Polymer Degradation and Stability 91 (2006) 703e711

www.elsevier.com/locate/polydegstab

Water resistance, mechanical properties and biodegradability

of methylated-cornstarch/poly(vinyl alcohol) blend film
Zhao Guohua a,*, Liu Ya a,b, Fang Cuilan a, Zhang Min a,
Zhou Caiqiong a, Chen Zongdao a
a
Food College of Southwest Agricultural University, Chongqing 400716, PR China
b
Food Engineering College of Shihezi University, Shihezi 832000, PR China
Received 11 March 2005; received in revised form 31 May 2005; accepted 6 June 2005
Available online 2 August 2005

Abstract

The main shortcomings of biodegradable starch/poly(vinyl alcohol) (PVA) film are hydrophilicity and poor mechanical
properties. With an aim to overcome these disadvantages, cornstarch was methylated and blend films were prepared by mixing
methylated-cornstarch (MCS) with PVA. The mechanical properties, water resistance and biodegradability of the MCS/PVA film
were investigated. It was found that MCS/PVA film had higher water resistance than the native starch/PVA film. However,
the water resistance of MCS/PVA films did not have significant difference with the increase in the degree of substitution (DS) of the
methylated starch from 0.096 to 0.864. Enzymatic, microbiological and soil burial biodegradation results indicated that
the biodegradability of the MCS/PVA film strongly depended on the starch proportion in the film matrix. The degradation rate of
starch in the starch/PVA film was hindered by blending starch with PVA. Both tensile strength and percent elongation at break of
the MCS/PVA film were improved as DS of the methylated starch increased. Conversely, increasing the methylated starch
proportion in film matrix deteriorated both tensile strength and percent elongation at break of the film.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Methylated-cornstarch (MCS); Poly(vinyl alcohol) (PVA); Mechanical properties; Water resistance; Biodegradability

1. Introduction including starch, cellulose and chitosan were tested,

alone or combined with synthetic polymers, for the
Synthetic plastics, such as polystyrene, polypropylene possibility to form a fully or partially biodegradable
and polyethylene, are used widely in daily life, in food film [1]. Of these materials, starch is the most attractive
industry, biomedical field and agriculture. A heavy candidate because of its low cost, easy availability and
environmental pollution accompanies their uses, because high production from annually renewable resources [7].
they need hundreds of years to degrade, and the disposal However, the low water resistance and high brittleness of
of waste plastics has become a serious problem [1]. starch films limited their extensive application [6,8,10].
Therefore, in the past two decades, biodegradable Therefore, many attempts have been made to over-
materials have been paid attention as alternatives to the come these problems by blending starch with synthetic
petroleum-derived plastics [1e9]. Natural biopolymers polymers. However, the biodegradability of starch film
decreased with addition of the non-degradable synthetic
polymers. Therefore, much interest lies in blending starch
* Corresponding author. Tel.: C86 23 68250350; fax: C86 23
with biodegradable synthetic polymers.
68251947. Poly(vinyl alcohol) (PVA) is a hydrophilic biodegrad-
E-mail address: zhaogh@swau.edu.cn (Z. Guohua). able polymer which is mainly composed of CeC

0141-3910/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2005.06.008
704 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711

