J Mater Sci

Chemical
C H E M I C A L R routes
O U T E S T Oto
M Amaterials
T E R I AL S

PLA degradation pathway obtained from direct

polycondensation of 2-hydroxypropanoic acid using
different chain extenders
C. A. Ramı́rez-Herrera1,2, A. I. Flores-Vela2, A. M. Torres-Huerta1,* , M. A. Domı́nguez-Crespo1, and
D. Palma-Ramı́rez1

1
Instituto Politécnico Nacional CICATA-Altamira, km. 14.5 Carretera Tampico-Puerto Industrial Altamira, C.P. 89600 Altamira,
Tamaulipas, Mexico
2
Instituto Politécnico Nacional, Centro Mexicano para la Producción más Limpia, Av. Acueducto s/n, la Laguna Ticomán,
C.P. 07340 Mexico City, Mexico

Received: 18 January 2018 ABSTRACT

Accepted: 26 April 2018
Ó Springer Science+Business
Media, LLC, part of Springer
Nature 2018
This work is focused on the structural, thermal and mechanical studies of direct
polycondensation of poly (lactic acid) (PLA) modified with three different chain
extenders (1,3-phenylene-bis-2-oxazoline, PBO; pyromellitic dianhydride,
PMDA; and 1,10 -carbonyl bis caprolactam, CBC). Three concentrations of PBO,
PMDA and CBC chain extenders (0.2, 0.5 and 1 wt%) were added during three
stages (S): monomer dehydration (80 °C, S1), oligomer polycondensation (130 °C,
S2) and melt polycondensation (160 °C, S3). FTIR, Raman and 1H-NMR spec-
troscopies revealed the presence of signals produced by interactions between OH
and C=O end groups of PLA and reactive functional groups of chain extenders. It
was found that the interaction with the PMDA chain extender decreased the PLA
crystallinity. Furthermore, data from thermal analysis revealed that the interac-
tion between PLA and chain extenders increased the chain mobility, which rep-
resented a decrease in its Tg. Enhanced mechanical properties, hardness, elastic
modulus and indentation creep were observed with the addition of chain
extenders, improving the performance with the addition of 1 wt% of PBO at S3,
1 wt% of PMDA at either S2 or S3 and 0.25 wt% of CBC at either S2 or S3.
Additionally to the synthesis, the degradation was mainly influenced by the
interaction more than by any specific stage of chain extender addition. Finally, the
thermal and structural characterizations revealed that the PLA-PBO, PLA-PMDA
and PLA-CBC systems were more resistant than PLA to UV light and humidity
during the accelerated weathering test.

Address correspondence to E-mail: atorresh@ipn.mx

https://doi.org/10.1007/s10853-018-2380-7

Introduction
Petroleum-based thermoplastic polymers are ideal
for the production of lightweight packages and other
consumer products due to features such as low pro-
cessing temperature (compared to metal and glass),
variable barrier properties that match end-use
applications, good printability, heat sealability, and
easy shape transformation [1, 2]. However, these
materials exert an undesirable effect on the environ-
ment that stems from their total non-biodegradabil-
ity, which causes waste deposition and utilization
problems [3]. Over the past decade, many research
works have reported on compostable polymers
derived from renewable sources as a solution to
alleviate solid waste disposal problems and lessen
the dependence on petroleum-based plastics [2, 4].
Recent trends in biodegradable polymers indicate
significant developments in terms of novel design
strategies and engineering to provide advanced
polymers with comparably good performance [5].
In the field of biodegradable polymers, polyesters
are the most extensively studied due to their impor-
tant diversity, synthetic versatility and potentially
hydrolysable ester bonds that make these materials
susceptible of degradation [3]. Lactic-acid-based
thermoplastic polyesters such as polylactic acid
(PLA) are known to be biodegradable and com-
postable, for they decompose rapidly and completely
to carbon dioxide, water and biomass in a compost
environment [6]. PLA is synthesized from lactic acid
produced by fermentation of carbohydrate-rich sub-
stances, mainly starch and sugar [7, 8]. Additionally,
PLA is one of the most investigated biodegradable
polymers and is considered as a promising material
owing to its thermoplastic processability, biological
properties such as biocompatibility and biodegrad-
ability [7, 9]. Nevertheless, PLA has certain limita-
tions regarding its dominant hydrophilic character,
fast degradation rate and unsatisfactory physical
properties in terms of mechanical strength and
dimensional stability, which restrain its applications
[10, 11]. An effective way to overcome these draw-
backs is by modifying this type of condensation
polymers with chain extenders [2]. In general, chain
extenders can have two or more functional groups
such as diisocyanates, dianhydrides, diamines,
epoxies, etc., to couple the two end groups of low
molecular weight polymer chains. The variety of
J Mater Sci
these compounds allows the bonding of specific
chain structures [2].
In previous studies, Tuominen et al. synthesized
lactic acid polymers from oligomers by adding highly
reactive 1,6-hexamethylene diisocyanate (HMDI) and
2,20 -bis(2-oxazoline) (BOX) as chain extenders. These
authors studied the effects of adding simultaneously
and sequentially extenders to high molecular weight
polylactic acids and concluded that the addition way
and extender amounts exerted a considerable effect
on the branching [10]. Yuanliang et al. modified the
chemical structure of PLA using multifunctional
epoxy compounds (Joncryl-ADR4370) as chain
extenders and reported a slight increase in the glass
transition (Tg) and melting temperatures (Tm) of
products [12]. Also, Gupta et al. [13] reported an
increase in different properties such as glass transi-
tion temperature, molecular weight and molecular
weight distribution depending on the concentration
of methylene diphenyl diisocyanate (MDI) and tin
octoate as catalyst. The addition of chain extenders
during polymerization not only allows the prepara-
tion of high molecular weight polymers with
improved thermal and mechanical properties, but
also provides possibilities for variation in the poly-
mer structure (like branching). Recently, Xu et al. [14]
obtained high molecular weight PLA by polycon-
densation of lactic acid and adipic acid using
bisphenol-A epoxy resin as chain extender.
Chain extension of PLA frequently is made by
obtaining composites or blends such as those repor-
ted by different authors: PLA/poly [butylene adi-
pate]-co-terephthalate] (PBAT), PLA/poly(butylene
succinate) blends, lactic acid-succinic anhydride
copolymer [P(LA/SA)], and PLA/organo-modified
clay nanocomposites. The addition of chain extenders
to PLA such as 1,3-phenylene-bis-2-oxazoline, PBO;
pyromellitic dianhydride, PMDA; and 1,10 -carbonyl
bis caprolactam, CBC has been reported with com-
patibilizers, where the most common is maleic
anhydride (MA) with just a few reports related to the
direct addition, and degradation study, of this type of
chain extenders to PLA during polymerization. For
this reason, the present research work was aimed at
studying the direct polycondensation of 2-hydrox-
ypropanoic acid (L-lactic acid), evaluating the effect
of different chain extenders (PBO, PMDA and CBC)
added at different concentrations (0.2, 0.5 and 1 wt%)
at different stages: monomer dehydration (80 °C),
J Mater Sci
oligomer polycondensation (130 °C) and melt poly-
condensation (160 °C).
Structural changes in PLA were measured by
Fourier transform infrared (FTIR), Raman and
nuclear magnetic resonance (1H-NMR) spectro-
scopies in addition to X-ray diffraction (XRD); addi-
tionally, thermal properties were analyzed by
differential scanning calorimetry (DSC), whereas
mechanical properties such as hardness, elastic
modulus and creep indentation were measured by
nanoindentation tests.
The degradation mechanism under the accelerated
weathering test (UV light and humidity) is discussed
in terms of the chain extender effect on structural and
thermal properties. Finally, hydrolytic degradation
tests were used to evaluate the degradation process
under each condition by monitoring pH and weight
loss%.
Materials and methods
Materials
2-Hydroxypropanoic acid (L-lactic acid, 88 (v/v%) in
water, [ 97% optically pure) was supplied by
Alquimia Mexicana Ltd. (Mexico), and Tin (II)
2-Ethylhexanoate (95%) was purchased from Sigma-
Aldrich (Mexico). Three different chain extenders
were used in this study: PBO and CBC ([ 99%)
purchased from DSM New Business Development
ALLINCOÒ (Netherlands) and PMDA (97%) sup-
plied by Sigma-Aldrich (Fig. 1a–c), which were dried
for 2 h at 80 °C before addition.
(a) (b)
Figure 1 Molecular structure of chain extenders: a PBO, b PMDA and, c CBC.
PLA synthesis
A direct polycondensation process from L-lactic acid
was carried out using three typical stages: monomer
dehydration, oligomer polycondensation, and melt
polycondensation. First, 100 mL of L-lactic acid were
added to a 250-mL three-neck flask, which was
immersed into a mineral oil bath. The monomer was
purified by distillation (Stage 1) at reduced pressure
at 80 °C for 2 h and kept under constant magnetic
stirring to remove the free water; hereinafter, it will
be referred to as S1. Afterward, 0.5 mol of tin (II)
2-Ethylhexanoate were added as catalyst, and then,
the temperature was increased to 130 °C (Stage 2, S2)
and kept constant for 3 h under constant stirring and
reduced pressure conditions that led to the formation
of lactic acid oligomers. Subsequently, by raising the
temperature to 160 °C (Stage 3, S3), the polyconden-
sation continued for 6 h under the same conditions.
At the end of the reaction, a white solid was depos-
ited on glass and cooled down to room temperature
for further characterizations.
Chain extension reactions
The synthesis of the PLA-chain extender was per-
formed by adding separately the chain extenders at
concentrations of 0.2, 0.5 and 1 wt%. The addition at
S1 was after the monomer distillation while at S2 and
S3; it occurred at the beginning of the stages. Reaction
products were deposited on glass for further analysis.
Characterization of samples
FTIR spectra were recorded on a LabRAM HR800
Spectrometer (Horiba Jobin–Yvon) coupled to a near
IR module and a micro-attenuated total reflectance
probe (ATR) using a 2-mm diamond tip.
(c)

