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ARTICLE

The Morphology and Spherulite Growth of Stereocomplex in

the Linear and Branched PLLA/PDLA Blends: Effect of

CrystEngComm Accepted Manuscript

Published on 23 November 2015. Downloaded by Tufts University on 28/11/2015 02:01:17.

Received 00th January 20xx, Molecular Weights and Structure

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x Jun Shaoa,*, Yanmei Guoa, Sheng Xiangb, Dongdong Zhoub, Xinchao Bianb, Jingru
www.rsc.org/
Sunb, Gao Lib and Haoqing Houa

The linear and three armed poly(L-lactide)/poly(D-lactide) (PLLA/PDLA, 3PLLA/3PDLA and 3PLLA/PDLA) specimens were
prepared through solution mixing method, and the morphology and the spherulites growth of poly(lactide) stereocomplex
crystalllites (PLA sc) from the melt with various structures and molecular weights were investigated. The polarized optical
microscope pictures revealed that the regular spherulites and legible frontier were developed in all the PLLA/PDLA blends
with relative lower molecular weights (Mn < 20 kg/mol for each branch), and irregular spherulites formed after the
molecular weights of PLA polymers were higher than 60 kg/mol. The growth rate of the spherulite (G) increased at first,
and then decreased as molecular weights increasing in all the PLLA/PDLA, 3PLLA/3PDLA and 3PLLA/PDLA specimens. The
highest G value in all the specimens was achieved when the average molecular weights of each branch were ~10 kg/mol.
With similar molecular weights for each branches, the G reduced gradually as the three armed PLA added in the blend (i.e.,
PLLA/PDLA > 3PLLA/PDLA > 3PLLA/3PDLA).

6
Introduction develops crystallites at a faster speed. Thus, the PLA sc materials
As the oil shortage and the environmental pollution issues become with higher thermal stability can be prepared and present wider
bad to worse, the bio-based polymers, including the ones application potentials. Systematic studies reveals that the PLA sc
6-10
chemically synthesized from various naturally occurring resources could develop from binary linear blends, the di-, tri-, and multi-
11-16
and those produced by microorganisms, are attracting more and block copolymers, and also formed in the linear/branched and
17-20
more attentions from the past two decades. Among a large number branched/branched structures. The crystallization and melting
of the bio-based polymers, thermoplastic aliphatic polyester, such behaviours of PLA sc presents various regularities at different
as poly (lactide) (PLA), has been intensively investigated and structures and conditions, and diverse morphology of PLA sc also
9, 21
developed as an alternative to conventional non-degradable formed in different specimens.
synthetic polymers because of its mechanical performances, Different strcuture would present various morphology, and the
renewable and disposable properties.
1, 2
However, PLA based morphology formed in polymer determines its usage and
22
material has its intrinsic defect, its low heat resistance temperature, application field. Although the morphology of PLLA/PDLA blends
6,
which could be a major obstacle to the practical applications in a with different weight ratios and molecular weights were studied,
23, 24
large scale. There are three types of PLAs (PLLA, PDLA and PDLLA) the variation of spherulite growth of PLA sc with different
due to the different sequential structure of chiral carbon in the molecular weights are not clear yet. In addition, the melt viscosity
main chain of the macromolecule. For PLA with higher optical of linear PLA reduces rapidly as temperature increasing during
purity, i.e., PLLA and PDLA, their melting temperature usually at melting extrusion, which limits the processing temperature window
~180 °C. The melting temperature of PLLA (PDLA) decreases rapidly of PLA, especially for the PLA sc materials as it is melted at higher
and crystallization capacity weakens drasaticlly after the optical temperature. Introducing branched polymers will enhance the
3,4
purity decreasing. One interesting phenomenon of PLA is that the viscosity after melting and which would in favour of the processing
25, 26
PLA stereocomplex crystallites (sc) form after PLLA blend with PDLA, PLA sc materials. The stereocomplex formation between multi-
19, 27
5
which possess higher melting temperature, 230 °C, and the blend armed enantiomeric PLAs has been reported in various aspects,
However, the distinction of spherulite growth between linear and
branched structures are still an unclear issue. These issues are
College of chemistry and chemical engineering, JiangXi Normal University, critical and which could supply instruction for the process of PLA sc
Nanchang 330022, China. Email: jun.shao@jxnu.edu.cn materials. In this study, the linear and three armed PLLA and PDLA
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry,
Chinese Academy of Sciences, Changchun, 130022, China. were synthesized separately, and they were blended together to

