The toughening behavior of PLLA and its asymmetric PLLA/PDLA

blends with lower optical purity

Yanmei Guo, Jun Shao, Haoqing Hou
College of Chemistry and Chemical Engineering, JiangXi Normal University, Nanchang 330022, China
Correspondence to: J. Shao (E - mail: 5566789sj@live.cn or jun.shao@jxnu.edu.cn)

ABSTRACT: Linear poly(D-lactide) (PDLA) with various molecular weights is synthesized and incorporated into commercial poly(L-lac-
tide) (PLLA) with different optical purities. And then, the crystallization, mechanical and thermal properties of the PLLA and PLLA/
PDLA cast films are investigated. In the PLLA and PDLA/PLLA specimens with lower optical purity, few homochiral crystallites (HC)
form in all the specimens and only a small amount of PLA stereocomplex crystallites (SC) are observed in the blends. The elongation
at break of all the specimens is extraordinary high, >300%. Dynamic mechanical analyses indicate that the destruction temperature
increases at first, and then depresses as enlarging the molecular weight of PDLA in these blends. For the PLLA and PLLA/PDLA with
higher optical purity, more content of HC develops in neat PLLA, and both SC and HC produce in the PLLA/PDLA specimens.
However, the strains of neat specimens and binary blends are much lower than that of specimens with lower optical purity. The
specimens with higher optical purity exhibit higher destruction temperatures and lower loss factors. The high content of crystals (SC
and HC) would act as the physical cross-linking points and provide a key factor to impede the deformation of neat PLLA and binary
blends during stretching, which should result in the fragile behavior of the PLLA and PLLA/PDLA blends with higher optical purity.
C 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44730.
V

KEYWORDS: poly(D-lactide); poly(L-lactide); poly(lactide) stereocomplex; toughening

Received 5 September 2016; accepted 27 November 2016

DOI: 10.1002/app.44730

INTRODUCTION copolymerized to the PLA.14–18 However, for most of the PLLA

Since its monomer, lactic acid, derives from renewable agricul-
tural sources, and its product, poly(lactide) (PLA), is considered
as a green alternative thermoplastic and has the potential to
replace a number of petrochemical based polymers, the PLA
receives much interest from a wide variety of applications rang-
ing from medical devices to engineering materials.1,2 However,
the inferior performances of PLA with respect to the low heat
deflection temperature and fragile property tremendously
impede its applications.3,4 Numerous reports revealed that the
key to manufacture the high-performance PLA lies in sufficient
control of crystallinity and toughening its brittleness.5 Among
huge number of investigations that incorporation of fillers or
other polymers to enhance the crystal nucleation activity in
poly(L-lactide) (PLLA),6–10 one of the turning points in the
development of crystalline control in PLLA comes in the 1987,
when Ikada et al. discovered that adding poly(D-lactide)
(PDLA) to PLLA generated the racemic stereocomplex crystals
(SC) with a melting point at 230 8C, far surpassing that of
enantiomeric PLLA or PDLA homochiral crystals (HC) with an
astounding promotion of over 50 8C.11–13 When referring to the
toughening of PLA, flexible polymers are incorporated into or
composites, such far research works reveal that the improve-
ments of heat resistance temperature (HRT) and mechanical
properties are at the compensation of sacrificing the toughening
of the materials. For the PLLA/PDLA binary blends, although
the HRT is highly improved due to the higher melting tempera-
ture and fast crystallization rate, the elongation at break of these
blends hardly varies19–21 or becomes even worse.22,23
In general, it is thought that the processing condition, degree of
crystallinity, the crystalline size, crystallization rate, and the
chain conformation distribution of the amorphous phase are
responsible for the mechanical performances of semicrystalline
polymers.24–26 Our previous studies imply that the melting tem-
peratures of PLA SC and HC reduce with depressing the optical
purity of PLA, and the micro-phase separation behavior
between PLLA and PDLA are dependent on both the optical
purity and molecular weight of the enantiomeric polymers.27,28
However, limited concerns focus on the mechanical behaviors
of PLLA/PDLA specimens with different optical purity. Since
the PLA with 100% isotactic structure is very difficult to pro-
duce during manufacturing process or under nature circumstan-
ces, and most of the PLA products are present different optical