Measurements were obtained in the transmission
mode within the spectral region from 4000 to
400 cm-1.
Raman spectra were obtained with a LabRAM
HR800 Micro-Raman Spectrometer (Horiba Jobin–
Yvon) equipped with multiple laser sources at 532,
633 and 785 nm. Samples were excited at 785 nm by a
diode laser with a spot size of 1 lm. The scan range
was in the 200–3100 cm-1 region.
1
H-NMR spectra were carried out using a Bruker
Ascend 750 (750 MHz) NMR Spectrometer for liquids
at room temperature using deuterated chloroform
(CDCl3, 1H: d = 7.26 ppm) as solvent and tetram-
ethylsilane (TMS, d = 0.00 ppm) as internal reference.
X-ray diffraction patterns were performed on an
X’Pert PRO MRD X-ray Diffractometer from PANa-
lytical using Cu-Ka radiation (k = 0.15406 nm). The
data were collected over a range of scattering angles
(2h) of 10°–60° at room temperature, 40 kV, 40 mA,
and scan rate of 0.01° min-1.
MALDI-TOFMS was carried out to analyze the
molecular weight of the samples using a MALDI-TOF
Autoflex Speed Mass Spectrometer (Bruker Daltonics
Inc.).
Thermal analysis by DSC was performed on a TGA
Labsys EVO differential scanning calorimeter (Se-
taram Instrumentation) at a heating rate of 10 °C/
min from 25 to 200 °C and cooling rate of 10 °C/min
from 200 to 25 °C under argon atmosphere.
Nanoindentation tests were carried out at room
temperature on a TTX-NHT nanoindenter (CSM
Instruments) using a Berkovich diamond indenter. A
loading rate of 10 mN/min was maintained during
the progressive increase in the load until the indenter
reached a maximum load of 5 mN, which was held
constant for 20 s to account for creep effects before
the indenter was unloaded. Five measurements were
made for each sample on randomly selected locations
to obtain average values of hardness, H, elastic
modulus, Es, and creep indentation. During a typical
nanoindentation test, force and displacement are
recorded as the indenter tip is pressed on the surface
with a prescribed loading and unloading profile,
taking place both elastic and plastic deformations.
The response of interest is the load–displacement
curve [15, 16]. From this curve, hardness, H, elastic
modulus, Es and indentation creep can be obtained.
In accordance with the method developed by Oliver
and Pharr [17], nanoindentation hardness is defined
as the indentation peak load (Pmax) divided by the
J Mater Sci
projected contact area of the indentation (A) as shown
in Eq. (1), which is the mean pressure that a material
can withstand under load [18]:
Pmax
H¼ ð1Þ
A
where Pmax represents the maximum load applied
between the indenter and the sample surface. For a
Berkovich indenter (triangular diamond pyramid), A
is a function of contact depth which is measured
in situ by the nanoindenter during the test. The
elastic modulus, Es, of the indented sample can be
inferred from the initial unloading contact stiffness,
S = dP/dh, i.e., the slope of the initial portion of the
unloading curve. Based on relationships developed
by Sneddon [19] for the indentation of an elastic half
space by any punch that can be described as a revo-
lution solid of a smooth function, a geometry-inde-
pendent relation involving contact stiffness, contact
area, and elastic modulus can be derived from
Eq. (2):
rffiffiffiffi
A
S ¼ 2b Er ð2Þ
p
where b is a constant that depends on the indenter
geometry (1.034 for the Berkovich indenter) and Er is
the reduced elastic modulus that accounts for the fact
that elastic deformation occurs in both the sample
and the indenter. Er is given as follows in Eq. (3):
1  v2 1  v2i
Er ¼ þ ð3Þ
E Ei
In this equation, E and v are Young’s modulus and
Poisson’s ratio for the sample, respectively, and Ei
and vi are the same quantities for the indenter. For
diamond, Ei = 1141 GPa and vi = 0.07 [17]. To cal-
culate the elastic modulus, Es, from Eqs. (2) and (3),
the contact stiffness and projected contact area is
determined from the load–displacement curve. Con-
sidering Eq. (4):
pffiffiffi
p Smax
Er ¼ pffiffiffiffi ð4Þ
2 A
where Smax is the slope of the unloading curve at the
point of maximum load.
On the other hand, the time-dependent deforma-
tion occurred under the application of a load which
may be the result of viscoelastic or viscoplastic
deformation, which is called indentation creep, (CIT),
[15, 20], and is determined from Eq. (5):
J Mater Sci
h2  h1
CIT ¼  100
h1
where h1 and h2 are the indentation depths at t1,
when the force begins to remain constant and the
indentation depth at the last time t2, respectively.
The PLA degradation was evaluated through a
weathering test by using a QUV/SE UV chamber
equipped with condensation and solar eye irradiance
control. The experiments were performed during two
cycles of UV irradiation (8 h), condensation (4 h)
using an irradiance lamp at 313 nm and 50 °C.
Hydrolytic degradation (aging) of the as-obtained
samples was carried out by adding 1.5 g of each
sample to identical flasks containing 50 mL of
degradation medium (pH = 10, NaOH) at 60 °C for
15 days. After selected degradation times (3, 6, 9 and
15 days), samples were taken out, washed several
times with deionized water, dried at 50 °C for 24 h
and weighed. During each measurement, pH was
recorded to evaluate reaction degradation in the
media.
Weight loss of the plates was evaluated by
weighing. The weight loss percentage (WL ð%Þ) was
calculated from the following equation:
Wo  Wt
W L ð% Þ ¼  100
Wo
where Wo and Wt are the initial and the residual
weight of the dried samples within the time interval.
Results and discussion
FTIR spectroscopy
FTIR spectra were recorded to analyze the chemical
structure of neat PLA and chain extenders as well as
the changes occurred in modified PLA by studying
the characteristic signals of each sample (Fig. 2, 3, 4a–
c). Vibrational absorption bands of PLA at
wavenumbers of 2991 and 2941 cm-1 correspond to
CH3 symmetric and asymmetric stretchings; the
stretching vibration of carbonyl groups (C=O) is
observed at 1749 cm-1, and the peaks at 1453 and
1373 cm-1 correspond to the symmetric and asym-
metric deformations of C–H. The C–O–C asymmetric
and symmetric stretching bands can be observed at
1183, 1122 and 1085 cm-1. Additionally, the stretch-
ing vibration of C–C–O–O is observed at 869 cm-1,
whereas the C=O deformation was obtained at
750 cm-1 [21–24]. By comparing neat PLA and neat
ð5Þ
chain extender spectra with those obtained for mod-
ified PLA with PBO, none of the wavenumbers of the
characteristic bands are shifted to higher or lower
wavenumbers, suggesting a low interaction between
PLA and PBO (Fig. 2a–c). An intensity increase was
observed in the peaks correlated to C=O, CH3, C–H,
C–C and C–O vibrations, which are related to the
sum of polymer and chain extender.
On the other hand, by adding PMDA during the
different stages of the polycondensation process
(Fig. 3a–c), changes were detected in the shape and
intensity of the absorption bands at 1183 and
1122 cm-1, which are assigned to C–O–C asymmetric
and symmetric stretching bands, which are probably
due to the interaction between OH and C=O end
groups of PLA and the reactive functional groups of
chain extenders. Furthermore, overtones or combi-
nation bands between 2000 and 1980 cm-1 suggested
the presence of aromatics groups in the PLA struc-
ture as a result of the reaction with the chain exten-
ders. The FTIR spectra of modified PLA with CBC are
shown in Fig. 4a–c. The addition of CBC chain
extenders during the polycondensation stage did not
show (as PBO) a strong chemical interaction with
PLA, intensity increments in the stretching vibration
ð6Þ
of C=O (1749 cm-1), the deformation and stretching
of CH3 and CH bonds (2991, 2944, 1453, 1373, 869 and
750 cm-1) and ester CO bonds at 1183, 1122, 1085,
and 1038 cm-1. Small interactions can also be
observed in the absorption bands at 1183 and
122 cm-1 during the addition of the extender at
Stages 2 or 3, which are correlated with the interac-
tion of the PLA hydroxyl group and C=O groups
contained in the CBO extender. From FTIR studies, it
was observed that it is possible to increase the
chemical interaction of PLA with the chain extender
either depending on the addition during the different
stages or varying the quantity of carbonyl groups
contained in the chain extenders.
Raman spectroscopy
Additional information concerning the structure of
PLA-chain extenders was obtained through Raman
spectroscopy analyses. Raman spectroscopy is usu-
ally a complementary technique to measure the
completely vibrational modes of a molecule [25] and
to evaluate accurately its structural changes. Fig-
ures 5, 6 and 7a, b show Raman spectra of PLA
 J Mater Sci

