International Biodeterioration & Biodegradation 115 (2016) 257e265

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International Biodeterioration & Biodegradation

journal homepage: www.elsevier.com/locate/ibiod

Biodegradability of polymer film based on low density polyethylene

and cassava starch
Dang Mao Nguyen a, b, Thi Vi Vi Do a, Anne-Cecile Grillet b, Huy Ha Thuc c,
Chi Nhan Ha Thuc a, *
a
Department of Polymer and Composite Materials, Faculty of Materials Science, University of Science, Vietnam National University, Ho Chi Minh City,
227 Nguyen Van Cu, Viet Nam
b
LOCIE, Polytech Annecy-Chamb
ery, Universit
e de Savoie Mont Blanc, Campus Scientifique, 73376 Le Bourget du Lac Cedex, France
c
Department of Polymer Chemistry, Faculty of Chemistry, University of Science, Vietnam National University, Ho Chi Minh City, 227 Nguyen Van Cu,
Viet Nam

a r t i c l e i n f o a b s t r a c t

Article history: Bio-based materials with linear low density polyethylene (LLDPE) and a high content of thermoplastic
Received 22 May 2016 starch (TPS) were prepared using the twin-screw extruder. The 25 mm thick films were blown with a
Received in revised form Haake Polydrive internal mixer using a temperature profile with three zones: 160
C, 170
C and 165
C.
31 August 2016
Morphology as well as thermal properties of the materials was investigated by field emission scanning
Accepted 3 September 2016
electron microscopy (FE-SEM), differential scanning calorimeter (DSC) and thermogravimetric analysis
Available online 14 September 2016
(TGA). As revealed by FE-SEM, a good dispersion of the TPS phase in LLDPE matrix was obtained. The DSC
result confirmed the remarkable influence of TPS phase on crystallinity of LLDPE. Biodegradation of
Keywords:
Biodegradability
material in the form of film specimens were determined by weight loss, morphological surface change
LLDPE/TPS film and mechanical properties. The results show more than 10% of the bio-film's weight is degraded after 5
Bio-based materials months in the compost environment.
Compost environment © 2016 Elsevier Ltd. All rights reserved.
Cassava starch

1. Introduction Rodriguez-Gonzalez et al., 2003; Raj et al., 2004; Borghei et al.,

Linear low density polyethylene (LLDPE) is widely used for in-
dustrial packaging and appliances. A large amount of post-
consumer LLDPE product discarded every year causes major eco-
nomic and environmental issues. Hence, a lot of researchers focus
on the replacement (partially or totally) of traditional plastics by
biomaterials. However, the development of totally biodegradable
materials seems to be more difficult because of their limited in-
dustrial application. Therefore, the development of bio-based ma-
terial from polyethylene (PE) can be achieved by blending it with
biodegradable fillers, which can reduce the volume of plastics by
partial degradation. Thermal plastic starch (TPS) is a renewable,
biodegradable and hydrophilic polymer which could be used as a
filler in blend with PE to promote the degradable process of the
material after its use (Dave et al., 1997; Psomiadou et al., 1997;
* Corresponding author. Department of Polymer and Composite, University of
Science, Vietnam National University Ho Chi Minh City, 227 Nguyen Van Cu,
Vietnam.
E-mail address: htcnhan@hcmus.edu.vn (C.N. Ha Thuc).
2010; Gupta and Sharma, 2010; Jagadish and Raj, 2011). Even
though bio-based materials based on TPS and traditional polymers
have been studied for many years, their industrial application is still
limited. Thus, there are more research groups focusing their studies
to develop and expand the usability of bio-based materials (Aure lie
et al., 2014; Jutarat and Wanida, 2014; Sabetzadeh et al., 2015;
Anderson et al., 2016; Nguyen et al., 2016). PE is a hydrophobic
polymer whereas starch is hydrophilic, which makes them more
difficult to blend. Polyethylene grafted anhydride maleic (PE-g-AM)
has been used as compatibilizer to enhance the compatibility be-
 et al., 2013; Mortazavi
tween PE and starch (Dave et al., 1997; Cercle
et al., 2013). Studying bio-based material based on TPS, processing
conditions and suitable devices must be carefully chosen to
perform this material. There are some melt processing methods to
prepare this material such as: extruding, injection-molding
(Parveen et al., 2014; Raju and Peter, 2014), and mixing the com-
bined with a blow film by the Haake Polydrive (Nguyen et al., 2016).
The mechanical, biodegradable and thermal properties of PE/starch
blends were studied at different starch contents (Psomiadou et al.,
1997; Rodriguez-Gonzalez et al., 2003; Raj et al., 2004; Borghei