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prepare the linear and branched PLA sc materials. After the blends range of 30 to 255 °C, and the first heating of the specimens were
were melted completely, the growth speed of the spherulites and recorded.
their morphology of sc were studied. This investigation would
Table 1. The characterization of linear and three armed PLA
supply instructions for the application of the PLA sc with linear and
branched structures.
Experimental Section Codea Mn(GPC) (kg/mol) PDI Tm (°C)

Materials and sample preparation L4 4 1.2 133.8

The L-lactide (L-LA) and D-lactide (D-LA) (optical purities ≥ 99.5%)
were bought by Purac and recrystallized in anhydrous ethyl acetate. L8 8 1.2 158.1

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Tin (II) 2-ethylhexanoate (Sn(Oct)2, 95%) was purchased from

L15 15 1.2 165.6
Aldrich and was directly used without purification. Isopropanol (≥
99.5%) and propanetriol (≥ 99.5%) were bought from Aladdin. L32 32 1.5 174.1
Linear PLLA and PDLA were synthesized by ring-opening
polymerization of L-LA and D-LA, respectively, initiated by L50 50 1.4 176.3
isopropanol and catalyzed by Sn(Oct)2 at 120 °C in dry toluene for
8
24 h, and the LA/toluene ratio was 1/10 in w/v. The three armed L70 70 1.7 175.8
PLLA (3PLLA) and PDLA (3PDLA) were polymerized as the same
27 D5 5 1.3 145.8
method, and the propanetriol was used as initiator. The molecular
weights of linear and three armed PLA polymers were regulated by
the LA/initiator mole ratio. The crude products were precipitated in D7 7 1.1 157.6
ethanol and dissolved in dichloromethane twice to purification. The
D11 11 1.3 160.8
purified products were dried under vacuum at 60 °C to constant
weight. Linear and three armed PLLA and PDLA used in this study D14 14 1.3 166.8
were list in Table 1. The linear and three armed PLLA were coded as
L and 3L, separately, and the linear and three armed PDLA were D22 22 1.4 170.3
abbreviated to D and 3D, respectively. The numbers after linear and
branched PLLA and PDLA were their number average molecular D31 31 1.1 173.5
weight, separately.
The stereocomplexed PLLA/PDLA blends were prepared from the D42 42 1.1 174.9
28
linear and three armed PLLA and PDLA as follows. Firstly, PLLA,
PDLA, 3PLLA and 3PDLA were dissolved separately in D52 52 1.5 175.2
dichloromethane as a concentration of 10.0 g/l. And then, the PLLA
D68 68 1.8 176.9
and PDLA, 3PLLA and 3PDLA, 3PLLA and PDLA were admixed
together respectively under vigorous stirring for 3 h, and the 3L10 10 1.4 150.2
proportion of PLLA:PDLA in the blends were maintained at 1:1 by
weight. Finally, these solutions were poured into petri dishes for 3L35 35 1.4 162.1
evaporation at room temperature to obtain the PLLA/PDLA,
3PLLA/3PDLA and 3PLLA/PDLA blending films. All these casted films 3L60 60 1.4 171.5
were dried at room temperature for 24 h, and were dried to
constant weight at 50 °C prior to measurements. 3L95 95 1.5 173.4

Gel permeation chromatography (GPC) 3L130 130 1.3 175.1

The molecular parameters of obtained PLAs were characterized by 3D9 9 1.1 145.8
Waters GPC (USA) at 35 °C, equipped with two styragel HR gel
columns (HR2 and HR4). It was calibrated with polystyrene 3D33 33 1.1 163.9
standards that covered the range of molecular weight 1000–
600,000 kg/mol. Chloroform was used as the eluent at a flow rate 3D57 57 1.4 170.8
of 1.0 ml/min.
3D105 105 1.6 175.8
Differential Scanning Calorimetry (DSC)
a
The PLLA was coded as L and PDLA was abbreviated as D, the three armed
Thermal properties of PLLA/PDLA, 3PLLA/3PDLA and 3PLLA/PDLA
PLLA and three armed PDLA were code as 3L and 3D, respectively. The numbers
samples were investigated on a differential scanning calorimeter
after L or D were their number-average molecular weights.
(DSC, Q100, TA Instrument) in nitrogen atmosphere. The specimens
were scanned at a constant rate of 10 °C/min over the temperature Polarized Optical Microscopy (POM)