Figure 2 FTIR spectra of neat (a) (b)

PLA, extenders and PLA 1.0 wt.% FBO-S3 1.0 wt.% FBO-S3

modified with different PBO 0.5 wt.% FBO-S3 0.5 wt.% FBO-S3
concentrations.
0.25 wt.% FBO-S3 0.25 wt.% FBO-S3

1.0 wt.% FBO-S2 1.0 wt.% FBO-S2

Transmittance (a.u.)
Transmittance (a.u.)
0.5 wt.% FBO-S2 0.5 wt.% FBO-S2

0.25 wt.% FBO-S2 0.25 wt.% FBO-S2

1.0 wt.% FBO-S1 1.0 wt.% FBO-S1

0.5 wt.% FBO-S1 0.5 wt.% FBO-S1

0.25 wt.% FBO-S1 0.25 wt.% FBO-S1

Neat PLA Neat PLA

1373
1183
1453
869 750
1749 Extender PBO
1491 1085 1038
1581

1648
C=O

823
1376
1235

913

692
665
1073

Extender PBO 2000 1900 1800 1700 1600 1500

-1
2000 1750 1500 1250 1000 750 Wavenumber (cm )
-1
Wavenumber (cm )

(c)
1.0 wt.% FBO-S3

0.5 wt.% FBO-S3

0.25 wt.% FBO-S3

1.0 wt.% FBO-S2

Transmittance (a.u.)

0.5 wt.% FBO-S2

0.25 wt.% FBO-S2

1.0 wt.% FBO-S1

0.5 wt.% FBO-S1

0.25 wt.% FBO-S1

Neat PLA

Extender PBO

C-O-C

1250 1200 1150 1100 1050

-1
Wavenumber (cm )

modified with PBO, PMDA and CBC using different (Fig. 5a), it exhibits some sharp lines related to the
concentrations (0.25, 0.5 and 1 wt%) and added at presence of crystalline domains in the sample, while
different synthesis stages. For comparison purposes, the broad lines correspond to the amorphous PLA
the Raman spectra of the neat PLA and pure chain phase, suggesting that the PLA obtained in this study
extenders are shown in Figs. 5, 6 and 7. Kister et al. is a semi-crystalline material. CH and CH3 stretching
[26] investigated the Raman spectra of PLA regarding band regions of neat PLA (3100–2800 cm-1) show
some details. Their studies revealed the differences bands at 2998, 2945 and 2881 cm-1. The Raman line
between the crystalline and amorphous PLA spectra. assigned to the C=O stretching mode was slightly
In accordance with the Raman spectrum of neat PLA split into two components. These modes were
J Mater Sci

(a) (b)
1%PMDA-E3 1 wt%PMDA-E3

0.5%PMDA-E3 0.5 wt. %PMDA-E3

0.25%PMDA-E3 0.25 wt.%PMDA-E3
1%PMDA-E2 1 wt.% PMDA-E2
0.5%PMDA-E2 0.5 wt.%PMDA-E2
Transmittance (a.u.)

Transmittance (a.u.)
0.25 wt.%PMDA-E2 0.25 wt.%PMDA-E2
1 wt.%PMDA-E1 1 wt.%PMDA-E1
0.5 wt.%PMDA-E1 0.5 wt.%PMDA-E1
APL-0.25%PMDA-E1 0.25 wt.%PMDA-E1
Neat PLA Neat PLA
869 750
1373
1453

1038 Extender PMDA

1183

1749 1085
1513

1382

1080
1116
1846
1814

1696
1760

702
765
1217

C=O
921
889

PMDA Extender
2000 1900 1800 1700 1600 1500
2000 1750 1500 1250 1000 750
Wavenumber (cm -1 )
Wavenumber (cm -1 )

(c)
1 wt%PMDA-E3

0.5 wt. %PMDA-E3

0.25 wt.%PMDA-E3
1 wt.% PMDA-E2
Transmittance (a.u.)

0.5 wt.%PMDA-E2

0.25 wt.%PMDA-E2
1 wt.%PMDA-E1
0.5 wt.%PMDA-E1
0.25 wt.%PMDA-E1
Neat PLA

Extender PMDA

C-O-C

1250 1200 1150 1100 1050

-1
Wavenumber (cm )

Figure 3 FTIR spectra of neat PLA, extenders and PLA modified with different PMDA concentrations.

observed at 1768 and 1751 cm-1 corresponding to the assigned to symmetric and asymmetric COC
crystalline PLA part. It has been stated that the C=O stretching modes of ester groups. Bands at 1127 and
stretching mode in PLA(s) is sensitive mainly due to 1042 cm-1 correspond to CH3 asymmetric rocking
its morphology and conformation [26]. In CH3 and and C–CH3 stretching modes, respectively. The
CH bending regions, the symmetric and asymmetric intense line located at 871 cm-1 was assigned to C–
deformation modes appeared at about 1452, 1385 and COO stretching. In the low-frequency region, a weak
1295 cm-1. Raman lines at 1182 and 1094 cm-l are band at 708 cm-1 corresponding to the C=O out-of-
 J Mater Sci

Figure 4 FTIR spectra of neat (a) (b)

PLA, extenders and PLA 1 wt.% CBC-E3 1 wt.% CBC-E3
modified with different CBC
0.5 wt.% CBC-E3 0.5 wt.% CBC-E3
concentrations.
0.25 wt.% CBC-E3 0.25 wt.% CBC-E3

1 wt.% CBC-E2 1 wt.% CBC-E2

Transmittance (a.u.)
0.5 wt.% CBC-E2 0.5 wt.% CBC-E2

Transmittance (a.u.)
0.25 wt.% CBC-E2 0.25 wt.% CBC-E2

1 wt.% CBC-E1 1 wt.% CBC-E1

0.5 wt.% CBC-E1 0.5 wt.% CBC-E1

0.25 wt.% CBC-E1 0.25 wt.% CBC-E1

Neat PLA Neat PLA

1373
1183
1453
869 750
1749 1038
1085
Extender CBC Extender CBC
C=O

2000 1900 1800 1700 1600 1500

2000 1750 1500 1250 1000 750 Wavenumber (cm ) -1

Wavenumber (cm-1)

(c)
1 wt.% CBC-E3

0.5 wt.% CBC-E3

0.25 wt.% CBC-E3

1 wt.% CBC-E2
Transmittance (a.u.)

0.5 wt.% CBC-E2

0.25 wt.% CBC-E2

1 wt.% CBC-E1

0.5 wt.% CBC-E1

0.25 wt.% CBC-E1

Neat PLA
C-O-C
Extender CBC

1250 1200 1150 1100 1050

-1
Wavenumber (cm )

plane deformation was observed whose intensity is modes. The shape and intensity of this band reflect
related to the presence of amorphous domains in once again the presence of amorphous domains in
PLA [27]. Similarly, bands in the 410–396 cm-1 PLA [22]. As it is observed, it was possible to analyze
region are attributed to the C–C–O deformation molecular order and orientation features in both
modes. These two bands are overlapped to give a domains, crystalline and amorphous, in PLA from
broad band corresponding to the amorphous part of vibrational spectroscopy.
PLA. The broad band located at 306 cm-1 is attrib- In order to analyze the influence of chain extenders
uted to the COC and C–CH3 deformation coupling on PLA, Figs. 5, 6 and 7 show the enlarged Raman
J Mater Sci

Figure 5 Raman spectra of (a) (b)

neat PLA, PBO chain extender C-N
1 wt.% PBO-E3 1 wt.% PBO-E3
and PLA modified with PBO
using different concentrations 0.5 wt.% PBO-E3 0.5 wt.% PBO-E3
(0.25, 0.5 and 1 wt%) added at 0.25 wt.% PBO-E3 0.25 wt.% PBO-E3
different synthesis stages:
1 wt.% PBO-E2
a 300–3500 cm-1 interval and 1 wt.% PBO-E2
391 406 1765 391 406 1765
b enlarged Raman spectra in 0.5 wt.% PBO-E2

Intensity (a.u.)
1747

Intensity (a.u.)
0.5 wt.% PBO-E2 1747
the 300–1850 cm-1 interval. 0.25 wt.% PBO-E2
0.25 wt.% PBO-E2
999 C-N 999 C-N
1 wt.% PBO-E1 1 wt.% PBO-E1

