EUROPEAN

POLYMER
European Polymer Journal 43 (2007) 3976–3987
JOURNAL
www.elsevier.com/locate/europolj

Studies on the properties and characteristics of

starch–LDPE blend films using cross-linked, glycerol modified,
cross-linked and glycerol modified starch
Sangeeta Garg, Asim Kumar Jana *

Department of Chemical and Bioengineering, National Institute of Technology, Jalandhar – 144 011, Punjab, India

Received 22 December 2006; received in revised form 8 June 2007; accepted 25 June 2007
Available online 6 July 2007

Abstract

Corn starch was modified by cross-linking with epichlorohydrin and plasticizer glycerol. X-ray diffraction studies
showed that relative crystallinity of the native and cross-linked starch were similar and were not affected by cross-linking.
Different films were prepared by blending corn starch, cross-linked starch or glycerol modified starch in LDPE. The
mechanical properties of the films were studied for tensile strength, elongation, melt flow index, and burst strength.
The properties of the blend films were compared with LDPE films. It was observed that with the blending of 7.5% native
starch, there was a decrease in tensile strength, elongation and melt flow index but burst strength increased. The tensile
strength, elongation and melt flow index of the films containing cross-linked starch was considerably higher than those
containing native starch but the burst strength showed a reverse trend. For native starch and cross-linked starch modified
with glycerol, the elongation and melt flow index of the films increased but burst strength decreased. Surface scanning of
the blend films were done by scanning electron microscope. Film containing cross-linked starch/glycerol modified starch in
the blend was observed to be smoother than the native starch blend films.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Starch; Cross-linked starch; Glycerol modified starch; Starch–LDPE blend films; Mechanical properties; SEM

1. Introduction for environment and economic reasons [2,3]. Blend-

Synthetic materials like polyolefins are not
degraded by microorganisms in the environment,
which contribute to their long life and ever increas-
ing volume of plastic waste [1]. Therefore, recycling
and degradations of plastics is an important issue
*
Corresponding author. Tel.: +91 181 2690301x252; fax: +91
181 2690320.
E-mail address: janaak@nitj.ac.in (A.K. Jana).
ing has become an economical and versatile route to
obtain polymers with a wide range of desirable
properties. Partially biodegradable polymers
obtained by blending biodegradable and non-biode-
gradable commercial polymers can effectively
reduce the volume of plastic waste by partial degra-
dation. They are more useful than completely biode-
gradable ones due to the economic advantages and
superior properties, imparted by the commercial
polymer used as a blending component. In order