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The morphology and growth rate of PLA sc spherulite in the films

was observed using a Carl Zeiss Axio Imager A2m (Germany)
polarized optical microscope, which equipped with a heating
cooling stage and a temperature controller (THMS-600, Linkam
Scientific Instruments, UK). A small piece of sample was squeezed
between two microscope slides, then inserted in the hot stage. The
films were heated from 30 to 260 °C at a rate of 30 °C/min, held at
this temperature for 1 min, then cooled to a desired isothermal
crystallization temperature (Tc) at 100 °C/min, and then held at the
Tc and observed the spherulite growth here. The radii of growing
crystals were monitored during solidification by taking

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photomicrographs at appropriate intervals of time. Spherulite radii

were measured with the software Image-Pro Plus 3.0. Dry nitrogen
gas was purged throughout the hot stage during all the
measurements and thermal treatments.

Results and discussion

The DSC of linear and three armed PLLA/PDLA blends

The DSC results of linear PLLA/PDLA specimens were shown in Fig.

1a. Endothermic signals were observed above 200 °C in all the
specimens, which should be ascribed to the melting peak of PLA sc.
An additional endothermic signal was found around 175 °C in the
L70/D68 specimen, which should be due to the melting of PLA
homochiral crystallites (hc). In the DSC curve of 3PLLA/3PDLA (Fig.
1b) and 3PLLA/PDLA (Fig. 1c) specimens, the signals around 220 °C
were obviously observed in all the specimens. Besides, signals
assigned to PLA hc were also found around 170 °C in the
3L95/3D105 and 3L130/D42 specimens. From Fig. 1a to 1c, it found
that the PLA hc appeared when the total number average molecular
weight of linear PLLA/PDLA was 138 kg/mol (Mn,PLLA+ Mn,PDLA), and
this value was 200 and 172 kg/mol, respectively, for the
3PLLA/3PDLA and 3PLLA/PDLA blends. The total molecular weight,
which developed PLA hc, increased as three armed PLA added in
the specimens. However, the number average molecular weight for
each branch, 69 kg/mol in PLLA/PDLA, 43 kg/mol in 3PLLA/PDLA
and 33 kg/mol in 3PLLA/3PDLA, reduced as the three armed PLA
added in the blends. In addition, the melting temperatures of PLA sc
in all the specimens were not higher than 250 °C. And according to
the reported literature, the highest melting temperature of PLA sc
also did not exceed to 250 °C.8, 18, 27, 29, 30 Thus, all the specimens
were heated to 260 °C and held for 1 min, which could ensure that
all the PLA sc are melted completely and the heat history are
eliminated thoroughly. On the other hand, both the PLA sc and hc
crystallites would form at relative lower crystallization temperature Fig. 1 The DSC of PLLA/PDLA (a), 3PLLA/3PDLA (b) and
in the specimens with higher molecular weights.31, 32 Thus, all the 3PLLA/PDLA (c) blends.
crystallization temperatures of specimens were selected at 180 and
190 °C, respectively, which were higher than the melting observed, but the frontier of spherulite in the L4/D5 was not as
temperature of PLA hc. Accordingly, it is reasonable to assume that ordered as the L8/D7 and L15/D14 specimens. The contrast
only PLA sc formed in all the linear and branched blends. between the bright and dark regions of Maltese cross was legible
and the orientation of the crystals along the radius direction was
The morphology and spherulite growth of PLLA/PDLA blends
distinct when the molecular weights of PLAs were not higher than
15 kg/mol. However, this contrast reduced for the specimens which
Fig. 2 presented the morphology of linear PLLA/PDLA blends
molecular weights were 32 kg/mol or higher, and the orientation of
annealed at 180 °C for 5 min with various molecular weights. In the
the crystals along the radius direction was disturbed. Such
L4/D5 specimen, the spherulite with obvious Maltese crosses was
structural disorder should be attributable to the decreased

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orientation of lamellae, because the entanglement increased as

