth. Fungus growth was
notably faster in LLDPE/starch blends than in
MA-g-LLDPE/starch blends.
3.9 Fourier transform infrared spectroscopy
The FTIR spectra of LLDPE film show
characteristic C-H stretching bands within the
3000-2840 cm-’ region, medium-strong C-H
bending bands within the 1465-1450cm-’ re-
gions, and C-H out-of-plane bending within the
740-719cm-’ region (Fig. 7 and Table 3). All the
bands are also present in MA-g-LLDPE except
1846 and 1779 cm-’ (Fig. 7). Peaks at 1779 and
1846 cm-’ can be assigned to grafted anhydride,
because five membered cyclic anhydrides exhibit
an intense band near 1780 cm-’ and a weak band
near 1850cm-‘, due to symmetric and asymmet-
ric C=O stretching, respectively.“8 The charac-
teristic bands for starch are tabulated in Table 3.
LLDPE/starch blend films showed a broad O-H
stretching absorbance in the 3600-3000 cm-’
region and strong set of C-O stretching band in
the 1190-960cm-’ region.‘” The other bands
independent of LLDPE are the OH bands;
however, these bands are unreliable for quantita-
 Biodegradation of polyethylene and starch blends
Fig. 6. Fungus growth of MA-g-LLDPE/starch blends after 28 days of incubation
tive analysis due to their dependence on water
content and atmospheric condition.4”
In the blends the 1640cm-l band, which is a
measure of the water content,41’42 may vary
significantly between degraded and undegraded
samples. Albertsson et a1.43 analyzed the changes
in the PE matrix by two indices to monitor
degradation rates in polyethylene: the
1715/1465 cm-’ ketone/carbonyl index (-CO-)
and 1640/1465 cm-l double bond (-C=C-) index.
They also examined the bands at 1740 cm-’ (the
ester carbonyl -COO-), 905-915 cm-’ (the
double bond -CH=C-), and doublet band at
720-730 cm-‘, in which the relative intensity
gives information about crystallinity. Both the
carbonyl and double-bond indices are expected
to increase, at least initially, if the matrix is being
degraded. In our studies no significant change
was observed in the FTIR of MA-g-LLDPE
195
(a) 100/O; (b) 70/30; (c) 60/40 and (d) 40/60.
before and after degradation, indicating that the
polymer matrix did not degrade under these
experimental conditions.
The only trend that was observed in the
MA-g-LLDPE/starch blend before and after
biodegradation with fungi was a slight decrease in
the 1645 cm-’ band after degradation (Fig. 8).
This could be attributed to a decrease in the
absorbed water starch band as starch is removed
rather than any change in the polymer matrix.
The other significant trend that was observed in
the MA-g-LLDPE/starch blend before and after
biodegradation with fungi was a slight change in
the C-O stretching band (960-1190cm-‘) after
degradation, indicating that the starch is pre-
ferentially removed, leaving the MA-g-LLDPE
matrix (Fig. 8). A slight decrease in the O-H
stretching band in the 3600-3000 cm-’ region was
also observed.
 R. Chandra, Rem Rustgi

3200 24002000 1600 1200 800 400

I I ‘I’ I. ” I ” t ” 1 Wavenumber (cm-‘)
3200 24002000 1600 1200 800 400
Wavenumber (cm-‘) Fig. 8. FTIR spectra of MA-g-LLDPE/starch blend (a)
undegraded and (b) degraded samples.
Fig. 7. PTIR spectra of (a) LLDPE and (b) MA-g-LLDPE.

blends. The sample containing a higher content

3.10 Opacity of the starch exhibited color changes, indicating
heavy microbial growth. All the samples
Figure 9 shows the effects of soil burial and exhibited increase in opacity due to starch
fungal degradation on MA-g-LLDPE/starch removal. The decrease in transmittance was most

Table 3. Infrared vibrations and assignments for LLDPE/starch and MA-g

LLDPE/starch blends

Major i.r. bands of components

Wavenumber (cm- ‘) Assignment and remarks

LLDPE
2896 (s) C-H stretching
1466, 1455 (m-s) CH, scissor and asymmetric bend
1378, 1369, 1353 (w) C-H bend due to CH, and CH,
724 CH, rocking
772 -CH,-CH, ethyl group attached to backbone
MA-g-LLDPE
1846 C=O asymmetric stretching band
1779 C=O symmetric stretching band
920 C-O cyclic anhydride
Starch
3000-3650 (s, br) O-H stretching with absorbed water
2926 (s) C-H stretching
1640 (w-m) S (O-H) band (absorbed water)
1461 (m, sh) CH2 bending
144-1325 (m-s) C-H bending and wagging
1244 (m-s) C-O stretching (C-O-C and C-O-H)
400-930 (w-m, br) O-H deformation (broadened by water), C-O-C ring vibration

w, weak; m, medium; s, strong; sh, shoulder; br, broad.