bonds [6]. However, its water solubility is related to its 2.2. Preparation of methylated-cornstarch
degree of hydrolysis, molecular weight, and the modi-
fication while blending with other processing additives Cornstarch was methylated by dispersing starch
[11], with a maximum value at the degree of hydrolysis granules in an aqueous suspension at pH 10 and using
of 88% [12]. From the cost and practicality points, it is dimethyl sulfate as methylating reagent. After modifi-
preferable that the blend contains as much starch as cation, the reaction mixture was neutralized, dialyzed
possible. However, the properties of the blend films and dried. Samples with different DS values were
deteriorated as starch proportion in the film formulation obtained by varying the reaction parameters (Table 1).
increased. This might result from a poor compatibility
between starch and PVA [13] and phase separation 2.3. Degree of substitution
during film preparation [14]. Moreover, the water
resistance of the native starch/PVA film deteriorated DS indicates the average number of substituted
compared to that of the PVA film. groups (methyl) per anhydroglucose unit in methylated
The techniques for increasing the compatibility starch. Since three free hydroxyl groups are available in
between starch and synthetic polymers include adding each anhydroglucose unit of native starch, the maximum
a compatibiliser to the blends [15], chemical modifica- DS is 3. DS values were determined by the Morgane
tions of the synthetic polymers [1,16] and starch. They Zeisel method [23]. The MorganeZeisel assay was based
have been proved as effective measures to improve the on ether-cleavage by hydrogen iodide resulting in the
properties of film. A number of methods are available in formation of iodomethane, which was led by a nitrogen
starch modification including esterification, oxidation, flow into a trap solution of Ag(I)eethanol to form Ag(I)
etherification and cross-linking [2,4,7,8,10,17e19]. Of solid. Dried methylated starch (25 mg) and 0.5 ml of
these methods, methylation, as one etherification phenol were added into a conical flask, followed by the
method, was used widely in elucidating the structure addition of 0.2 ml of propionic anhydride (AR grade) in
of polysaccharides and the substitution pattern in a drop-wise manner. After the starch was dispersed fully,
polymer chains [20e23]. Theoretically, methylation is the flask was cooled in an ice bath, and 5 ml of hydrogen
an effective way to increase the hydrophobicity of the iodide was added. Dried nitrogen was introduced into
starch and to improve the compatibility between starch the solution through the needle with a rate of 60e70
and PVA (hydrolysis degree 99.5%). However, no bubbles per minute. The flask was heated to 90
C for 2 h
information was available on the methylated starch- to completely convert the methyl group to iodomethane.
based film. Therefore, the objective of this work was to The resulting iodomethane was driven out of the flask
methylate starch and to prepare blend film by mixing and absorbed by 0.05 M AgNO3ealcohol solution to
methylated starch with PVA. Water absorption capacity, give an Ag(I) solid. A reflux-condenser also was used to
mechanical properties and biodegradability of the prevent the loss of iodomethane. The DS values were
blended films were evaluated. calculated on the weight basis of the Ag(I) produced.

2.4. Characterization by Fourier transform infrared

spectrophotometry
2. Experimental
Changes in the chemical structure of the starch
2.1. Materials molecules were confirmed with a Fourier transform
infrared spectrophotometer (FT-IR) (model 2000,
The raw materials used in our experiments are PerkineElmer, USA). After drying in the vacuum oven
available as commercial products. The cornstarch, at 60
C overnight, samples (2 mg) were prepared in the
a white fine powder with 10 wt% moisture content form of KBr (10 mg) pellets. The spectra were recorded
containing 30 wt% amylose and 70 wt% amylopectin, over the wavenumber from 450 cm1 to 4000 cm1,
was purchased from Tuoketuohua Starch Company operating with a 4 cm1 resolution.
(Neimeng, China). PVA, with a hydrolysis degree of
99.5% and the polymerisation degree of 1700, was Table 1
obtained from Weilun Company (Changshou, Chongqing, Degree of substitution as a function of reaction parameters
China). a-Amylase (5.0 ! 104 U/g) and b-amylase Temperature Concentration Dimethyl Time DS
(2.0 ! 103 U/g) were supplied by Xingda Bioengineering (
C) of starch sulphate addition (h)
Company (Wuxi, Jiangsu, China). Bacillus subtilis and slurry (%) (g/g starch)
Aspergillus oryzae were maintained in our laboratory. 45 20 0.4 1.0 0.096
Pseudomonas aeruginosa (CICC10204) and Aspergillus 50 15 0.4 2.5 0.275
niger (CICC2089) were purchased from China Centre of 50 15 0.8 1.5 0.581
50 15 0.8 2.0 0.864
Industrial Culture Collection (CICC).
 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711 705