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Table I. The Characterizations of PLLA and PDLA The Preparation of PLLA/PDLA Solution-Cast Films
The PLLA and PDLA are separately dissolved in dichlorome-
LA/DE ratio Mn Tm thane at a concentration of 12.0 g/L. The solutions are admixed
code (m/m) (kg/mol) PDI (8C) together after the specimens are dissolved completely, and the
PLLA143 — 185.7 1.3 143.1 mixed solutions are stirred for 3 h at room temperature, using
PLLA162 — 107.4 1.5 162.3 a stirrer with a speed of 700 rpm. The mixed solutions are
poured into flat petri-dishes with a diameter of 90 mm (Beijing
PLLA173 — 124.9 1.6 173.2
Synthware glass). The solution-cast specimens are obtained by
PDLA9 70/1 9.4 1.7 163.0
solvent evaporation at room temperature and further vacuum-
PDLA18 140/1 18.4 1.7 169.2
drying at 40 8C for 72 h. The weight ratios of PLLA: PDLA in
PDLA24 210/1 23.6 1.6 172.2 this study are fixed at 90:10. In the PLLA/PDLA specimens, the
PDLA35 280/1 35.0 1.6 176.8 neat PLLAs are coded as L143, L162, and L173, and the num-
PDLA67 560/1 67.4 1.8 176.9 bers after L are their melting temperatures, respectively. For the
PDLA102 840/1 102.2 1.6 177.5 blends L143/PDLA, they are labeled as DXX, where the numbers
after D are their number molecular weights (Mn), respectively.

purity in actual case. Thus, the mechanical behaviors of PLA Characterizations

with different optical purity and its stereocomplex formation
with its isomer are very important for their application. In this
study, the commercial grade neat PLLA with various optical
purity and the PLLA/PDLA asymmetric blends (10 wt %
PDLA) are prepared by solution casting, and the crystallization
behavior, mechanical properties and dynamic thermal mechani-
cal performance of the neat PLLA and PLLA/PDLA specimens
are investigated. Results reveal that the mechanical properties
depend on the optical purity and the crystallinity of the speci-
mens. This investigation would provide a new sight on the
application of PLA materials with different optical purity.
EXPERIMENTAL
Materials
The PLLAs with different optical purity are commercial grade
products which are kindly supplied by Zhejiang Hisun biomate-
rials Co., Ltd. The tin (II) 2-ethylhexanoate (Sn(Oct)2, 95%) is
bought from Sigma-Aldrich, and used as received. The diethy-
lene glycol monomethyl ether (DE) (>99.5%) is purchased
from Aladdin. Dextrorotatory-lactide (D-LA) (optical purity
99.5%) is supplied by Changchun Sino Biomaterials Co., Ltd.
(China), and is recrystallized thrice in dry ethyl acetate before
use. The toluene is refluxed with sodium and distilled under
nitrogen prior to use. These materials are preserved under iner-
tia atmosphere before used.
The Synthesis of PDLA
The PDLA is synthesized by ring-opening polymerization of D-
LA at 120 8C for 24 h in anhydrous toluene, catalyzing by
Sn(Oct)2 (0.5 wt %) and initiating by DE. The molecular
weight is regulated by the D-LA/DE molar ratio.12,13,28 The
PDLA toluene solution is precipitated in large amount of frozen
ethanol (the V/V of toluene/ethanol is 1/10). The precipitated
polymer is dissolved in dichloromethane and precipitated in
ethanol again. The white purified solid product is received after
filtrating, and is dried at 60 8C in vacuum to constant weight
before used. The characterizations of PLLA and PDLA are listed
in Table I. The numbers after PLLA in the code name is its
melting temperature, and the numbers after the PDLA is its
number average molecular weight (Mn).
The Mn and molecular weight distribution (PDI) of PLLA and
PDLA samples are evaluated by a Waters gel permeation chro-
matography system (GPC), which is equipped with two Styragel
HR gel columns, i.e., HR2 and HR4. The measurement is car-
ried out at 35 8C by using chloroform as the elution solvent,
and the flow rate of elution is 1 mL/min. Monodispersed poly-
styrene standards purchased from Waters Co. with a molecular
weight ranging from 1790 to 6.0 3 105 g/mol are used to gener-
ate the calibration curve.
The crystalline structures are characterized using wide-angle X-
ray diffraction (WAXD) with a Bruker D8 Advance X-ray dif-
fractometer. The X-ray diffractometer uses a Cu-Ka radiation
source (k 5 0.154 nm, 40 kV, 25 mA), with the scanning angle
ranges of 2u 5 10 2 308 and at a scanning speed of 0.58/min.
The thermal properties are analyzed by differential scanning cal-
orimetry (DSC) with a DSC 200F3 (NETZSCH, Germany)
under a 20 mL/min nitrogen gas flow. The specimens are heated
at a fixed rate, 10 8C/min, from room temperature to 250 8C.
The first heating of all the specimens is recorded.
The cast films are yielded a plate shape and with a thickness of
0.120 6 0.015 mm. Rectangular strips of 25 3 6 mm2 are cut
from the cast films to investigate the mechanical performances.
All the specimens are measured by a universal testing machine
(SANS, Shenzhen, China) at a constant crosshead speed of
5 mm/min and are stretched at ambient temperature (30 6
2 8C). The Young’s modulus was measured between 0.05% and
0.25% strain. In order to obtain an average value and relative
standard deviation, five paralleled measurements are carried out
for each sample. The measurement of strain (EH) is defined as:
EH 5 k 5 ½ðb2b0 Þ=b0 Þ3100% (1)
where k is the draw ratio, b0 and b are the lengths of samples
between the tensile fixture before and after deformation.
The dynamic mechanical analysis (DMA) is performed on a
Perkin-Elmer Pyris diamond analyzer (DMA), using stretching
mode. The temperature scan starts from ambient temperature
(30 8C) to destruction, and the specimens are heated at a con-
stant rate of 3 8C/min under the nitrogen, the frequency of
dynamic force is 1 Hz and the amplitude is 10 lm. The