http://dx.doi.org/10.1016/j.ibiod.2016.09.004
0964-8305/© 2016 Elsevier Ltd. All rights reserved.
258 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265
et al., 2010; Gupta and Sharma, 2010; Jagadish and Raj, 2011). The
mechanical properties of PE/TPS blends were decreased with an
increase of TPS content (Mortazavi et al., 2013; Sabetzadeh et al.,
2015), then rapidly reduced around the phase inversion point
(Mortazavi et al., 2013). The biodegradability study of PE/TPS film is
required before applications. The biodegradability tests usually
include some property determinations such as molecular weight,
chemical structure, tensile strength, thermal properties, and mi-
crobial growth (Restrepo-Flo  rez et al., 2014). Some methods to
investigate the biodegradability of different materials by using
natural soil burial environment, aerobic compost environment or
specialized machine for biodegradation tests (Gu et al., 1993, 1994;
Gu, 2005; Funabashi et al., 2007a; Kim et al., 2006; Nguyen et al.,
2016).
To date, there is more research related to the degradability of PE
and material based on PE in the compost soil environment. One of
the latest was studied by adding titania nanoparticles in humid
environment (Mehmood et al., 2015). The results showed that
polyethylene film containing 20% titania nanoparticles had a
maximum of 60% weight loss after 90 days exposed to visible light
and UV. Another paper studied the improvement biodegradation of
LDPE modifying with dye sensitized titania and starch (Mehmood
et al., 2016). The results confirmed the shopping bags from these
materials may easily be degraded in open environment after use
through evaluating the keto carbonyl, ester carbonyl and vinyl bond
index. Further, another study looked at the degree of decomposi-
tion of PE/TPS film containing 30% (w/w) TPS in compost envi-
ronment (Dave et al., 1997). The results show a total weight loss of
6.3% after 48 weeks in compost soil environment and 84.5% (w/w)
of the TPS is decomposed during the same time. Starch decompo-
sition is accompanied by changes of polyethylene chains structures.
The models and kinetics of CO2 emission during biodegradation
test of PE and PE/starch blend under composting environment has
been reported (Leejarkpai et al., 2011; Orhan and Buyukgungor,
2000). The results show that PE and PE/starch have low degrada-
tion with only 0.56% and 11.5% in weight for 4 months respectively,
and a maximum of 7 g CO2 emission for LDPE/starch blend (88/12%
(w/w)) in blank soil. The degradation level of potato starch/LDPE
blend was studied in compost soil for 8 months the degradation
rates of PE and PE/potato starch are respectively 0.43% and 2.19% in
weight. This is confirmed by IR analyst is with the significant
decrease of the peak intensity at 1700 cm1 corresponding to the
degradation of carbonyl groups of potato starch in PE/potato blend
(Borghei et al., 2010). The morphology of sago-starch (15% (w/w))/
LLDPE blend during biodegradable test in soil burial shows the
presence of holes on the composite surface after 3 months and a
significant degradation after 12 months due to the microbial
activity.
Moreover, the mechanical properties of this material gradually
decrease when the burial time increases (Danjaji et al., 2002). An
important aspect during biodegradation in compost soil is the
growth of microbial which mainly promotes significant biodegra-
dation of bio-based material during the period test (Gu et al., 1994;
Orhan and Buyukgungor, 2000). To investigate the biodegradation
of materials under controlled conditions, some researchers have
studied poly(caprolactone) and poly (lactic acid) (Kunioka et al.,
2006; Funabashi et al., 2007b). The test used in their work de-
termines biodegradation degree by the measurement of the pro-
duced CO2 amounts of tested samples via absorption columns for
carbon dioxide. The bio-materials based on poly (lactic acid) and
flax fibers have been studied (Bayerl et al., 2014), with the results
indicating that the fibers enhance the biodegradation by contrib-
uting to the decaying process during tested period.
In this study, we use a special extruder which connects two
vacuum pumps in order to remove water during producing the
LLDPE/TPS compounds to prevent the perforation of film during
blowing period. Indeed, the compounds usually contain moisture in
their structure which was not completely removed during drying
period. Then the high TPS content (40% (w/w)) LLDPE/TPS film is