0014-3057/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2007.06.030
 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
to ensure homogeneity in the blends at microscopic
level, it is necessary to reduce the interfacial tension,
so that the characteristics of the blend components
are improved or at least retained.
Pure starch does not form a film due to hydro-
philic nature. The extrusion and viscous behavior
of the starch is known to depend on temperature,
moisture and thermo-mechanical treatment [4,5].
Starches could be blended with various plastic mate-
rials up to a certain amount and sheets or films
could be made by conventional process. Since the
starch is biodegradable, it would be metabolized
by a wide array of organisms. Modified plastics
derived from blend with biodegradable agricultural
feed stocks, like starch offers an elegant approach
to meet the requirements of responsible and ecolog-
ically sound utilization of resources and to guaran-
tee at least a partial degradation [6].
Different types of biodegradable fillers used in the
blend were dry granular starch in LDPE [7], gelati-
nized starch [8], plasticized starch in polyethylene
[9], hydroxypropylated starch in polyethylene [10],
and corn starch in recycled LDPE [11]. Native corn
starch and hydroxypropylated starch based plastic
films by using short pulp fiber as reinforcement
and glycerol as plasticizer have also been prepared
[12]. Cross-linked starch has been employed in var-
ious studies [13–15]. The effect of cross-linking
depended on the botanical source of starch and
the cross-linking agent [16,17].
It has been observed from the previous studies
that blending of starch with LDPE drastically
reduced the mechanical properties of the film and
was difficult to increase the concentration of starch.
Behind the poor quality film, one of the problems
identified was that the immiscible mixture of hydro-
philic starch and hydrophobic LDPE. It is interest-
ing to study the interfacial properties between starch
and polyolefins to improve their hydrophilic and
hydrophobic characters, respectively, responsible
for mechanical properties.
Chemical modification of starch is being used to
introduce desirable properties to starch. Cross-link-
ing of starch with epichlorohydrine is the most com-
mon method used in polysaccharide industry [14].
Cross-linking of starch by reaction with bi- or
poly-functional reagents is widely used in numerous
industrial applications of wet-rub-resistant starch
paper coatings, permanent textile sizes and water
resistant adhesives [17]. In this paper, systematic
studies has been done to see the effect of compatibil-
ity of LDPE on addition of cross-linked starch,
3977
glycerol modified starch separately and also by
using cross-linked starch further treated with glyc-
erol in the blend by measuring the mechanical prop-
erties and morphological properties of the films.
2. Materials and methods
2.1. Materials
Low density polyethylene (LDPE) used in this
study was made by Indian Petrochemical Corpora-
tion Ltd., Baroda and Starch (corn starch) was
made by Sukhjit Starch and Chemicals Ltd., Phagw-
ara (India). Epichlorohydrine, sodium hydroxide,
acetic acid, acetone, glycerol used were all reagent
grade chemicals.
2.2. Cross-linked starch
Cross-linked starch was prepared from the corn
starch by the treatment of cross-linking agent epi-
chlorohydrin under alkaline conditions [13]. Corn
starch was suspended in distilled water at 60%
(w/w) and slurry was prepared by high speed impel-
ler agitation for 2 h. Epichlorohydrin was added to
the solution to give 2% final concentration based on
the starch dry weight and pH adjusted to 10.5 with
NaOH solution. The mixture was stirred for 24 h at
room temperature. The pH of the slurry was
adjusted to 5.5 with acetic acid. The slurry was
filtered and washed with distilled water and subse-
quently with 85% acetone. The cross-linked starch
was dried at 40 C in a hot air oven for 48 h to
the constant weight.
2.3. Glycerol modified starch
Glycerol modified starch was prepared by treat-
ment of glycerol with the starch/cross-linked starch
in a Tumbler mixer. It is a vertical double cone
mixer, having maximum diameter of 55 cm at the
center. Feed opening was at the 60 cone and the
discharge opening 30 cone. A batch was charged
into the mixture to 50% full and the ends were
closed. The partly filled mixture was rotated about
the horizontal axis with 30 rpm speed. The time of
mixing for each batch of feed was 15 min.
2.4. Degree of cross-linking
The degree of cross-linking of the modified starch
was determined from the viscosity values, according
3978 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
to the method of Chatakanonda et al. [18]. The peak
viscosity of the starch samples were recoded using a
rotating spindle viscometer (Brookfield DV II, spin-
dle no. 1, speed 200 rpm). The starch slurry (10% by
weight) was heated from 50 to 95 C at 12 C/min
with stirring and was then held at 95 C for 2 min.
Afterwards the paste was cooled to 50 C at
12 C/min and finally kept at 50 C for 2 min. The
degree of cross-linking was calculated using the fol-
lowing equation [18]
Degree of cross-linking ¼ ½ðA  BÞ=A  100
where, A is the peak viscosity of the native starch
and B is that of the cross-linked starch.
2.5. X-ray diffraction and crystallinity
X-ray diffractions of native and cross-linked
starches were recorded by X-ray diffractrometer
(Philips PW 1710, tube anode Cu, tube voltage
was 35 kV and generator current was 20 mA). The
range of diffraction angle was 5–40 (2h), intensity
ratio 0.50, wavelength 1.54060 Å and 1.54439 Å,
minimum and maximum peak widths were 0 and
1 (2h), respectively. The crystallinities were mea-
sured by ratio of the relative area of crystalline peak
to total area of the diffractogram. The diffraction
peak area and total diffraction area were calculated
by Leica Image analyzing system (UK).
2.6. Starch–LDPE blend film
Different films were prepared by incorporating
starch, cross-linked starch, glycerol modified starch
and cross-linked starch modified with glycerol in
LDPE. The blend mixture was prepared by taking
the different components in appropriate ratios in
tumbler mixture for 15 min with 30 rpm speed.
The blend was propelled continuously through the
single screw extruder to be melted, compacted and
finally forced through the die. Single screw extruder
had a screw length to screw diameter ratio of 26 and
length of 495 mm. The temperature of the extruder
was fixed at 135 C at the feed end after some trials.
The extruder barrel was thermo-controlled at
135 C at the feed end and increased in the direction
of extrusion to 152 C. After extrusion, films were
made by an integrated blow film plant (Konark
Instruments Ltd., India). Tubular die was used in
the blow film plant, from which a hollow tube of
