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Energy Procedia 34 (2013) 73 82

10th Eco-Energy and Materials Science and Engineering

(EMSES2012)

Degradation behaviors of different blends of polylactic acid

buried in soil
Chaniga Chuensangjuna, Chiravoot Pechyenb, c* and Sarote Sirisansaneeyakula, c*
a
Department of Biotechnology, Kasetsart University, Chatuchak, Bangkok, 10900,
0 Thailand
Department of Packaging and Materials Technology, Kasetsart University, Chatuchak,
k Bangkok 10900, Thailand
c
Center for Advanced Studies in Tropical Natural Resources, National Research University-Kasetsart
University,
Kasetsart University, Chatuchak, Bangkok, 10900, Thailand (CASTNAR, NRUU KU, Thailand)

Abstract
Polylactic acid (PLA), as the biodegradable polymer becomes more attention as a green material for industrial
applications. Lipase-catalysed polymerization with Lecitase Ultra and Lipozyme TL IM were applied to synthesize
PLA to decrease the chemical-catalysts utilization which having toxicity interferes in products. PLA products were
characterized by end group/HPLC analyses for Mn/Mw determination. The results indicated that low molecular weight
PLA could be successfully produced from commercial lactic acid by using the commercial lipases. With using
Lipozyme TL IM as biocatalyst, obtainable Mn and Mw of PLA were 7,933 Da and 194 Da, respectively. For Lecitase
Ultra used as biocatalyst obtainable Mn and Mw of PLA were 8,330 Da and 216 Da, respectively. Subsequently, the
resulting PLA products from this method were prepared as PLA films blended with commercial PLA beads varying
the blending ratios by casting on glass plate. Their degradable behaviors were studied under controlled soil burial
laboratory conditions. The characteristics of PLA blend films were analyzed using visual observations, measuring
weight loss, DSC and FTIR analysis. The results observed that the different blends ratios of PLA films showed more
flexible than pure PLA film. Besides, the different blends of PLA films were disintegrated in soil within the short
burial time.
2013
Authors.
Published
by Elsevier
B.V. Open
access under CC BY-NC-ND license.
2013The
The
Authors.
Published
by Elsevier
B.V.
Selection
peer-review
under responsibility
of COE of Sustainalble
System,
Rajamangala
University
of Technology
Selectionand
and/or
peer-review
under responsibility
of COE of Energy
Sustainable
Energy
System,
Rajamangala
Thanyaburi
University(RMUTT)
of Technology Thanyaburi (RMUTT)
Keywords:
d Polylactic acid; Lipase-catalysed polymerization; Blend film; Soil burial

__________
* Corresponding author. Tel.: +66 2-562-5295, +66 2-562-5086; fax: +66 2-562-5046, +66 2-579-4096.
E-mail address: chiravoot.p@ku.ac.th, sarote.s@ku.ac.th

1876-6102 2013 The Authors. Published by Elsevier B.V. Open access under CC BY-NC-ND license.

Selection and peer-review under responsibility of COE of Sustainalble Energy System, Rajamangala University of Technology
Thanyaburi (RMUTT)