2.5. Film preparation temperature up to the equilibrium (24 h). Each specimen
was taken off from the container, removed the surface
The films were prepared by a casting method. Firstly, water by adsorbing with filter paper, and then weighed.
PVA and starch hot water solutions were prepared and The result of each sample represents the average of
were mixed in a flask with a stirrer and a thermometer. three tests. The water absorption capacity (WAC) was
The flask was placed in a water bath at a temperature of calculated as:
85
C, and the mixture was vigorously stirred for 8 h.
The pH of the gel-like mixture was adjusted to 2e3 by WAC%ZðWA  WI Þ=WI !100
the addition of phosphoric acid. After that, glycerine
was added as a plasticiser at a concentration of 10% where WA is the weight of the specimen at the adsorbing
(v/w, on dry basis of the weight of starch and PVA) equilibrium and WI is the initial dry weight of the
[24]. Following, formaldehyde was added as a hydroxyl specimen.
cross-linking reagent at a concentration of 1% (v/w, on
dry basis of the weight of starch and PVA) [25], and the 2.9. Enzymatic degradation test
resulting mixture was stirred further for 0.5 h. Ammonia
was added to neutralize the pH of the mixtures. After The enzymatic reaction mixture, comprising 1 ml of
being degassed under vacuum, the warm mixture was a-amylase solution, 4 ml of b-amylase solution and
cast on framed glass plates, and then dried at 65
C for 95 ml of distilled water, was placed in the clean conical
5 h. Starch and PVA films were also prepared in the flasks. The dried samples were cut into 4 ! 4 cm square
same way and used as control. specimens, weighed, and immersed in the conical flasks.
The flasks were placed in a shaking incubator with a rate
2.6. Mechanical properties tests of 120 rpm for 36 h at 30
C. The samples were removed
and rinsed with distilled water to remove the enzyme,
Tensile strength and percent elongation at break were and dried in a desiccator under vacuum for 24 h before
determined as mechanical indexes of the film in a controlled they were weighed. The degree of enzymatic degradation
environment (25
C, 55% relative humidity). All of the (DED) was calculated as:
tested film sheets, equilibrated to 50% relative humidity for
at least 48 h at 25
C prior to testing, were cut into strips DED%ZðWI  WH Þ=WI !100
(15 ! 150 mm). Tensile strength and percent elongation at
break were measured by using XLW(G)-PC intelligent where WH is the dry weight of the specimen after
electronic tensile tester (Languang, Tsinan, China) with enzymatic treatment and WI is the initial dry weight of
a crosshead speed of 30 mm/min and an initial gauge the specimen.
length of 100 mm. Film thickness was measured with
a micrometer calliper. Tensile strength and percent 2.10. Microbiological degradation test
elongation at break of each sample were averaged from
five tests. The specimens were stored under controlled Two bacteria (B. subtilis and P. aeruginosa), two
temperature and conditions prior to testing. fungi (A. oryzae and A. niger) and a soil suspension were
used. Nutrient salt agar was prepared by dissolving
2.7. Morphology analysis potassium dihydrogen phosphate (0.700 g), magnesium
sulfate (0.700 g), ammonium nitrate (1.000 g), sodium
The surface morphology of the films, before and after chloride (0.005 g), ferrous sulfate (0.002 g), manganese
biodegradation, was investigated with a camera-linked sulfate (0.001 g) and agar (15.000 g) in 1 L of distilled
light microscope (BHA-1, Olympus) or a scanning water. After the medium was sterilized at 121
C for
electron microscope (SEM) (AMRAV, USA) operating 25 min, its pH was adjusted in the range of 6.5e7.0 by
at 10 kV. The SEM samples were coated with a 50-mm the addition of sterilized 0.1 M NaOH. The hot pulpy
thick gold film in an automatic sputter coater, prior to mixture was poured into sterilized petri dishes having
testing to make the sample conductive. a 5 mm thick agar layer. The microorganism suspension
or soil suspension was sprayed on the surface of the
2.8. Water absorption test medium, and the xerothermically sterilized specimens
were placed tightly on the surface of the agar layer. The
The water absorption capacity of the films was petri dishes were incubated at 30
C for 14 days. The
measured with a plastic sheet of 30 ! 30 mm. The rate of microorganism growth was assessed visually at
specimens first were dried in a vacuum oven at 50
C for the end of the test. The recorded parameter (S ) is
24 h, and then cooled in a desiccator and immediately the area fraction of the specimen’s surface covered
weighed. The conditioned specimens were fully immersed by macroscopic colonies [S ! 5% (0, nil growth),
in a container filled with distilled water at room 5 % S! 25% (C, sparse growth), 25 % S ! 50%
706 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711

(CC, medium growth), S R 50% (CCC, abundant et al. [22], while it distinguished from the results of
growth)]. The surface morphologies of the specimens, Mischnick and K} uhn [20] and van der Burgt et al. [23].
before and after microorganism treatment, were re- Besides the reaction condition, other factors, such as
corded using a camera-linked light microscope. starch composition (amylose/amylopectin) and starch
crystalline structure (amorphous/crystalline) possibly
2.11. Soil burial degradation test led to this difference.