the product was extruded vertically upward like a
film tower. The tube was blown into a thin cylindri-
cal film by air blown through the die and trapped in
the film bubble. At the top of the tower, the blown
film was squeezed through two chilled rolls of diam-
eter 76 mm and width 250 mm. The produced films
after the squeeze rolls were collected in an inte-
grated winder with take off speed 8 m/min. The film
thickness was controlled by air flow rate and the
speed of the rollers. The thicknesses of the films
were 0.1 ± 0.01 mm. Then the films were kept for
conditioning for 48 h at room temperature 25 C,
70% R.H.
2.7. Tensile strength and percent elongation
Tensile strength and percent elongation of the
films were determined by Instron Universal Testing
Machine (Lloyd instruments, UK) at load cell
100 N, load range 5 and cross-head speed
100 mm/min. Samples were cut into strips 3 cm ·
1 cm according to standard ISO – 527 in the longi-
tudinal direction of extrusion and were conditioned
to equilibrium moisture content in the room at 70%
relative humidity for 24 h at 25 C prior to testing.
Measurements were done in five replicates.
2.8. Melt flow index (MFI)
MFI was measured by using Melt Flow Index
Tester (Lloyd instruments, UK) at temperature
199 C and 2.16 kg load. Preheat time was set to
5 min. Extrudate cut timer was set to 30 s. The first
extrudate was rejected and next five extrudates were
collected for calculation of MFI
Average weight of extrudate
MFI ¼
Cut off time
2.9. Burst strength
Burst strength of the films were measured by
burst strength tester (CIPET, India) at varying
gauge pressure and the maximum pressure at which
the sample undergoes failure was noted. Values
were measured in five replicates.
2.10. Scanning electron microscopy of films
Scanning electron microscopy of the films were
examined and photographed in scanning electron
microscope (JEOL JSM – 6100 Jeol Ltd., Tokyo,
Japan). The range of accelerating voltage was 0.3–
30 kV. The samples were first sputter coated with
 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
a thin layer of gold and then observed at magnifica-
tion of 100· and 5000·.
3. Results and discussion
3.1. Cross-linking of starch
Starch and LDPE give poor quality blend and
reduced mechanical properties of the films. Changes
in the properties of starch would possibly enhance
the blend quality and film properties. Starch was
modified by cross-linking with epichlorohydrin
under alkaline conditions. About the requirement
of epichlorohydrine, concentration of epichlorohy-
drine with respect to starch dry weight in the
reaction mixture was varied and the degree of
cross-linking was measured. The degree of cross-
linking was determined from the viscosity values.
It was observed that at lower level of epichlorohy-
drine (0.25–1.5%) the degree of cross-linking was
not detectable by viscosity method used. The degree
of cross-linking of these starches was not enough to
restrict the swelling of the granules and exhibited
high viscosity values. However, an increase in the
amount of epichlorohydrine used resulted in higher
degree of cross-linking. At 2% reagent level, nearly
85% cross-linking was observed.
Epichlorohydrine has been known as cross-link-
ing agent which can react with dialcohol groups.
Earlier literatures predicted that the reaction of epi-
chlorohydrine with starch in presence of alkali led
to the formation of glycerol mono and diethers
[19,20]. Based on kinetic evidences, a three step
mechanism for cross-linking reaction in alkaline
condition have been proposed [21,22]. In the first
step, the hydroxyl groups of the starch are con-
verted to alcoholic anions. In the second and third
steps, two alcoholic anions from two different starch
molecules form glycidyl ether linkages on the both
sides of the epichlorohydrin through nucleophylic
attack of the epoxide ring structure of epichlorohy-
drin. A bridge is being formed between the two
starch molecules.
Kim and Lee [13] calculated the molar degree of
cross-linking of potato starch in moles of epi-
chlorohydrine and product yield by determining
the amount of unreacted epichlorohydrine in the
reaction mixture. They reported 90% reaction yield
and degree of cross-linking 3.3% in 24 h of reaction
at 2% epichlorohydrine applied. The degree of
cross-linking increased with concentration of epi-
chlorohydrine in use used. Hollinger, Kuniak and
3979
Marchessault [23] reported this amount to be less
than 5% of the added epichlorohydrine. The degree
of cross-linking also increased with % epichlorohy-
drine in reaction for the cassava starch and 82%
cross-linking was observed at 1% epichlorohydrine
[24]. Kuniak and Marchessault [14] reported that
depending upon conditions of time, temperature
and mole ratio of reagents, 5.25% of the applied epi-
chlorohydrine is bound in the starch as a glycerol
mono ether substituent.
3.2. X-ray diffraction of starch
Modification of starch using reaction of starch
hydroxyl functional groups and epichlorohydrin
caused the bridging of the starch molecules. To
observe that whether it affected the morphology of
starch, X-ray diffraction patterns of native and
cross-linked starch particles were studied by X-ray
diffractrometer.
Fig. 1 show the X-ray diffraction patterns of
native starch and cross-linked starch. Variation in
intensity of light with angle (2h) was recorded.
Diffractrogram of native starch showed 6 peaks at
angles 15.26, 17.17, 17.97, 20.06, 22.97 and
33.77 (2h). However, in cross-linked starch diffrac-
trogram, it showed 5 peaks without the angle of
33.77. Table 1 showed the d-values at the various
angles of native and cross-linked starch. It was
observed that d-values for native starch decreased
from 5.08 to 2.66 with increase in angle from
15.26 to 33.77 (2h) at the wavelength 1.54060 Å.
d-values for the cross-linked starch decreased from
5.89 to 3.87 with the increase in angle from 15.0
to 22.99 (2h) at the fixed wavelength. In both the
cases, it was observed that pattern of the peaks
and changes in intensity with the angle were similar.
The peaks were not sharp and flattened. This indi-
cated that both the native starch and cross-linked
starch are semi-crystalline in nature.
The relative crystallinities of the native starch
and cross-linked starch were calculated as ratio of
the area under the peaks to the total area given
and showed in Table 2. Results envisaged that rela-
tive crystallinities of the native and cross-linked
starch were similar and not affected by cross-link-
ing. Semi crystalline nature of the starch have also
been observed earlier and could adopt different crys-
talline structures (A, B, C, and V) [25,26]. The A, B
and C structures consisted of packed double helix.
The V-type structure was a single helix structure.
Peaks observed in our study showed that the native
3980 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987

