Industrial Crops and Products 33 (2011) 648–658

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Industrial Crops and Products

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Degradation behaviour of poly(lactic acid) films and fibres in soil under

Mediterranean field conditions and laboratory simulations testing
E. Rudnik 1 , D. Briassoulis ∗
Department of Agricultural Engineering, Agricultural University of Athens, Iera Odos 75, 11855 Athens, Greece

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

Article history: Long-term degradation/disintegration behaviour, indicative of the biodegradation in soil behaviour of
Received 25 November 2010 poly(lactic acid) films and fibres, was studied in natural Mediterranean soil environment during an
Received in revised form eleven-month trial in the experimental field. In parallel, simulated soil burial experiments were car-
21 December 2010
ried out under controlled laboratory conditions. The degradation/disintegration behaviour of PLA was
Accepted 23 December 2010
analysed using visual inspection, mechanical testing, DSC and FTIR analysis. The influence of the thick-
Available online 22 January 2011
ness and the type of the materials (film vs. fibre) on disintegration was investigated under the given mild
conditions. For comparison purposes, degradation/disintegration of PLA film was also studied under low
Keywords:
Biodegradation
temperature composting conditions (house composting). During long-term exposure under natural soil
Biodegradable materials environment dominated by complex and uncontrolled biotic–abiotic conditions and Mediterranean cli-
Agricultural films matic conditions and under house composting conditions, PLA film samples of different thicknesses were
Poly(lactic acid) partially, to a rather low degree, degraded mechanically or slightly disintegrated. The results showed that
Composting degradation behaviour of bio-based polymers like poly(lactic acid) in a real soil environment is a complex
Biodegradation in soil phenomenon, following different patterns regarding morphological changes.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction Poly(lactic acid) (PLA) is the first polymer based on renewable

Poly(hydroxyalkanoates) (PHAs) and poly(lactic acid) (PLA)
represent two families of biodegradable polymers derived from
renewable resources. Polyhydroxyalkanoates (PHAs) are a fam-
ily of polyhydroxyesters of 3-,4-,5- and 6-hydroxyalkanoic acids,
produced by a variety of bacterial species under nutrient-limiting
conditions with excess of carbon. These water-insoluble storage
polymers are biodegradable in general, exhibit thermoplastic prop-
erties and can be produced from renewable carbon sources (Ishida
et al., 2005; Hazer and Steinbüchel, 2007; Philip et al., 2007; Rudnik,
2008). The main members of the PHA family are the homopolymers
poly(3-hydroxybutyrate) (PHB) and copolymers such as poly(3-
hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Biodegradability
of these polymers in soil has been investigated in several works
(e.g. Pickering and Vansco, 2001; Song et al., 2003; Lim et al., 2005;
Rychter et al., 2006; Corrêa et al., 2008; Kukade et al., 2010). It
appears that biobased plastics made from PHAs are completely
biodegradable in a wide range of environments – including soil –
at the end of useful product life, at various rates.
∗ Corresponding author. Tel.: +30 210 5294011; fax: +30 210 5294023.
E-mail addresses: ewa.rudnik@ichp.pl (E. Rudnik), briassou@aua.gr
(D. Briassoulis).
1
Present address: Industrial Chemistry Research Institute, Rydygiera 8, 01-793
Warsaw, Poland.
raw materials commercialized at a large scale. It is a compostable
material, meeting the specifications of international standards
(CEN, 2000). However, the biodegradation behaviour of PLA in soil
is not clear (Messias de Bragança and Fowler, 2004). There are no
studies available concerning the behaviour of PLA in soil under
Mediterranean climatic conditions.
The primary mechanism of degradation of PLA is hydrolysis,
catalyzed by temperature, followed by bacterial attack on the frag-
mented residues. Many studies concern biodegradation of PLA
in different environments such as aquatic system, solid, com-
post. Some recent reviews are given elsewhere (Rudnik, 2008;
Nampoothiri et al., 2010; Shi and Palfery, 2010). It should be
noteworthy that most publications report biodegradation studies
performed at high temperature, typically about 58 ◦ C. For exam-
ple, Kale et al. (2007) investigated the biodegradation performance
of polylactide (PLA) bottles under simulated composting condi-
tions according to ASTM (ASTM, 2003) and ISO (ISO, 2005, 2007)
standards and in real composting conditions. However, literature
about long-term biodegradation behaviour of PLA in real soil envi-
ronment is scarce and concerns specific, usually tropical or North,
climatic conditions (Ho et al., 1999; Gallet et al., 2001; Urayama
et al., 2002; Shogren et al., 2003; Kamiya et al., 2007). In real soil
environment the temperature usually does not exceed 30 ◦ C. Long-
term behaviour is especially important for agricultural applications
where biodegradable polymers are intended to biodegrade prefer-
ably in soil.