blown. There are a few studies that have been done to date with
this high TPS content. We also characterize the morphology as well
as the mechanical and thermal properties to observe the influence
of TPS phase on LLDPE matrix. Finally, we evaluate the biodegrad-
ability of LLDPE pure and bio-based films for 5 months under
natural soil and compost soil environments. The most important of
this study is to promote the degradation of polyethylene by adding
cassava starch. The interaction of microorganisms on surface of
materials is determined by the mass consumption over the course
of experiments.
2. Materials and methods
2.1. Materials
Vietnamese cassava starch (24% (w/w) amylose) is supplied by
Thanh Vu Co. Ltd, Viet Nam. The Linear Low Density Polyethylene
(LLDPE, Mw ¼ 339,300 and Mn ¼ 22,500) for blow film, which has a
density of 0.926e0.940 kg/m3and melt flow index (MFI) of 0.6 g/
10 min (190 ºC/2.16 kg), is purchased at Eastern Petrochemical Co.
Ltd, Saudi Arabia. The commercial compatibilizer maleic anhydride
grafted polyethylene (PE-g-MA, MFI ¼ 1.75 g/10 min, MAH graft
level ¼ 1.15% (w/w)) was provided by DuPont Co. Ltd. (USA). All the
materials are required to be dried in an air-circulating oven at 80
C
for 5 h before use.
2.2. Preparation of LLDPE/TPS compounds and films
The pellet compounds containing different content of TPS are
manufactured by using extruder connects to two vacuum pumps in
order to remove moisture during processing. The temperature
zones of the extruder are setup from 110 to 200
C and the speed of
the rotor is 220 rpm. The components of compounds are listed in
Table 1.
Finally, the 25 mm thickness bio-based film blown from 40% (w/
w) TPS compound is processed with a three zones temperature
profile setup at 160e170e165
C by using the blowing film option
of Polydrive Haake.
2.3. Characterization of mechanical properties
LLDPE/TPS compounds are placed into a mold under heat and
pressure using a laboratory hydraulic press (T ¼ 160
C, t ¼ 5 min,
P ¼ 1500 psi). The formed samples are removed from the mold after
cooling to room temperature. Tensile test specimens of each blend
are tested according to the ASTM D638 (IV) standard as well as the
tensile specimens of film before and after biodegradation are tested
according to ASTM D882 standard by using an AG-X plus Series
Precision Universal Tester (Shimadzu Inc., Japan). All test specimens
are conditioned at 25
C for 24 h before being tested. The average
values of the young's modulus, yield stress and elongation at break
Table 1
Components of the samples.
Samples LLDPE (% (w/w)) TPS (% (w/w)) PE-g-MA (% (w/w))
PES0 100 0 0
PES20 75 20 5
PES30 65 30 5
PES40 55 40 5
PES50 45 50 5
 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265
are calculated for at least 5 measurements.
2.4. Morphology characterization
To observe the dispersion and to estimate the size of TPS phase
in blends, the films surface morphology before and after degrada-
tion in natural and compost soil for 150 days are investigated by
Field Emission Scanning Electron Microscopy (FESEM), (Hitachi S-
4800).
2.5. Thermal properties of bio-based materials
Thermal analysis of all blends are performed by using a PT1000
differential scanning calorimeter (DSC) (Mettler Toledo,
Switzerland), under nitrogen atmosphere with a flow rate of 30 mL/
min, at a heating rate of 10
C/min. Two heating cycles are used for
each sample. The samples are first heated from room temperature
to 160
C to eliminate their thermal history, and then cooled to
room temperature and immediately reheated from 80
C to
160
C. The thermograms refer to the second heating. Melt tem-
perature (Tm), enthalpy of fusion (DH) and crystallize temperature
(Tc) were determined from DSC curves. The crystallinityratio (Xc) of
LLDPE of each sample is calculated using the following equation:
DH
%Xc ¼  100
w  DHf 0
where DH is the enthalpy of fusion, obtained from DSC curve, DHfo
is the enthalpy heat of 100% crystalline LLDPE (289 J/g) (Guo et al.,
2009), and w is the weight fraction of LLDPE in the sample.
Thermogravimetric analyses of all blends are evaluated by using
a TGA Q500 (TA Instruments, USA) under nitrogen atmosphere. The
heating rate is10
C/min, the samples are heated from room tem-
perature to 600
C to investigate the thermal degradation of all
samples.
2.6. Water absorption of bio-based film
The water absorption (WA) of films is measured according to
ASTM D570-63. All specimens of each sample are conditioned at