doi:10.1016/j.egypro.2013.06.735

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

1. Introduction
In the recent years many use of synthetic polymers and plastic materials produced from petroleumbased which are non-degradable plastics. The residues of plastic wastes have led to the serious
environment pollution which has affected widely on a human life on earth. There are many attempts to
solve this problem such as recycling plastics, fighting to decrease demanding to use plastics of human
including the development of the production of biodegradable polymers derived from renewable
resources. Biodegradable polymers produced from natural biopolymers are innovative for an
environmentally-friendly material due to it can be converted into the substrates for production of the
monomer for polymerization later, as well as the cycle of plastics life. The biodegradation of polymers in
nature involves several processes. The natural microorganisms influence abiotic degradation through
physical, chemical and enzymatic reactions [1]. Degradation steps of biodegradable polymers started to
hydrolyze polymers which catalyzed by temperature control followed by microorganisms actions on the
fragmented residues. Some literatures present behavior of biodegradable in soil. Biopolymers such as
gelatin, starch were modified, blending with petrochemical plastics such as polystyrene, casting for films
production and were degraded in soil [2, 3].
Polylactic acid (PLA) is the one type of biodegradable polymer based on renewable resources,
as lactic acid which obtained from microbial fermentation. Under appropriate conditions, PLA can be
degraded by the simple action of microorganisms in the environment. Moreover, PLA has been attentive
to apply for packaging, clothing and biomedical products due to the good properties such as
high-strength, high-modulus, brightness, barrier and good moisture management biocompatible and
bioabsorbable [4]. However, applications of PLA for materials production and ability of biodegradation
depend on their molecular weight and chemical compositions. Therefore, there are several attempts to
improve the properties of PLA for making the suitable polymers for a specific application including
the appropriate biodegradation properties. Blending poly(L-lactic acid) with linear low-density
polyethylene was applied to improve the molecular-weight polymers for applications in the industry
and this makes the materials more ability for biodegradation [1]. Moreover, PLA films and fibers
showed the degradation behavior in soil under Mediterranean field conditions for eleven-month [5].
PLA becomes more attention as the green materials due to the process to receive PLA was derived
from polymerization process of lactic acid which obtained from renewable resources. Furthermore, there
were works to synthesize PLA via the bioprocess using an enzyme based catalysts such as lipases instead
of chemical processes, which are non-toxic and to make the real green material entirely [4, 6, 7].
However, PLA products from lipase-catalyst polymerization resulted in low-molecular weight. This
affects hardly to develop for film forming, and to cast for PLA film. Blending PLA products from lipasecatalyst with some commercial PLA beads has primarily solved the problem. PLA blends showed the
better ability of film forming and biodegradation behavior than single type of PLA [4].
In this study, the PLA was synthesized by commercial lactic acid using microbial lipase-catalysed
polymerization. Then, to characterize PLA produced from commercial lactic acid and to produce PLA
blend films forming between commercial PLA beads and PLA products with different blending ratios.
The appropriate ratio of blending was determined and the degradable behavior of different PLA blend
films were studied under controlled soil burial laboratory conditions. These are the alternative routes for
the production of environmental friendly biomaterials.

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

2. Experiments
2.1. Materials
Commercially available lactic acid (liquid, 85%), was obtained from Ajax Finechem, Australia. The
commercial lipases, i.e. Lipozyme TL IM and Lecitase Ultra were procured from Novo Nordisk A/S,
Denmark. Toluene was obtained from Panreac, Spain. Potassium hydroxide and sodium hydroxide were
purchased from Ajax Finechem, Australia. Absolute ethanol was obtained from Merck, Germany;
isopropyl ether was obtained from CARLO ERBA, Italy. Chloroform was procured from RCI Labscan,
Thailand and dichloromethane was purchased from Fisher Scientific, UK.
2.2. Methods
2.2.1 Polymerization reactions of PLA synthesis
Polymerization experiments were designed according to the methodology described earlier [4]. The
mixtures of commercial lactic acid (LA) and toluene were heated to give a homogeneous solution. Then,
the enzyme (Lipozyme TL IM or Lecitase Ultra) was added to the mixtures. All reaction mixtures were
stirred under nitrogen atmosphere. After the reaction, PLA products were isolated by precipitation
method. The lipase was separated and the PLA products were dissolved in CH 2Cl2 with the ratio of 4:2.
Then water was added to precipitate the polymer and was isolated after solvent evaporation for 24 h.
Afterwards, the quantity of commercial PLA beads and chloroform were determined for the preparation
of PLA blend films.
2.2.2 Preparation of PLA blend films
The PLA products from the polymerization experiments and commercial PLA beads were prepared
with the ratios as follows, 40:60, 60:40 and 70:30; and then dissolved the mixture in chloroform while
mixing vigorously at room temperature. The dissolved solution was casted onto the glass plate and then
allowed to dry for about 24 h at room temperature. The specimen of film was peeled from the casting
surface and to characterize the properties of film further [8, 9].
2.2.3 Soil burial biodegradation test
PLA blend films were evaluated by soil burial test under laboratory conditions. The experiments were
carried out in bioreactors (4L plastic boxes containing soil). Samples were cut
(2 x 2 cm2) and placed into an envelope of plastic nets and buried at 8 cm depth from the soil surface. The
relative humidity was kept approximately 40%. The experiments were performed at room temperature for
14 days [2, 5].
2.3. Polymer Characterization
2.3.1 Weight loss of PLA blend films were determined according to %WL equation [2].
(1)
Where m0 is an initial mass at initial day and mt is the residual mass at an interval burial time.