0926-6690/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.indcrop.2010.12.031
 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658
The degradation of PLA films in Costa Rican soil was investigated
by Ho et al. (1999). The average soil temperature and moisture con-
tent were 27 ◦ C and 80%, respectively. The average degradation rate
of PLA films in the soil of banana field was 7675 Mw (average-weight
molecular weight)/week. Films of poly(l-lactide) (PLLA) were
buried in outdoor environment in south Finland during two years
(Gallet et al., 2001). No lactic acid was observed during the first
year of soil burial. Urayama et al. (2002) found only a 20% decrease
in molecular weight of PLA (l-rich) plates after 20 months in soil.
Injection moulded tensile bars composed of native starch (0–70%),
poly(d,l-lactic acid) (95% L) (PLA, 13–100%) and poly(hydroxyester-
ether) (PHEE, 0–27%) were buried in soil for 1 year in order to
study the effects of starch and PHEE on rates of biodegradation
(Shogren et al., 2003). Rates of weight loss increased in the order
pure PLA (0%/year) < starch/PLA (0–15%/year) < starch/PHEE/PLA
(4–50%/year) and increased with increasing starch and PHEE
contents. Studies of the microbial communities responsible for
the decomposition of poly(␧-caprolactone) (PCL), poly(butylene
succinate) (PBS), poly(butylene succinate-co-adipate) (PBSA) and
poly(lactide) (PLA), were performed in two Japanese soils (Kamiya
et al., 2007). The PCL, PBS and PBSA films were considerably
degraded within 50 days at 25 ◦ C under upland dark conditions
in one soil, while the PLA film was not degraded at all after 120
days in soil. In another study (Suyama et al., 1998), no soil bacterial
colonies that degrade PLA were found.
The aim of the present research work was to offer a better under-
standing and enrich the existing knowledge about the long-term
biodegradation in soil behaviour, of PLA films of various thick-
nesses and of PLA fibres, under real Mediterranean soil conditions.
The biodegradation behaviour in the natural complex biotic–abiotic
soil environment was studied by full scale field experiments and
by simulated soil burial experiments under controlled laboratory
conditions. The biodegradation behaviour was studied through
monitoring the evolution of several important degradation sen-
sitive properties along with the disintegration behaviour of the
tested materials, considered as indicators, but not measures, of the
biodegradation process. The results obtained by the full-scale field
experiments were compared against the results obtained through
laboratory simulations of PLA degradation/disintegration in soil
and the results of composting of PLA films under farm conditions.
2. Experimental studies
2.1. Materials
Poly(lactic acid) (PLA) samples in various forms (films with
various thicknesses and fibres) were obtained from commercial
suppliers and used in the experimental studies. According to the
suppliers, these materials were made out of Nature Works PLA
pellets [NatureWorks LLC, http://www.natureworksllc.com/] (no
further information was made available though, for reasons of con-
fidentiality, concerning processing, plasticisers, etc.). Filter paper
(Whatman) and poly(ethylene) (PE) film were used as a positive and
negative reference, respectively. The characteristics of the materi-
als studied are given in Table 1.
Biodegradation under real soil conditions in the field was
determined indirectly through the study of the degradation and
disintegration of the materials, both used as strong indicators (but
not as a quantitative measures) of biodegradation. The approach
used is a normal approach adopted by researchers in this RTD area,
including major producers of agricultural biodegradable films. This
approach is justified based on the fact that the research objec-
tive concerns testing biodegradability under real soil environment
where it is not possible to measure and quantify biodegradation in
the way it is measured in the lab under controlled conditions by
649
standard respirometric testing methods (Briassoulis and Dejean,
2010). The field experimental degradation results were monitored
through systematic sampling, measurements and analysis of sev-
eral key properties of the materials in the lab and confirmed by
simulated soil burial and composting conditions.
2.2. Full-scale field experiments
Biodegradation studies under real Mediterranean field condi-
tions were carried out at the experimental field of the Agricultural
University of Athens in Spata. The latitude of the site is 37◦ 58 49 N,
longitude 23◦ 54 49 E and altitude 119 m. The soil in Spata is clay
loam. The detailed soil characteristics of the field at the experimen-
tal site are given elsewhere (Rudnik and Briassoulis, 2011).
A first set of materials was studied in the experimental field of
AUA in Spata for a period of 11 months, starting from October 2007
till September 2008 (winter–summer period). Samples (size of 1/2
A4 in the case of films and approx. 2 g of mass for fibres) were placed
in envelopes of plastic nets and buried in the soil 10–15 cm beneath
the surface, in a pattern arranged along 11 lines.
During the test period, the weather and soil parameters were
recorded by a data logger (Campbell) with sensors. The following
parameters were monitored and recorded regularly:
• meteorological conditions (air temperature & humidity, total
irradiation, UV irradiation);
• soil conditions (soil temperature and soil water content).
The following two-day irrigation cycle was applied: one day of
irrigation and one day without irrigation. During rain period the
irrigation was interrupted.
Samples were taken off every month, or at appropriately modi-
fied time intervals, depending on the evaluation of the results, and
analysed following the experimental protocol.
2.3. Laboratory simulations set-up
In parallel to field testing, laboratory biodegradation studies
were carried out. The laboratory experiments were performed in
two solid environments: in soil using “bioreactors” and under com-
posting conditions. For the simulated laboratory experiments soil
taken from the experimental field in Spata was used. A flexible
periodicity of samples recovery during laboratory and field experi-
ments was established according to the degradation/disintegration
progress, being continuously monitored.
2.3.1. Laboratory experiments for biodegradation in soil
The degradation/disintegration studies on biodegradation were
carried out in “bioreactors” (4 l plastic boxes containing condi-
tioned soil). Each “bioreactor” contained about 2 kg of soil collected
from the experimental field of AUA in Spata and sieved using 2 mm
size sieve. Studies were performed at room temperature during an
11 month-period and water content was periodically adjusted at
a constant level (40%). Samples (films and fibres) were placed in
envelops of plastic nets and buried in the conditioned soil contain-
ing boxes. Two representative PLA films with thickness 30 ␮m and
75 ␮m were chosen for the laboratory studies (PLA 30 and PLA 75).
Filter paper (Whatman) and polyethylene (PE) film were used as a
positive and negative reference, respectively.
Each “bioreactor” contained 1 sample of a given film in the
form of 1/2 A4 (for tensile testing) and 5 samples in the form of
2 cm × 2 cm pieces (for mass change measurements).
2.3.2. Composting studies
The composting studies were performed outdoors using a com-
post bin of 100 l volume with perforated wall for improved air
650 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658