Soil burial degradation was performed as described by 3.2. Characterization by FT-IR

Thakore et al. [2] with a slight modification. The garden
pots with approximate capacity of 10 L were filled with The methylation reaction was characterized by
the soil, taken from a culture field in Chongqing City comparing the FT-IR spectra of both the modified and
(China). The plastic samples were cut into 30 ! 100 mm native starch. Fig. 1 shows the FT-IR spectra of the
pieces and buried in the soil at the depth of 10 cm. The native cornstarch and the modified starch (DS 0.275).
pots were placed in an uncovered gazebo. The soil was The broad band in the region of 3430 cm1 is due to the
kept moist by sprinkling water at a regular time interval hydroxyl stretching vibration and the band in the region
to maintain 20e40% humidity. The excess water was of 2929 cm1 is due to CH2 asymmetric and symmetric
drained through the hole at the bottom of the pot. The stretching vibration [7,18]. The peak at 1454 cm1 was
degradation of the specimen was determined at a regular assigned to CH2 bending vibration [26]. Compared to
time interval (15 days) by taking the specimen carefully the native starch, for the modified starch with a DS of
from the soil and washing it gently with distilled water to 0.275, the peak at 3430 cm1 became narrower and
remove the soil. The specimen was dried under vacuum lower and the peak at 1454 cm1 became broader and
until a constant weight was obtained. Weight loss of the higher (Fig. 1). Significant changes were observed in the
specimen with time was used to indicate degradation rate intensity of the peaks in terms of peak area (data not
in the soil burial test. The soil burial degradation test shown), demonstrating that the cornstarch was success-
started on September 16 of 2003 and ended on March 16 fully partially methylated. However, although only
of 2004. slight increases in peak height and base width were
observed for peak at 2929 cm1 on methylation,
a considerable increase met with its intensity.
3. Results and discussion
3.3. Water absorption
3.1. Preparation of methylated starch
The water absorption capacity and the degradability
A number of methods have been reported for the are the most important properties for biodegradable
methylation of starch and different methylating reagents materials [27]. The MCS/PVA blend films were de-
were used, such as dimethyl sulfate, iodomethane and graded by surface absorption of moisture and micro-
Li-Dimsyl [20e23]. In the present work, the MCS organisms, such as fungi and bacteria. The water
samples were prepared by methylating starch granules in absorbed on the materials allowed the microorganisms
an aqueous suspension with dimethyl sulfate as meth- to grow and to utilize the material as an energy source.
ylating reagent. The reaction conditions for preparing Figs. 2 and 3 show the effects of DS and starch
MCS with various DS values are listed in Table 1. proportion in film matrix on the water absorption
The reaction conditions, including temperature, capacity of film. It can be observed that the water
concentration of starch slurry, addition of dimethyl absorption capacity of the MCS/PVA films was lower
sulfate and reaction time, played important roles in than that of the unmodified one (Fig. 2). The relatively
degree of substitution while methylating starch. How- lower water absorption capacity of the MCS/PVA film
ever, the DS of the methylated starch is non-linearly was contributed to the increase in the hydrophobicity of
related to the reaction parameters, i.e. there was an the films with methyl group replacing the hydroxyl
optimum value for each reaction parameter correspond- group in the starch molecules. However, MCS/PVA
ing to the maximum DS. The optimum concentration of films did not have significant change in water absorption
starch slurry was 15%, while the optimum addition of capacity with DS increasing. The water absorption
dimethyl sulfate, temperature and time were 0.4e0.8 g/g capacity of the PVA film was lower than those of the
starch (dry weight), 50
C and 2e3 h, respectively. A MCS/PVA and MCS films, indicating the PVA used in
similar result was reported in the modification of starch the present experiment was more hydrophobic than the
by propionic anhydride [10]. By varying these condi- MCS with a DS of 0.275 (Fig. 3). The water absorption
tions, MCS with DS ranging from 0 to 1 was obtained capacities of the PVA, MCS/PVA and MCS films were
(Table 1). DS of the present result was similar to those found to have significant difference. This was consistent
of Steeneken and Woortman [21] and van der Burgt with the results of Follain et al. [28] and indicated that
 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711 707

1.810

1.5 3430.08

1.0
A

b
2929.97 1454.22
0.5

0.000
4000 3000 2000 1000 450
cm-1

Fig. 1. FT-IR spectra of the native cornstarch (a) and MCS with a DS of 0.275 (b).