50 ± 1
C for 24 h and weighed (M0) before being tested. The
specimens are immersed in distilled water at 25
C. After 24 h, all
specimens were removed from water, drained and weighed (M1).
Then they are dried at 50
C for 24 h and finally weighed again (M2).
The water absorption is calculated by the equation below:
M1  M2
WAð%Þ ¼  100
M0
2.7. Biodegradability test
In this study, the biodegradability of films is investigated with
two methods: natural soil burial test and aerobic compost envi-
ronment test exposed to controlled composting environment. The
components of aerobic compost soil are prepared according to
ASTM D6003-96, the temperature conditions of compost soil at
T ¼ 30 ± 2
C. Every15 days, the specimens are removed from the
soil, then washed in distilled water and dried at 60 ± 2
C for 24 h.
Finally, the specimens are weighted and compared with specimens
before testing. The percentage weight loss is calculated using the
following equation:
W0  W1
WLð%Þ ¼  100
W0
259
where W0 is the initial mass and W1 is the mass after degradation.
The weight loss (%) is the average of at least five specimens of each
sample.
The biodegradability test of materials in compost environment
is a good and performance method to evaluate the weight loss of
tested specimens and better understand how compost composi-
tions influence on the rate of materials degradation such as: Cel-
lulose acetate (CA) film (Gu et al., 1994), biofilms on coupons of
fiber reinforced polymeric composites (Gu et al., 1997) and LDPE
films modified with Bionolle polyester (Nowak et al., 2011).
3. Results and discussion
3.1. Thermal analysis of materials
The DSC thermograms of samples refer to the second heating
and the results are listed in Table 2 and Fig. 1. A slight change of the
blends melting temperature (Tm) of all blends is recorded when the
TPS rate increases. In particular, the Tm value tends to slightly
decrease from 132
C for PES0 to 130
C for PES30, PES40 and
128.5
C for PES50 samples. The melting temperature Tm of TPS is
lower than that of LLDPE. Therefore, the Tm of the blend tends to be
slightly reduced when amount of TPS in blends increases. This
phenomenon confirms the good miscibility between TPS and LLDPE
matrix which is also mentioned in other reports (Andre a and Ruth,
2016; Nguyen et al., 2016). The melting enthalpy (DH) of each blend
is used to calculate the crystallinity ratio (Xc) of LLDPE in the blend
(Table 2). The crystallinity degree of LLDPE increases from around
22% for PES0 to 30% in PES30, 48% in PES40 and 63% in PES50
samples. We can observe that increasing the quantity of TPS in
blends leads to a significant increase of the LLDPE crystallinity. This
result is explained by the existence of hydrogen bonds in the starch
structure, so it is stiffer and has a higher crystallinity than semi-
crystalline polymers such as LLDPE. The influence of TPS on the
LLDPE crystallinity has been studied by numerous authors but the
results are quite different. The LLDPE crystallinity increases in the
blends with TPS due to the fact that the TPS acts as nucleating agent
for the crystallization of LLDPE (Anderson et al., 2016). Some au-
thors report that lower crystallinity of PE is recorded after blending
it with starch (Chandra and Rustgi, 1997; Jagadish and Raj, 2011;
Sabetzadeh et al., 2015; Andre a and Ruth, 2016). However, some
reports show a stable crystallinity ratio after blending (Raj et al.,
2004; Fang-Chyou et al., 2009). The variations of the crystallinity
ratio of polyethylene depend on crystallinity of pure polyethylene
and on the dispersion phase into matrix polymer. The DSC data also
show the crystallization temperatures (Tc) of blends but there is no
significant change after adding different quantity of TPS into LLDPE.
The TPS phase has no influence on Tc of the blends.
The determination the crystallization level of PE after adding
cassava starch is very important because the biodegradable pro-
cedure relate to amorphous regions of polymer. The amorphous
regions are consumed first by accessible of microorganisms. This
result is confirmed by increasing in percentage crystallinity after
consuming amorphous portions (Sudhakar et al., 2008; Restrepo-
rez et al., 2014).
Flo
Table 2
Melt temperature and crystallinity ratio of blends.
Sample Tc (oC) Tm (oC) DH (J g1) Xc (%)
PES0 111 132 62.6 22
PES30 111 130 60.7 30
PES40 111.5 130 84.3 48
PES50 112 128.5 91.7 63
260 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265