Table 1
Characteristics of the materials studied for biodegradation in soil.

Material (commercial name) Producer Form Characteristics Abbreviation

used in the
paper

PLA (EarthFirst® PLA)a P1 (Plastic Suppliers Inc.; Sidaplax v.o.f.) Film Thickness: 20 ␮m transparent PLA 20
PLA (EarthFirst® PLA) P1 (Plastic Suppliers Inc.; Sidaplax v.o.f.) Film Thickness: 30 ␮m transparent PLA 30
PLA (EarthFirst® PLA) P1 (Plastic Suppliers Inc.; Sidaplax v.o.f.) Film Thickness: 40 ␮m transparent PLA 40
PLA (EarthFirst® PLA) P1 (Plastic Suppliers Inc.; Sidaplax v.o.f.) Film Thickness: 50 ␮m transparent PLA 50
PLA (EarthFirst® PLA) P1 (Plastic Suppliers Inc.; Sidaplax v.o.f.) Film Thickness: 75 ␮m transparent PLA 75
PLA (NatureWorksTM PLA polymer 2002D) P2 (FOLIETECHNIEK International BV) Film Thickness: approx. 400 ␮m transparent PLA 400
PLA (PLSTD-013NRR-1950) P3 (MiniFIBERS, Inc.) Fibres Length, 19 mm 1.3 denier per filament; white PLA fib
a
Based on IngeoTM resin of NatureWorks® LLC.

circulation. The composting medium was prepared by blending
sheep manure and sawdust in a ratio of 5:1 (w/w). Temperatures
outside and inside the compost bin were monitored, as well as
water content. Initial water content was 52%. The composting pro-
cess was evaluated systematically by Solvita respiration testing
[Solvita, http://solvita.com/]. For composting studies Whatman cel-
lulose paper was chosen as positive reference. PLA film of 30 ␮m
thickness (PLA 30) and PLA fibres (PLA fib), were chosen for com-
posting studies. Film samples of 1/2 A4 size and fibres of approx.
2 g were placed in envelopes of plastic nets and buried in the
composting medium. The period of the composting studies was
11 months.
2.4. Methods of analysis and testing
at a rate of 10 ◦ C min−1 from 20 ◦ C to 200 ◦ C, then was held for 1 min
at 200 ◦ C and cooled at a cooling rate of 10 ◦ C min−1 to 20 ◦ C. The
procedure was repeated twice.
For the polylactic samples (PLA) the glass transition, crystal-
lization, and melting temperatures (Tg , Tc and Tm , respectively),
as well as the enthalpy of fusion (Hf ), the enthalpy of crystal-
lization (Hc ), and crystallinity (Xc ) were determined. Tm and Hf
were determined by the first scan, while Tg and Tc were determined
by the second scan. The repeatability of DSC measurements was
checked for selected samples.
The Xc values were calculated according to the following equa-
tion:
Hc + Hf
Xc (%) = 100 × (1)
93