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

2.3.2 Fourier transform infrared spectroscopy (FTIR) was carried out using a Bruker Tensor 27
instrument for recording transmission spectra in the range of 4000 400 cm . The PLA spectra were
measured after evaporating the solvent [5].
2.3.3 DSC method was used for analysis of the thermal property (Tg, Tm and Tc) of PLA blend films by
carried out using a Mettler Toledo DSC1 Stare System. The sample (3-10 mg) was heated at a rate of
10C min-1 from 20C to 200C, then was held for 1 min at 200C and cooled at a cooling rate of 10 oC
min-1 to 20C [5].
3. Results and Discussion
3.1. Polymerization reactions
The production of PLA from commercial LA was synthesized according to experimental design for
the polymerization. The reaction mixtures containing LA, toluene and lipase were controlled
to form PLA polymer. After the reaction, PLA polymers were separated from the solvent (toluene) into
the bottom phase. The recoverable PLA products were viscous increasingly. From the previous work
explained that the viscosity of the reaction mixtures increased as the function of time to form polymer
products due to an increasing molecular weight of polymer (data not shown). This was an affectation on
the mobility in the solution [4]. PLA products were characterized by FTIR. The number of average
molecular weight (Mn) and the molecular weight (Mw) of PLA products were analyzed by end-group
analysis and HPLC analysis, respectively. The results showed the appropriate conditions for PLA
synthesis were 1.25 wt.-% of enzyme, 450 (mg mL-1) lactic acid, and reaction temperature 70C for
6 hours by using Lipozyme TL IM as biocatalyst, the obtained M n and Mw of PLA were 7,933 Da
and 194 Da, respectively. For Lecitase Ultra used as biocatalyst, the obtained M n and Mw of PLA were
8,330 Da and 216 Da, respectively, with using 1.25 wt.-% of enzyme, 450 (mg mL-1) lactic acid, and
reaction temperature 60C for 4 hours. The PLA products were dissolved in CH 2Cl2 with
the ratio of 4:2. Then water was added to precipitate the polymer, which was isolated after solvent
evaporation for 24 h.
3.2 Visual observations of PLA blend films
Visual observations of PLA blend film samples were studied during biodegradation. The different
blend ratios of PLA films demonstrated the degradable behaviors as shown in Fig.1.
During 14 days of burial time in soil, the specimens were disintegrated gradually upon the time course.
Changes of PLA blend films showed similarly the degradability from the previous work at the blending
ratio of 50:50 [10]. Some characteristics were changed such as brittle and turbidity after 7 days of soil
burial time. This might due to re-crystallization in the structure of PLA blend films under fluctuating
temperature during biodegradation [5]. Besides, the burial time and humidity are the other factors which
affected on degradable behaviors. An increase of degradability was found a function of the ratio PLA
blends. Therefore, different blends of PLA films gave different degradable behaviors. Concomitantly,
the water intake within the PLA films enhanced the microbial growth and to initiate the biodegradation
[2, 5]. Furthermore, comparing with the commercial PLA film (0:100), all ratios studied of the
PLA blend films presented more flexible.

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

0d

1d

7d

14 d

Lec 40

Lec 60

Lec 70

Lipo 40

Lipo 60

Lipo 70

C0

Fig. 1. Changes of PLA blend films during biodegradation in soil burial experiment (ASTM D5338);
Lec 40, Lec 60, Lec 70 are abbreviated from Lecitase Ultra with its percentage of the synthesized PLA;
Lipo 40, Lipo 60, Lipo 70 are abbreviated from Lipozyme TL IM with its percentage of the synthesized PLA;
0 d, 1 d, 7 d, 14 d are represented the time of soil burial experiment.