0.5 wt.% PBO-E1 0.5 wt.% PBO-E1

1127 1094
1042 0.25 wt.% PBO-E1 0.25 wt.% PBO-E1

396
306

1094
410

1042
871 2945

1127
396

1385
306

2998
1295

1452
410

708 17511768 871

2881

708
737

1295 1385 1452

Neat PLA

2953

933 999
1042

1370
Neat PLA653

2982
13701459 1648 2935 1648
1459
999
724

1580
653 1580

3067
Extender PBO
1272

1336
1336
893

1272
1192

1603
724
933

1603
Extender

893
2911
1192

2879 PBO

500 1000 1500 2000 2500 3000 300 600 900 1200 1500 1800

Raman shift (cm-1) Raman shift (cm-1)

Figure 6 Raman spectra of (a) (b)

871
871

1 wt.% PMDA-E3
neat PLA, PMDA chain
1127
1042

1042
1127
400 16231764 1182 1764
737

extender and PLA modified

737
400
920

920
1182 1623
708 1 wt.% PMDA-E3 708
with PMDA using different
0.5 wt.% PMDA-E3 0.5 wt.% PMDA-E3
concentrations (0.25, 0.5 and
1 wt%) added at different 0.25 wt.% PMDA-E3 0.25 wt.% PMDA-E3
1042

1127 1623 1764

synthesis stages: 396410
737
871
920
708

1182 1182 1 wt.% PMDA-E2

920
1 wt.% PMDA-E2 1623
a 300–3500 cm-1 interval and 1764
Intensity (a.u.)

Intensity (a.u.)

0.5 wt.% PMDA-E2 0.5 wt.% PMDA-E2

b enlarged Raman spectra in
the 300–1850 cm-1 interval. 0.25 wt.% PMDA-E2 0.25 wt.% PMDA-E2
1 wt.% PMDA-E1 1 wt.% PMDA-E1
0.5 wt.% PMDA-E1 0.5 wt.% PMDA-E1
1124 1127 1094
1042

0.25 wt.% PMDA-E1

750

0.25 wt.% PMDA-E1

871 2945
396

1385
306

2998
1221 1295

1452
410

708 17511768
2881
794 737

396

1127
306

Neat PLA
410

1094
1042

Neat PLA 871

640 708

1295 1385 1452

1298 1780 1863 3089
490

704

1623
640

1324 Extender PMDA

490

737

1780
704

1337 Extender PMDA

794

1124 1221 1298 13241623

1337

500 1000 1500 2000 2500 3000

300 600 900 1200 1500 1800
-1
Raman shift (cm ) -1
Raman shift (cm )

spectra in the interval ranging from 300 to 1850 cm-1. new bonds and the presence of physical interactions
Raman spectra of PLA modified with PBO chain among the molecules that promote changes in the
extender display a Raman line of low intensity at chemical environment of PLA. It is important to
999 cm-1 assigned to C–O–C stretching modes highlight some features in the spectra, for instance,
because of the chain extender on PLA structure. when 0.25 wt% of PBO is added to PLA (Stage 1),
Moreover, weak signals between 1650 and 1584 cm-1 important reductions in the Raman intensities are
are observed, which can be attributed to the presence observed with broader bands featuring semi-crys-
of C-N bonds derived from the ring opening of oxa- talline characteristics, where amorphous domains
zoline in PBO. These results suggest the formation of prevailed. By adding 0.5 wt%, the most important
 J Mater Sci

Figure 7 Raman spectra of (a) (b)

neat PLA, CBC chain extender
and PLA modified with CBC 1 wt.%CBC-E3
1 wt.%CBC-E3
using different concentrations 0.5 wt.%CBC-E3
0.5 wt.%CBC-E3
(0.25, 0.5 and 1 wt%) added at
0.25 wt.%CBC-E3
different synthesis stages: 0.25 wt.%CBC-E3
a 300–3500 cm-1 interval and 1 wt.%CBC-E2
1 wt.%CBC-E2

Intensity (a.u.)
Intensity (a.u.)
b enlarged Raman spectra in 294 312 920 1763
708 0.5 wt.%CBC-E2
0.5 wt.%CBC-E2
the 300–1850 cm-1 interval. 400

0.25 wt.%CBC-E2
0.25 wt.%CBC-E2
1 wt.%CBC-E1
1 wt.%CBC-E1
0.5 wt.%CBC-E1
0.5 wt.%CBC-E1
871 1094 0.25 wt.%CBC-E1
0.25 wt.%CBC-E1
1127

1127
306

1042
396
396
306

410
1042
410

1385
708

2945 2998
1337 1295 Neat PLA

1094
871

1670 1452
1751 1768 2945

2881
737

1693

708
Neat PLA 1295 1385 1452

1337

1713
643 1030 1042 1445 1693Extender2865 1030 1042 1445

1089
643 792
1089

1670
1474
1474
424 792 2844 424 844
844 1713 CBC
Extender CBC
500 1000 1500 2000 2500 3000 300 600 900 1200 1500 1800
-1 -1
Raman shift (cm ) Raman shift (cm )

changes are observed at Stage 2, where the C=O Furthermore, a low-intensity signal located at
stretching was shifted to 1765 and 1747 cm-1, and the 918 cm-1, which is assigned to C–C stretching and
bands at 396–410 cm-1 slightly increased their the CH3 rocking coupling mode, was detected. This
intensity due to the existence of crystalline regions. signal was attributed to 103 helix conformations
As the PBO concentration was increased up to 1 wt%, assigned to the crystalline part of PLA [26, 27].
the band located at 999 cm-1, corresponding to Finally, by adding to PMDA, the Raman lines of neat
asymmetric COC stretching modes of ester groups, PLA at 396 and 410 cm-1, assigned to CCO defor-
displays a weak signal independently of the stage mation modes, they were turned into a sharper and
where the chain extender is added, which suggests a intense single line at 400 cm-1. This change is also
weak influence on the PLA structure. associated with PLA crystallinity increase.
In general, all the Raman bands increased their As it is stated, the CH and CH3 bands
intensity depending on the extender concentration (3100–2800 cm-1) are insensitive to chemical inter-
and temperature. Specially, the most evident changes actions; however, the addition of CBC to the PLA
were appreciated with an amount of 1 wt%. The matrix during Stage 2 provoked important changes in
shape of bands corresponding to the C=O stretching the intensity of Raman lines. Remarkable changes are
was modified with respect to neat PLA. The bands of observed in PLA (C=O stretching) when CBC was
neat PLA at 1768 and 1751 cm-1 were joined to give a added at Step 2 containing 0.25 and 0.5 wt%. Again,
sharper and intense Raman line at 1764 cm-1, sug- two Raman lines are combined to form a single line of
gesting the increase in crystalline PLA domains. This higher intensity at 1763 cm-1, which suggests an
modification can be attributed to the influence of the increase in the crystallinity of the samples. A weak
symmetric and rigid structure of the PMDA chain signal at 920 cm-1, assigned to the C–C stretching
extender on the main PLA chain. Additionally, the and/or CH3 rocking modes, is also observed. This
weak signals observed at 1612 and 1567 cm-1 were signal is characteristic of the transformation of some
assigned to C=C stretching modes which are char- spherulitic zones into 103 helix conformations. Also,
acteristic of aromatic rings in the PMDA chain Raman lines were assigned to C–COO stretching
extender. In the CH3 and CH deformation regions (871 cm-1), C=O deformation (708 cm-1), and C–C–
and the COC stretching region between 1452 and O deformation (400 cm-1), which increased their
1042 cm-1, the Raman lines show a remarkable intensities by using these extender concentrations;
intensity with respect to neat PLA, especially when nevertheless, this effect was also observed when
the extender was added at Stages 2 and 3. 0.25 wt% of CBC was added at Stage 3. Thus, in
J Mater Sci
agreement with the FTIR results, the CBC chain
extender and PLA matrix displayed a weak chemical
interaction, but it can be enhanced depending on the
addition stage and quantity of carbonyl groups con-
tained in the chain extenders.
1
H-NMR studies
To confirm the interaction between OH and C=O end
groups of PLA and the reactive functional groups of
chain extenders, 1H-NMR studies were carried out.
Particularly, Fig. 8 shows the 1H-NMR spectrum of
neat PLA in comparison with the spectra of PLA
modified with 1 wt% of PBO and 1 wt% of PMDA at
Stage 3 because at this stage more significant changes
in FTIR and RAMAN spectroscopies were detected.
The 1H-NMR spectrum of neat PLA (Fig. 8a) exhibits
the multiple signals for proton corresponding to =CH–
methine groups (a) centered at 5.17 ppm. By extending
this signal, the quadruple signal is clearly observed at
5.15, 5.16, 5.17 and 5.18 ppm, which is related to cou-
pling between CH and CH3 PLA protons, whereas the
signal of CH3 methyl group protons (doublet) (b) lo-
cated at 1.58 and 1.59 ppm is assigned to the repeating
PLA unit. Moreover, the multiple signal attributed to
neighboring protons of the CH group (c) attached to
the OH end group of PLA can be seen, which is located
at 4.35, 4.36, 4.37 and 4.38 ppm [12, 13].
On the other hand, in the PLA-1%PBO-S3 spectrum
(Fig. 8b), low-intensity signals within the
3.52–3.83 ppm interval (as shown in extended sig-
nals) were detected, which are attributed to CH2
aliphatic group protons attached to a N atom, which
was possibly produced by the ring opening of oxa-
zoline of PBO as well as in the 7.54–8.23 ppm inter-
val; signals corresponding to CH (/) protons of
aromatic groups in PBO were identified. These sig-
nals confirm chemical interactions between PLA
carboxyl end groups and the PBO chain extender.
Similarly, in the 1H-NMR spectrum of PLA modified
with 1 wt% of PMDA at S3 (Fig. 8c), slight modifi-
cations in the chemical shifts of the CH3 and CH
proton signals with respect to neat PLA were
observed; in addition, low-intensity multiple signals
located between 8.05 and 8.23 ppm, assigned to
protons of CH (/) of aromatic groups, were detected.
Table 1 summarizes the chemical shifts of all the
analyzed samples, where the effect of both chain
extenders can be seen from the addition at Stage 1.
These results suggest that the addition of chain
extenders to PLA produce changes in the chemical
environment of 1H protons in the PLA structure,
confirming the modifications previously reported by
FTIR and Raman spectroscopies.
Reactions conducted by adding chain extenders to
PLA were also confirmed by detecting an increase in
the molecular weight (see Figures I-III in the sup-
plementary material), especially when the PMDA
chain extender is incorporated to PLA chains.
Interactions between PLA and chain
extenders
Oxazoline compounds such as PBO can generate a
blocking reaction, where the chain extender molecule
reacts with the end carboxyl group from the PLA
chain and also a coupling reaction that consists of an
extender molecule reacting with 2 polymer chains
[28]. J. Tuominen et al. reported that bis (2-oxazoline)
is inert to aliphatic alcohols and reacts selectively
with the carboxyl end group of polyester through the
opening of the ring at position 1 and 5; this reaction
produces compounds that possess both amide and
ester bonds [10, 29]. Based on the literature and
structural characterization, the most probable mech-
anism is exhibited in Fig. 9: modified PLA with PBO
at S2 and S3 with registered signals corresponding to
aromatic groups, which are attributed to chain
extender presence within the PLA structure.
The results from the structural characterization
indicate that signals assigned to CH protons in the
PMDA aromatic group were detected, confirming the
interactions between PLA hydroxyl end groups and
the C=O of PMDA.
Three possible reactions between PLA and PMDA
are possible: coupling, branching and complex
branching or crosslinking (Fig. 10). The coupling
reaction takes place when anhydride functionalities
of one molecule of PMDA interact with terminal
polyester hydroxyl end groups of two PLA chains,
giving the formation of two carbonyl groups per
incorporated PMDA moiety. The branching reaction
takes place when more than two PLA chains react
with one PMDA molecule. The complex branching
reaction occurs when more than one PMDA molecule
react with more than two PLA chains, generating a
crosslinking structure or gel; however, it has been
reported that this could be achieved by using 1 wt%
of PMDA [30, 31]. Diverse authors have also
 J Mater Sci