Fig. 1. X-ray diffraction patterns of native starch and cross-linked starch.

Table 1 Table 3
Important results from X-ray diffraction studies of native starch Composition of starch–LDPE blend films
and cross-linked starch Film Composition (% w/w)
Native starch Cross-linked starch
Starch Cross-linked LDPE Glycerol
Angle (·2i) d-value Angle (·2i) d-value (NS) starch (CLS)
15.26 5.0815 15.01 5.8895 LDPE – – 100 –
17.17 5.1602 17.06 5.1932 LDPE – 7.5 NS 7.5 – 92.5 –
17.97 4.9323 18.14 4.8864 LDPE – 7.5 CLS – 7.5 92.5 –
20.06 4.4228 20.23 4.3969 LDPE – 7.5 MS 7.5 – 87.5 5
22.97 3.8782 22.99 3.8740 LDPE – 7.5 CLSM – 7.5 87.5 5
33.77 2.6586 LDPE – 15 MS 15 – 65 20
LDPE – 15 CLSM – 15 65 20
NS, native starch; CLS, cross-linked starch; MS, starch modified
Table 2 with glycerol; CLSM, cross-linked starch modified with glycerol.
Relative crystallinity of native and cross-linked starch
Type of starch Crystallinity = (Ac/Ac + Aa) (%)
than the LDPE film under similar die, pressure
Native 48.82 and temperature conditions. Starch particles could
Cross-linked 48.54
be viewed separately in the matrix of the LDPE film.
Ac: Crystalline area; Aa: amorphous area. Films containing 7.5% cross-linked starch in the
blend were smoother than the native starch blend
corn starch and cross-linked corn starch resembles films. With the addition of 5% glycerol in blends,
to B type structure. films were smoother and very few starch particles
in the films were visible.
The processing of the blend containing 15%
3.3. Blend film starch and 20% glycerol was difficult, as it tend to
stick together and to the walls of the hopper. The
Films were prepared by incorporating native, mixtures were kept for 30 min in oven at 50 C
cross-linked, glycerol modified starch and cross- and then send through extruder. Films made from
linked glycerol modified starch in LDPE. The the blend had air gaps due to entrainment of air.
compositions of the various films prepared are sum- This entrainment of the air was may be because of
marized in Table 3. the higher moisture present in the blend due to
It was observed that the surface of the film con- increase in starch content. Another reason may be
taining 7.5% native starch in the blend was rough flow through the die was not uniform at higher
 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987 3981