Fig. 1. DSC curves of blends at different TPS concentration: (a) crystallization temperatures (Tc); (b) melt temperature (Tm).

3.2. Morphology of bio-based materials
The FESEM micrographs of cassava starch and its blends are
shown in Fig. 2. The spherical and semi-spherical objects observed
in Fig. 2d correspond to the cassava starch particles with an average
diameter about 100 mm. The addition of different amounts of TPS to
LLDPE matrix leads to a significant decrease of the TPS diameter
size. Particularly, for the PES30 sample, there is no TPS phase
observed on fractured surfaces of blend and the surface is smoother
and homogenous (Fig. 2a). This result confirms the totally misci-
bility and the good compatibilization between the both polymers at
30% (w/w) of TPS. For PES40 sample, due to the increase in the TPS
content, the TPS particles tend to coalesce together leading to the
lengthening of TPS fibers in blend (Rodriguez-Gonzalez et al.,
2003). So, we can observe the formation of TPS fibers on frac-
tured surfaces of blend via FESEM (Fig. 2b). However, it is difficult to
distinguish the LLDPE from the TPS phase and to identify the
diameter of the TPS phase in this blend. At high TPS content

Fig. 2. FE-SEM observations of fracture surfaces of (a) PES30, (b) PES40, (c) PES50, (d) cassava starch.
 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265 261

(PES50), the TPS phase has tendency to be condensed in large

spherical particles with a diameter higher than 10 mm (Fig. 2c).

