J Polym Environ (2018) 26:330–341
DOI 10.1007/s10924-017-0951-3
ORIGINAL PAPER
Biodegradation in Soil of PLA/PBAT Blends Compatibilized
with Chain Extender
Paula Alessandra Palsikowski1 · Caroline N. Kuchnier1 · Ivanei F. Pinheiro1 ·
Ana Rita Morales1 
Published online: 7 February 2017
© Springer Science+Business Media New York 2017
Abstract  This paper presents a study of biodegradation,
in soil, of samples of poly(butylene adipate-co-terephtha-
late)(PBAT), poly(lactic acid) (PLA) and blends of these
materials prepared in torque rheometer with the addition
of a chain extender. Film samples of these materials were
buried in soil under controlled laboratory conditions. The
degraded samples were regularly taken from soil and ana-
lyzed by visual inspection, size exclusion chromatography,
differential scanning calorimetry and infrared spectros-
copy. Respirometry biodegradation tests were conducted
to assess samples mineralization degree. Blends showed
higher degree of crystallinity compared to pure polymers.
Crystallinity degree enhanced during the biodegradation
process in all samples, being able to causing the samples to
degrade slowly. The study showed the great complexity of
the biodegradation process of PLA and PBAT blends when
compatibilized with a chain extender. The biodegradation
rate showed different results depending on the characteris-
tic applied to evaluate it: visual, molecular weight or miner-
alization. The chain extender had strong influence in PBAT
and blends degradation, slowing the process as observed
by the variation of molecular weight and carbonyl index.
Blends showed an intermediate behavior compared to the
original polymers.
Keywords  Poly(lactic acid) · Poly(butylene adipate-
co-terephthalate) · Biodegradation · Soil biodegradation ·
Compatibilized blends
* Ana Rita Morales
morales@feq.unicamp.br
1
School of Chemical Engineering, State University
of Campinas (UNICAMP), Av. Albert Einstein 500,
Campinas, SP 13083‑852, Brazil
13
Vol:.(1234567890)
Introduction
Increased production and consumption of plastic materials
has a direct effect on waste disposal causing a considerable
concern about the environmental impacts of the polymeric
materials, which has led researchers to search alternatives
in the biodegradable materials field [1–5]. Besides biode-
gradable polymers presents potential for many different
applications including medical such tissue engineering,
drugs delivery, orthopedic devices or packaging applica-
tions. However most of these materials have some lack
of properties that are object of study to be overcome by
modification as blends or composites [6]. One of the most
studied material is the poly(lactic acid) (PLA), which is an
aliphatic polyester that can be synthesized from renewable
resources. PLA is brittle and presents low susceptibility to
microbial attack on natural environment. Its degradation is
highly dependent on environmental conditions due to its
high glass transition temperature (­ Tg) [7, 8]. The T
­ g of PLA
is above room temperature, which limits composting condi-
tions biodegradation, therefore soil degradation is very low
[1, 7].
PLA has been widely used in packaging, nevertheless its
application could be extended with mechanical properties
optimization aiming to brittleness reduction and improvement
of soil degradation susceptibility. Blends with poly(butylene
adipate-co-terephthalate) (PBAT) have been extensively
studied with purpose of producing materials with both PLA
and PBAT advantageous properties [2, 8–18]. PBAT is an
aliphatic–aromatic biodegradable polyester produced from
fossil sources [19]. The aromatic fraction provides excel-
lent physical properties whereas aliphatic chains promote its
degradation in several conditions, including soil degradation
without the need of temperature control [19, 20]. PBAT can
modify PLA fragile properties, although it was reported to be
J Polym Environ (2018) 26:330–341 331
incompatible with PLA [11]. Many studies aimed at improv-
ing compatibility between these materials, by functional
groups chemical reaction like in-situ compatibilization using
dicumyl peroxide as a free-radical initiator [2, 21, 22] or
using a chain extender with multifunctional groups that can
react with both carboxyl and hydroxyl groups during the pro-
cessing of PLA and PBAT [9–11, 16, 18, 23, 24]. Multifunc-
tional chain extenders are thermally stable substances that
promote increase in molecular weight by generation of long
linear or branched chains. Their action is dependent on poly-
mers chains scission that occurs during processing, which
generates reactive groups [25]. The most common chain
extender, Joncryl® ADR-4368, has epoxy groups capable of
reacting with the OH and COOH and promote the recovery
of recycled polymer properties like poly(ethylene terefhtha-
late) (PET) [25–28].
PLA degradation has been widely studied as pristine
polymer [1, 7, 29–31] and, recently, as modified polymer
[19, 32–38]. The mechanical properties of PLA/PBAT
blends were reported in many works were the brittle prop-
erties of PLA could be modified by the addition of PBAT
probably related to the presence of a soft elastomeric phase
and the compatibilization effect of the Joncryl ® ADR-
4368 [39]. The elongation at break of the PLA/PBAT
blends was reported to increased with the incorporation
of Joncryl® ADR-4368 more than 100% which was asso-
ciated to formation of ester linkages between PLA, PBAT,
and Joncryl® ADR-4368 at the interface of the polymers.
Blown films prepared from similar systems showed a sig-
nificant improvement in the ductility as a combination of
interfacial tension and blends viscosity ratio that resulted
in a finer and homogeneous morphology [10]. The studies
show that amounts from 0.25 up to 1% of Joncryl® ADR-
4368 are enough to promote improvement of general prop-
erties. Thus the addition close to 1% of chain extender Jon-
cryl® ADR-4368 was used in this work, as it has shown
an improvement on the thermal stability and mechanical
properties of PLA and PBAT [11, 42]. Even though PLA/
PBAT blends have been, extensively studied, lacking has
been reported about soil biodegradation and those studies
were limited for non-compatibilized blends [41, 42], or car-
ried out in alkaline solution [23].
The complexity of the biodegradation process motivated
this work, which objective was the study of the biodegra-
dation process of PLA/PBAT blends compatibilized with a
chain extender in the soil under laboratory conditions.
Materials and Methods
Materials
The materials used were:
PLA Ingeo 4042D, density 1.24  g/cm3, average molec-
ular weight (Mw ) 201,000  g/mol and number-average
molecular weight (Mn) 101,000 g/mol from Natureworks;
PBAT Ecoflex® F BX 7011, density 1.25  g/cm3, Mw
105,000 g/mol and Mn 47,000 g/mol, from BASF and ;
Multifunctional chain extender Joncryl ® ADR-4368,
density 1.08 g/mL, Mw 6,800 g/mol and equivalent weight
of functional epoxy groups of 285 g/mol, from BASF.
Sample Preparation
The polymers pellets were dried in an oven at constant
temperature (PLA 80 °C for 4  h and PBAT 70 °C for 40
min). Samples were blended in the proportions: 100%PLA
(PLA), 75%PLA/25%PBAT (75/25), 25%PLA/75%PBAT
(25/75) and 100%PBAT (PBAT), all added with 1 part of
chain extender per hundred parts of resin (1 phr) and pro-
cessed in a torque rheometer HAAKE Rheomix 600P with
a rotation speed of 120 rpm for 5 min at 180 °C. Samples
were pressed in a hydraulic press LP20-B from Labtech
Engineering Co. Ltd. The molten polymers were molded
at constant pressure of 800 psi at 120 °C (PBAT), 160 °C
(PLA) and 150 °C (blends) for 1 min. Then, samples were
cooled at room temperature, obtaining films with thick-
ness of approximately 0.3 mm. All conditions were applied
based on a previous work [43].
Evaluation of Soil Biodegradability
Although the most usual studies for the biodegradation
for PLA are done under composting conditions, our work
aim to evaluate the behavior of the blends in soil, since
the PBAT was supposed to bring to the system the char-
acteristic of high disintegration rate in soil conditions. The
biodegradation process of pure polymers and blends was
analyzed in three ways: visual analysis, molecular weight
monitoring and carbon mineralization.
Soil Preparation
The soil preparation followed the ASTM D5988-12,
which is the standard for determining aerobic biodegrada-
tion of plastic materials in soil. A mixture of soil aliquots
collected into three different regions was used to ensure
microbial biodiversity. The mixed soil was dried for 72 h at
room temperature (25  ±  2 °C) and then sieved in order to
obtain particle sizes smaller than 2 mm. The soil was char-
acterized and adjusted to fit the tests according to specific
methodologies related with their characteristics shown in
Table 1.
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332 J Polym Environ (2018) 26:330–341