water absorption of the mixture was retarded by mixing blending native starch and PVA [14], no phase
MCS with PVA. On the other hand, the amount of separation was observed in the present study, indicating
starch in the film did not noticeably affect the water a good compatibility between modified starch and PVA,
absorption capacity of the MCS/PVA film. A dramatic which improved the tear-resistance and stretch of the
decrease in the mechanical properties of the film was blend films. The tensile strength significantly increased
observed after water absorption. as DS of methylated starch increased from 0.096 to
0.275, while the increase became less obvious with
further increasing DS from 0.275 to 0.864.
3.4. Mechanical properties As far as the starch proportions in the blends were
concerned, it was found that percent elongation at break
Mechanical properties of MCS/PVA films and native continuously decreased as the amounts of starch in the
starch/PVA films are shown in Figs. 4 and 5. Tensile matrix increased and a sharp decrease was observed in
strength and percent elongation at break represent the tensile strength when the starch percentage increased
force per unit area required to tear the film and the from 0 to 35%. However, the tensile strength did not
ability of the film to stretch [17]. Both tensile strength change significantly with the starch proportion further
and percent elongation at break of MCS/PVA films increasing from 35 to 100% (Fig. 5). Similar findings
increased continuously as DS increased, and they are were reported by Wu [1] and Ishiaku et al. [5] regarding
noticeably higher than those of their unmodified mechanical properties of polycaprolactone/starch com-
counterparts (Fig. 4). Unlike the reported fact that posites.
phase separation occurred during film preparation by

350 350
300 300
250 250
WAA/%
WAA/%

200 200
150 150
100 100
50 50
0 0
0 0.096 0.275 0.581 0.864 0 35 50 65 80 100
DS of methylated starch Starch percentage in film matrix

Fig. 2. Effects of DS on the water absorption capacity of the MSC/ Fig. 3. Effects of starch proportion in film matrix on the water
PVA films [MCS/PVA (w/w): 50/50.]. absorption capacity of the MSC/PVA films (MSC with a DS of 0.275.).
708 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711

13.5 165 95

13.3
Tensile strength/MPa

75

Percent elongation
160
13.1 55

DED/
12.9 155 35

12.7 15
150
12.5 -5
0 3 6 18 36
12.3 145 Enzyme treatment time/h
0 0.096 0.275 0.581 0.864
DS of methylated starch Fig. 6. Enzymatic degradability of the native starch film (-), the
MSC/PVA film (C) [MCS/PVA (w/w): 50/50; MSC with a DS of
Fig. 4. Effects of DS on the tensile strength (C) and percent elongation 0.275] and the PVA film (:).
at break (-) of the MSC/PVA films [MCS/PVA (w/w): 50/50].

approximate 50% degradation, indicating that a full

3.5. Degradation behaviour
degradation could be reached with the MCS after
exhaustive degradation by amylases. The methylated
Degradability of polymers is a critical functionality
starch in the MCS/PVA films had a slower degradation
for their application. Currently, no official standard
rate compared to starch in the counterpart matrix. The
method was established in determining biodegradability
degradation rate of the methylated starch in the blend
of polymers. The enzyme method [29], the microbiolog-
film was retarded with substitution of hydroxyl group
ical method [30] and the soil burial method [31,32] have
with methyl group in starch molecule. Two reasons
been used by different researchers. Moreover, the
were assumed to exist behind this phenomena: (a) the
biodegradability was also recorded by diverse indexes
presence of methyl substituents in starch molecules
even in the same method [9]. In order to get an overall
inhibited the catalytic reaction of amylases, which also
biodegradability, the enzyme method, the microbiolog-
was previously reported by van der Burgt et al. [22]; and
ical method and the soil burial method were performed
(b) the dispersion of some starch molecules within the
simultaneously in the present study.
chains of the PVA increased the difficulty for enzymes to
b-Amylase and a-amylase function in different ways
reach the starch molecules [24].
to hydrolyse the acetal bonds of starch. b-Amylase
In order to further investigate the biodegradability,
generally hydrolyses only the main chain acetal bonds,
the effects of microorganic treatment on the modified
and does not affect the branch points, whereas
starch-based films were studied. B. subtilis, A. oryzae,
a-amylase can cleave the bonds either in main chain or
A. niger, P. aeruginosa and soil suspension were used
in branch. Considering a possible enzymatic degrada-
because B. subtilis, A. oryzae and A. niger are amylase
tion pattern, the effects of amylases on the MCS/PVA
producing microorganisms and Pseudomonas strains
films were investigated in a pure enzymatic suspension.
had a good degradability on PVA film [33]. During
As seen in Fig. 6, the PVA film could not be degraded by
exposure of the samples to microorganism on the solid
amylases, while the native starch film and MCS/PVA
medium, macroscopic colonies of the microorganisms
film are prone to degradation induced by amylases. The
were observed on the surface of the starch film and
MCS/PVA film with a starch fraction of 50% had
starch/PVA film, even within the initial 7 days of
incubation, while no significant growth of four pure
40 400
microorganisms was observed on the surface of the PVA
film. Approximately 10% surface of PVA film speci-
Tensile strength/MPa

