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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
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.
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
Figure 1. The WAXD (a) and DSC (b) of the as-cast neat PLLA and PLLA/
is blended with PLLA with lower optical purity.27 Consequently,
PDLA specimens. [Color figure can be viewed at wileyonlinelibrary.com]
the melting peak around 176 8C is assigned to the melting of
HC from the PDLA homopolymer (Thc2). The WAXD results
temperature dependent curves of storage modulus (E0 ), loss implying that only SC produce in the binary blends, and the
modulus (E00 ), and loss factor (tan d) of the specimens are residual PLLA and PDLA polymers are at amorphous state, but
recorded. the DSC curves reveal that all the specimens have a melting
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]
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 in the L162-D24 specimen, implying that more content of
deformation. 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 Effect of Optical Purity on the Mechanical Properties the intensity of diffraction assigned to HC reduces and reflec-
In order to investigate the influence of optical purity on the tions belong to SC are evident for the L173-D24. In the DSC
mechanical properties, the neat L162, L173 and their blends of these original specimens [Figure 5(b)], both the L162 and
with PDLA24 are also prepared, The WAXD profiles are L173 have an exothermic peak during heating, indicating that
shown in Figure 5(a). For the neat L162, only a weak diffrac- these two specimens do not crystallize completely during
tion peak at 16.98 is observed, indicating a small amount of solution evaporation. However, no obvious exothermic signal
HC crystallites form in the solution cast film. However, obvi- is observed in their blends, which reveals that the SC form in
ous diffraction peaks locate at 12.08 16.98, 19.18, and 21.08, solution mixing would accelerate the development of HC dur-
and weak diffractions at 14.88, 22.58, and 24.08 are detected ing solution evaporation.
The stress–stain curves of these specimens are displayed in Fig- the more content of amorphous molecular chains and chain seg-
ure 5(c), similar to the L143, the L162 and L173 exhibit a yield ments in the neat PLLA and its blends with lower optical purity
behavior around 5% before broken, while the difference is play a key role to provide this remarkable toughening perfor-
that the EHs of the two specimens are around at 7%, much low- mance. This investigation would provide a new sight for the
er than L143. For the L162-D24 and L173-D24 specimens, both application of PLLA with various optical purities.
of the blends are broken before yielding, and the EH declines
ACKNOWLEDGMENTS
slightly after incorporating the PDLA into the PLLA matrix.
The variation mechanical behaviors of L162-D24 and L173-D24 This work was financially supported by the National Natural Sci-
are similar to that of L143/PDLA specimens, which should be ence Foundation of China (Grants No.: 51403089, 51373169,
due the reason that more content of crystallites generate in the 21574060, and 21374044), the Major Special Projects of Jiangxi
binary blends than the neat PLLA specimens, and the molecular Provincial Department of Science and Technology (Grant No.:
chains and segments would be restricted in a more rigid envi- 20114ABF05100), and the Technology Plan Landing Project of
ronments. However, for the L143 and its corresponding blends, Jiangxi Provincial Department of Education (GCJ2011–243).
their EH are much higher than corresponding L162, L173, and
related blends, which should be ascribed to the reason that
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