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

The weight losses of PLA blend films were determined, as shown in Fig. 2. The PLA blend films from
Lecitase Ultra and Lipozyme TL IM as biocatalysts, deteriorated as a function of degradation time.
Different ratios directly affected on degradable behavior, the PLA products resulted from either Lecitase
Ultra or Lipozyme TL IM blended with the commercial PLA beads showed the highest weight loss
initially during soil burial experiment. Then, their weight losses decreased slowly until the 8 days of soil
burial time and increased again after 8 days of soil burial condition. This result was observed that there
was water removal from the structure of PLA blend film at the initial of soil burial condition until kept
constantly. Then after 8 days, there was degradation of the structure of film further. Interestingly, these
were greater than that obtained from only commercial PLA film (PLA com). Due to the higher molecular
weight of commercial PLA film which affect to the structures were stronger than PLA blend film.
Therefore, there was the degradable behavior of commercial PLA film less than PLA blend film in short
times. For a pure synthesized PLA, could not be casted for PLA film due to its low molecular weight.
(a)

30.00
25.00

WL (%)

20.00
15.00
10.00
5.00
0.00
-5.00

10

11

12

13

14

11

12

13

14

Time (days)
Lec 40

(b)

Lec 60

Lec 70

PLA com

45.00
40.00
35.00

WL (%)

30.00
25.00
20.00
15.00
10.00
5.00
0.00
-5.00

10

Time (days)
Lipo 40

Lipo 60

Lipo 70

PLA com

Fig. 2. Relative weight loss as a function of degradation time in soil burial;

(a) Lec 40, Lec 60, Lec 70 are abbreviated from Lecitase Ultra with its percentage of the synthesized PLA;
(b) Lipo 40, Lipo 60, Lipo 70 are abbreviated from Lipozyme TL IM with its percentage of the synthesized PLA.

Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

3.3. Characterization of PLA blend films

The PLA blend films were evaluated chemical modifications into their structure by Fourier transform
infrared spectroscopy (FTIR). For the transmission spectra of PLA film samples, the types of enzyme
used as biocatalyst and the blending ratios for polymerization were compared as shown in Fig. 3 and
4. From both of all samples appeared the typical transmission spectra of PLA in two main regions as
follows: the C=O stretching, between 1,600 and 1,800 cm-1; and the C-O stretching, between 1,000 and
1,200 cm-1 [11]. The PLA peaks located at 1,751, 1,182, 1,128, 1,084 and 1,044 cm -1 for the commercial
PLA film before demonstrated in soil. After demonstrated in soil, their PLA peaks located
at the same positions. In all experiments, the blend films in which before and after buried in soil showed
significantly no changes of the chemical structures. Moreover, the PLA blend films produced from
Lecitase Ultra and Lipozyme TL IM, gave similar peaks of PLA located likely the commercial PLA film.
However, to compare the quantity of chemical peaks, the C=O stretching and the C-O stretching, the peak
of specimens after buried in soil showed insignificantly the reduction of chemical structures residues.
Furthermore, to compare changes of the quantity of chemical peaks of the PLA blend films before to after
in soil burial found that there were the reduction of chemical structures of the PLA blend films produced
from Lecitase Ultra-catalyst more quantity than Lipozyme TL IM-catalyst. These indicated that
there was a minor degradation during biodegradation in soil burial and observed more obviously in
Lecitase Ultra than Lipozyme TL IM due to the water residue from the liquid enzyme of the former,
which increased the flexible of the films structure [1].
Table 1. Glass Transition (Tg) and Melting (Tm) Temperatures of PLA blend films before/after soil burial biodegradation
Tg (oC)

Tm (oC)

Before

After

Before

After

PLA blend (Lec 40)

52.08

59.75

133.86

140.00

PLA blend (Lec 60)

52.08

60.28

133.86

140.75

PLA blend (Lec 70)

52.55

60.08

136.96

140.69

PLA blend (Lipo 40)

73.18

48.10

135.36

137.85

PLA blend (Lipo 60)

41.60

59.26

126.32

141.86

PLA blend (Lipo 70)