33
molecular weight increasing. At the same time, the interdiffusion
of PLLA and PDLA molecular chains would also embarrass the
enantiomeric PLAs rearrange side by side alternately. The number
of nucleus increased notably when the molecular weights of PLA
polymers were higher than 30 kg/mol, and the Maltese crosses was
not distinctly observed in the L70/D68 specimen. The radius of the
spherulite increased at first, and was highest in the L8/D7
specimen, then decreased as the molecular weight of PLAs
increasing from 4 to 70 kg/mol. After these specimens were
annealed at 180 °C for 10 min, The POM of these specimens were

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shown in Fig. 3. It found that the size of spherulites in all the

specimens became larger. In L8/D7, the only one spherulite covered
almost the observed picture even annealed for 7.7 min. The
racemic crystallites fulfilled the whole horizon in the L32/D31 after
annealed for 10 min, which should be ascribed to more nucleation
points were produced in this specimen as its higher degree of
supercooling (ΔT= Tm–Tc). In the case of L70/D68 specimen, no
discernable orientation of the crystals along the radius of
spherulites were observed even annealed for a longer time, which
should be interpreted that the viscosity and chain entanglement at
this molecular weights were grievous, the orientation of the crystal
along the radius was impeded, and resulted to the crystals arranged
in a irregular shape.
When the specimen were annealed at 190 °C for 5 min, the
pictures were presented in Fig. 4. The L4/D5 did not form any
spherulites even annealed for a longer time (60 min), which should Fig. 2 The morphology of linear PLLA/PDLA blends at 180 °C for
be due to the formation of PLA sc became very difficult under that 5min. (a) L4/D5, (b) L8/D7, (c) L15/D14, (d) L32/D31, (e) L50/D52
supercooling condition (ΔT ≈ 15 °C), and its picture did not show and (f) L70/D68.
here. Compared to the Fig. 2, the diameter of the spherulites which
annealed at 190 °C were obviously smaller than that of
corresponding specimens annealed at 180 °C, which was ascribed to
the lower speed of spherulites growth at the higher annealing
temperature (lower degree of the ΔT). The size of the spherulites
decreased as molecular weight increasing from 8 to 70 kg/mol, but
the number of the nucleus tended to increase as molecular weight
increasing, which should be ascribed to the viscosity enhanced as
molecular weight enlarging, and which in favor of generating more
nucleating points. In the L70/D68 specimen, no obvious spherulites
were observed after annealing for 5 min, but spherulites appeared
after annealing for longer time, and the pictures annealing for
longer time were exhibited in Fig. 5. After annealed at 190 °C for
longer time, the radius of spherulites increased in all the specimens
(shown in Fig. 5). A small amount of additional spherulites
developed in the L50/D52 specimen, and a large number of new
spherulites appeared in the L70/D68 specimen.
The diameters of spherulites at different time of the specimens
which annealed at 180 °C were presented in Fig. 6. In L4/D5 and
L8/D7, only one line was presented in the graph, which indicated
that only one spherulites was observed and calculated. In other
specimens, more spherulites were observed and calculated, and
they were plotted as different colored lines in the graph. It could
be seen that the diameters of spherulites increased linearly with
time in most of the specimens except the L70/D68. The deviation of
Fig. 3 The morphology of PLLA/PDLA blends at 180 °C for 10 min. (a)
the diameter in L70/D68 should be due to the fact that, the
L4/D5, (b) L8/D7 for 7.7 min, (c) L15/D14, (d) L32/D31, (e) L50/D52
entanglement and the interdiffusion between isomer polymers
and (f) L70/D68.
were grievous in the melting state, and the crystals which located

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rates of spherulites (G) with different specimens were plotted in

Fig. 7. Here, the G values were estimated from the slopes of
spherulite diameter plotted in Fig. 6. When the specimens were
annealed at 180 °C, the G value increased at first, then decreased as
molecular weights enlarging from 4 to 70 kg/mol. When the
molecular weights of PLA polymers were ~8 kg/mol, the G value
reached the highest value. It is known that, the polymers with lower
molecular weight exhibited higher mobility. However, the higher
mobility would not in favour of nucleating. As molecular weight
increasing, the chain entanglement and viscosity enhanced, and
which would be convenient for nucleating. Notwithstanding, the

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improvement of chain entanglement and viscosity of the specimens

would limit the migration of molecular chain, and depressed the
growth rate of spherulites. Accordingly, the biggest G value
appeared in the blends with moderate molecular weight. After the
specimens were annealed at 190 °C, the G value decreased as
molecular weight increased from 8 to 70 kg/mol, which exhibit
Fig. 4 The morphology of linear PLLA/PDLA blends at 190 °C for 5 similar regularity as the specimens annealed at 180 °C.
min. (a) L8/D7, (b) L15/D14, (c) L32/D31 and (d) L50/D52. Furthermore, all the G value reduced as the temperature elevated
from 180 to 190 °C, which should be due to the nucleation became
difficult at that higher annealed temperature.