Percent elongation

30 300 mens, incubated in the soil suspension, was covered with

macroscopic colonies at the end of the experiment
20 200 (Table 2). Although P. aeruginosa could moderately
degrade the starch film, its degradability for MCS/PVA
10 100 film was similar to that of the soil suspension in PVA
film. The surface morphologies of MCS/PVA films,
0
before and after biodegradation, were recorded with
0
0 35 50 65 80 100 a camera-linked light microscope (BHA-1, Olympus)
Starch percentage in film matrix (Fig. 7). A similar result was observed as in the visual
Fig. 5. Effects of starch proportion in film matrix on the tensile
test. The colonization of the film surface due to
strength (C) and percent elongation at break (-) of the MSC/PVA microorganisms led to a dramatic decrease of the
films (MSC with a DS of 0.275). mechanical characteristics of the MCS/PVA film.
 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711 709

Table 2 100
Microorganism growth on the surface of the films after 14 days

Degradation/%
incubation at 30
C 75
Microorganism or Microorganism growth efficiency
its origin 50
Starch filma MCS/PVA filmb PVA film
B. subtilis CCCc CCC 0 25
P. aeruginosa CC C 0
A. oryzae CCC CCC 0 0
A. niger 0

0
15
30
45
60
75
90

5
0
5
0
5
0
CCC CCC

10
12
13
15
16
18
Soil suspension CCC CCC C Test time/day
a
Made out of the native cornstarch.
b
MCS/PVA (by weight): 50/50; DS of MSC: 0.275. Fig. 8. Degradability of the native starch film (-), the MSC/PVA film
c
CCC, Abundant growth; CC, medium growth; C, sparse (C) [MCS/PVA (w/w): 50/50; MSC with a DS of 0.275.] and the PVA
growth; 0, nil growth. film (:) in the soil burial test.

The soil burial test is an outdoor experiment, and that a two-stage degradation took place in soil burial
provides a realistic environment where soil humidity, test: (a) the diffusion of the water into the film samples
temperature and type and amount of microorganisms resulted in the swelling of the films and allowed the
are in less control and change with season. All the tested growth of microorganism on the film; (b) enzymatic and
specimens had the same shape and size to avoid the other secreted degradation caused a weight loss and
effects of the film’s shape on its biodegradability [3]. disruption of the film samples. In addition, as both
Biodegradability of the samples was studied by evalu- starch and PVA had overall hydrophilic properties,
ating weight loss of the films over time (Fig. 8). The dissolution of MCS, PVA and their partially degraded
starch film degraded rapidly in the initial 15 days, and products would be another factor causing the weight
complete degradation was obtained after 60 days. For loss of the film. Under the soil environment, the
the MCS/PVA film, a rapid degradation occurred in the mechanical properties of films, such as tensile strength
initial 45 days, followed by a slow degradation until the and percent elongation at break, also deteriorated. An
end of the experiment. In contrast, the PVA film exhibited almost homogeneous surface of the MCS/PVA film
a higher resistance against soil burial biodegradation. before soil burial test broke up after the treatment,
Together with literature on this point, it was proposed indicating a biodegradation of the film [34] (Fig. 9).

Fig. 7. Microbiological degradation of the MCS/PVA films [MCS/PVA (w/w): 50/50; MSC with a DS of 0.275.] recorded with camera-linked light
microscope (400! magnification). (a) Control; (b) Bacillus subtilis; (c) Pseudomonas aeruginosa; (d) Aspergillus oryzae; (e) Aspergillus niger; (f) soil
suspension.
710 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711

Fig. 9. The surface SEM pictures (1000! magnification) of the MCS/PVA films [MCS/PVA (w/w): 50/50; MSC with a DS of 0.275.]. (a) Before the
soil burial degradation test; (b): after the soil burial degradation test.