starch concentrations. Depending upon the size of
the bubbles, the films were perforated at some
points.
3.4. Mechanical properties
3.4.1. Tensile strength and % elongation
Tensile strength is the capacity of the film to take
the load and percent elongation is its ability to
stretch. Tensile strength and percent elongation of
the films were measured and the results are shown
in Fig. 2. It was observed from the Fig. 2 that the
tensile strength and percent elongations varied with
different starch blends. To isolate the effect in indi-
vidual blend and for comparison, a comprehensive
result of the properties and their changes relative
to the control sample LDPE film has been shown
in Table 4. It was observed that the tensile strength
of LDPE films were 16.08 MPa and higher than
all the blend films. With the addition of 7.5%
native starch, the tensile strength of the blend films
(LDPE – 7.5 NS) reduced to almost 54%. But the
films using the cross-linked starch (LDPE – 7.5
CLS), there was an increase in tensile strength as
compared to native starch in the blend. The tensile
strength of these films (LDPE – 7.5 CLS) were much
higher and was almost 92% of the LDPE films. The
results showed that in the glycerol modified starch
blend films, tensile strength increased from native
starch blend films but to a small extent. The tensile
strength for cross-linked glycerol modified starch
blend films (LDPE – 7.5 CLSM) were higher than
the glycerol modified starch blend films (LDPE – 7.5
MS), but less than the cross-linked starch blend
films (LDPE – 7.5 CLS). With the increase in the
starch content to 15% in blend (LDPE – 15 MS),

800
18
16 700
Tensile Strength (MPa)

14 600

% Elongation
12 500
10
400
8
300
6
200
4
2 100

0 0
LDPE 7.5% NS 7.5% 7.5% 7.5% 15% MS 15%
+ LDPE CLS + MS + CLSM + + LDPE CLSM +
LDPE LDPE LDPE LDPE

Tensile Strength % Elongation

Fig. 2. Tensile strength and % elongation of starch–LDPE blend films.

