polymers

Article
Isothermal Cold Crystallization, Heat Resistance,
and Tensile Performance of Polylactide/Thermoplastic
Polyester Elastomer (PLA/TPEE) Blends: Effects of
Annealing and Reactive Compatibilizer
Sisi Wang 1,2 , Sujuan Pang 1,2 , Lisha Pan 1,2 , Nai Xu 1,2, * and Tan Li 3
1 College of Materials and Chemical Engineering, Hainan University, Haikou 570228, China;
sisi.wang@ugent.be (S.W.); psjuan@hainu.edu.cn (S.P.); happylisap@hainu.edu.cn (L.P.)
2 Hainan Provincial Fine Chemical Engineering Research Center, Hainan University, Haikou 570228, China
3 Shiner National & Local Joint Engineering & Research Center, Shiner Industrial Co., Ltd., Haikou 570125,
China; tanlishiner@gmail.com
* Correspondence: xunai@hainu.edu.cn; Tel.: +86-898-6627-9161

Academic Editor: Shiao-Wei Kuo

Received: 17 October 2016; Accepted: 28 November 2016; Published: 8 December 2016
Abstract: The combined influences of crystallinity and reactive compatibilizer—a multifunctional
epoxide (ADR)—on morphology, tensile performance, and heat resistance of polylactide/thermoplastic
polyester elastomer (PLA/TPEE) (80/20) blends were investigated. Annealing involved an isothermal
cold crystallization of PLA matrix was performed to increase crystallinity of the samples.
First, isothermal cold crystallization kinetics were investigated using differential scanning calorimetry
measurement. It was found that the addition of ADR decreased the crystallization rate of the
samples. The maximum crystallinity of the annealed samples also decreased from 40% to 34%
while ADR loading increased from zero to 1.0 phr. Furthermore, influence of crystallinity on
mechanical performances of the PLA/TPEE sample was researched. The heat resistance of the
sample showed a significant enhancement while increasing its crystallinity. Meanwhile, the tensile
ductility of the crystallized PLA/TPEE sample became very poor due to the embrittlement with
increased crystallinity and the incompatibility between PLA and TPEE. However, the annealed
PLA/TPEE/ADR samples with high crystallinity kept a higher tensile ductility because ADR greatly
improved the interfacial compatibility. Differences in tensile fracture behaviors of the quenched and
annealed PLA/TPEE samples with and without ADR were discussed in detail. At last, crystallized
PLA/TPEE/ADR blends with excellent heat resistance and high tensile ductility were obtained by
annealing and reactive compatibilization.

Keywords: poly(lactic acid); thermoplastic polyester elastomer; annealing; tensile property;

heat resistance

1. Introduction
Due to their unique range of properties, polymeric materials currently have important roles in the
lives and production of humanity. Innovation in polymers will thus make a valuable contribution to
help solve environmental problems. In recent years, researchers have been paying increasing attention
to renewable polymers due to the benefits of preserving the environment and saving petrochemical
polymers. Due to its good biocompatibility, biodegradability, and high mechanical strength, poly(lactic
acid) (PLA), produced from renewable resources (such as corn, sugarcane, beets, and so on) through
bioconversion and polymerization, is being considered for use in a wide range of fields including
electric appliance bodies, automobile components, and packaging materials, etc. [1–4]. However,
its brittleness, slow crystallization rate, and poor heat resistance limit its usage in practical applications.