Visual Analysis and Monitoring of Molecular Weight was constructed with polystyrene with molecular weight in
a range of 1.1 kDa and 3.8 MDa.
Samples were degraded as described by ASTM D5988-
12. Soil moisture was adjusted and maintained at 60% of Respirometry Test
its retention capacity, maximum amount of water that the
soil can retain after the excess has been drained, accord- The respirometry test was performed according to ASTM
ing ASTM D5988-12. Eight square samples of 3  cm x D5988-12 standard adapted according to the methodology
3 cm and thickness around 0.3 mm were subjected to soil proposed by Anderson [44]. Films were subjected to ele-
degradation in a closed container maintained at room tem- mental analysis to determine carbon amount (mg/100  mg
perature (25  ±  2 °C). The container base was covered with sample) from the stoichiometry of carbon reaction (C)
soil (approximately 1.5  cm); samples of each material (Eq. 1) 12 g of C produced 44 g of carbon dioxide ­(CO2).
were placed on this layer being subsequently covered with
approximately 6 cm of soil. Every 30 days, one sample of
C + O2 → CO2 (1)
each material was taken for visual appearance evaluation Thus:
and buried again.
44 ∗ Y
During this period, one fragment of each material was MtCO2 (mg) = (2)
removed for monitoring of the molecular weight by Size 12
Exclusion Chromatography (SEC). In this analysis, the where MtCO2: ­CO2 theoretical mass. Y is the amount of C
samples were solubilized in THF stabilized with BHT (mg) in the sample.
(2,6-Di-tert-butyl-4-methylphenol), concentration of The actual amount of ­CO2 produced (mg) is given by
250 ppm, 99.9%, Scharlau, HPLC degree with 5 mg/mL of Eq. (3).
concentration. It was used three columns in series (Shodex,
KF-806M); all are filled with a copolymer of styrene and
MpCO2 (mg) = (Vcn − Vam) ∗ 22 ∗ 0.5 (3)
vinyl benzene, with exclusion band from ­103 to ­106. Ana- where MpCO2: mass of ­CO2 produced (mg). Vcn is the
lyzes were performed by a chromatograph Viscotek model volume of HCl 0.5  N used in the titration of the negative
GPC Max, using refractive index detector model VE3580 control flask; Vam is the volume of HCl 0.5 N used in the
at 40 °C under a flow of 1 mL/min. The calibration curve titration of the sample flask; 22: Equivalent gram of C ­ O2;
0.5: Normality of HCl.
Portions of 200 g of dried soil were placed in glass flasks
with sealing caps. The films, in duplicate, were weighed
Table 1  Soil characteristics and buried in the soil portions. Two flasks containing only
Tests Parametermethodology Results soil as blank samples and other two flasks containing soil
and cellulose were used as positive control. Deionized
Visual analysis, monitor- Moisture (%)a 41 water was added to each flask so that the moisture was 60%
ing of molecular weight Retention capacity (HC) (%)a 75 of the soil retention capacity (36% moisture). Into each
Moisture test (%) 45 flask a beaker with 20.0 mL of NaOH 0.5 N was placed to
pHb 7.3 capture the C ­ O2 and a beaker with 50 mL distilled water
Organic matter (g/dm3)b 72 was placed in order to keep the moisture. It is important
Organic carbon (g/dm3)3 40 to mention that the presence of the water does not inter-
Nitrogen (g/kg)b 2.7 fere in the capture of the ­CO2, since the reaction between
C/N Ratio 14.8 ­CO2 and H ­ 2O generates H­ 2CO3 which converts again to
Mineralization test Moisture (%)a 4.7 ­CO2 and ­H2O. The flasks were opened, the beaker with
Retention capacity (HC) (%)a 60 NaOH was removed, and 1.0  mL of saturated solution of
Moisture test (%) 36 barium chloride ­(BaCl2) was added to cause the carbonate
pHb 6.3 precipitation. The solution of NaOH 0.5 N was then titrated
Organic matter (g/dm3)b 45 with HCl 0.5 N in order to obtain the ­CO2 captured by the
Organic carbon (g/dm3)c 25 NaOH solution. After titration, a beaker with the same vol-
Nitrogen (g/kg)c 1.5 ume of NaOH 0.5 N freshly prepared was added for another
C/N Ratio 16.7 degradation period. Beakers containing distilled water were
a
 Casado (2009) replaced by fresh distilled water at every titration. In the
b
 methodologies described by the Ministry of Agriculture, Livestock first 30 days, these evaluations were made twice a week,
and Supply (MAPA, 2007) and then once a week for the last 90 days. This experiment
c
 Kiehl (1985) was performed in duplicate.