Table 4
Mechanical properties of the blend films and variations relative to LDPE film
Films Tensile strength Elongation Melt flow index Burst strength
MPa Relative to % Relative to g/10 min Relative to MPa Relative to
LDPE (%) LDPE (%) LDPE (%) LDPE (%)
LDPE 16.08 ± 1.09 100 569.95 ± 39.89 100 3.84 ± 0.27 100 0.148 ± 0.01 100
LDPE – 7.5 NS 8.67 ± 1.56 53.9 136.05 ± 21.77 23.9 3.57 ± 0.71 93.0 0.184 ± 0.03 124.3
LDPE –7.5 CLS 14.82 ± 1.94 92.2 181.81 ± 23.63 31.9 3.75 ± 0.56 97.6 0.131 ± 0.02 88.5
LDPE – 7.5 MS 9.46 ± 1.56 58.8 228.34 ± 34.25 40.0 3.79 ± 0.61 98.7 0.174 ± 0.03 117.6
LDPE –7.5 CLSM 12.84 ± 1.06 79.8 293.13 ± 24.92 51.4 3.82 ± 0.33 99.5 0.122 ± 0.01 82.4
LDPE – 15 MS 4.21 ± 1.74 26.2 79.72 ± 31.89 14.0 4.77 ± 1.19 124.2 0.186 ± 0.05 125.7
LDPE – 15 CLSM 9.71 ± 1.81 60.4 145.3 ± 29.06 25.5 4.34 ± 0.99 113.0 0.176 ± 0.03 118.9
3982 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
tensile strength decreased to a lowest value. How-
ever, it increased with the addition of cross-linked
starch in blend (LDPE – 15 CLSM).
Percent elongations of the LDPE films were max-
imum. With the addition of 7.5% starch in the
blend, the percent elongation of the films (LDPE –
7.5 NS) decreased to 25%. Percent elongation of
the films increased by using cross-linked starch in
the blend (LDPE – 7.5 CLS) and by glycerol modi-
fied starch in the blend (LDPE – 7.5 MS) gradually.
For the films using cross-linked starch modified
with glycerol (LDPE – 7.5 CLSM), percent elonga-
tion further increased up to 52% of the LDPE film.
Results showed that with the increase in starch con-
tent from 7.5% to 15% in blend (LDPE – 15 MS), %
elongation reduced to a large extent. However, it
improved to a small extent with the addition of
15% cross-linked starch in blend (LDPE –
15 CLSM).
The above results clearly show that the addition
of native starch, cross-linked or glycerol modified
starch reduced the tensile strength and percent elon-
gation of the blend films. The extent of decrease
depended on the properties of the starch and the
concentration of starch in the blend as well. Fig. 2
clearly showed that at the same concentration of
starch, the tensile strength and percent elongation
increased to a large extent due to cross-linking
and/or modification by glycerol.
Chemically starch is a polymer of glucose having
a-1, 4 and a-1, 6 linkages as amylose and amylopec-
tin. Native starch granules exhibit hydrophilic prop-
erties and strong inter-molecular association via
hydrogen bonding due to hydroxyl groups on the
granule surface. The strong hydrogen bonding asso-
ciation and crystallization leads to poor thermal
processing and unstable blending with hydrophobic
LDPE. In case of cross-linked starch the hydroxyl
groups on starch molecules react with epichlorohy-
drin and mono/di-glycerol ether starch are pro-
duced [19,20]. The bridging of starch molecules
may also occur through nucleophilic attack of
starch alcoholic anions to epoxide ring structure
of the epichlorohydrine [21,22]. The hydrophilic
nature of cross-linked starch decreased because of
reduction in the functional hydroxyl groups by the
reaction with epichlorohydrin. The homogeneity
and compatibility of the blend with LDPE
increased. Earlier literature report showed that
cross-linked starches showed lower solubilities in
water at 90 C than the native starch [24]. The solu-
bility decreased with increase in epichlorohydrine
concentration, which could be attributed to the
increase in the degree of cross-linking. Decrease in
the swelling property was also observed [24]. Due
to strengthening of the starch granules through
cross-links, less disintegration takes place during
gelatinization. Random cross-linking also enhances
the property of the film by reinforcing characters
of the blend polymer. The changes in properties of
the starch in lowering of the solubility in water were
observed by Liu, Ramsden and Corkr [27]. They
observed the lowering of solubility of cross-linked
waxy rice starches. Cross-linking restricts the swell-
ing of the granules and also lower solubility by
increasing chain length. A decrease in the water
uptake of rice starch upon cross-linking with epi-
chlorohydrine have also been reported [28].
In glycerol modified starch, the starch was plasti-
cized by glycerol. This enhanced the miscibility of
the starch in blend with LDPE and improved the
thermal processibility. Smits, Kruiskamp, van Soest
and Vliegenthart [29] has showed the time interac-
tion with plasticizers affects the molecular mobility
and therefore with the material properties. Due to
interaction with plasticizers starch mobility
increases, viscosity reduces, and the material
behaves like a rubber. Therefore, LDPE films con-
taining plasticized starch showed higher tensile
strength and elongation properties than the films
containing native starch. In the film containing
cross-linked starch further modified with glycerol
(LDPE – 7.5 CLSM), the tensile strength was inter-
mediate between the native starch film and cross-
linked starch film. But % elongation for this film
was much higher as compared to other films because
of reduction in the hydrophilic functional groups of
the starch and effect of plasticizer. A crucial role of
polymer network in formation of the film structure
in the presence of plasticizer has been observed ear-
lier [30]. Glycerol and starch polymers strongly
interacted, and at low glycerol content it’s interac-
tion resulted in more brittle structure for both amy-
lose and amylopectin polymer networks. Increase in
elongation was observed when more than 20% of
glycerol was added to amylose. At higher glycerol
concentrations amylose could form films upto 70%
glycerol, but from amylopectin only fluid like mate-
rial was produced above 20% glycerol.
The effect on tensile strength and percent elonga-
tion by cross liking of starch was made by Kim and
Lee [13] in a study using cross-linked potato starch
and LLDPE cast films. Cross-linking of the starch
improved the mechanical properties blend. In the
 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987 3983