Fig. 5 The morphology of linear PLLA/PDLA blends at 190 °C. (a)

L8/D7 for 8 min 9 s, (b) L15/D14, (c) L32/D31, (d) L50/D52 and (e)
Fig. 6 The diameter of spherulites with different time in the
L70/D68 for 10 min, (f) L70/D68 for 20 min.
PLLA/PDLA specimens (180 °C).
nearby the entanglement point would not exclude the entangled
The morphology and G value of 3PLLA/3PDLA blends
molecular chains, which resulted to the spherulites presented in an
irregular shape. Thus, the calculation of the diameter could not as
After melted and subsequently annealed at 180 °C for 5 min, the
precise as other specimens.
morphologies of 3PLLA/3PDLA blends with different molecular
The growth of spherulites in the linear PLLA/PDLA specimens
weights were shown at Fig. 8. Obvious spherulites formed in all the
which annealed at 190 °C were similar to the Fig. 6, and were not
specimens but the 3L95/3D105 sample. Ordered spherulites
presented here, whereas, the diameter was much smaller than the
morphology was observed when the molecular weights were not
corresponding specimens annealed at 180 °C. The radius growth
higher than 35 kg/mol, and disordered spherulites developed when

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the molecular weight was 95 kg/mol. After annealed for 10 min (Fig.
9), all the size of spherulites became larger, and more spherulites
formed in all the specimens but the 3L10/3D9. The number of
nucleus tended to increase as molecular weights increasing,
especially for the 3L95/3D105 specimens. This should be due to the
melt viscosity improved as molecular weight increasing, and which
made the nucleation at the favourable condition.
When these specimens were annealed at 190 °C for 30 min (Fig.
10), the spherulites developed were similar to 180 °C, but the speed
of spherulites growth was much slower than that annealed at 180
°C. According to the spherulites growth at 180 °C in different

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specimens, the diameters of the 3PLLA/3PDLA specimens plotted

with time were shown in Fig. 11. The diameter of spherulites in
most specimens grew linearly as time but the 3L95/3D105, which
should be due to the same reason explained in the linear
PLLA/PDLA specimens.

Fig. 9 The morphology of 3PLLA/3PDLA blends at 180 °C for 10 min.

(a) 3L10/3D9, (b) 3L35/3D33, (c) 3L60/3D57 and (d) 3L95/3D105.

Fig. 7 The G values in the linear PLLA/PDLA blends.

Fig. 10 Morphology of 3PLLA/3PDLA blends at 190 °C for 30 min. (a)

3L10/3D9, (b) 3L35/3D33, (c) 3L60/3D57 and (d) 3L95/3D105.

Fig. 8 The morphology of 3PLLA/3PDLA blends at 180 °C for 5 min.

(a) 3L10/3D9, (b) 3L35/3D33, (c) 3L60/3D57 and (d) 3L95/3D105.
Fig. 11 The diameter of spherulites growth in the 3PLLA/3PDLA
blends with different molecular weight (180 °C).

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annealing temperature adopted in this investiagtion) is low, due to

its lower melting temperature of PLA sc. When the molecular
weight were much higher than this critical molecular weight, the
chain entanglement happens and aggravates, and which would be
convenient for the nucleation, but higher molecular weights
decrease the mobility of chain segments. at the same time, the
PLLA and PDLA would interdiffuse with each other and form
entanglement point, which would impede the enantiomeric PLA
arrange side by side. Consequently, the highest G value was
received when the molecular weights of PLAs were around this
critical entanglement molecule weight.

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Fig. 12 The G value in 3PLLA/3PDLA blends with different molecular

weights.