 Biodegradation
w
-undeg.
_---_soikleg.
..__. Fungi-&g.
0 10
I@. 9. Percent opacity profile of MA-g-LLDPE/starch
noticeable for the samples containing 40, 50 and
60% starch. The samples with 10, 20 and 30%
starch retained considerable clarity. This be-
havior is consistent with the observation and
computer-simulation analysis that little degrada-
tion of PE/starch blends occurs below the
percolation threshold of 31% by volume, or 40%
by weight of starch.33,35However, samples buried
in soil showed higher degradation than fungal
degradation. Pure samples of MA-g-LLDPE
were unaffected by the degradation.
3.11 Surface morphologies
Scanning electron microscopy (SEM) has been
used widely to study the surface morphologies
and biological problems. Enhanced resolution of
a sample by SEM permits higher magnification
probing of surfaces without loss in detail. In
addition, due to the depth of the field of SEM,
the micrographs retain a three-dimensional
appearance of the samples. SEM was used to
study the surface morphological changes after the
biodegradation of the samples.
Figure 10(a)-(d) were used to exemplify the
effect of soil and fungi environments on the
MA-g-LLDPE/starch (40/60) blend. After soil
burial the blend exhibited color changes and
weight loss due to the microbial growth on the
starch. Micrographs [Fig. 10(c) and (d)] show
black holes and white traces; starch is bio-
degraded, leaving behind a laced structure of
MA-g-LLDPE for further biodegradation. The
micrographs of a fungal-degraded sample [Fig.
of polyethylene and starch blends 197
/’
0
0
0
I’ .,--’
0 s-
/ s-
/ I’
20 30 40 50 50
%swch
blends in different biotic environments.
10(b)] shows the colonization behavior of fungi at
some particular places within channels of the
matrix which were initially occupied by starch.
3.12 Crystallization studies
Crystallinity is a state of molecular structure
referring to a long-range periodic geometric
pattern of atomic spacings. In semicrystalline
polymers such as polyethylene, the degree of
crystallinity influences the degree of stiffness,
hardness and heat resistance. Crystallinity can be
calculated from a differential calorimetry curve
by dividing the measured heat of fusion by the
heat of fusion of 100% crystalline material.
LLDPE is a semicrystalline thermoplastic
polymer which, upon the application of heat,
undergoes a process of fusion or melting where
the crystalline character of the polymer is
destroyed. While polymers melt over a tempera-
ture range due to differences in the size and
regularity of the individual crystallites, the
melting point of a polymer is generally reported
as a single temperature where the melting of the
polymer is complete. An additional parameter
for the characterization of LLDPE is its per cent
crystallinity.
The crystallinity of LLDPE was found to be
more than MA-g-LLDPE. The endotherms for
LLDPE and grafted LLDPE showed complete
melting at 125 and 117”C, respectively, indicating
a lower melting point (T,) for grafted LLDPE
than that for LLDPE. This is the direct
consequence of the lowering in PE crystallites in
 R. Chandra, Renu Rust@

Fig. 10. SEM micrographs of MA-g-LLDPE/starch (40/60) blend (a) undegraded sample; (b) degraded in mixed fungi
inoculum; (c) and (d) degraded in soil environment.