3.3. Thermal decomposition of bio-based materials

The thermal stability of blends at different contents of TPS is

showed in Fig. 3. In general, the TPS component reduces the ther-
mal stability of the blends. From TGA and DTG curves of TPS sample,
the first shift around 100
C is produced by water evaporation. The
second shift starts around 303
C and is due to the main thermal
decomposition of TPS. The total weight loss of TPS sample reaches
more than 90% (w/w) at 600
C. The thermal decomposition of PES0
has only one shift around 461
C and the total weight loss is 100%
(w/w) at 600
C. The thermal decomposition curves of PES30 and
PES40 blends show the first shift around 303
C for PES30 and
308
C for PES40 due to release of low molecular substances and
decomposition of TPS phase in blends. The final shifts are observed
at about 444
C for PES30 and about 454
C for PES40, that are the
thermal decomposition of LLDPE in blends which is lower than that
of pure LLDPE. The results confirm the effect of TPS phase on
thermal stability of blends which decreases when TPS is added. The
thermal stability of these materials is also reported in a previous
article (Rodriguez-Gonzalez et al., 2003). Through TGA results, the
amount of TPS in each blend can be verified and optimized con-
ditions for film blowing can be determined in order to prevent
thermal decomposition during processing.
3.4. Tensile properties of bio-based materials
The bar chart (Fig. 4) shows the tensile property of LLDPE and its
blends at different TPS contents. The elastic modulus and yield
stress of blends are slightly increased with increasing TPS contents
because of hydrogen bonding in starch structure which is stiffer
and on the other hand, of higher crystallinity than pure LLDPE.
Moreover, the good dispersion of TPS in LLDPE matrix (FE-SEM,
Fig. 2a, b) leads to improved tensile properties of blends. Whereas
the elongation at break of blends tends to decrease, because of the
weakness interface between LLDPE and TPS phase. At high TPS
concentration (50% (w/w)) the yield stress and elongation are
remarkably decreased. This result is due to the formation of TPS
aggregates (Fig. 2c). This tensile behavior is commonly found in
polymer blend materials reinforced by natural fillers such as starch
Fig. 4. Tensile properties of blends at different TPS concentration.
(Rodriguez-Gonzalez et al., 2003; Sabetzadeh et al., 2015; Nguyen
et al., 2016). Therefore, in this study, the TPS content is added to
LLDPE matrix at 40% (w/w) and the blend of LLDPE/TPS still keeps
tensile properties sufficiently high to blow films.
3.5. Morphology of bio-based films
In this study, the PES40 film was blown and all the properties of
this film such as morphology, water absorption, mechanical and
biodegradability were investigated. In the FESEM image of this film,
we can observe the good dispersion of TPS in LLDPE matrix (white
spheres (TPS) on dark matrix (LLDPE)) (Fig. 5b). The diameter of TPS
phase is under 0.5 mm (Fig. 5c) which is 20 times smaller than that
of original starch (q > 10 mm). This result confirms the good
miscibility between the both polymers leading to the diameter
reduction of TPS phase during melt processing. The good dispersion
of TPS phase in polyethylene matrix with smaller diameter is good
condition for microorganisms consuming the bio-film during
biodegradable test (see Fig. 5).
3.6. Water absorption of bio-based films
Biodegradable materials are well known to be sensitive to
water and this behavior limits their industrial applications. How-
ever, water absorption of bio-based materials is greatly important

Fig. 3. TGA (a) and DTG (b) curves of TPS, PES0, PES30, PES40 blends.
262 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265
Fig. 5. FE-SEM observations of film (a) PES0, (b) PES40 at 10 mm scale, and (c) PES40 at 1 mm scale.
to promote their biodegradability. The bio-based materials must
be hydrophobic for industrial application but they must adsorb
water after using to promote degradability because most of mi-
croorganisms are really efficient in high moisture environment.
Therefore the biodegradable materials must be suitable both for
application and biodegradability. The water absorption of films
PES40 shows, in Fig. 6, a high water uptake rate during the first 16
days and then reaches the equilibrium state until 30 days. The
amount of water uptake of PES40 film is 2.3% more than that of PE
film (0.6%). This is due to TPS content in PES40 film. Indeed, starch
is a water sensitive polymer, hydrogen bonds can be formed be-
tween water and its hydroxyl groups (Majid et al., 2009;
Sabetzadeh et al., 2015). Thus, it can be seen that this material
becomes to more hydrophilic surfaces are more easily consumed
by microorganisms. On the other hand, the surface of PES40 film is
not homogeneous (Fig. 5b, c). The TPS particles and holes can be
observed, the water molecules can be located at the interface
between LLDPE and TPS and also in the holes. Comparing with
previous literature, LDPE/potato starch (7.5% (w/w)) with 3%
moisture uptake (Gupta and Sharma, 2010), 10% water uptake of
PEO/TPS (40% (w/w)) film (Jagadish and Raj, 2011), the lower
water absorption of PES40 film (2.3%) may guarantee both the
application and the biodegradability.
Fig. 6. Water absorption isotherms at 30
C of PES0 and PES40 films.
3.7. Biodegradability of films in compost environment
The biodegradability of PES0 and PES40 films in natural and
compost environment is shown in Fig. 7. The result indicates that
the biodegradable percentage of films in compost soil is higher than
that in natural soil. In compost soil, the weight of PES40 film is
gradually decreased without equilibrium state, corresponding to
about 9.45% (w/w) for PES40 compared to 1% (w/w) for PES0 films
after 5 months. The burial environment parameters (temperature,
pH, moisture, nutrition) have a great impact on biodegradation of
films, especially the amount of microorganisms. Thus, the number
and the growth of microorganisms of this standard were reported
in previous literature (Kim et al., 2006). Microorganisms attack and
consume the cassava starch leading to fracture the film structure
and the polyethylene chains which promote biodegradation pro-
cess. Moreover, according to ASTM D6003-96 standard, the
compost soil environment is complemented with components rich
in carbon and nitrogen to give optimized conditions for the
development of microorganisms. Therefore, the presence of mi-
croorganisms in compost soil is more numerous than in natural
soil, resulting in a higher biodegradation percentage compare with
that in natural soil (Dave et al., 1997; Psomiadou et al., 1997; Kim
et al., 2006). Indeed, the weight of PES40 film in compost soil
Fig. 7. Weight loss of PES0, PES40 films in natural and compost soil for 150 days.
 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265 263