Figure 8 1H-NMR spectra of (a) b

a neat PLA and PLA modified O CH 3
a
O
Neat PLA c C [ CH ] O a C
with b 1 wt% of PBO and HO
CH O C n
CH OH
c 1 wt% of PMDA at Stage 3. CH 3 O CH 3
b b
b

1.59
1.58
5.17

5.16
5.18

5.15
1.60 1.56

4.38
4.37
4.36
4.35
1
δ ( H , ppm)

5.18 5.17 5.16 5.15 5.14

1
δ ( H , ppm) TMS
a
4.36
1
δ ( H , ppm)
CDCl 3 c

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
1
δ ( H , ppm)

(b)
PLA-1 w t.%PBO-S3
8.00
7.98
8.23

7.55
7.54

3.52
3.83

3.71

8 .3 8 .1 7 .9 7 .7 7 .5
1 3. 9 3. 8 3. 7 3. 6 3. 5
TMS
δ ( H , ppm) 1
δ ( H , ppm)
CDCl 3
3.83
3.71
3.52
8.23
8.00
7.98

7.55
7.54

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
1
δ ( H , ppm)

(c)
5.11
5.10
5.09
5.08

1.52
1.51

PLA-1 w t.%PMDA-S3

5.10 5.07
1
δ ( H , ppm)
8.23
8.21

4.31
4.30
4.29
4.28
8.15

8.11

8.05

1.52 1.48 1.32

1
δ ( H , ppm)

8.25 8.20 8.15 8.10 8.05 8.00

1
δ ( H , ppm) 4.32 4.28 TMS
1
δ ( H , ppm)
8.21
8.15
8.11
8.05

CDCl3

9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0
1
δ ( H , ppm)
J Mater Sci

Table 1 1H-NMR chemical

shifts of neat PLA and PLA Sample d CH(/) d CH(a) d CH(c) d CH2 d CH3(b)
modified with 1 wt% of PBO
Neat PLA – 5.15 4.35 – 1.58
and 1 wt% of PMDA at
5.16 4.36 1.59
different synthesis stages
5.17 4.37
5.18 4.38
PLA-1%PBO-S1 7.58 5.15 4.35 3.50 1.58
8.19 5.16 4.36 3.68 1.59
8.28 5.17 4.37 3.80
5.18 4.38
PLA-1%PBO-S2 7.58 5.17 4.37 3.52 1.60
8.19 5.18 4.38 3.69 1.61
8.30 5.19 4.39 3.74
5.20 4.40
PLA-1%PBO-S3 7.54 5.17 4.37 3.52 1.60
7.55 5.18 4.38 3.71 1.61
7.98 5.19 4.39 3.83
8.00 5.20 4.40
8.23
PLA-1%PMDA-S1 8.09 5.11 4.31 – 1.54
8.15 5.12 4.32 1.55
8.19 5.13 4.33
8.24 5.14 4.34
8.25
PLA-1%PMDA-S2 8.04 5.08 4.28 – 1.51
8.11 5.09 4.29 1.52
8.15 5.10 4.30
8.20 5.11 4.31
8.23
PLA-1%PMDA-S3 8.05 5.08 4.28 – 1.51
8.11 5.09 4.29 1.52
8.15 5.10 4.30
8.21 5.11 4.31
8.23

demonstrated that CBC works as an adequate chain
extender for polycondensates such as PLA [32, 33].
Thus, the reaction can happen in two ways, where
the terminal OH group of PLA reacts with the CBC
chain extender, giving an intermediate, followed by a
reaction with the other end of the chain. Figure 11
displays a schematic representation of the possible
reactions between the OH group in PLA and C=O of
the chain extender, CBC. According to the figure, the
nucleophilic attack of the terminal OH group either at
the central carbonyl group or carbonyl of the rings in
caprolactam takes place. Intermediate reactions are
formed by substitution or opening of one of the rings
in caprolactam and subsequently forming carbonates,
urethane and urea. In this context, it was observed
that only samples with 1 wt% of CBC added at S1
and S3 registered structural modifications, which
suggests that the methane group joined to OH reacts
with the C=O in the chain extender, CBC.
X-ray diffraction
X-ray diffraction is another useful tool to study the
structural modifications of these systems. Generally,
depending on the synthesis conditions, two different
crystal structures, a and b, may be obtained for PLA
[34]. Figure 12a, b shows the X-ray diffraction pat-
terns of neat PLA and PLA modified with 1 wt% of
PBO and 1 wt% of PMDA at different synthesis
stages. As it can be seen, the diffraction pattern of
neat PLA shows peaks located at 2h = 13.4°, 16.8°,
19.1° and 22.8°, corresponding to (103), (110/200),
(203) and (210) planes, respectively. These reflections