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RESULTS AND DISCUSSION

The Properties of PLLA/PDLA with Lower Optical Purity
The XRD spectra of the as-cast neat PLLA and its blends are
shown in Figure 1(a). In the spectrum of neat PLLA, no obvi-
ous diffraction peak is observed, implying that most of the
molecular chains are amorphous. In the D9, D18 and D24
specimens, diffraction peaks at 2u 5 12.18, and 21.08 appear and
enhance, which are assigned to the 110, 300/030 planes of
SC.11–13 As the molecular weight of PDLA further increasing,
the peak at 2u 5 12.18 depresses rapidly, and the diffraction at
21.08 reduces and vanishes finally, which reveals that the content
of SC reduces with further increasing the molecular weight of
PDLA.

Figure 1. The WAXD (a) and DSC (b) of the as-cast neat PLLA and PLLA/
PDLA specimens. [Color figure can be viewed at wileyonlinelibrary.com]
temperature dependent curves of storage modulus (E0 ), loss
modulus (E00 ), and loss factor (tan d) of the specimens are
recorded.
The DSC curves of the cast films present in Figure 1(b), and
the processed data of the DSC are summarized in Table II. The
melting temperature of neat PLLA (Thc1) is found at 140.9 8C
with a melting enthalpy (DHhc1) of 2.7 J/g, indicates that few
HC crystallites form in the specimen. For the PLLA/PDLA
specimens, besides the small melting peak at 140 8C, an obvious
peak around at 200 8C is observed in all the blends, which is
ascribed to the melting of PLA SC. The melting temperature of
SC (Tsc) increases at first before declining, while the melting
enthalpy of SC (DHsc) depresses progressively with increasing
molecular weight of PDLA. In addition, another endothermic
peak at 176 8C is detected after the molecular weight of PDLA
reaches to 67 kg/mol or higher, this temperature is similar to
that melting temperature of PDLA described in Table I. In our
previous investigations, the PLLA and PDLA would form HC
crystallites separately and these crystallites are melted at differ-
ent temperatures when the PDLA with higher molecular weight
is blended with PLLA with lower optical purity.27 Consequently,
the melting peak around 176 8C is assigned to the melting of
HC from the PDLA homopolymer (Thc2). The WAXD results
implying that only SC produce in the binary blends, and the
residual PLLA and PDLA polymers are at amorphous state, but
the DSC curves reveal that all the specimens have a melting