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J Polym Environ (2018) 26:330–341 333
The mineralization (amount of polymer C converted
in ­CO2) of the formulations was calculated according to
Eq. (4).
MpCO2
Mineralization (%) = (4)
MtCo2
where ­MpCO2CO2 mass produced (mg), ­ MtCO2 = Total
theoretical ­CO2 mass (mg).
Mineralization tests were performed with PLA, PBAT
and the 25/75 and 75/25 blends, all with chain extender
addition. To evaluate the soil activity, ASTM D5988-12
recommends the use of a biodegradable material as refer-
ence to evaluate soil activity; cellulose was used in this
work. The average amount of released C ­ O2 was monitored
as a function of time, and two replicates were performed
for each material.
Samples Characterization
Fourier Transform Infrared Spectrometer Analysis (FTIR)
Identification of functional groups in the chemical struc-
tures of the materials was carried out by Fourier Transform
Infrared Spectrometer Analysis (FTIR), using a Thermo
Nicolet spectrometer, model Nexus 470, Thermo Scientific.
One sample of each material was analyzed from 4000 to
675 cm−1 with resolution of 4 cm−1. These analyzes were
performed before and after 360 days of degradation.
Differential Scanning Calorimetry Analysis (DSC)
To evaluate the thermal transitions of samples and the
degree of crystallinity, Differential Scanning Calorimetry
Analysis (DSC) was performed on a DSC-2920 Modulated
DCS equipment, TA Instruments, under N ­ 2(g) flow of 100
mL/min. According to ASTM D3418-12 standard, the steps
performed were: heating from room temperature to 200 °C,
10 °C/min, isotherm for 5 min at 200 °C; cooling from 200
to −80 °C, 10 °C/min, isotherm for 5 min at −80 °C; heat-
ing from −80 to 200 °C, 10 °C/min. As biodegradation ini-
tiates, changes in the material crystallinity can occur, so
these analyzes were performed before and after 360 days of
degradation, one sample of each material.
X‑Ray Diffraction (XRD)
Crystallinity was also analyzed by X-Ray Diffraction
(XRD) using a diffractometer model X’Pert-MPD, Philips
Analytical X Ray, scanning range from 5° to 35° (2ϴ), Ka
radiation of Cu (λ  = 1.54  Å), 40  kV, 40  mA, 0.02° step,
0.02º/s, at room temperature. Crystallinity was calculated
as the ratio between the crystalline area (peaks) and amor-
phous halo, by Eq. (5):
Ic
%C = × 100 (5)
Ic + Ia
where %C is the crystalline fraction. Ic is the diffraction
peaks area. Ia is the amorphous halo area.
Fityk 0.8.0, an open-source curve-fitting and data anal-
ysis software (distributed under the terms of GNU Gen-
eral Public License), was used to obtain the area of the
amorphous halo and of the crystalline peaks.
Results and Discussion
Visual Analysis
Changes in samples appearance related to different degra-
dation times are shown in Fig. 1. Samples were gradually
degrading over time when buried in soil. Biodegradation
under laboratory conditions are not as aggressive as the
actual conditions, especially in terms of temperature. Even
in milder cases, microbiological attack on samples was
apparent, presenting yellowing and dark brown spots on
the surface of the films. Although the non-compatibilized
blends are not interesting for not presenting satisfactory
mechanical properties, a shorter assessment of these sys-
tems was chosen, 30 days, in order to understand the partial
results, especially related to PBAT with chain extender that
did not show any signs of degradation. It was observed that
pristine PBAT became very fragile and brittle, leaving only
fragments after 30 days of degradation, preventing continu-
ity of visual and molecular weight analysis. Changes were
not visually observed in samples of PLA and 75/25 blend
after 30 days of degradation, whereas 25/75 blend had some
yellow spots. For materials modified with chain extender
we observed, after 120 days, minor yellow spots on the
PBAT film surface, which had the first break after 180
days; after 270 days it was already too brittle and after 360
days only small dark fragments were left. The PLA sample
presented cracks after 270 days and breaks after 360 days.
By visual analyses, PLA showed to be much less degrada-
ble than samples containing PBAT. The higher resistance
to biodegradation of PLA in soil has been already reported
and is assumed to be due to its glass transition temperature
­(Tg), around 60 °C [1]. Blend samples showed intermediate
behavior compared to pure materials. First, blends showed
yellowing followed by some deformations, and then breaks
after 180 days. The blend with higher amount of PBAT
was less resistant to degradation. These results indicate the
influence of chain extender, delaying the PBAT degradation
process that when pure, presented very high degradation
rate, consistent with other studies [42].
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334 J Polym Environ (2018) 26:330–341