the presence of the MA groups. The presence of It is clear from the Table 4 that as the starch
MA also impeded the process of crystallization, content increased the heat of fusion and
leading to a greater extent of supercooling, and, crystallinity decreased for MA-g-LLDPE/starch
hence, a lower crystallization temperature (T,).*” blends. DSC plots of MA-g-LLDPE/starch
The crystallization temperatures were 107 and
94°C for LLDPE and MA-g-LLDPE,
respectively. Table 4. DSC comparison data of blends before and after
The per cent crystallinity was calculated on the degradation obtained from the second beating thermograms
assumption that the heat of fusion of 100%
crystalline LLDPE is 289 J gp’.44 As the heat of Blend Heat of fusion (J/g) % Crystallinity
composition
fusion is directly proportional to the amount of M~-Fz-I,IJJPE/ A B A B
crystalline LLDPE in the sample, it decreases as
the grafting percentage increases. An apparent
decrease in the heat of fusion was due to the 100/o 89.00 89.18 30.80 30.86
90110 66.69 68.72 23.07 23.78
decrease in the weight fraction of crystalline SO/20 62.70 66.70 21.69 23.08
LLDPE in the copolymer due to an incorpora- 70130 59.56 65.05 20.61 22.51
tion of MA. A similar trend was observed by 60140 47.49 53.40 16.43 18.48
50150 38.94 43.96 13.47 15.21
Kenyon and Duffey45 for PP-g-MA. The lowering
40160 26.98 33.41 9.33 11.56
of crystallinity in MA-g-LLDPE is understan-
dable in light of the intrusion of the bulky MA A; before degradation.
groups in the crystallite formation.2y~4h B; after degradation in soil.
 Biodegradation of polyethylene and starch blends 199

maximum decomposition temperature of grafted

LLDPE were considerably higher than those of
ungrafted LLDPE (Fig. 12). Similar results were
obtained by Sathe et ~1.~~ when MA was grafted
95.97”C
38.93 J/g with isotactic polypropylene using benzoyl
13.47% crystaked
peroxide as an initiator and toluene as a solvent.
DTG (first derivative of TG curve with respect
to time) was used for the calculation of
percentage of residual starch contents after
degradation in the MA-g-LLDPE/starch blends
-0.6
20 40 60 80 100 120 140 160 1 before and after degradation.
Temperature (“C) DSC V2.2A A very distinct weight loss is seen in all
DuPont 9900
samples within the temperature range of
Fig. 11. Second heating DSC thermogram of MA-g- 250-350°C at a heating rate of 10°C min-I. The
LLDPE/starch (50/50) blend,
TG curve of the MA-g-LLDPE sample (Fig. 13)
shows only a negligible weight loss in the same
temperature interval, suggesting the weight loss is
blends containing starch content from 50% are due to partial or complete pyrolytic volatilization
shown in Fig. 11. Decrease in crystallinity and of the starch in the blends. This loss in weight
heat of fusion can be explained as the content of might therefore be used to quantify the starch
starch increases, as do the amorphousness and content in the sample, or the residual starch
hydrophilicity of the blends also increases. content after degradation.
After 6 months of exposure to alluvial soil The DTG of the starch shows only about 68%
environment, the biodegraded samples were weight loss in the range of 250-350°C. A gradual
again analyzed for crystallinity. The results loss in weight occurs above this temperature and
obtained for all compositions of MA-g- at 8OO”C, which may be calculated as char yield.
LLDPE/starch blends are tabulated in Table 4, According to a number of opinions the weight
In all the composition of blends the heat of loss observed between 120 and 250°C deals with
fusion and crystallinity increased after biodeg- the 1,6-bond formation between two chains of
radation. During the biodegradation process, glucose units or with intermolecular 1,6-
generally the amorphous fraction of material is dehydration to form leavoglucosan.50 On the
exposed to microorganism attack. Therefore, the other hand, several volatile products are
microbial degradation results in an increase in reported” to be evolved at temperatures up to
the overall degree of crystallinity of the sample. 250°C. Among them carbon dioxide and other
Albertsson4’ and Kestelman et ~1.~’ noticed a lower aldehydes and ketones as well as some
similar change in the crystallinity of polyethylene methylfuranes could be identified apart from
after biodegradation. The latter investigators48 water.
used a fungus to study PE degradability. They
demonstrated a higher water uptake in PE,
120
overseeded with growing Aspergillis orzyae
molds, as a function of time. The increase in
water uptake was accompanied by a considerable
100
1
2 80
increase in the crystallinity of PE after attack by -i

the microorganisms, This finding is in agreement

with a similar observation made here,

3.13 Differential themogratimetry analysis of

the starch content in the blends
20
I
The TGA curves of LLDPE and MA-g-LLDPE
0
I
Temperature (“C) General V2.2A
show that a considerable change has occurred in DuPont 9900
the thermal behavior of LLDPE upon grafting. Fig. 12. TG thermograms of LLDPE (----) and
The initial decomposition temperature (IDT) and MA-g-LLDPE (- - -).
200 R. Chandra, Renu Rust@

li” 120 T

ioo-
I 100

80
2
a

2 60
.$

3
40

20- 20

O-

100 200 300 400 so0 600 160 260 300 460 5dO 660
Temperature (“C) General V2.2A Temperature (“C) General V2.2A
DuPont 9900 DuPont 9900