The degradation/disintegration process in soil was followed
by visual inspection (digital images), as well as by mechanical
properties testing (tensile properties for films) and FTIR analy-
sis. Morphological changes were investigated using the differential
scanning calorimetry (DSC) method.
2.4.1. Mechanical testing
Tensile properties were measured using an Instron 4204 mate-
rials testing machine. Cross-speed rate was 10 mm/min. Five
specimens were tested for each film sample. Samples were con-
ditioned at 23 ◦ C and 50% humidity in a climate chamber for 24 h
before testing.
where Hf is the melting enthalpy, Hc is the crystallization
enthalpy and 93 (J/g) the melting enthalpy of 100% crystalline PLA
sample (Ahmed et al., 2009).
2.4.3. FTIR analysis
A qualitative surface analysis by attenuated total reflectance
(ATR) infrared spectroscopy was carried out using a Bruker Tensor
27 instrument. Resolution: 1 cm−1 , range; 600–4000 cm−1 .
3. Results and discussion
3.1. Meteorological data

2.4.2. DSC method Fig. 1 presents some of the weather data (temperature and rel-
Thermal analysis was carried out using a Perkin Elmer Pyris DSC ative humidity) recorded in Spata during the field experiments for
6 Differential scanning calorimeter. The sample (≈3 mg) was heated the period October 2007–September 2008. Total rainfall ranged

30 80

70
25

60

20
Temperature, oC

50
Humidity, %

15 40

30
10

20

5
10

0 0
Oct Nov Dec Jan Feb Mar Apr May Jun Jul Aug Sep
2007 2007 2007 2008 2008 2008 2008 2008 2008 2008 2008 2008
Temperature Humidity

Fig. 1. Temperature and air humidity data during the period October 2007–September 2008 in Spata (monthly averages).
 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658 651

Fig. 2. Photos of PLA 20 (a), PLA 40 (b), PLA 75 (c) and PLA 400 (d) films during biodegradation studies in the experimental field of AUA (period 1: October 2007–September
2008), at different stages of degradation (left to right: November 2007 1-month, March 2008 3-months, May 2008 7-months and September 2008 11-months).

from 10 mm (February 2008), 8–6 mm (October–December 2007)
to 2 mm (March, April, September 2008) and nearly zero mm (Jan-
uary, May, July, August 2008). Soil water content during the period
May 2007–October 2008 was in the range 34–47% (monthly aver-
ages). Soil temperature measured at 30 cm below soil surface varied
in the range 16–21 ◦ C.
3.2. Field test results
3.2.1. Visual observations
Photos of PLA samples recovered during the biodegradation
studies in the experimental field of AUA in Spata are shown in Fig. 2
for selected PLA 20, PLA 40, PLA 75 and PLA 400 film samples.
During 11 months of burial in soil, fragmentation and disin-
tegration of PLA film samples was observed. The first significant
changes were observed after 7 months. It seems that the increase
in temperature in May 2008 correlates with the onset of fragmen-
tation of the PLA film samples. Then the extent of fragmentation
and disintegration proceeded faster. At the end of 11 months burial
samples disintegration of the materials could be clearly observed
(a strong indication of the associated stage of the biodegradation of
the material process). However, the degree of disintegration of the
material was still rather low. Obviously, thickness influences the
extent of degradation of PLA films. The thinner the films, the more
pronounced changes can be observed, in general.
All PLA films became brittle after 1 month of soil burial. Many
cracks could be seen in the samples of thin PLA films. It is notewor-