Fig. 1  Visual aspect of the

samples during degradation in
soil

Monitoring of Molecular Weight
SEC analysis were performed before and after 60, 120 and
180, 240, 300 and 360 days of degradation, for samples
containing chain extender and after 30 days of degrada-
tion for samples without chain extender. Results for number
average molecular weight (Mn), weight average molecu-
lar weight (Mw) and polydispersity (PDI) are shown in
Table 2.
The hydrolysis process was evaluated considering Mw
because it is less affected by low molecular weight than
Mn [23]. Figure  2 shows the Mw results. Generally, there
was a decrease in average molecular weight over the deg-
radation time indicating the occurrence of chain scission.
Mw values of samples without chain extender are also pre-
sented. Initially (t = 0 days) it was observed that the molec-
ular weight of PLA was much smaller than the molecu-
lar weight of PLA with Joncryl® ADR-4368, which was
expected since the epoxide groups of the extender are very
reactive with the carboxyl and hydroxyl groups of PLA,
increasing the size of chains. However, Joncryl® ADR-
4368 was less effective in the blends and did not alters to
much the PBAT molecular weight, a result also reported
[43]. However, comparing Mw of PBAT with and without
the chain extender, it is noted that the chain extender influ-
enced PBAT degradation process.
For a better understanding of the biodegradation behav-
ior, we can see in Fig. 2b the Mw on percentage as a func-
tion of degradation time in which it is evident the influ-
ence of chain extender on the materials degradation. It was
observed that there was initially a small reduction on PBAT
Mw and that after 180 days the Mw increased. Such behav-
ior indicates that the epoxide groups of the chain extender
are reacting with the groups that are originated during
PBAT degradation process, increasing Mw. Although
PBAT degradation visually occurs, the results indicate a