Fig. 13. TG thermograms of MA-g-LLDPE (-

Fig. 14. TG and DTG themograms of MA-g-LLDPE/starch
MA-g-LLDPE/starch 90/10 (- - -) and SO/20 (- -‘;
(50/50) blend; undegraded sample( -), exposed to fungi
blends.
(- - -) and soil (- -) environments.

To be of practical use, an analytical method for linkage between the starch and MA-g-LLDPE,
determining of starch in a polyolefin film must be which is susceptible to biodegradation by the
applicable to samples that have been exposed microorganisms and the hydrolytic enzymes
under different environmental conditions in order produced by them. The blends containing higher
to introduce at least a partial biodegradation of percentages of starch (40, 50 and 60%) show
the starch fraction. Exposure to biotic environ- significant degradation in the case of
ments causes enzymatic hydrolysis of some of the LLDPE/starch blends when exposed to a soil
starch and also invasion of the polymer matrix by environment. In the case of fungal exposure, not
microbial biomass. The presence of microbial more than 24-26% starch degradation was
biomass within the plastic material may introduce observed in both the series. TG and DTG
additional polysaccharides material into the thermograms obtained for the MA-g-
polymer, which undergoes thermal degradation LLDPE/starch (50/50) blend before and after
in the same or lower temperature range as starch degradation in the soil and fungi environment is
and interferes with the TGA technique. shown in Fig. 14. The percentage of degraded
MA-g-LLDPE/starch blends were exposed to starch in the MA-g-LLDPE/starch blends are
two biotic environments, buried under soil for 6 given in Table 5.
months and incubated to five selected mixed
fungi inoculum according to ASTM G21-70 for
28 days. LLDPE and MA-g-LLDPE demon-
4 CONCLUSIONS
strated 0.37 and 0.20% weight loss, respectively,
within the specified temperature interval, pos-
The following conclusions can be drawn from our
sibly due to the moisture or low molecular weight
studies:
components.
In LLDPE/starch blends with starch content (1) The final mixing torque and total torque
up to 30%, no significant decrease in the amount were found to be higher for blends containing
of starch (about 3.5%) was observed after arthydride functional LLDPE and starch than
exposure to both biotic environments. This might the corresponding nonfunctional LLDPE and
be explained in terms of limited accessibility of starch blends. This could be due to the reaction
starch to microbes. At higher percentage of of the anhydride group in the LLDPE with the
starch in the matrix, faster, readily observable hydroxyl group in the starch. Melt temperature
biodegradation of starch was noticed in both the was also higher for MA-g-LLDPE and starch
environments. However, in the case of MA-g- blends due to an increase in the viscosity of the
LLDPE blends, the degradation was relatively blends.
higher (about 12%) for the same range of starch (2) The torque and totalized torque increased
content. The relative higher degradation may be with increasing amounts of starch for lo-50%
explained on the basis of the presence of ester starch content blends. Further increase in the
 Biodegradation of polyethylene and starch blends 201

Table 5. Effect of the environmental exposure on stpreh content for MA-g-LLDPE/starch blends

Blend composition % Starch % Starch Percentage of Percentage of

MA-g-LLDPE/starch before exposure after exposure residual starch degraded starch

Exposure to Fungi inoculum

90110 6.4 5.93 92.4 7.6
80120 12.79 11.45 89.4 10.6
70130 18.32 16.18 88.2 11.8
60140 25.54 22.32 87.3 12.7
50150 27.24 21.24 80.1 20.0
40160 37.13 28.29 76.1 23.9

Exposure to Laboratory Soil Environment

90110 6.4 6.25 97.6 2.4
80120 12.79 11.60 89.7 8.7
70130 18.32 16.46 89.7 10.3
60140 25.54 21.15 82.7 17.3
50150 27.24 20.37 74.6 25.4
40160 37.13 25.25 67.8 32.2