4. Conclusions of LDPE/modified starch blends. European Polymer Journal

2001;37:151e60.
[3] Yang H-S, Yoon J-S, Kim M-N. Dependence of biodegradability
The mechanical properties of the MCS/PVA films of plastics in compost on the shape of specimens. Polymer
were improved with methylation of cornstarch, com- Degradation and Stability 2005;87:131e5.
pared to the native starch/PVA film and native starch [4] Kiatkamjornwong S, Thakeow P, Sonsuk M. Chemical modifi-
film. These might result from high compatibility cation of cassava starch for degradable polyethylene sheets.
between MCS and PVA. However, the mechanical Polymer Degradation and Stability 2001;73:363e75.
[5] Ishiaku US, Pang KW, Lee WS, Ishak ZAM. Mechanical
properties of the MCS/PVA films were lower than those properties and enzymic degradation of thermoplastic and
of PVA films. The starch proportion in the film granular sago starch filled poly(3-caprolactone). European Polymer
formulations and DS of the methylated starch promi- Journal 2002;38:393e401.
nently governed the water absorption capacity and [6] Zhang X, Burgar I, Lourbakos E, Beh H. The mechanical
biodegradability of the starch/PVA film. A better water property and phase structures of wheat proteins/polyvinyl alcohol
blends studied by high-resolution solid-state NMR. Polymer
resistance could be obtained for the cornstarch/PVA 2004;45:3305e12.
film on methylation of cornstarch, while higher water [7] Demirgöz D, Elvirs C, Mano JF, Cunha AM, Piskin E, Reis RL.
resistance of the MCS/PVA film could not be expected Chemical modification of starch based biodegradable polymeric
by increasing the DS of the modified starch. Besides blends: effects on water uptake, degradation behaviour and
mechanical properties, water absorption capacity and mechanical properties. Polymer Degradation and Stability
2000;70:161e70.
biodegradability, optical quality, gas transportation and [8] Kim M. Evaluation of degradability of hydroxypropylated potato
aging properties are also important indexes in evalua- starch/polyethylene blend films. Carbohydrate Polymers 2003;54:
tion of the polymer-based films and these indexes of the 173e81.
MCS/PVA film need further research. [9] Kim M-N, Lee A-R, Yoon J-S, Chin I-J. Biodegradation of
poly(3-hydroxylbutyrate), Sky-GreenÒ and Mater-BiÒ by fungi
isolated from soils. European Polymer Journal 2000;36:
Acknowledgements 1677e85.
[10] Santayanon R, Wootthikanokkhan J. Modification of cassava
The authors are grateful for the financial support starch by using propionic anhydride and properties of the starch-
blend polyester polyurethane. Carbohydrate Polymers 2003;51:
from the Science and Technology Committee of
17e24.
Chongqing (Project No. 7382). We are also grateful to [11] Alexy P, Bakoš D, Crkoňová G, Kramárová Z, Hoffmann J,
Professor Kan Jianquan and Mr. Han Xinnian for the Julinová M, et al. Poly(vinyl alcohol)-collagen hydrolysate
helpful discussion. We highly appreciate the kind thermoplastic blends: II. Water penetration and biodegradability
assistance in measurement of mechanical properties by of melt extruded films. Polymer Testing 2003;22:811e8.
[12] Coffin DR, Fishman ML, Ly TV. Thermomechanical properties
associate professor Zhou Wenbin in Chongqing Tech-
of blends of pectin and poly(vinyl alcohol). Journal of Applied
nology and Business University. Polymer Science 1996;61:71e9.
[13] Lawton JW. Effect of starch type on the properties of starch
containing film. Carbohydrate Polymers 1996;29:203e8.
References [14] Lawton JW, Fanta GF. Glycerol-plasticised films prepared from
starchepoly(vinyl alcohol) mixtures: effect of poly(ethylene-co-
[1] Wu C-S. Physical properties and biodegradability of maleated- acrylic acid). Carbohydrate Polymers 1994;23:275e80.
polycaprolactone/starch composite. Polymer Degradation and [15] Avella M, Errico ME, Lauriennao P, Martuscelli E, Raimo M,
Stability 2003;80:127e34. Rimedio R. Preparation and characterization of compat-
[2] Thakore IM, Desai S, Sarawade BD, Devi S. Studies on ibilised polycaprolactone/starch composites. Polymer 2000;41:
biodegradability, morphology and thermomechanical properties 3875e3881.
 Z. Guohua et al. / Polymer Degradation and Stability 91 (2006) 703e711 711