Fig. 3. Photo of filter paper after 1 month (a), PE film (b) and PLA fibres (c) after 11 months of soil burial in the experimental field of AUA in Spata, respectively (period 1:
October 2007–September 2008).
652 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658
Fig. 4. Tensile properties after 1 month of burial in Spata: tensile strength for PLA
20 and PLA 50 films (top figure); elongation at break for PLA 20 and PLA 50 films
(bottom figure).
thy that during burial in the real soil environment worms and roots
of plants clearly contributed to degradation (mechanical fragmen-
tation and disintegration) of samples.
Filter paper (cellulose) used as positive reference biodegraded
completely after 1 month of burial (Fig. 3a). On the contrary for the
PE film used as negative control sample no degradation signs were
observed during the field experiments (Fig. 3b). The PE film surface
was not found to be broken even by the activity of plant roots.
Fig. 5. FTIR-ATR spectra of PLA 75 film: initial (top) and after 11 months of soil burial (bottom) in Spata.
As far as the fibres are concerned, no visual changes were
observed (PLA fib), during 11 months soil burial at the experimental
field in Spata (Fig. 3c).
The degree of disintegration of the studied PLA fibres under real
field conditions was shown to be even lower (non-detectable) than
that of the films. This is attributed to the limited contact of PLA
fibres with soil, as they were put in the form of a mass of fibres in
the plastic net envelope. Further, it is known that the thickness and
the form of tested material (i.e. fibres) influences the biodegrada-
tion rate (Yang et al., 2005; Starnecker and Menner, 1996) It has also
been reported that the degradation rate of PLA can be affected by
many factors, including crystallinity (Auras et al., 2004; MacDonald
et al., 1996). Thus, the higher crystallinity of PLA fibres in compari-
son to PLA films (cf. DSC analysis) may also have contributed to the
slow degradation/disintegration process of these materials in the
Mediterranean soil environment.
In a relevant work, Tokiwa and Calabia (2006) explained that
PLA-degrading microorganisms are not widely distributed in the
natural environment and thus, PLA is less susceptible to micro-
bial attack in the natural environment than other microbial and
aliphatic polyesters. Thus, the slow degradation/disintegration rate
of PLA films and fibres in soil observed in the present study
suggests a scarcity of PLA-degrading microorganisms also in the
Mediterranean natural environment as it has been reported already
for tropical and north soil climatic conditions. Another factor
contributing to this behaviour is the relatively low temperature
prevailing in soil under real field conditions in all these climatic
conditions (as compared to industrial composting conditions).
3.2.2. Testing of mechanical properties
After one month burial in the experimental field, PLA film sam-
ples of 30, 40, 75 and 400 ␮m thickness were too brittle and they
were broken when trying to cut specimens as a result of the first
stage of the material degradation. Only for PLA 20 and PLA 50 sam-
ples it was possible to cut specimens for tensile testing and this only
for the early period of soil burial (first month). The results for the
tested PLA films are presented in Fig. 4 (the initial values were found
to be close to those reported for PLA (98% l-lactide) in Auras et al.
(2004)). The tensile properties of both PLA samples with different
thicknesses decreased significantly after a burial period of just one
month. The tensile strength for the PLA 20 film decreased almost
 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658 653

64

62

60

Glass transition Tg,ºC

58

56

54

52

50

48

46
0 1 3 5 7 9 11
Time, months

PLA 20 PLA 30 PLA 40 PLA 50 PLA 75 PLA 400 PLA 30-lab PLA 75-lab

Fig. 6. Glass transition temperatures for PLA films during soil burial in the field in Spata and at laboratory.

to one-third its initial value, from 53.8 to 14.9 MPa, whereas for the
thicker PLA 50 film, the decrease was half the initial value, i.e. from
53.2 to 24.0 MPa. The elongation at break values was decreased dra-
matically for both tested PLA films. This explains the fact that most
PLA film samples were found to be too brittle, after one month of
burial, already with cracks. The tensile properties of the polyethy-
lene film used as negative control were not affected, as expected.
The early drastic decrease of the tensile strength and elonga-
tion at break values of the PLA films exposed to Mediterranean
field soil burial conditions (one month exposure) suggests that,
the first stage of the PLA biodegradation in soil process results in
severe degradation of the mechanical properties of the material (i.e.
embrittlement), leading to gradual slow disintegration of the mate-
rial. Analogous results were obtained with the PLA films exposed
to the laboratory simulated soil burial conditions. The decrease of
the elongation at break was found to be higher than that of the ten-
sile strength in all cases tested under both soil burial conditions.
This confirms similar research results reported earlier under dif-
ferent climatic conditions. Thus, for example, it has been reported
by Maharana et al. (2009) that non-enzymatic hydrolysis of PLA
is preceded by an apparently inert first stage of degradation with-
out weight loss but resulting in random cleavage of polymer chain
backbone (endo-type degradation) with a concomitant substantial
decrease in molecular weight, leading to a decrease in mechanical
properties such as tensile strength and elongation at break.
3.2.3. FTIR-ATR analysis
FTIR-ATR spectroscopy was used to evaluate chemical modifi-
cations occurring on film surface. The FTIR-ATR spectra of PLA 75
before its use and after 11 months burial in the soil under real field
conditions are presented in Fig. 5. The two spectra seem similar.
No shifts of characteristic bands or formation of new bands are
observed. However, the intensity of absorbance at 1748 cm−1 , cor-
responding to carbonyl C = 0 stretching band, decreased after 11
months of soil burial. Similar tendencies are observed in the spec-
tra obtained for PLA film of various thicknesses. After 11 months