Fig. 8. The morphology of PES0 film: (a) before biodegradable, (b) biodegradable in natural soil, and (c) biodegradable in compost soil for 150 days.

was decreased about 9.45% (w/w) for 5 months. It can be suggested
that only thermoplastic starch in PES40 film was degraded whereas
the carbonecarbon backbone of polyethylene was cut into smaller
chains leading to reduce the molecular weight of polymer. This
result can be confirmed by FE-SEM image on the surface of the
specimen in compost soil. This result can be explained that poly-
ethylene film is well known a non-biodegradable polymer and it
was reported about 0.2% weight loss in 10 years (Albertsson, 1980)
and appearance the whitening points on the surface of film after
soil burial for 32 years (Otake et al., 1995). The polyethylene poly-
mer must be depolymerized until lower molecular size about
500 Da (Daltons) which can be consumed by several microorgan-
isms by pass the semi-permeable outer bacterial membranes, and
then to be utilized as carbon and energy sources (Shah et al., 2008).
Addition, from the biodegradation test result, it can be
confirmed that changing the condition of biodegradable test
(temperature, pH, moisture, and complemented nourishment)
leads to change the percentage of biodegradation of bio-based film
(Gu et al., 1994; Gu, 2003). When condition of biodegradable tests is
changed by using different equipment and standards, the biodeg-
radation result shows more than 60% in weight of LLDPE/TPS (40%
(w/w)) film is degraded into CO2, H2O, methane and biomass after 5
months in compost soil environment which is reported in our
previous research (Nguyen et al., 2016). Thus, the percentage
biodegradable of film based on LLDPE and cassava starch on
compost environment depended on test conditions (temperature,
pH, moisture, and complemented nourishment) and the thermo-
plastics starch promotes the biodegradable procedure by attractive
and accessible to microorganisms. However, in this study, the lower
degradation of PES40 film (9.45%) compared to other materials as