[16] Bikiaris D, Panayiotou C. LDPE/starch blends compatibilised [26] Kim D-H, Na S-K, Park J-S. Preparation and characterization of
with PE-g-MA copolymers. Journal of Applied Polymer Science modified starch-based plastic film reinforced with short pulp fiber.
1998;70:1503e21. I. Structural properties. Journal of Applied Polymer Science
[17] Kim M, Lee S-J. Characteristics of crosslinked potato starch and 2003;88:2100e7.
starch-filled linear low-density polyethylene films. Carbohydrate [27] Arajúo MA, Cunha AM, Mota M. Enzymatic degradation of
Polymers 2002;50:331e7. starch-based thermoplastic compounds used in protheses: identi-
[18] Xu YX, Miladinov V, Hanna MA. Synthesis and characterization fication of the degradation products in solution. Biomaterials
of starch acetates with high degree of substitution. Cereal 2004;25:2687e93.
Chemistry 2004;81:735e40. [28] Follain N, Joly C, Dole P, Bliard C. Properties of starch based
[19] Xu YX, Miladinov V, Hanna MA. Starch acetateemaleate blends. Part 2. Influence of poly vinyl alcohol addition and
mixed ester preparation and characterization. Cereal Chemistry photocrosslinking on starch based materials mechanical proper-
2005;82:336e40. ties. Carbohydrate Polymers 2005;60:185e92.
[20] Mischnick P, K} uhn G. Model studies methyl amyloses: correlation [29] Tomasi G, Scandola M, Briese BH, Jendrossek D. Enzymatic
between reaction conditions and primary structure. Carbohydrate degradation of bacterial poly(3-hydroxybutyrate) by a depoly-
Research 1996;290:199e207. merase from Pseudomonas lemoignei. Macromolecules 1996;29:
[21] Steeneken PAM, Woortman AJJ. Substitution pattern in meth- 507e13.
ylated starch as studied by enzymic degradation. Carbohydrate [30] Benedict CV, Cook WJ, Jarrett P, Cameron JA, Huang SJ,
Research 1994;258:207e21. Bell JP. Fungal degradation of polycaprolactones. Journal of
[22] van der Burgt YEM, Bergsma J, Bleeker IP, Mijland PJHC, van Applied Polymer Science 1983;28:327e34.
der Kerk-van Hoof A, Kamerling JP, et al. Distribution of methyl [31] Mergaert J, Webb A, Anderson C, Wouters A, Swings J.
substituents in amylose and amylopectin from methylated potato Microbial degradation of poly(3-hydroxybutyrate) and poly(3-
starches. Carbohydrate Research 2000;325:183e91. hydroxybutyrate-co-3-hydroxyvalerate) in soils. Applied Environ-
[23] van der Burgt YEM, Bergsma J, Bleeker IP, Mijland PJHC, mental Microbiology 1993;59:3233e8.
van der Kerk-van Hoof A, Kamerling JP, et al. FAB CIDMS/MS [32] Xu YX, Hanna MA. Preparation and properties of biodegrad-
analysis of partially methylated maltotrioses derived from able foams from starch acetate and poly (tetramethylene
methylated amylose: a study of the substituent distribution. adipate-co-terephthalate). Carbohydrate Polymers 2005;59:
Carbohydrate Research 2000;329:341e9. 521e9.
[24] Jang BC, Huh SH, Jang JG, Bae YC. Mechanical properties and [33] Chiellini E, Corti A, Roberto S. Biodegradation of poly(vinyl
morphology of the modified HDPE/starch reactive blend. Journal alcohol) based blown films under different environmental
of Applied Polymer Science 2001;82:3313e20. conditions. Polymer Degradation and Stability 1999;64:305e12.
[25] Kumbar SG, Kulkarni AR, Dave AM, Aminabhavi TM. [34] Singh RP, Pandey JK, Rutot D, Degée P, Dubois P. Bio-
Encapsulation efficiency and release kinetics of solid and liquid degradation of poly(3-caprolactone)/starch blends and composites
pesticides through urea formaldehyde crosslinked starch, guar in composting and culture environments; the effect of compatibi-
gum, and starch C guar gum matrices. Journal of Applied lization on the inherent biodegradability of the host polymer.
Polymer Science 2001;82:2863e6. Carbohydrate Research 2003;338:1759e69.