168

167

166
Melting temperature, oC

165

164

163

162

161

160

159

158
0 1 3 5 7 9 11
Time, months

PLA 20 PLA 30 PLA 40 PLA 50

PLA 75 PLA fibers PLA 30-lab PLA 75-lab

Fig. 7. Melting temperatures of PLA films and fibres during soil burial in the field in Spata and at laboratory.
654 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658

70

60
Crystallinity, %

50

40

30

20

10

0
0 1 3 5 7 9 11
Time, months
PLA 20 PLA 30 PLA 40 PLA 50 PLA 75 PLA fib

Fig. 8. Crystallinity of PLA films and fibres during soil burial in the field in Spata.

of soil burial the carbonyl index decreased from 3.24 to 2.44 and
from 3.6 to 3.5, respectively for PLA 30 and PLA 75 films. The
carbonyl index was calculated as the ratio of the intensity of the
1748 cm−1 carbonyl peak in the FTIR spectrum to a reference peak
(1451 cm−1 ). These changes, i.e. no significant shifts or formation of
new bands suggest that while slow hydrolysis of ester bonds pro-
ceeds, no degradation by-products were emerged on the surface of
the specimens.

3.2.4. DSC analysis

Morphological changes during degradation/disintegration
under real conditions in the experimental field were determined
by the DSC method. An endothermic event superimposed on the
glass transition Tg was observed during the first heating of PLA film
sample. This endothermic relaxation is considered to result from
secondary molecular re-ordering undergone in the amorphous
phase of semicrystalline polymers (Auras et al., 2003). The second
heating curve showed a glass transition temperature of 57.4 ◦ C
for PLA 30 film. Peak crystallization temperature and melting
temperature for PLA 30 were at 94.2 ◦ C and 163.7 ◦ C, respectively.
DSC curves of all PLA samples were similar except for PLA 400 film
and PLA fibres. PLA 400 film is the thickest film investigated in
this study. It exhibited only strong glass transition at 59.8 ◦ C. PLA
fibres are highly crystalline materials with melting temperature at
163.5 ◦ C.
Changes in characteristic thermal properties, i.e., glass
transitions and melting temperatures during degrada-
tion/disintegradation in soil in the experimental field (and at
laboratory) are given in Figs. 6 and 7.
As far as glass transition temperature is concerned after soil
burial under real soil conditions and laboratory conditions, an
increase generally was observed during the first 3 months then the
glass transition remains almost stable.
As far as the melting temperature is concerned, this also
increased slowly for the first 3 months of soil burial, during the
biodegradation in soil (hydrolysis) process of the PLA films under
Fig. 10. Tensile properties during simulated burial at laboratory: tensile strength
for PLA 30 and PLA 75 films (top figure); elongation at break for PLA 30 and PLA 75
films (bottom figure).
real field conditions, and then stabilized. This behaviour may be
explained by a possible thickening of the PLA crystallites probably
due to a decrease in chain mobility in the amorphous region.
It is noteworthy that the tendencies under real field conditions
are consistent with those observed or measured during the simu-
lated soil burial tests at laboratory (Fig. 6; refer to next section).
Crystallinity changes based on DSC analysis during soil burial
in Spata are given in Fig. 8 for both PLA films and PLA fibres.
Crystallinity of PLA films did not change significantly during degra-
dation/disintegration under real field conditions in Spata (Fig. 8).
Some fluctuations are observed. However, in general, crystallinity
remained at the same level. An exception is noticed with the PLA
fibres for which a clear decrease in crystallinity was observed
(Fig. 8).
Morphological changes observed during soil burial of PLA film
and fibres follow different patterns, reflecting slow degradation in
natural soil environment dominated by complex and uncontrolled

Fig. 9. Photos of PLA 30 (a), PLA 75 (b) and PE film (c) samples after 11 months of soil burial at the laboratory.
 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658 655

45

40

35

Temperature,ºC
30

25

20

15

10

0
1 3 5 7 9 11 13 15 17 19 21 23 25 27 29 31 33 35 37 39 41 43 45 47 49
Time, days
Temperature outside Temperature inside 1 Temperature inside 2

Fig. 11. Temperature profile during composting.