Figure 9 Reaction mechanism for PLA and PBO chain extender.
were indexed in agreement with the PDF #00-054-
1917 card and Brizzolara et al. [35], which are con-
sistent with some signals of a pseudo-orthorhombic
crystal structure that adopts a 103-helix conformation
for the a-form reported by Barrau and De Santis and
Kovacs [34, 36]. This conformation was predomi-
nantly suggested for pure PLA [35, 36]. Nevertheless,
studies have demonstrated that the PLA structure
has not been completely established [37]. In this
sense, the diffraction pattern of neat PLA indicates a
semi-crystalline material that although it presents
some crystalline domains corresponding to a pseudo-
orthorhombic structure, the amorphous domains are
predominant in its structure, as it was observed by
Raman spectroscopy.
The X-ray diffraction patterns of PLA modified
with PBO chain extender do not show significant
modifications compared with neat PLA. However, in
PLA-1 wt% PBO-S3, some slight traces of crystallinity
which coincide with those exhibited by neat PLA are
observed. Meanwhile, in X-ray diffraction patterns of
PLA modified with PMDA at Stages 2 and 3, the
broad signal at 2h ca. 16.8° did not appear. Instead of
this signal, a diffraction model indicative of a crys-
talline material was identified, showing peaks at
2h = 14.8°, 16.4°, 18.8°, 22.1° and 31.1°, corresponding
to the (010), (200), (203), (210) and (306) planes,
respectively. These signals are assigned to the
J Mater Sci
pseudo-orthorhombic crystal structure of PLA [35],
confirming that the PMDA chain extender modified
the low crystallinity of PLA, which is attributed to its
predominant amorphous nature by means of rear-
ranging amorphous chains into crystalline regions
[38]. According to Hung et al. [39], these results are
associated with the fact that the chain extender acts as
a nucleating agent that promotes PLA crystallization;
besides, the behavior of the PLA-PMDA system is
strongly influenced by the symmetric and rigid
structure of the chain extender, which leads to a
higher structural order in PLA. Therefore, the exis-
tence of chemical interactions between PLA and
PMDA, which were also observed by FTIR, Raman
and NMR spectroscopies, can be confirmed.
Thermal analysis by DSC
Thermal properties such as glass transition temper-
ature (Tg), melting temperature (Tm) and crystalliza-
tion temperature (Tc) of PLA modified with chain
extenders were analyzed and acquired by DSC
results. In Fig. 13, DSC thermograms of neat PLA and
PLA modified with 1 wt% of PBO and 1 wt% of
PMDA at different synthesis stages are shown.
From the results, it is observed that neat PLA
shows its amorphous domain characteristics at 60 °C
(Tg), which is found within the 50–70 °C interval,
J Mater Sci
Figure 10 Reaction
mechanism for PLA and
PMDA chain extender.
which has been reported by several authors
[21, 40, 41]. Another PLA characteristic is evidenced
by an exothermic peak related to cold crystallization
through chain folding and subsequent ordering of the
crystalline domains located at 86 °C (Tc) while a
poorly defined broad endotherm identified at 115 °C
and another signal at 132 °C were associated with the
transition from the crystalline phase to melt (Tm).
Cold crystallization is attributed to a high nucleation
density and a very fast crystallization process and
occurs at temperatures below the melting point, far
from equilibrium [42]. Lim et al. [43] reported that the
Tm is a function of the optical purity of PLA; how-
ever, typical Tm values for PLA are within the
130–160 °C interval. The presence of Tg and Tm
indicate that PLA is a semi-crystalline material;
although in this case, the shape and intensity of sig-
nals apparently reflect predominant amorphous
domains in PLA. Table 2 summarizes the values of
thermal transitions obtained from DSC thermograms
of all tested samples.
In the case of the addition of PBO chain extender,
samples obtained at Stages 1 and 2 showed a reduc-
tion in the Tg = 50 °C, which is probably due to the
poor interaction between the chain extender and
PLA. On the other hand, the incorporation of PBO at
Stage 3 displayed Tg = 66 °C, which indicates the
lowest chain mobility that is mainly due to the
interaction between the PBO chain extender and PLA
at the highest temperature. In this case, Tg was

Figure 11 Reaction mechanism for PLA and CBC chain extender.
increased from 60 to 66 °C with PBO extender com-
pared with the unmodified PLA. Similarly, the crys-
tallization behavior is modified depending on the
reaction conditions. For example, no Tc is detected for
the product obtained at Stage 1, indicating that this
system does not crystallize completely [44]. Instead,
there was an increase in Tc as it went from Stage 2
(Tc = 79 °C) to Stage 3 (Tc = 102 °C); this behavior
trend is correlated with the mobility of chain seg-
ments of the glassy part, which increases gradually,
and is known as cold crystallization [45]. Tm was
found to be between 120 and 124 °C, compared to Tm
detected for neat PLA.
On the other hand, the incorporation of PMDA
chain extender to PLA at Stage 1 provoked a
remarkable Tg reduction in the products obtained at
different stages: Tg = 56 (for Stage 1), Tg = 51 (for
Stages 2 and 3). This fact is attributed to the nature of
the chain extender, which tends to have hard seg-
ments, and after the interaction with PLA, the chains
are harder and therefore, Tg decreases. This result is in
agreement with that reported by S. H. Chiu with
phosphorus units added to polyurethanes [46].
J Mater Sci
Compared to the melting point after the addition of
PBO, which was detected between 120 and 124 °C, the
other chain extender, PMDA, generates higher melt-
ing points c.a. 140 °C. This fact is explained by better
interaction between PLA and PMDA compared to
PBO, which produces longer chains. As it is known,
higher molecular weight chains are more difficult to
melt and consequently, the melting point is increased.
The addition of PMDA and PBO did not change
significantly the decomposition temperature since the
decomposition temperature (Td) was found in the
290–283 °C interval.
The measurement and crystallinity degree values
were obtained from Eq. (1). The total integral over the
melting peak is defined as the melting enthalpy
(DHm ), and it is calculated from the DSC thermo-
grams. The crystallinity degree ðXc Þ was calculated
from the fusion heat (DHm ) values of synthesized
PLA, PLA modified with PMDA and PBO and the
enthalpy value at 100% (for PLA, 93 J/g) using the
following equation:
DHm
Xc ð%Þ ¼ 100 ð7Þ
DH0
J Mater Sci

(a) and material formulation, which in turn reflect the

(203)
(010) (200)
(103)
response to a load or applied stress [47].
PLA-1 wt.%PMDA-S3 The calculated hardness (H), elastic modulus

(200)
(306)
(E) and depth profiles at a maximum indentation
PLA-1 wt.%PMDA-S2 load of 5 mN for neat PLA and PLA modified with
Intensity (a.u.)

PLA-1 wt.%PMDA-S1 chain extenders are shown in Table 3 and Fig. 14.
Neat PLA displayed the typical H and E reported
PLA-1 wt.%PBO-S3
in the literature with an indentation depth of
PLA-1 wt.%PBO-S2 1009 nm [48]. PLA-1 wt% CBC-S1 (1000 nm) and
PLA-1 wt.%PBO-S1 PLA-0.25 wt% CBC-S3 (992 nm) had no influence on
Neat PLA the depth penetration, whereas PLA-0.25 wt% CBC-
S1 (1065 nm), PLA-0.25 wt% CBC-S2 (1089 nm) and
PLA-1 wt% CBC-S2 (1056 nm) showed weaker sur-
10 15 20 25 30
faces to penetration by the indenter compared to that
2θ (degrees)
of pure PLA. The only sample that had a better
resistance to surface penetration was PLA-1 wt%
(b) Neat PLA CBC-S3 (887 nm); this sample was less hard and
(200)

PLA-1 wt.% PBO-S1

softer than PLA (H = 245 ± 9 MPa,
PLA-1 wt.% PBO-S2
PLA-1 wt.% PBO-S3 E = 4.08 ± 0.06 GPa). Another observation was the
(010)
(203)

PLA-1 wt.% PMDA-S2 decrease in H with 1 wt% of CBC at the different

PLA-1 wt.% PMDA-S3 stages (from S1 to S3).
Intensity (a.u.)

(103)

PLA-1 wt.% PMDA-S1

The results indicate that the PBO chain extender
(306)
(210)

exerts either no influence or promotes a significant

0 10
Figure 12 X-ray diffraction patterns of neat PLA and PLA
modified with 1 wt% of PBO and 1 wt% of PMDA at different
synthesis stages.
From the obtained results, the amorphous domains
tend to prevail more in the synthesized PLA than in
the crystalline ones because Xc was of 37%. As
expected, the Xc of PLA decreases with the addition
of chain extender (PMDA or PBO); the % values were
found in the 32–31% interval.
Nanoindentation tests
Hardness, elastic modulus and creep measurements
As it is well known, the mechanical performance of a
material depends on different parameters such as
crystallinity, polymeric structure, molecular weight
decrease in penetration resistance of the whole
material in all compositions and stages, which is
similar to what was reported by Shen et al. [47]. For
example, PLA-1%PBO-S1 shows a relative decrease
of 40% (172 ± 5 MPa) compared to neat PLA
20 30 40 50 60 70 (282 ± 3 MPa). The best sample for penetration to
2θ (degrees) surface resistance (866 nm) was PLA-1 wt% PBO-S3,
which was more rigid and less hard
(E = 4.58 ± 0.05 GPa, H = 247 ± 7 MPa). It was
observed that H and E are reduced in all samples,
except with 0.25 wt% of CBC, where it was increased
to 4.72 ± 0.05. With 0.25 wt% of PBO, H is reduced,
and E changes from 4.24 ± 0.06 to 3.83 ± 0.04 MPa
from S1 to S2 and it is maintained at 4.72 ± 0.05 MPa
while reducing the surface penetration. On the other
hand, with 1 wt%, H and E are increased propor-
tionally from S1 to S3; in this case, the surface pene-
tration was improved.
According to Fischer-Cripps [49], hardness mea-
surements are important because they are related, in
many cases, to strength or fracture toughness of the
sample. Furthermore, it is evident that the elastic
modulus decreased in most samples.
By considering the error margin, PMDA addition
shows no significant changes between the different
stages of addition and PLA. The only difference was
 J Mater Sci