present study, the plasticizing effect of glycerol has
further improved the mechanical properties particu-
larly the percent elongation.
3.5. Melt flow index and burst strength
Melt flow index define the grades of material in
extrusion, injection or blow molding processes.
Burst strength is the load applied per unit area to
burst a film. Melt flow index and burst strength of
the films are shown in Fig. 3. It showed the varia-
tions of the burst strength and melt flow index with
different starch blends. To isolate the effect in indi-
vidual blend and for comparison, a comprehensive
result of the properties and changes relative to the
control sample LDPE film has been presented in
Table 4.
It was observed that the melt flow index of the
LDPE films were 3.85 g/10 min. With the addition
of 7.5% native starch in the blend films (LDPE –
7.5 NS), melt flow index decreased. There was
increase in melt flow index for the blend films due
to addition of either cross-linked starch (LDPE –
7.5 CLS), glycerol modified starch (LDPE –
7. MS) or cross linked and glycerol modified starch
(LDPE – 7.5 CLSM) in the blend. The melt flow
indexes of these films were close to the LDPE films.
Further, the results showed that with the increase in
starch content from 7.5% to 15%, the melt flow
index of blend films increased and observed to be
higher than the LDPE films.
It was observed from the results that burst
strength of the LDPE films were 0.148 MPa and
increased with the addition of 7.5% native starch

12
0.24

Melt Flow Index(g/10 min)

0.21 10
BurstStrength (MPa)

0.18
8
0.15
0.12 6
0.09 4
0.06
2
0.03
0.00 0
LDPE 7.5% NS 7.5% 7.5% MS 7.5% 15% MS 15%
+ LDPE CLS + + LDPE CLSM + + LDPE CLSM +
LDPE LDPE LDPE

Burst Strength Melt Flow Index

Fig. 3. Melt flow index and burst strength of starch–LDPE blend films.

Fig. 4. SEM micrographs (2000X) of native starch (a) and cross-linked starch (b).
3984 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987

in the blend films (LDPE – 7.5 NS). However, burst
strength decreased with the addition of cross-linked
starch (LDPE – 7.5 CLS). With the addition of glyc-
erol modified starch, burst strength of the films
(LDPE – 7.5 MS) increased and higher than the
LDPE films but it was lower than the corresponding
native starch blend films (LDPE – 7.5 NS). In the
films containing cross-linked starch modified with
glycerol (LDPE – 7.5 CLSM), the burst strength
decreased. Due to increase in starch content to
15%, the burst strength of the blend films increased
and were larger than the LDPE films.
The above results showed that with the addition
of starch in the blend film, the melt flow index
decreased. The addition of starch contributed to
the increase in viscosity of the melt and poor misci-
bility of starch and LDPE. In case of cross-linked
starch, miscibility of starch and LDPE improved