Fig. 9. The photos and morphology of PES40 film (a) before biodegradable, (b) biodegradable in natural soil, and (c) biodegradable in compost soil for 150 days.
264 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265
Fig. 10. Tensile properties of PES0, PES40 films in natural and compost soil burial for 150 days.
poly (butylene succinate) filled with 40% (w/w) rice-husk flour (17%
w/w) (Kim et al., 2006), poly(lactic acid) or cellulose (100% w/w)
(Funabashi et al., 2009) due to the high crystallinity, hydrophobic,
molecular weight and non-biodegradability of low liner density
polyethylene (LLDPE) (Arvanitoyannis et al., 1998; Gu et al., 2000;
Kim et al., 2006; Shah et al., 2008; Sen and Raut, 2015). More-
over, polyethylene is reported with the strong resistance to mi-
crobial breakdown (Weiland et al., 1995) which affected on
biodegradability degree of its blends. Additionally, the polyethylene
may also prevent microorganism accessing to thermoplastic starch
(TPS) phase in the depth of the PES40 film because the hydrophobic
chains of polyethylene prevents hydrophilic enzymes accessing to
the TPS contained in the film (Nowak et al., 2011; Nakamura et al.,
2005).
3.8. Morphology of films during biodegradation test
The morphology of PES0 and PES40 films during biodegradation
test is observed in Figs. 8 and 9. Before being tested, the PES0 film
(Fig. 8a) exhibits a smooth and homogeneous surface morphology.
However, the morphology is changed in natural and compost soil.
Particularly, sporadic and sparse holes occur on the surface even
though the surface is still smooth after 5 months in natural soil
(Fig. 8b). But in compost soil, the surface morphology becomes
scabrous, deformed and there are more numerous large holes than
in the natural soil (Fig. 8c). This phenomenon shows the evidence of
biodegradation under attack by microorganisms (Gu et al., 1998;
Kim et al., 2005, 2006). It also confirms that the percentage of
biodegradation in compost soil is higher than in natural soil due to
the addition of the nutritional in the soil burial test (Ratto et al.,
1999; Kim et al., 2006). The PES0 film is not readily metabolized
by living organisms and must be considered as non-biodegradable
in short time in the soil. The morphology of PES40 film (Fig. 9a)
exhibits an inhomogeneous surface; the spherical objects observed
correspond to the TPS phase which is uniformly dispersed in LLDPE
matrix. The morphology of PES40 film during test in natural soil
and compost soil for 5 months is shown in Fig. 9b and c, respec-
tively. The film surface in compost soil is deformed, rougher and
somewhere completely destroyed (Kim et al., 2006; Massardier-
Nageotte et al., 2006). The mechanism of decomposition is the
consumption of the cassava starch by microorganisms leading to
destruction of LLDPE chains due to their molecular weight
decrease. Then, small polyethylene chains become more hydro-
philic and more attractive of microorganisms. Therefore, the blends
based on starch and polyethylene are attractive to replace the low
biodegradable plastics (Chandra and Rustgi, 1997; Dave et al., 1997;
Kim et al., 2005; Massardier-Nageotte et al., 2006).
3.9. The change of mechanical properties of films during
biodegradability test
Tensile properties of PES0 as well as PES40, before and after
biodegradable tests in natural and compost soil for 5 months, are
shown in Fig. 10. During initial biodegradation, the elongation of
PES40 and PES0 films has the same value of about 325%, but the
tensile strength value of PES40 is about 26 MPa. This is higher than
that of PES0 film (23.5 MPa), due to the hydrogen bonds in starch
(Chandra and Rustgi, 1997). The tensile strength and elongation of
PES0 film did not change in natural soil after testing, confirming
that PES0 film is non-biodegradable in natural soil during the
period test. Contrary to this, the tensile properties of PES40 films
are rapidly decreased after burial in both natural soil and compost
soil for 150 days. The tensile strength and elongation after
biodegradation are around 12 MPa and 50% in natural soil, about
12 MPa and 10% in compost soil respectively. This result indicates
that the degradation is faster in compost soil than in natural soil
because of the different amount of microorganisms between the
two environments. An environment rich in nutrients could stimu-
late the development of bacteria and fungi that consume TPS film
phase in short time and promote the biodegradation of poly-
ethylene chains.
4. Conclusion
This study shows the influence of different TPS contents on
LLDPE matrices and the morphology, mechanical and thermal
properties of blend changes with the increasing quantity of TPS.
The PES40 film (40% (w/w) TPS) is successfully prepared by the
blowing method. The biodegradation test shows that about 9% (w/
w) of film is degraded in compost soil for 150 days.
Acknowledgment
The authors thank the Editor-in-Chief for these early comments
of this manuscript and we also thank all colleagues for their
enthusiasm and cooperation in this research. This work was sup-
ported by grant from University of Science and Vietnam National
University of Ho Chi Minh City (VNU-HCM) under project number
 D.M. Nguyen et al. / International Biodeterioration & Biodegradation 115 (2016) 257e265
C2013-18-12.
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