(a)
Neat PLA Endothermic
0.9

0.6
process
60°C
0.3

0.0
20 40 60 80 100

PLA-1 wt.% PBO-S2 0.9 PLA-1 wt.% PBO-S3

0.9
0.6 50 °C 0.6
0.3
66 °C
0.3
0.0 0.0
20 40 60 80 100 20 40 60 80 100
Heat Flow (J/g)

0.9 PLA-1 wt.% PBO-S1 0.9 PLA-1 wt.% PMDA-S2

0.6 50 °C 0.6 51 °C
0.3 0.3
0.0 0.0
20 40 60 80 100 20 40 60 80 100

0.9 PLA-1 wt.% PMDA-S3 0.9 PLA-1 wt.% PMDA-S1

0.6 51 °C 0.6 56 °C
0.3 0.3
0.0 0.0
20 40 60 80 100 20 40 60 80 100

Temperature (°C)

(b) 0.00
exothermic
peaks
-0.01

-0.02
Heat flow (J/g)

endothermic
peaks
-0.03
Neat PLA
PLA-1 wt.%PBO-S2
-0.04 PLA-1 wt.%PBO-S3
PLA-1 wt.%PBO-S1
PLA-1 wt.%PMDA-S2
-0.05
PLA-1 wt.%PMDA-S3
PLA-1 wt.%PMDA-S1
-0.06
0 50 100 150 200 250 300 350
Temperature (°C)

Figure 13 DSC thermograms of neat PLA and PLA modified with 1 wt% of PBO and 1 wt% of PMDA at different synthesis stages.

Table 2 Thermal transitions

obtained from DSC Sample Tg (°C) Tc (°C) Tm (°C) Xc (%) Td (°C)
thermograms of neat PLA and
Neat PLA 60 86 114, 132 37 290
PLA modified with chain
PLA-1 wt%PBO-S1 50 – 120.4 27 290
extenders at different synthesis
PLA-1 wt%PBO-S2 50 79 124 21 283
stages
PLA-1 wt%PBO-S3 66 102 124–135 32 290
PLA-1 wt%PMDA-S1 56 76, 103 142.5–131 26 285
PLA-1 wt%PMDA-S2 51 100 140, 125 21 280
PLA-1 wt%PMDA-S3 51 76.5 141.0 31 286
J Mater Sci

Table 3 Values of hardness (H), elastic modulus (E) and inden- [50]. They reported that after the chain extension of
tation creep (CIT) of neat PLA and PLA modified with chain PLA, there were stronger interactions between
extenders at different synthesis stages molecules with higher molecular weight, which are
Sample H (MPa) Es (GPa) CIT (%) beneficial for the improvement of toughening
properties.
Neat PLA 282 ± 3 4.23 ± 0.05 4.8 ± 0.3 Additionally, the indentation creep obtained for
PLA-1 wt%PBO-S1 172 ± 5 2.99 ± 0.05 11.8 ± 0.5 samples modified with chain extenders was higher
PLA-1 wt%PBO-S2 208 ± 7 3.57 ± 0.02 7.6 ± 0.4
than that of neat PLA. This change was more signif-
PLA-1 wt%PBO-S3 247 ± 7 4.58 ± 0.05 6.2 ± 0.3
icant for PLA containing PBO and PMDA. The
PLA-1 wt%PMDA-S1 264 ± 5 4.58 ± 0.08 5.9 ± 0.2
PLA-1 wt%PMDA-S2 278 ± 35 3.60 ± 0.1 5.3 ± 0.8
observed creep behavior is closely related to struc-
PLA-1 wt%PMDA-S3 235 ± 19 3.09 ± 0.03 7.4 ± 0.7 tural changes occurring upon incorporating a chain
extender to PLA. The crystallinity decrease of PLA in
the presence of PBO chain extender observed by XRD
is probably the main reason for the increment of
observed in a decrease of E when 1 wt% is added at creep amount in accordance with that reported by
S2 and S3. Shen et al. [47]. However, other reports indicate that
These results suggest that chain extenders lead to a in some cases, when the crystallinity increases, it
decrease in the stiffness and an enhancement in the could provoke a better disposition of chains which
deformation of PLA, which may be related to the facilitates their slippage and orientation under
plasticization caused by the chain extension of PLA. deformation [18].
A similar behavior of PLA containing chain extenders In summary, the incorporation of chain extenders
was also observed by Najafi et al. [18] and Meng et al. at concentrations of 1 wt% to PLA leads to

(a) (b) Neat PLA

5 Neat PLA 5
0.25 wt.% CBC-S1 0.25 wt.% PBO-E1
1 wt.% CBC-S1 1 wt.% PBO-E1
4 0.25 wt.% CBC-S2 4 0.25 wt.% PBO-E2
1 wt.% CBC-S2 1 wt.% PBO-E2
Load (mN)

0.25 wt.% PBO-E3

Load (mN)

0.25 wt.% CBC-S3

3 1 wt.% CBC-S3
3 1 wt.% PBO-E3

2 L max. = 5 mN 2 L max. = 5 mN
Pause = 20 s Pause = 20 s

1 1

0 0
0 200 400 600 800 1000 0 200 400 600 800 1000 1200
Displacement (nm) Displacement (nm)

(c)
5 Neat PLA
0.25 wt.% PMDA-S1
1 wt.% PMDA-S1
4 0.25 wt.% PMDA-S2
1% wt. PMDA-S2
Load (mN)

0.25 wt.% PMDA-S3

3
1 wt.% PMDA-S3

2
P max. = 5 mN
Pause = 20 s
1

0
0 200 400 600 800 1000
Displacement (nm)

Figure 14 Nanoindentation load–displacement curve of the a PLA-CBC, b PLA-PBO and c PLA-PMDA systems at 0.25 and 1 wt% at
different stages (1, 2, 3).
 J Mater Sci

Figure 15 Raman spectra of (b)

the accelerated weathering
(a)
PLA-1 wt.%PBO-S3_ACW
(ACW) test of the a PLA- PLA-1 wt.%CBC-S3 _ACW
PLA-1 wt.%PBO-S3
CBC, b PLA-PBO and c PLA-
PLA-1 wt.%CBC-S3
PMDA systems at 0.25 and
PLA-1 wt.%PBO-S2_ACW
1 wt% at different stages (1, 2, PLA-0.25 wt.%CBC-S3 _ACW
3). PLA-1 wt.%PBO-S2
PLA-0.25 wt.%CBC-S3

Intensity (a.u.)

Intensity (a.u.)
PLA-1 wt.%PBO-S1_ACW
PLA-1 wt.%CBC-S2 _ACW
PLA-1 wt.%PBO-S1
PLA-1 wt.%CBC-S2

PLA-0.25 wt.%PBO-S1_ACW
PLA-0.25 wt.%CBC-S2 _ ACW

PLA-0.25 wt.%CBC-S2 PLA-0.25 wt.%PBO-S1

Neat PLA_ACW
Neat PLA_ACW

Neat PLA C-COO Neat PLA CH3 C=O

C-C-O C-COO CH 3 C=O C-O
C-O

300 600 900 1200 1500 1800 300 600 900 1200 1500 1800
Raman shift (cm -1) Raman shift (cm -1)

(c)
PLA-1wt.%PMDA-S3_ACW

APL-1%PMDA-S3
Intensity (a.u.)

PLA-1%PMDA-S2_ACW

PLA-1 wt.%PMDA-S2

Neat PLA_ACW

Neat PLA
C-COO C-H 3 C=O
C-O

300 600 900 1200 1500 1800

Raman shift (cm -1)

remarkable changes in the mechanical properties of evaluated by Raman Spectroscopy and differential
PLA. This suggests that the obtained materials exhi- scanning calorimetry (DSC) (Figs. 15 and 16).
bit less stiffness and good performance against Accelerated weathering had a clear effect on the
deformation compared with neat PLA. structural properties. UV light and humidity resulted
in a decrease in the intensity of C=O and C–O bands of
Structural and thermal behavior neat PLA. PLA samples modified with CBC, PBO and
upon accelerated weathering test PDMA showed a similar behavior. For example, C=O
bands located at 1768–1751 cm-1 in PLA modified
The structural and thermal changes recorded for neat with CBC were shift to 1775–1763 cm-1. Similarly, C–
PLA, PLA-CBC, PLA-PMDA, and PLA-PBO after C–O bands at 410–396 cm-1 were split into two bands
900 h of exposure to accelerated weathering were that are more defined. This band was more intense in
J Mater Sci

Figure 16 Comparison of
DSC thermograms of the neat PLA 1wt.%CBC-S3_ACW PLA-1 wt.%PBO-S3_ACW
PLA, PLA-CBC, PLA-PBO PLA 1wt.%CBC-S3
and PLA-PMDA systems PLA-1wt.%PBO-S3
PLA 0.25wt.%CBC-S3_ACW PLA-1wt.%PBO-S2_ACW
before and after the accelerated

<< Endo
weathering test.