Fig. 5. SEM micrographs (100·) of LDPE (a), 7.5% native starch–LDPE blend (LDPE – 7.5 NS) film (b), 7.5% cross-linked starch–LDPE
blend (LDPE – 7.5 CLS) film (c), 7.5% glycerol modified starch–LDPE blend (LDPE – 7.5 MS) film (d), and 7.5% cross-linked and
glycerol modified starch–LDPE blend (LDPE – 7.5 CLSM) film (e).
 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
and shifts towards a single phase behavior. So flow
ability improved and there was increase in melt flow
index. This may be also due to the effect on the vis-
cosity of the starch due to cross-linking. According
to the Wurzburg [17], corn starch containing lower
levels of cross-links, exhibited a somewhat higher
viscosity compared to that of the native starch and
the viscosity continued to increase on prolonged
heating. However, at higher levels of cross-links,
there were sufficient cross-links to inhibit the swell-
ing of the starch and there was decrease in viscosity.
At higher concentration of starch (15%), reverse
trend of melt flow index was may be due to the effect
of glycerol (20%) in the blend. With the addition of
the starch in the blend film, the burst strength
increased. However, in case of cross-linked starch
or cross-linked starch modified with glycerol the
burst strength decreased. The reason behind this is
not clear.
3.6. Scanning electron microscopy (SEM)
To examine the physical changes occurred in
starch particles due to cross-linking and morphology
of the blend films, surface scanning of the native
starch, cross-linked starch, and LDPE blend films
were observed by scanning electron microscope.
SEM micrographs of native starch and cross-linked
starch are shown in Fig. 4a and b. It can be observed
from micrographs that the surface morphology of
the starch did not change due to cross-linking.
Surface morphology of LDPE film, and starch–
LDPE blend films are shown in Fig. 5a–e. LDPE
film did not show any specific morphology due to
smooth surface structure of the film, whereas the
Fig. 6. SEM micrograph (100·) of 15% glycerol modified starch–LDPE blend (LDPE – 15 MS) film (a), and 15% cross-linked and glycerol
modified starch–LDPE blend (LDPE – 15 CLSM) film (b).
3985
micrographs of native starch (LDPE – 7.5 NS)
and cross-linked starch (LDPE – 7.5 CLS) blend
film had surface cracks and starch particles were
separately visible in LDPE matrix. Film containing
cross-linked starch showed less cracks and appeared
smoother than the native starch film although few
starch particles were still visible.
Micrograph of glycerol modified starch blend
(LDPE – 7.5 MS) film showed well-dispersed starch
particles in LDPE matrix. Film of cross-linked
starch modified with glycerol (LDPE – 7.5 CLSM)
was smoother. Starch particles seem to be embed-
ded in LDPE matrix, although very few surface
gaps, cracks and separate starch particles were visi-
ble in LDPE matrix.
Surface roughness in starch blend films appeared
due to resulting incompatible blend of starch and
LDPE. The phase separation between starch and
LDPE in the blend was overcome by cross-linking
of starch and led to smoother film. In case of gly-
cerol modified films, effect of plasticizing agent gly-
cerol further improved the surface of the film.
With the increase in starch to 15%, both the glyc-
erol modified starch and cross-linked starch modi-
fied with glycerol blend film exhibited a coarse
structure (Fig. 6a and b). Starch particles appeared
on the surface even with increased glycerol. Surface
cracks, air gaps were visible in the film. This may be
due to higher moisture content at high starch con-
centrations. The evaporation of moisture created
the air gap which could not escape from the film.
The micrograph of film containing 15% cross-linked
starch modified with glycerol (LDPE – 15 CLSM)
was smoother and the air gaps and surface cracks
were also less.
3986 S. Garg, A.K. Jana / European Polymer Journal 43 (2007) 3976–3987
4. Conclusion
The starch and LDPE blend characteristics was
improved through the reduction in hydrophilicity
of the starch by modification of starch by cross-link-
ing and by using plasticizer glycerol. Starch was
cross-linked by the use of the bi-functional cross-
linking agent epichlorohydrin under alkaline condi-
tions. X-ray diffraction studies showed that both the
native starch and cross-linked starch were semi-
crystalline in nature. Relative crystallinity of the
native and cross-linked starch was similar and was
not affected by cross-linking. Starch–LDPE films
were prepared by incorporating native starch,
cross-linked starch and glycerol modified starch in
the blend. Mechanical properties of the films were
tested for tensile strength, elongation, melt flow
index and burst strength. Cross-linked starch–
LDPE blend films had higher mechanical strength
than the native starch blend films. This was due to
reaction of starch with epichlorohydrin decreased
hydrophilicity, solubility and viscosity of starch,
and increase in the compatibility of the blend. Glyc-
erol modification of cross-linked starch did not
improve the tensile strength but percent elongation
of the film i.e. stretch-ability of the film increased.
Film containing cross-linked starch further modified
with glycerol was superior among all the films.
The glycerol requirement for modification after
cross-linking of starch is important because excess
quantity of glycerol for plasticizing will lead to poor
properties of the film. SEM studies showed that the
surface morphology of the starch particles did not
change due to cross-linking. Film containing cross-
linked starch in the blend was smoother than native
starch due to improved blend characteristics. With
glycerol modification after cross-linking of starch,
the compatibility further increased to give better
surface characteristics and uniformity of the blend
films.
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