A; No shredding, cutting, or grinding were used to increase the surface area exposed to microbes. B; Total weight
change was assumed to be due to complete pyrolysis of starch.

starch content of the blend resulted in the probably incomplete removal of starch. In
reduction of torque due to the presence of general, the rate of degradation depends on
unmelted starch. the starch content in the blends. Thus, the
(3) Tensile strength and modulus increased higher the starch content the higher the degree
with increasing the amount of starch in the of degradation.
blends, suggesting interfacial adhesion of the
two components of the blend due to reaction.
All the composition of MA-g-LLDPE/starch REFERENCES
blends, when exposed to a soil environment,
showed a higher percentage of degradation
1. Pierre, T. S. and Chiellini, E., J. Bioact. Compat.
than for fungi alone. This may be because in
Polym., 1987,2, 4.
soil other environmental factors such as 2. Holmes, P. A., Collins, S. H. and Wright, L. F., U.S.
oxygen, humidity, heat and microorganisms Pat. 4 477 654, 1984.
play a synergistic effect and further degrades 3. Gould, M. J., Gordon, S. H., Dexter, L. B. and
Swanson, C. L., In Agricultural and Synthetic Polymers:
the samples. Bidegradation and Utilization, ed. J. E. Glass and G.
(4) In all the compositions, water absorption Swift, ACS Symposium Series 433, ACS, Washington,
and opacity increased with increasing amount DC, 1990, p. 65.
4. Fanta, G. F. and Baglay, E. B., In Encyclopedia of
of starch in the blends. MA-g-LLDPE/starch Polymer Science, ed. H. F. Mark and N. M. Bikalas,
blends exhibited reasonably good water resis- John Wiley and Sons, New York, 1970.
tance compared to LLDPE/starch blends. 5. Fanta, G. F., In Block and Graft Copolymers, ed. R. J.
Ceresa, Wiley, New York, 1973, p. 1.
Thus, blends containing higher amounts of
6. Otey, F. H., Westhoff, R. P. and Doane, W. M., Znd.
starch (50 and 60%) could be made sig- Engng Chem. Prod. Res. Dev., 1980,19,592.
nificantly water resistant. Crystallinity of the 7. Otey, F. H. and Westhoff, R. P., Znd. Engng Chem.
blends increased after degradation due to the Prod. Res. Dev., 1984, 23, 284.
8. Otey, F. H., Westhoff, R. P. and Doane, W. M., Znd.
removal of starch from blends. Engng Chem. Prod. Res. Dev., 1987,26,1659.
(5) FTIR analysis and SEM studies of the 9. Willet, J. L., U.S. Pat. 5 087 650, 1992.
degraded samples showed only the degradation 10. Jane, J. L., Gelina, R. J., Nikolov, Z. and Evangelista,
R. L., U.S. Pat. 5 059 642, 1991.
of starch, while the MA-g-LLDPE matrix
11. Jane, J. L., Schwabacher, A. W., Ramrattan, S. N. and
remained intact. DTG and FTIR data showed Moore, J. A., U.S. Pat. 5 115 000, 1992.
an extensive removal of starch from high- 12. Liu, N. C. and Baker, W. E., Adv. Polym. Technol.,
percentage starch content blends (40, 50 and 1992, 11, 249.
13. Hogt, A. H., Proc. 46th Antec’88, 1988, p. 1478.
60%), whereas lower percentage starch blends 14. Hogt, A. H., Proc. Compalloy’90, 1990, p. 179.
(10, 20 and 30%) exhibited a slower and 15. Callais, P. A., Proc. Compalloy’90, 1990, p. 359.
202 R. Chandra,
16. Ruggeri, G., Aglietto, M., Petragnani, A. and Ciardelli,
F., Eur. Polym. J., 1983, 19, 863.
17. Macosko, C., Trolez, Y. and Bouilloux, A.. Proc. 33rd