Table 2  Data obtained by Sample Days 0 60 120 180 240 300 360 Sample 0 30
SEC analysis for different
degradation times PLA w/Joncryl® Mn—(KDa) 126 147 149 149 107 105 109 PLA 64 62
Mw—(KDa) 449 349 312 312 239 239 244 113 107
PDI 3.6 2.4 2.1 2.1 2.2 2.3 2.2 1.8 1.7
75/25 w/Joncryl® Mn—(KDa) 36 35 23 33 23 20 20 75/25 17 13
Mw—(KDa) 196 148 142 139 151 129 133 91 82
PDI 5.5 4.2 6.1 4.2 6.7 6.3 6.8 5.4 6.2
25/75 w/Joncryl® Mn—(KDa) 21 20 21 21 14 14 13 25/75 13 13
Mw—(KDa) 86 79 84 74 58 63 53 45 33
PDI 4.2 3.8 4.0 3.6 4.2 4.5 4.1 3.5 2.6
PBAT w/Joncryl® Mn—(KDa) 19 17 17 18 13 13 11 PBAT 23 18
Mw—(KDa) 44 43 45 42 56 46 29 51 29
PDI 2.3 2.5 2.6 2.3 4.4 3.5 2.5 2.2 2.1

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J Polym Environ (2018) 26:330–341 335

Fig.  2  a Weight average molecular weight (Mw) and b Relative molecular weight (Mw) as a function of degradation time

competitive effect: chains scission reduces the molecular
weight and creates functional groups, which react with the
chain extender, increasing the molecular weight and slow-
ing the process.
A degradation parameter k can be considered to evaluate
the chain scission as described by the Eq. (6) [7], where Mn
BD refers to the material before degradation and MnAD after
degradation. The results were shown in Table 3.
MnBD
k=
MnAD
Signori et  al. [8] reported the high stability of PBAT
upon processing. This behavior was also observed by Al-
Itry et  al. for the effect of the processing temperature on
the thermal stability for the same system studied here [11].
They showed k = 1.01 for PBAT processed at 180 °C. Using
the k factor for the degradation process we can observe
k = 1.28 for 30 days of buring. It means that the chains scis-
sions are very pronounced during the biodegradation even
at room temperature. As the Joncryl® acts on the OH and
COOH groups resulted of the biodegradation process, there
will be much more available points to react than during
the processing as can see by the k value of 1.12 for sam-
ples with Joncryl® after 60 days of buring. The difference
between SEC and visual results may be due to mainly deg-
radation of PBAT surface by the action of enzymes. Small
chain segments are consumed by microorganisms in soil,
not being measured by SEC analysis. Although the chain
extender has initially increased PLA molecular weight, it
did not slow the PLA degradation. The degradation behav-
ior of 25/75 blend with chain extender was very similar to
the PBAT with chain extender until the 120th day of deg-
radation, both in terms of Mw and visual characteristics.
Continuing the degradation process, the blend showed
behavior more similar to PLA with chain extender, with
Mw reduced at a greater rate between the 120th and the
(6) 240th day of degradation. This result may be associated
with material morphology. According to a previous study
[43] the 25/75 blend presents a PLA dispersed phase in the
PBAT matrix. The PBAT surfaces are available for the ini-
tial degradation and the blend behavior is similar to PBAT
degradation. Over degradation time, PBAT chains are bro-
ken and released to the medium and/or consumed by the
microorganisms, leaving the PLA rich phase more exposed
to the soil showing a behavior similar to PLA degradation.
The chain extender influenced the degradation of this blend
in the same way as PBAT. On the other hand, 75/25 blend
with chain extender showed initial degradation behavior
similar to PLA with chain extender addition; however, after
180 days this blend had an increase in Mw, most likely due
to chain extender action in PBAT phase. The initial deg-
radation behavior in the blends was similar to the matrix;
when the surface of the domains started to be exposed due

Table 3  K factor for the Sample /days 0 60 120 180 240 300 360 0 30
degradation process calculated
from the GPC data PLA w/Joncryl ® 1.00 0.86 0.85 0.85 1.18 1.20 1.15 PLA 1 1.03
75/25 w/Joncryl ® 1.00 1.02 1.57 1.09 1.58 1.77 1.83 75/25 1 1.29
25/75 w/Joncryl ® 1.00 1.01 0.98 0.99 1.49 1.45 1.62 25/75 1 1.00
PBAT w/Joncryl ® 1.00 1.10 1.10 1.03 1.49 1.46 1.67 PBAT 1 2.70