biotic–abiotic conditions and mild Mediterranean climatic condi-
tions. For north climatic conditions, it was observed by Gallet et al.
(2001) that thermal properties of PLA films (glass transition and
melting temperatures) were affected only during the second year
of soil burial in south Finland. This behaviour may be explained by
the phenomenon observed by Shi and Palfery (2010) that when the
degrading temperature is below PLA glass transition temperature,
sample degradation is slowed.
3.3. Laboratory test results
Photos of samples taken during biodegradation under simulated
soil burial conditions are given in Fig. 9. First changes for filter
paper (cellulose) used as positive reference were seen already after
1 month. Some small fragments remained in the soil. After 3 months
of soil burial at the laboratory cellulose disintegrated completely.
On the contrary PLA 30 and PLA 75 films were not disintegrated
after 11 months of burial. However, the PLA films become brittle as
in the case of the field experiments and creased with some cracks
indicating initiation of mechanical degradation (hydrolysis stage)
of the material. Similarly, small samples (size 2 cm2 ) destined to
determine mass loss remained optically unchanged. No mass loss
was observed for PLA films during the soil burial trial at the labora-
tory. No visible degradation traces were seen for the studied fibres
either. Obviously, PE film used as negative reference did not change
at all.
Fig. 10 shows the effects of burial time on the mechanical
properties of PLA 30 and PLA 75 films. Both, tensile strength and
elongation at break decreased during soil burial. For PLA 30 film
the tensile strength decreased up to 1/3 the initial value (16.1 MPa)
after 7 months, while the tensile strength of the thicker PLA 75
sample decreased to a smaller extent, i.e. up to 5/6 the initial value
(48.4 MPa), exhibiting a large variability during its burial in soil
period. The elongation at break of the PLA samples suffered a more