<< Endo
PLA-1wt.%PBO-S2
PLA 0.25wt.%CBC-S3 PLA-1wt.%PBO-S1_ACW

Heat Flow (mW)

Heat flow (mW) PLA-1wt.%CBC-S2_ACW T PLA-1wt.%PBO-S1
m
PLA-1wt.%CBC-S2 PLA-0.25wt.%PBO-S1_ACW

PLA-0.25wt.%CBC-S2_ACW PLA-0.25wt.%PBO-S1

PLA-0.25wt.%CBC-S2 Neat PLA_ACW

Neat PLA_ACW
Neat PLA
Neat PLA Tf / Int.
Tm/ACW Tf

50 75 100 125 150 175 200 40 60 80 100 120 140 160 180 200
Temperature (°C) Temperature (°C)

PLA-1wt.%PMDA-S3_ACW

PLA-1wt.%PMDA-S
Heat Flow (mW) <<Endo

PLA-1wt.%PMDA-S2_ACW

PLA-1wt.%PMDA-S

Neat PLA_ACW

Neat PLA

Tf / Int. Tf

40 60 80 100 120 140 160 180 200

Temperature (°C)

samples at S3 and it is attributed to the detection of PBO addition at 0.25 wt% at S1 displays an
crystalline and amorphous structures. As it is known, increase in intensity in C–C–O bands, suggesting an
at the beginning, the samples had more % of amor- increase in the degradation of the amorphous part,
phous regions, but by subjecting them to the acceler- similar to CBC. Nevertheless, the chemical structure
ated weathering test, they were degraded and of PBO helps to obtain a material that is less sus-
therefore, crystalline regions can be easily noticed in ceptible to degradation by adding 1 wt% to PLA
the spectra. [27]. Nevertheless, PLA modified with (Fig. 15b). PMDA at 1 wt% at S2 and S3 was found to
chain extender at S3 displays better stability to degra- have no significant changes (Fig. 15c).
dation. Low degradation can be explained in terms of The photodegradation of PLA and PLA modified
material crystallinity, which reduces the possibility of with chain extenders (CBC, PBO and PMDA) occurs
hydrolysis in the chains [51] (Fig. 15a). mainly by carbonyl chromophores that absorb UV-B
 J Mater Sci

24
24
22 22

20 20

Weight loss (%)

Weight loss (%)

18 18
16 16
14 14
12 12
Neat PLA Neat PLA
10 PLA-0.25wt.% CBC-S2 10 PLA-0.25wt.% PBO-S1
PLA-1wt.% CBC-S2 PLA-1wt.% PBO-S1
8 8
PLA-0.25wt.% CBC-S3 PLA-1wt.% PBO-S2
6 PLA-1wt.% CBC-S3 6 PLA-1wt.% PBO-S3
4 4
3 6 9 12 15 3 6 9 12 15
Days Days

24
22
20
Weight loss (%)

18
16
14
12
10
8 Neat PLA
PLA-1wt.% PMDA-S2
6 PLA-1wt.% PMDA- S3
4
2
3 6 9 12 15
Days

Figure 17 Weight loss of the neat PLA, PLA-CBC, PLA-PBO and PLA-PMDA systems before and after hydrolytic degradation.

radiation and undergo photolysis via the Norrish II
reaction, leading to chain scission [52].
The thermal properties of PLA and PLA modified
with chain extenders before and after the accelerated
weathering test were also evaluated by differential
scanning calorimetry (DSC). Tg was not detected in
samples after aging because the polymer degradation
begins first in the amorphous region than in the
crystalline. The most significant change during
weathering was the shifting of melting point (Tm) to
lower temperatures due to changes regarding crys-
tallite size, and molecular weight differences derived
from chain scission in the crystalline regions. This
behavior has been found in other polymeric systems
[53]. Another change was the disappearance of crys-
tallization peaks in all the samples, which means that
the polymer backbone has a low crystallization abil-
ity [54] (Fig. 16).
Hydrolytic degradation
The hydrolysis of PLA and PLA modified with chain
extenders was monitored by weight loss of the
specimens and measuring of the medium pH every 3,
6, 9 and 15 days, as it is observed in Figs. 17 and 18.
In comparison with neat PLA, all the samples
showed less weight loss, especially those that were
modified with PMDA, followed by PBO and finally
by CBC, which was found to be more susceptible to
degradation than the others. These results suggest
that aromatic groups in PBO and PMDA chain
extenders contribute to a slower degradation in PLA.
The addition of aromatic fractions to polymers such
as polyesters provides structural and hydrophobic
properties leading to decreasing degradability [55],
and it is mandatory to optimize the ratio between the
aromatic and aliphatic groups [56]. Hydrolytic
degradation of PLA-based materials implies the
scission of ester groups, and it is catalyzed by
hydronium o hydroxyl ions. As it is reported, a high
OH concentration in alkaline media accelerates the
degradation of PLA [3]. In this context, the medium
pH value decreases considerably from neat PLA,
from the 3rd immersion day (pH of 4.8). The pH
value decreases due to degradation, which suggests
autocatalysis that results in the concentration
increasing of COOH groups [57]. However, it was
observed that the decrease is more evident in samples
J Mater Sci

5.4 5.6
Neat PLA Neat PLA
5.2 5.4 PLA-0.25wt.% PBO-S1
PLA-0.25wt.% CBC-E2
PLA-1wt.% CBC-S2 PLA-1wt.% PBO-S1
PLA-0.25wt.% CBC-S3
5.2 PLA-1wt.% PBO-S2
5.0
PLA-1wt.% CBC-S3 PLA-1wt.% PBO-S3
5.0
4.8
pH

pH
4.8
4.6
4.6
4.4
4.4
4.2 4.2
3 6 9 12 15 3 6 9 12 15
Days Days

5.8
5.6 Neat PLA
PLA-1wt.% PMDA-S2
5.4 PLA-1wt.% PMDA-S3
5.2
5.0
pH

4.8
4.6
4.4
4.2
3 6 9 12 15
Days

Figure 18 pH monitoring of the neat PLA, PLA-CBC, PLA-PBO and PLA-PMDA systems before and after hydrolytic degradation.

with PMDA. The degradation of the chain end can be
explained by an intramolecular transesterification,
which consists in an electrophilic attack of the OH
thermal group over the 2nd carbonyl that is catalyzed
by a base and conducts to the formation of the lactide
ring [29, 41, 58–60]. The polymer is fragmented by the
hydrolysis of the resulting lactide (Fig. 18). Subse-
quently, the lactide is hydrolyzed into two molecules
of lactic acid. Finally, intramolecular degradation
occurs by a random alkaline attack over the carbon of
the ester group followed by hydrolyzation of the
ester bond, giving formation to different low molec-
ular fragments.
Conclusions
Lactic acid-based polymers modified with chain
extenders were synthetized by direct polycondensa-
tion. The potential range of properties of these
products was evaluated by structural, thermal and
mechanical analysis. Based on the FTIR, Raman and
NMR studies, slight modifications in the shape and
intensity of several signals as well as the presence of
new signals produced by interactions between OH
and C=O end groups of PLA were detected. Ade-
quate conditions for modifying PLA with chain
extenders were found to depend on the addition
stage and extender concentration. The most promis-
ing results were obtained by adding 1 wt% of PBO
(S3), 1 wt% of PMDA (S2 or S3) and 0.25 wt% of CBC
for samples labeled as S2 or S3. Independently of the
addition and type of chain extender, the crystallinity
of the pseudo-orthorhombic structure is reduced.
Thermal analysis by DSC revealed that the addition
of both chain extenders caused a decrease in Tg,
suggesting higher mobility of the PLA molecular
chain. The addition of chain extenders also showed a
remarkable decrease in hardness from 282 to
247 MPa, slightly increasing the elastic modulus
(4.2–4.5 GPa) and indentation creep (4.8–6.2%),
which led to a better performance compared to the
rigid neat PLA. Finally, the addition stage did not
affect the degradation mechanism because it depends
more directly on the interactions between PLA and
chain extenders. PLA is more sensitive to the degra-
dation process than PLA-chain extender systems,
which can potentially help packaging applications.

Acknowledgements
C. A. Ramı́rez-Herrera is grateful to CONACYT for
her graduate fellowship. The authors acknowledge
COFAA and SNI-CONACYT. CNMN-IPN and ESI-
QIE-IPN are recognized for the technical and exper-
imental support provided in the realization of this
research. Thanks to M. E. Adela E. Rodrı́guez-Salazar
for her technical support during the revision of the
manuscript.
Funding
This study was funded by Instituto Politécnico
Nacional through the SIP2013-0773, SIP2018-0496 and
SIP2018-1171 Projects. The authors are also grateful
for the financial support provided by the CONACYT
Research Fellowship-IPN-CICATA Altamira agree-
ment, 2014-1905 and CONACyT CB2015-252181
Projects.
Compliance with ethical standards
Conflict of interest The authors declare that they
have no conflict of interest.
Electronic supplementary material: The online
version of this article (https://doi.org/10.1007/
s10853-018-2380-7) contains supplementary material,
which is available to authorized users.
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