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336
to degradation, the behavior of the dispersed phase mate-
rial was observed. Other studies on the chain extender
effect and the PBAT presence in the PLA degradation in
alkaline solution at 60 °C showed that PLA hydrolysis was
little affected [23], differently from what was observed in
this study, indicating that the degradation process of these
blends is very sensitive to the adopted conditions.
Mineralization
Figure  3 shows the results of the biodegradation test by
mineralization of carbon. The amount of ­ CO2 released
from the cellulose (positive control) during biodegradation
increased rapidly in the first 20 days at a rate of 2.72 mg/
day, reaching approximately 20% mineralization in 30 days.
After that, the mineralization rate decreased. It can be seen
that cellulose has reached about 52% mineralization within
180 days, which, according to ASTM D5988-12 standard,
does not validate the test, since 70% of the carbon mate-
rial should be converted into ­CO2 after 180 test days. Since
microbiological activity in soil interferes with the degrada-
tion rate [45], this result indicates that the soil could have
low amounts of decomposing microorganisms. This is con-
sistent with previous studies of PLA and PBAT having cel-
lulose as positive control in two types of soil, a sterilized
and an inoculated with fungi; the latter had high biological
activity [46].
The mineralization rate of carbon for PLA was about
0.17  mg/day, reaching a percentage of mineralization of
approximately 16% in 180 days; results comparable to
those were reported a mineralization rate of 0.24  mg/day
and mineralization of 17% after 182 days [47]. In the first
days of the experiment, there was a very little release of
­CO2. This delay corresponds to the hydrolysis step of the
Fig. 3  Mineralization test of material tests and cellulose as the
ASTM D5988-12 at 28° C
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J Polym Environ (2018) 26:330–341
long chains that is required for subsequent mineralization
[46]. After 20 days of mineralization PLA reached less
than 2% of mineralization. PLA embrittlement occurs when
the molecular weight reaches a value close to 10–20 kDa,
which is a critical value for microorganisms continue the
degradation process, converting low molecular weight
components into metabolites [49, 55, 56]. Table  2 shows
that the average PLA molecular weight, even after 360 days
of degradation, is clearly above this value; however, dur-
ing the degradation few PLA chains on the material surface
can be broken releasing small segments to be consumed by
microorganisms.
PBAT had the highest degree of mineralization, reach-
ing approximately 9% after 60 days of degradation and
21% after 180 days, comparable with other studies [46].
The mineralization rate was 0.23  mg/day, being greater
in the first 60 days of testing. PBAT undergoes hydrolytic
and microbiological degradation due to presence of heter-
oatoms, carbonyl and aliphatic chain, being more suscep-
tible for biodegradation [3, 7]. Its degradation is acceler-
ated by the presence of enzymes that are released by the
microorganisms in soil. Considering the results of SEC
analysis, visual analysis and mineralization test we can say
that the PBAT degradation occurs preferably on the surface
of the material, which is primarily caused by the action
of enzymes, releasing low molecular weight chains to the
environment, which are consumed and converted into ­CO2
and are not measured by SEC analysis.
The blends showed lower mineralization degree val-
ues to those obtained for pristine materials, with rates of
0.15 mg/day for the 25/75 blend, and 0.12 mg/day for the
75/25 blend.
Infrared Spectroscopy (FTIR)
Table 4 shows the bands in the FTIR spectra of the samples
before and after 360 days of degradation in order to evalu-
ate what modifications occurred on the samples surface. No
differences before and after degradation were observed on
the bands, as the wave number changes are in the resolution
range of the equipment (4  cm−1). Rudnik and Briassoulis
[7] measured the intensity of the absorbance at 1748 cm−1
corresponding to carbonyl stretching band to monitorate
the degradation of PLA buried in soil. They found values
changing less than 1 from 3.24 to 2.44 and from 3.6 to 3.5
depending on the PLA grade. Tham et  al. [48], found an
increase of more than 2 of the CI after hydrothermal aging
and associated these increase to the hydrolysis of PLA.
From the spectra of our samples, the carbonyl index (CI)
was calculated as the ratio between the area of the carbonyl
peak and the area of the band of -CH- peak, chosen as
reference.
J Polym Environ (2018) 26:330–341 337

Table 4  Infrared spectral PBAT band position ­cm−1 Position of band 25/75 Position of band 75/25 PLA band position
analysis of the samples before ­cm−1 ­cm−1 ­cm−1
and after degradation
0 days 360 days 0 days 360 days 0 days 360 days 0 days 360 days

2998 2996
2957 2957 2956 2960 2958 2956 2946 2946
1756 1756 1754 1754
1712 1712 1712 1712 1712 1714
1475 1475
1455 1455 1458 1458 1456 1452 1454 1452
1409 1409 1409 1409 1409 1396 1361 1365
1387 1387 1390 1363
1359 1358
1271 1271 1272 1270 1270 1269 1268 1268
1221
1162 1166 1162 1168 1182 1184 1184 1184
10
1105 1105 1105 1105 1103 89 1132 1132
1087 1087
1045 1045 1045 1045
1018 1018 1018 1018 1018
932 937 933 935 931 917
873 873 873 873 873 871 866 867
727 727 727 727 729 730 750 750

depends of the environment where the degradation occurs.