Table II. The DSC Data Before and After Stretching

L143 D9 D18 D24 D35 D67 D102

Before stretching Thc1 (8C) 140.9 138.4 139.7 140.1 138.1 140.4 140.9
DHhc1 (J/g) 2.7 1.3 0.9 0.5 3.4 1.3 2.1
Thc2 (8C) 176.2 176.5
DHhc2 (J/g) 1.9 1.8
Tsc (8C) 203.8 203.8 205.2 203.1 200.9 199.3
DHsc (J/g) 16.1 15.4 15.6 11.4 6.0 3.6
Tcc (8C) 88.2 93.4 90.3 93.4 88.5 89.6 92.8
DHcc (J/g) 17.9 5.1 8.4 6.6 8.4 11.5 8.8
After stretching Thc1 (8C) 138.5 136.8 138.6 137.7 137.2 138.4 139.8
DHhc1 (J/g) 18.9 9.2 14.9 10.3 12.8 14.4 13.3
Thc2 (8C) 173.4 177.5 176.2 176.6
DHhc2 (J/g) 0.5 0.3 2.1 2.4
Tsc (8C) 203.5 204.7 204.8 205.2 201.1 199.3
DHsc (J/g) 16.4 15.2 15.1 11.5 6.1 3.4

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while the tensile strength are rely on both the crystallinity and
the degree of orientation of the specimen.
After all the specimens are stretched to break, the WAXD and
DSC curves of the stretched samples are presented in Figure 3.
The location of the specimens used to analyze is near the bro-
ken position. From the WAXD spectrum [Figure 3(a)], no obvi-
ous diffraction peak is detected in the neat PLLA, which implies
that few crystallites develop after stretching. However, the reflec-
tions at 12.1 and 21.08 assigned to PLA SC are observed in the
D9 specimen. The intensity of these two diffractions weakens
with increasing the molecular weight of PDLA. In addition, a
board and weak diffraction at 16.68 is observed in most of the
binary blends, which should be assigned to the PLA meso-
phase.29,30 The WAXD hints that PLA mesohpase produces in
the blended specimens after stretching. The DSC profiles of the
specimens are listed in Figure 3(b). Obviously, all the specimens
exhibit a big endothermic peak around the glass transition tem-
perature (Tg), the intensity of the endothermic peak become
larger after stretching, the increment of the endothermic peak
should be ascribed to the enthalpy relaxation of the stretched
specimens.31 During stretching, the molecular chains or

Figure 2. The stretching curves (a), and strain, modulus and strength (b)
of the PLLA/PDLA specimens with varied molecular weight of PDLA.
[Color figure can be viewed at wileyonlinelibrary.com]

peak for the PLLA HC, and some of the blends present the
melting peak of PDLA HC, which might be due to the lower
sensitivity of WAXD apparatus or these small amount of HC
are developed during the heating.
The tensile testing experiments of the neat L143 and corre-
sponding blends are displayed in Figure 2(a). Apparently, all the
specimens exhibit a typical yield transition at the stain of 5%
at first, and a plateau region is observed when the EH is not
higher than 100%, then the strain hardening behavior is noticed
subsequently before broken. In the neat PLLA specimen, the
sample is broken at a EH of 460%, for the PLLA/PDLA blends,
the elongations at break tends to decline before increasing as
the molecular weight of PDLA enlarges from 9 kg/mol to
102 kg/mol [Figure 2(b)], while the modulus of the specimens
increases at first, and then decreases as the molecular weight
enlarging. The specimens that exhibit higher EH present lower
modulus. The higher EH and lower modulus should be due to
fewer content of crystallites producing in the specimens, and
the molecular chains or segments could be stretched to a larger
scale. For the tensile strength, it increases at first then decreases
slightly as the molecular weight of PDLA increasing. It is
noticeable that the specimen which presents highest modulus
does not exhibit highest tensile strength, which is due to the Figure 3. The WAXD (a) and DSC (b) of the stretched PLLA/PDLA
Young’s modulus is calculated in the lower deformation district, specimens. [Color figure can be viewed at wileyonlinelibrary.com]