IUPAC Macro’90, 1990, Session 3.2.7.
18. Watanabe, Y. and Hatakeyama, T., J. Appl. Polym. Sci..
1989,37,1141.
19. Ho, R. M., Su, A. C., Wu, C. H. and Chen, S. I.,
Polymer, 1993,34(1.5), 3264.
20. Gaylord, N. G. and Mishra, M. K., J. Polym. Sci.
Polym. Lett. Edn, 1983, 21, 23.
21. Reid, D. E. and Spurlin, H. M., U.S. Pat. 3 414 551,
1968.
22. Rengarajan, R., Parameswaran, V. R., Lee, S. and
Rinaldi, P. L., Polymer, 1990, 31, 1703.
23. Singh, R. P., Prog. Polym. Sci., 1992, 17, 251.
24. Minoura, Y., Ueda, M., Mizunuma, S. and Oba. M., J.
Appl. Polym. Sci., 1969, 13, 1625.
25. Maldas, D. and Kokta, B. V., Polym. Engng Sci., 1991,
31, 1351.
26. Raj, R. G. and Kokta, B. V., Polym. Engng Sci., 1991,
31, 1358.
27. Wang, Y., Ji, D., Yang, C., Zhang, H., Qin, C. and
Huang, B., J. Appl. Polym. Sci., 1994, 52, 1411.
28. Cheremisinoff, N. P., Polymer Mixing and Extrusion
Technology, Chap. 7, Marcel Dekker, New York, 1987.
29. Cole, M. A., A protocol for conducting Soil Burial
Studied with Biodegradable Plastics, University of
Illinois Urbana-Chanpaign, Department of Agronomy,
3 March, 1989.
30. Qin, C., Ji, D., Tang, T., Yang, C., Wang, Y., Zhang,
H., Pang, D. and Huang, B., In Symp. on Polymers,
Chengdu, 14-18 November, Preprints, 1989, p. 1085.
31. Vinogradov, G. V. and Malkin, A. Y., Rheology of
Polymers. Mir, Moscow, 1980.
32. French, D., In Starch Chemistry and Technology, ed. R.
L. Whistler, J. N. BeMiller, and E. F. Pasohall.
Academic Press, New York, 1984, pp. 184-248.
33. Peanasky, J. S., Long, J. M. and Wool, R. P., J. Polym.
Renu Rustgi
Sci. Polym. Phys. Edn, 1991, 29, 565.
34. Wool, R. P., Peanasky. J. S., Long, J. M. and Goheen.
S. M. In Proc. First Int. Scientific Consensus Workshop
on Degradable Materials, Toronto. Canada, 2-4
November, 1989. p. 515.
35. Goheen, S. M. and Wool, R. P., J. Appl. Polym. Sci.,
1991, 42,269l.
36. Wool, R. P., and Goheen, S. M., Proc. Int. Symp. on
Biodegradable Polymers, Tokyo, 1990, p. 137.
37. Albertsson, A. C., J. Appl. Polym. Sci., 1978, 22, 3419.
38. Kenyon. A. S. and Duffey, H. J., Polym. Engng Sci..
1967, 7, 189.
39. Breslin, V. T. and Li, B., J. Appl. Polym. Sci., 1993, 48,
2063.
40. Smith, A. L., Applied Infrared Spectroscopy. Wiley,
New York, 1979, pp. 158.225-227, 254-256.
41. Casu, B., Gaglioppa, G. and Reggiani. M., Die Starke.
1965,12,386-389.
42. Pimental, G. C. and McClellan, A. L., The Hydrogen
Bond, ed. W. H. Freeman, San Francisco, CA. 1960, pp.
172, 196. 277. 329-331.
43. Albertsson, A. C., Andersson, S. 0. and Karlsson, S.,
Polym. Degrad. Stabil., 1987, 18, 73.
44. Lavengood, R. E., Nicolais, L. and Narkis, M., .I. Appl.
Polym. Sci., 1973, 17, 1173.
45. Kenyon, A. S. and Duffey, H. J.. Polym. Engng Sci.,
1967, 7, 189.
46. Greco, R., Musto, P., Riva, F. and Maglio, G.. J. Appl.
Polym. Sci., 1989, 37, 789.
47. Albertsson, A. C., In Int. Conf: on the Advances in the
Stabilization and Controlled Degradation of Polymers,
ed. A. V. Patnis, Technomic, West Chester, PA, 1986.
48. Kestelman, V. N., Yaravenko, V. L. and Melnikova, E.
I., Int. Biodeter. Bull., 1972. 81, 15.
49. Sathe, S.N., Rao, G. S. S. and Surekha. D., J. Appl.
Polym. Sci., 1994, 53, 239.
50. Tomasik, P., Baczkowicz. M. and Wiejak, S.,
StarchlStarke. 1986, 38(12), 410-413.