It was observed discreet CI variations and no IR spectra
alterations after degradation. These results indicate that the
degradation process was slow and that there was no forma-
tion of byproducts on the samples surface [6]. Moreover,
slight changes corroborate the chain extender action during
the degradation process.

Analysis of Differential Scanning Calorimetry (DSC)

Figure 5 shows the curves of the first heating on the DSC.

Fig. 4  Carbonyl index of the samples before and after 360 days of
degradation
The results are shown in the Fig.  4. For PLA, CI was
calculated for the band at 1754  cm−1 (C = O) and at
1452 cm−1 (reference) and changed from 4.94 to 5.13. For
the PBAT, bands at 1712 and 1455 cm−1 were considered,
and CI changed from 2.96 to 4.54. The CI of the 25/75
blend changed from 3.06 to 3.48 and for the 75/25 blend,
the CI changed from 4.63 to 3.09. These different results
suggest that the degradation is quite complex and that
The data regarding Tg and Tm in Table 5 were taken from
second heating.
Figure  5 shows enthalpy relaxation for PLA that has
been observed in other studies [36, 49, 50] and typically
occurs for polymers with glass transition temperature near
room temperature. An exothermic peak can be seen related
to cold crystallization for pristine PLA, for samples before
and after 360 days of degradation, for 75/25 blend before
degradation and it was not observed for 25/75 blend. This
phenomenon occurs when polymer molecules, under heat-
ing, acquire sufficient mobility to rearrange its crystal
structure. The melting of PBAT is shown as a wide tem-
perature range and is very close to PLA cold crystalliza-
tion such that these effects were overlapped in blends. This
fact hinders the analysis of PBAT melting and PLA cold
crystallization effect in blends, leading to inaccurate values

13

338 J Polym Environ (2018) 26:330–341

PLA cold crystallization, which may become in crystalline

Fig. 5  Curves of the first heating of DSC analysis. a PLA—0 days;
b PLA—360 days; c 75/25—0 days; d 75/25—360 days; e 25/75—0
days; f 25/75—360 days; g PBAT—0 days; h PBAT—360 days
in calculation of the PLA crystallinity. Due to this super-
position, XRD analyzes were performed to obtain the total
degree of crystallinity of the blends (%C), which is also
shown in Table 4.
In the first heating curve a shoulder preceding the melt-
ing peak of the 75/25 blend was observed, which may be
related to the existence of two crystalline phases in this
blend. PBAT may have induced the formation of a new
crystalline structure in PLA [12]. According to Fukushima
et  al., (2009) the melting crystalline phase at lower tem-
perature is called phase α, whereas the higher temperature
melting peak is characteristic of crystals of type. The heli-
cal conformations of the PLA chains in structures α and β
have approximately the same energy, it is believed that the
way each of them is organized is the main reason for the
existence of two different crystalline structures [58]. Also
a disordered crystalline phase α’ has been described during
form ordered α [50, 51].
The curves for the second heating are shown in Fig. 6.
There was not large variation before and after 360 days
of degradation. Identifying the PBAT fusion peak in the
75/25 blend was not possible neither was the PLA cold
crystallization in the 25/75 blend due to the superposition
of transitions. Also the Tg of PLA in the blends had no
important variation, which was expected since the materi-
als are immiscible, although a decreasing trend could be
related to a little degree of miscibility caused by the chain
extender. The Tg of PBAT in the blends was only observed
in 25/75 blend, since the lowest PBAT concentration in the
75/25 blend did not allow the measurement by the limited
DSC sensitivity. However, after degradation, both PLA
and PBAT undergo a slight increase in their Tg. The larg-
est segments of chains of the amorphous phase are less
restricted by the crystalline phase (lower Tg) and are easily
broken being bio-assimilated or crystallized. The remain-
ing segments in the amorphous phase are smaller and are
restricted by the crystalline phase, presenting greater diffi-
cult to degrade resulting in the highest Tg values.
Crystallinity degree was calculated to assess the effect of
degradation in the crystallization as Eq. (7).
ΔHf − ΔHcc
Xc1 =
w.ΔHf∞
× 100 (7)
where ΔHf is the heat of fusion; ΔHcc is the enthalpy of
cold crystallization of PLA; ΔHf∞ is the enthalpy of fusion
for a crystal with infinite thickness (93 J.g− 1 for PLA and
114 J.g− 1 for PBAT) [11]; w is the PLA mass fraction.
Xc1was calculated from the first heating curves as repre-
senting the conditions of the specimens and Xc2 from the
second heating as the characteristic of the materials, where
ΔHcc has not been subtracted, since the objective was to
calculate any crystallinity present in the material.