The G values in 3PLLA/3PDLA blends with different molecular

weights were presented at Fig. 12. Similar to the linear PLLA/PDLA
blends, the G increased at first, and then decreased as molecular
weight increasing. When the molecular weights of 3PLAs were c.a.
35 kg/mol, and the molecular weights for each branch were ~11
kg/mol, the G value was highest.
The morphology and G value of 3PLLA/PDLA specimens

In the 3PLLA/PDLA specimens, the molecular weight of PDLA was

similar with the branch of 3PLLA in each specimen. Fig. 13 exhibited
the morphology of 3PLLA/PDLA specimens annealed at 180 °C. It
could be seen that normal spherulite formed in the specimens with
relative lower molecular weights, and the size of the spherulites
formed in the blends increased at first, and then decreased as the
molecular weight increasing. In the G value of 3PLLA/PDLA blends
with different molecular weights (Fig. 14), it also found that the G
value increased at first then decreased as molecular weights Fig. 13 the morphology of 3PLLA/PDLA blends at 180 °C (a) 3L10/D5,
increasing, and the highest G value was received in the 3L35/D10, (c) 3L35/D10, (d) 3L60/D21, (e) 3L95/D31 and (f) 3L130/D42 for 5
where the molecular weight for each branch was ~10 kg/mol. min, (b) 3L10/D5 for 10 min.
Combined with the results of G values presented in Fig. 7, Fig.
12, and Fig. 14, it could be confirmed that the growth rate of
spherulites with different molecular weights displayed identical
regularity, i.e., the G value increased at first, and then decreased as
molecular weight increasing. In the linear PLLA/PDLA blends, the
highest G value observed when the molecular weight was ~8
kg/mol. For the 3PLLA/3PDLA specimens, this highest value was
found when the number average molecular weights of each branch
was c.a. 11 kg/mol. In the case of 3PLLA/PDLA, that value of
molecular weight was ~10 kg/mol for each branch. It is interesting
to find that this molecular weight for each branch was almost at the
same in all the specimens. According to the reported literature, the
34
critical entanglement molecule weight of PLLA is ~8 kg/mol. When
the molecular weights of PLA polymers are lower than this critical
molecular weight, the motion capacity of molecular chain and chain
segment is high, the PLLA and PDLA could move freely after melted
and no chain entanglement between inter or intra molecular weight Fig. 14 The G value in 3PLLA/PDLA blends with different molecular
happens. However, this high mobility make the nucleation become weights.
difficult, and the degree of the supercooling (compared to the

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During crystallization from the melt, lots of factors could restrict 8 J. Shao, S. Xiang, X. Bian, J. Sun, G. Li and X. Chen, Ind. & Eng.
the molecular chains discharging into the lattices, such as, the end Chem. Res., 2015, 54, 2246-2253.
group, viscosity, the core limitation and steric hindrance from the 9 S. Brochu, R. E. Prud'homme, I. Barakat and R. Jerome,
branch structures, etc. In the linear PLLA/PDLA blends, both the end Macromolecules, 1995, 28, 5230-5239.
group and viscosity have influences on the rearrangements of 10 J. Shao, J. Sun, X. Bian, Y. Zhou, G. Li and X. Chen,
molecular chains. Thus, it could form PLA sc in a facilitated CrystEngComm, 2013, 15, 6469-6476.
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CrystEngComm Accepted Manuscript

Published on 23 November 2015. Downloaded by Tufts University on 28/11/2015 02:01:17.

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DOI: 10.1039/C5CE02017D

The graphical abstract for The morphology and spherulite

growth of stereocomplex in the linear and branched

PLLA/PDLA blends: effect of molecular weights and structure

Jun Shaoa,*, Yanmei Guoa, Sheng Xiangb, Dongdong Zhoub, Xinchao Bianb, Jingru

CrystEngComm Accepted Manuscript

Published on 23 November 2015. Downloaded by Tufts University on 28/11/2015 02:01:17.

Sunb, Gao Lib and Haoqing Houa

a
College of chemistry and chemical engineering, JiangXi Normal University,

Nanchang, 330022, China

b
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry,

Chinese Academy of Sciences, Changchun 130022, China

* Corresponding author, email address: jun.shao@jxnu.edu.cn

Tel./Fax: +86 791 88120536.

For graphical abstract

G increased firstly, then decreased as Mn, PLA increased in the blends, and G

reduced as three armed PLAs added.