57.71

60.13

140.48

142.45

Commercial PLA

54.41

43.95

142.16

141.03

The morphological changes of different ratios of the PLA blend films during biodegradation in soil
burial experiment were determined by DSC method. Two important parameters, namely glass transition
temperature (Tg ) and melting temperature (Tm) were used to derive them from the estimation [5]. The
results were summarized in Table 1. To demonstrate the PLA films in soil burial, the PLA blend films
produced from Lecitase Ultra found increasing their approximate Tg values from at 52C to 60C after in
soil burial. For the PLA blend films produced from Lipozyme TL IM found an increasing of approximate
Tg values from 41-73C to 48-60C after in soil burial. For Tm values after soil burial, their changes were
from approximately 133-136C to 140oC for the PLA blend film produced from Lecitase Ultra, and from
126-140C to 137-142C for the PLA blend film produced from Lipozyme TL IM, respectively. These
results indicate that during biodegradation occurred the change of structures within the films due to there

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Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

was the humidity from water in the environment taken into the structure of the films. Moreover, heat
evolution during soil burial would activate re-arranging the structure of the films. Therefore, water in film
and heat evolution was mainly the factors to increase the temperatures of Tg and Tm and evolved causing
the structural change of the films [10]. However, in the experiments, there were insignificantly the
relationships of the effect of blending ratios on the degradable behavior of PLA films produced from both
Lecitase Ultra and Lipozyme TL IM. As compared with the commercial PLA film, the PLA blend films
showed similarly the behavior of degradation with the pure commercial PLA films under the specified
condition. However, the more experiments needed for better explaining of all factors relationship, PLA
degradation should be considerably extended longer over 14 days to disintegrate its mass completely in
soil, for example both 2-11 months and a year are recommendable [3, 5].
1.6
Com. PLA 0:100 (after)

1.4

Transmittance (%)

1.2

Com. PLA 0:100 (before)

1.0

Lec 70:30 (after)

0.8

Lec 70:30 (before)

Lec 60:40 (after)

0.6

Lec 60:40 (before)

0.4

Lec 40:60 (after)

Lec 40:60 (before)

0.2
0.0

Wave number cm-1

Fig. 3. FTIR Spectra of PLA blend films using Lecitase Ultra-catalyst before/after soil burial biodegradation
1.6
1.4

Com. PLA 0:100 (after)

1.2
Transmittance (%)

Com. PLA 0:100 (before)

1

Lipo 70:30 (after)

Lipo 70:30 (before)

0.8

Lipo 60:40 (after)

0.6

Lipo 60:40 (before)

0.4

Lipo 40:60 (after)

Lipo 40:60 (before)

0.2
0

Wave number cm-1

Fig. 4. FTIR spectra of PLA blend films using Lipozyme TL IM-catalyst before/after soil burial biodegradation

Chaniga Chuensangjun et al. / Energy Procedia 34 (2013) 73 82

4. Conclusion
The investigations revealed that PLA polymers could be synthesized by Lecitase Ultra and Lipozyme
TL IM catalysed polymerization from the commercial lactic acid. However, the PLA products derived
from lipase-catalyzed polymerization could not likely form the PLA films due to the lower molecular
weight of the PLA polymer than PLA products from chemical-catalyzed polymerization.
In any cases, this is not the prefix to develop a new material. Interestingly, this was that the PLA from
using lipase-catalyzed polymerization found possible under its mild condition. Consecutively, this
environmental friendly PLA could be blended with the commercial PLA (pure PLA). This gives
a promising alternative route for creating a new material. PLA of different blend ratios between the PLA
blend films produced from lipase-catalyst and the commercial PLA film showed more flexible and
degradable behavior greater than the only commercial PLA (pure PLA). An increasing of PLA blend
ratios increased the ability of PLA degradation in soil due to more water intake within the structures.
Indefinitely, an optimization of the PLA blending ratio will be needed to improve the quality of PLA
polymer for readily exploitation in the material industry. Nevertheless, the optimal conditions for PLA
degradability will support an explanation for its high capability and short time of the degradation
behavior in soil. Finally, this finding is quite potential as valuable tool for the production of bioplastics
to drive forward recently our new green biomaterials.
Acknowledgements
The research was financially supported by the Departments of Biotechnology, Packaging and
Materials Technology, Faculty of Agro-Industry, Kasetsart University, and Thailand Research Fund
(TRF-MRG545S102 awarded in 2011). Ms.Apinya Boontanimitr, Mr.Sombat Yensodsai and
Ms.Kanyarat Lerlertvanich, from the Department of Packaging and Materials Technology, Kasetsart
University, are grateful for their experiment assistances.
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