Table 5  Thermal properties of Sample-days of Tg (oC) Tcc (oC) Tm (oC) Xc1(%) Xc2(%) %C (%)
the samples before and after 360 degradation
days of degradation PLA PBAT PLA PLA PBAT

PLA—0 60 – 115 148 – 0.9 22.2 0

PLA—360 61 – 116 150 – 1.3 25.7 0
75/25—0 59 – 126 150 – 13.1* 11.1* 35.4
75/25—360 60 – 128 152 – 40.6* 13.9* 41.3
25/75—0 58 −34 – – 129 11.3* 27.7* 28.2
25/75—360 60 −31 – – 132 20.2* 42.6* 30.2
PBAT—0 – −32 – – 130 15.2 8.4 17.8
PBAT—360 – −31 – – 132 15.3 12.2 26.5

*Regarding the PLA crystallization in the blend

%C crystallinity degree from XRD, Xc1 crystallinity degree from DSC 1st heating; Xc2 crystallinity degree
from DSC 2nd heating;

13
J Polym Environ (2018) 26:330–341 339
Fig. 6  Curves of the second heating of DSC analysis. a PLA—0
days; b PLA—360 days; c 75/25—0 days; d 75/25—360 days; e
25/75—0 days; f 25/75—360 days; g PBAT—0 days; h PBAT—360
days
Fig. 7  XRD patterns of a PLA, b 75/25 blend, c 25/75 blend and d PBAT before and after 360 days of degradation
The higher degree of crystallinity of the blends before
degradation shows that the PBAT influenced PLA
crystallization.
All samples presented an increase in the degree of crys-
tallinity after the degradation. The increase of Xc1 indicates
that PLA hydrolysis occurs at a greater rate in the amor-
phous region that reduces the size of chain segments in this
region, which acquire mobility increasing the crystallinity
of the material as degradation occurs [30]. The increase of
Xc2,after degradation, is one more evidence that the crys-
tallization of the PLA is favored by the reduction of the
molecular weight and the presence of PBAT.
X‑ray Powder Diffraction (XRD)
One XRD analysis was performed for each material in
order to monitor changes in the structural order of the poly-
mers due to degradation. Figure 7 shows the XRD patterns
of samples before and after 360 days of degradation, all
13

340
with the addition of the chain extender. The degree of crys-
tallinity (%C) is shown in Table 5.
In PLA XRD patterns a broad peak at 2θ = 16° is
observed, indicating a predominantly amorphous structure.
These results are consistent with the DSC, which showed
a crystallinity degree around 1%, as it was very small it
was not detectable by the XRD analysis. PBAT XRD pat-
terns before and after degradation show characteristics of a
semi-crystalline structure, with five well-defined diffraction
peaks at about 16.1°, 17.5°, 20.6°, 23.2° and 25.0°. All the
XRD patterns of the 25/75 blend (before and after degrada-
tion) showed diffraction peaks similar to PBAT. The 75/25
blend, different from the pristine polymers, presented a
peak at 2θ = 16.9° before degradation and 2θ = 16.6° after
of degradation and low intensity peaks at 14.8°, 19° and
22.3°. This data has been reported in other studies assigned
to the crystalline phase of PLA [52, 53]. The presence of
these diffraction peaks indicate that in this composition
PBAT influenced PLA crystalline structure, reinforcing the
behavior observed in the curves in the first DSC heating
where 75/25 blend showed a bimodal endothermic peak.
By the XRD technique, except for the PLA, all samples
had an increased degree of crystallinity due the degrada-
tion. This increase in crystallinity is one of the evidences
of the biodegradation process [29, 30, 33, 54]. There is a
difference between the results obtained by the DSC and
XRD techniques. However, for pure polymers, these results
are quite consistent, and for the blends it is necessary to
remember that the calculated value corresponds to crystal-
linity of both materials in the blends, while in relation to
DSC, PLA crystalline fraction was not possible due to the
superposition effect of transitions already reported.
Final Remarks
The study showed the great complexity of the biodegrada-
tion process of PLA and PBAT blends when compatibilized
with a chain extender. Pristine PBAT, which has high rate
of degradation in soil, has suffered strong reduction on this
rate by the presence of the chain extender, which reflected
in the behavior of the blends. The chain extender func-
tional groups reacted with the groups generated during the
polymers degradation in a competitive effect with molecu-
lar weight reduction, causing biodegradation delay. The
blends showed intermediate behavior compared to original
polymers, and the polymeric matrix behavior predominated
until the surface of the dispersed phase was available for
the biodegradation process. Other factors, such as increased
crystallinity in the blends and morphology had also influ-
enced on the biodegradation process. The expectation of
accelerating PLA biodegradation in soil by compatibiliza-
ted blending with PBAT was not achieved.
13
J Polym Environ (2018) 26:330–341
Acknowledgements  The authors would like to thank the Foun-
dation for Research of the State of São Paulo—FAPESP (Process
2014/09883-5) and National Council of Scientific and Technological
Development CNPQ for the financial support, and the MICROMAT
(Prof. Lucia Innocentini Mei) for the mineralization tests.
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