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Figure 4. The DMA data of the PLLA and PLLA/PDLA specimens (a–c).
[Color figure can be viewed at wileyonlinelibrary.com]
segments align along the stress direction, the molecular and seg-
mental mobility lead to volume relaxation and thus reduction
of the free volume. Therefore, when the specimens are heated,
more energy is required for completing the glass transition,
WWW.MATERIALSVIEWS.COM 44730 (5 of 8)
which results in the increment of endothermic peak and higher
Tg after they are stretched. An apparent cold crystallization peak
appears at 90 8C in the DSC curve for all the specimens. This
appearance of the cold crystallization peak would be inter-
preted that, the molecules or segments cannot disorientate (or
relax) freely at this temperature due to the restriction from crys-
tallites (either SC or HC). In addition, the existed crystallites
could act as nucleator to facilitate the crystallization of the ori-
entated molecules or segments. Accordingly, the orientated
structures and the mesophase in the specimens would form
crystals at a convenient environment. However, the total melting
enthalpy of PLLA and PDLA HC (DHhc11DHhc2) of the PLLA/
PDLA specimens increases after stretching although the DHsc
hardly changes, which is due to the reason that the formation
of SC is adequate during solution mixing, and it is stable and
the content of SC do not change during the stretching. Howev-
er, the melting enthalpies of HC are highly improved after
stretching, which indicates that the orientation of molecular
chains and segments mainly induce the development of HC
during heating.
The temperature dependent curves of storage modulus (E0 ), loss
modulus (E00 ), and loss factor (tan d) of the specimens present
in Figure 4(a–c). The L143, D67, and D102 exhibit similar ther-
mal mechanical behaviors during heating, and their E0 and E00
reduce monotonously as the temperature increasing from 35 8C
to higher temperature. The L143 is broken at the lowest temper-
ature (84 8C), this temperature is 90 8C for D102, and it
increases to 94 8C for the D67. In the case of the other speci-
mens, the E0 and E00 reduce at first as the temperature increases
from 35 to 90 8C, and then increase when the temperature ele-
vates from 100 to 130 8C, this enhancement of E0 and E00 is
attributable to the occurring of cold crystallization in this tem-
perature range. In addition, these specimens show higher
destroyed temperature, 140 8C, which is close to the melting
temperature of L143. The higher destruction temperature of
D67 and D102 specimens than neat PLLA should be due to SC
crystallites formed in the PLLA/PDLA specimens, and that rea-
son for the other specimens would be due to relative higher
content of SC and the cold crystallization during heating, which
leads to the samples maintain higher modulus above the Tg. In
the tan d curves, the loss factor reduces at first, and then
increases as the molecular weight of PDLA increasing. More
content of crystallites develops in the specimen would lead to
the lower tan d values during the glass transition.
The mechanical properties imply that the remarkable toughen-
ing behaviors are observed in the neat L143 and its binary
specimens. For the neat L143, the glass transition would appear
at a lower temperature under stress due to most of the molecu-
lar chains are amorphous, and results in the higher elongation
at break than most of reports.19–23 In the case of the PLLA/
PDLA specimens, besides a large amount of amorphous PLLA
molecular chains, the SC is produced in these samples, these SC
would act as physical cross-linking points to restrict the mobili-
ty of amorphous molecular chains, and these cross-linking
agents would impede the destruction of specimens during
deformation, Thus, higher content of SC corresponding to
J. APPL. POLYM. SCI. 2017, DOI: 10.1002/APP.44730
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Figure 5. (a) WAXD, (b) DSC, (c) tensile testing, (d) and (e) DMA curve of PLLA/PDLA specimens. [Color figure can be viewed at wileyonlinelibrary.
com]