Fig. 12. Tensile properties changes during composting for PLA 30 film.
656 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658
Fig. 13. Photos of cellulose (positive control) (a; 1, 3, 7 weeks) and PLA 30 (b; 3 weeks, 8, and 11 months) during composting studies.
drastic reduction, a behaviour analogous to the one observed with
the samples exposed under real field conditions. From the begin-
ning of the laboratory simulated soil burial the values of elongation
at break of both PLA films decreased dramatically. After 1 month
of burial the elongation at break decreased already from 17.5%
down to 1.3% and from 3.5% down to 1.8%, for PLA 30 and PLA 75,
respectively. For the thinner PLA 30 film the effect of soil burial
on the degradation, measured by the tensile properties, is more
pronounced as compared with thicker PLA 75 film. The tensile prop-
erties of the PE film were not affected during the simulated soil
burial laboratory experiments. It is noteworthy that after 7 months
simulated burial under laboratory conditions PLA samples were
too brittle to determine mechanical properties. It was difficult to
cut the specimens for mechanical testing. In general, PLA samples
buried in soil under real field conditions degraded faster than those
tested under laboratory conditions. This is indicated by the faster
decrease of the elongation at break values of most PLA films buried
in the field under Mediterranean conditions that become too brittle
to cut specimens even after only one month of burial. This explains
also the higher degree of disintegration observed for the samples
exposed under real filed conditions as compared to the samples
exposed to the simulated laboratory conditions.
The measurement of biodegradation through the BOD based
respirometric method confirmed that the tested PLA materials were
almost not degraded at 30 ◦ C after 20 days of incubation (Rudnik
and Briassoulis, 2011). Biodegradation of PLA films and fibres was
at a rather low level of about 10%. Further, PLA fibres degraded more
slowly in comparison with PLA films.
3.4. Composting studies results
Composting refers to a biodegradation process of a mixture of
organic substrates carried out by a microbial community composed
of various populations in aerobic conditions and in solid phase
(Rudnik, 2008; Diaz et al., 2007). The exothermic process produces
energy in the form of heat, which results in an increase of the tem-
perature in the mass. Composting process proceeds in three phases
(Rudnik, 2008; Diaz et al., 2007):
1. Mesophilic phase.
2. Thermophilic phase.
3. Cooling (called second mesophilic phase) and maturation phase.
The highest temperature is reached during the thermophilic
phase (35–65 ◦ C), when thermophilic bacteria and fungi take over,
and the degradation rate of the waste increases. After the easily
degradable carbon sources have been consumed, the compost starts
to cool. After cooling, the compost is stable. Mesophilic bacteria and
fungi reappear, and the maturation phase follows.
Temperature profiles, i.e. temperature outside as well as tem-
perature inside the compost bin (2 sensors) measured during
biodegradation of PLA 30 films under home/farm type Mediter-
ranean composting conditions in the present study are shown
in Fig. 11 (daily averages). Water content was in the range
45–60%. The highest temperature was recorded during the
first week of composting then the second mesophilic phase
proceeded.
Solvita respirometric tests confirmed the temperature profile
of the compost medium. Solvita compost maturity test index at the
beginning of the experiments was 3, indicating active compost with
the fresh ingredients. After 7 weeks of composting the condition of
the compost changed and the compost was moving past the active
phases of the decomposition and was ready for curing (value of
Solvita maturity index increased to 5).
The tensile properties of PLA 30 film samples taken during vari-
ous composting phases are presented in Fig. 12. The tensile strength
of the PLA 30 film did not change significantly during 7 weeks of
composting except during the last week when the tensile strength
reduced to 2/3 the initial value. However, a major decrease in elon-
gation at break, down to 1/8 the initial value, was observed already
after 1 week of composting. Then the low elongation at break value
reaches a plateau.
The exposure of the PLA films to home composting conditions
revealed that the elongation at break values decrease drastically
and abruptly already after 1 week of exposure, while the tensile
strength values decrease gradually and only after one month of
exposure. It is noteworthy that the high sensitivity of the elon-
gation at break property follows the same pattern under both
Mediterranean soil and composting environments, with a dras-
tic reduction of the elongation at break during the early stage of
biodegradation. It appears that during the first stage, the prelimi-
nary steps of the hydrolysis mechanism induce degradation of the
mechanical properties of the material leading to serious embrit-
 E. Rudnik, D. Briassoulis / Industrial Crops and Products 33 (2011) 648–658
tlement under both, soil and composting conditions. This early
embrittlement phenomenon, affecting predominantly the elonga-
tion at break value, has also been observed and reported for several
biodegradable materials exposed to open field conditions during
their useful life-time, through monitoring of the evolution of their
mechanical properties before their burial in soil (i.e. degradation
under UV radiation, etc.) (Briassoulis, 2006, 2007).
Photos taken during composting are shown in Fig. 13. First
changes due to degradation can be observed for filter paper (cellu-
lose) already after 1 week of composting. Then degradation process
of cellulose proceeds. After 3 weeks a few small fragments of cel-
lulose remained and after 7 weeks the cellulose is disintegrated
completely. However, PLA 30 film was not disintegrated during the
composting experiments.
The rather low degree of disintegration of PLA films was
also observed under the composting conditions. This may be
explained by the fact that the performed composting stud-
ies reflect conditions usually achieved for gardening and house
or farm composting. These conditions are closer to those of
soil burial rather than to industrial composting (Briassoulis
et al., 2010). PLA is a material compostable at industrial com-
posting facilities, but will not disintegrate sufficiently fast in
domestic composting piles since the minimum required condi-
tions are typically not met (Messias de Bragança and Fowler,
2004; Kale et al., 2007). This is verified now under Mediter-
ranean farm composting conditions as well. The temperature
achievable under industrial composting conditions is about
65 ◦ C.
4. Conclusions
The soil burial tests show that the degradation of PLA in soil
environment under Mediterranean real field conditions is slow and
that it takes a long time for the material disintegration to start, even
though degradation of the mechanical properties appears to start
earlier. Laboratory simulated soil burial results were found to be
consistent with those obtained under real field conditions in the
experimental field.
Besides, thickness and also form of material was shown to play
a crucial role in the biodegradation process under soil burial and
home composting conditions (i.e. surface area of material exposed
to soil or composting medium; film vs. fibres; single specimens vs.
mass of material).
The results showed that degradation behaviour of bio-based
polymers like poly(lactic acid) in a real soil environment is a
complex phenomenon, following different patterns regarding mor-
phological changes.
In general, during long-term biodegradation under Mediter-
ranean natural soil environment and home composting conditions
PLA of different thicknesses became brittle very early during their
exposure, while they were partially degraded mechanically and dis-
integrated to a low degree at the end of 11 months trials. These
materials need a much longer time and/or higher temperatures for
a complete biodegradation to be achieved, taking into account that
composting of PLA at industrial facilities proceeds at higher temper-
ature (usually at 60 ◦ C during thermophilic phase). It is noteworthy
that during soil burial under real conditions in the experimental
field the air and the soil temperatures never exceeded 40 ◦ C and
21 ◦ C, respectively. Taking into account that the field studies were
carried under the favourable conditions of the warm Mediterranean
climate of Greece, higher temperatures under real conditions may
not be realistically achievable, and so PLA materials, regardless of
the form, need longer time to biodegrade under Mediterranean
conditions.
657
Acknowledgments
The work has been carried out under the project BIODESOPO
funded by the European Commission (Marie Curie Fellowship of
Dr. Ewa Rudnik).
Dr. Ewa Rudnik expresses her thanks to Mr. D. Giannopoulos for
his help during experiments.
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