lower elongation at break and the higher modulus during
deformation.
The Effect of Optical Purity on the Mechanical Properties
In order to investigate the influence of optical purity on the
mechanical properties, the neat L162, L173 and their blends
with PDLA24 are also prepared, The WAXD profiles are
shown in Figure 5(a). For the neat L162, only a weak diffrac-
tion peak at 16.98 is observed, indicating a small amount of
HC crystallites form in the solution cast film. However, obvi-
ous diffraction peaks locate at 12.08 16.98, 19.18, and 21.08,
and weak diffractions at 14.88, 22.58, and 24.08 are detected
in the L162-D24 specimen, implying that more content of
HC as well as SC develop in the blend.11–13 For the neat
L173, apparent reflections present at 16.98 and 19.18, while
the intensity of diffraction assigned to HC reduces and reflec-
tions belong to SC are evident for the L173-D24. In the DSC
of these original specimens [Figure 5(b)], both the L162 and
L173 have an exothermic peak during heating, indicating that
these two specimens do not crystallize completely during
solution evaporation. However, no obvious exothermic signal
is observed in their blends, which reveals that the SC form in
solution mixing would accelerate the development of HC dur-
ing solution evaporation.

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The stress–stain curves of these specimens are displayed in Fig-
ure 5(c), similar to the L143, the L162 and L173 exhibit a yield
behavior around 5% before broken, while the difference is
that the EHs of the two specimens are around at 7%, much low-
er than L143. For the L162-D24 and L173-D24 specimens, both
of the blends are broken before yielding, and the EH declines
slightly after incorporating the PDLA into the PLLA matrix.
The variation mechanical behaviors of L162-D24 and L173-D24
are similar to that of L143/PDLA specimens, which should be
due the reason that more content of crystallites generate in the
binary blends than the neat PLLA specimens, and the molecular
chains and segments would be restricted in a more rigid envi-
ronments. However, for the L143 and its corresponding blends,
their EH are much higher than corresponding L162, L173, and
related blends, which should be ascribed to the reason that
more content of crystallites produce in the cast films as the
optical purity enhanced, and the crystallites would have a larger
restriction on the movement and orientation of molecular
chains and segments. The DSC and WAXD curves of the L162,
L173, and their blends after stretching are almost the same at
the as-cast specimens, thus, they were not present here, which
implies that no structure vary before and after stretching.
Figure 5(d,e) present the DMA curves of the L162, L173 and
their blends, the tan d reduce after the PLLA blended with
PDLA, and the tan d decreases with increasing optical purity of
PLLA. The storage (do not show here) and loss modulus reduce
monotonously after the temperature is higher than 60 8C, and
no obvious increment of the modulus is observed during heat-
ing, which indicates that more crystallites form in the solution
evaporation, and higher modulus achieve and lower loss factor
are observed at higher temperature in the specimens with
higher optical purity.
In this investigation, the PLLA neat specimens with lower optical
purity present higher elongation at break during stretching, and
the elongation at break drops with increasing optical purity.
When the PDLA incorporates into the PLLA matrixes, the elon-
gation at break becomes smaller than the neat PLLA specimens.
More content of crystallites (HC and SC) develop in the neat
PLLA and PLLA/PDLA specimens with higher optical purity,
which leads to the lower value of elongation at break, higher
modulus and lower loss factors. This investigation would provide
applications for the PLLA specimens with different optical purity.
CONCLUSIONS
In this study, the PLLAs with various optical purities are blended
with synthesized PDLAs adopting solution casting method. The
crystallization behaviors, mechanical properties, and dynamic
mechanical performances of these specimens are investigated.
Interestingly, the elongation at break is much higher in the neat
PLLA and its PLLA/PDLA blends with lower optical purity. After
the optical purity increasing, more content of crystallites forms
in the specimens and the elongation at break reduces rapidly.
The DMA measurement reveals that, the specimens which pre-
sent lower optical purity exhibit higher loss factors and lower
modulus than corresponding PLLA and PLLA/PDLA specimens
with higher optical purity. WAXD and DSC results indicate that,
WWW.MATERIALSVIEWS.COM 44730 (7 of 8)
the more content of amorphous molecular chains and chain seg-
ments in the neat PLLA and its blends with lower optical purity
play a key role to provide this remarkable toughening perfor-
mance. This investigation would provide a new sight for the
application of PLLA with various optical purities.
ACKNOWLEDGMENTS
This work was financially supported by the National Natural Sci-
ence Foundation of China (Grants No.: 51403089, 51373169,
21574060, and 21374044), the Major Special Projects of Jiangxi
Provincial Department of Science and Technology (Grant No.:
20114ABF05100), and the Technology Plan Landing Project of
Jiangxi Provincial Department of Education (GCJ2011–243).
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