Polymers 2016, 8, 417; doi:10.3390/polym8120417 www.mdpi.com/journal/polymers

Polymers 2016, 8, 417 2 of 16

One of the promising approaches to enhance the toughness and ductility of PLA is blending it
with other suitable polymers. Many elastomers and ductility polymers—such as polyamide 11 (PA 11),
thermoplastic polyurethane (TPU), thermoplastic polyester elastomer (TPE), poly(butylenes-adipate-
co-terephtalate) (PBAT), polycaprolactone (PCL), etc.—can be mixed into PLA matrix to increase the
toughness and ductility of PLA materials [5–9].
As a block copolymer with hard segments of polybutylene terephthalate blocks and soft segments
of poly(tetramethylene ether) glycol terephthalate blocks, thermoplastic polyester elastomers (TPEE)
possess many excellent properties, such as strong thermal and mechanical properties. Due to its high
toughness, TPEE is a good alternative for toughening PLA [6,7,10]. Maleic anhydride (MA)-grafted
PLA (PLA-g-MA) was prepared to enhance the compatibility of PLA/TPE blends [6]. It was confirmed
by IR spectroscopy that the anhydride groups of the PLA-g-MA chains reacted with the functional
groups in the polybutylene terephthalate blocks of the TPE chains, and thus greatly enhanced the
compatibilization between PLA matrix and TPE domains. SEM photographs indicated that the
compatibilization effect of PLA-g-MA largely reduced the size of TPE domains. As a result, a higher
level of surface area was produced for more interfacial interactions. Toughness results showed that
Charpy impact toughness and fracture toughness (KIC and GIC ) of PLA increased greatly when
the PLA/TPE samples were compatibilized with PLA-g-MA. For instance, GIC of PLA increased as
much as 166%. The toughening effect of TPEE on PLA was reported by Haydar U. Zaman et al. [7].
A diisocyanate compound (4,40 -Methylene bis(phenylisocyanate), MDI) was used as a reactive modifier
to improve the compatibility of PLA and TPEE. With the incorporation of TPEE, the fracture mode of
PLA transformed from classic brittle fracture to ductile fracture. Furthermore, the compatibilization
effect of MDI led to a more remarkable increase (about 300%) in the tensile ductility of the PLA/TPEE
sample, compared with that of the PLA/TPEE sample without MDI. The reactive compatibilization
of MDI on the PLA/TPEE blends was attributed to the coupling reaction of PLA and TPEE
macromolecules with MDI, because the isocyanate groups of MDI were highly reactive with the
terminal –OH and –COOH groups of the polyesters. As a result, the interfacial adhesion and
compatibilization between PLA matrix and TPEE domains were enhanced markedly. It was reported
by our research team that a multifunctional epoxide (ADR) was used to enhance the compatibility and
ductility of PLA/TPEE blend [10]. The epoxy groups of ADR chains reacted with carboxyl terminal
and hydroxyl terminal of the polyesters, which extended the molecule chain and compatibilized the
immiscible PLA and TPEE phases. With the incorporation of ADR, TPEE domains became smaller and
phase interface became fuzzy, leading to a great improvement in the tensile ductility of the samples.
However, because of the slow crystallization rate of PLA matrix, PLA products prepared by melt
processing moldings usually show a low crystallinity (below 10%), resulting in a poor heat resistance
(Vicat softening temperature of around 60 ◦ C) [11], which will restrict its applications in elevated
temperature environments.
A couple of methods have been tested to improve the crystallinity and heat resistance of
PLA materials, including annealing treatment [12], incorporation of nucleating agents [11,13],
and a combination of annealing and nucleating agents [14], etc. It was found that annealing treatment
and incorporation of a nucleating agent greatly improved the crystallinity of PLA, as well as enhancing
its heat resistance. However, it was found that, with increasing the crystallinity, crystalline grains
contacted each other and physical crosslinking points formed in the PLA matrix. Furthermore,
the crystalline structure forced the random PLA chains and segments to arrange regularly and tightly,
and free volume for macromolecule chains decreased, leading to a decrease of plastic deformation
and an increase of brittleness of PLA matrix [15]. As a result, the increased crystallinity usually
had a markedly negative effect on the ductility of PLA and its blends due to the brittleness and the
vanishing of multiple crazes in the crack-tip region with crystallinity [16,17].
So far, the influences of crystallinity on microstructure, mechanical performance, fractured
behavior, and heat resistance of PLA/elastomer blends are not well understood yet. How to prepare
highly crystallized PLA blends with excellent ductility and heat resistance is still a challenging issue
with huge practicability.
Polymers 2016, 8, 417 3 of 16

In the present study, two kinds of PLA blend—PLA/TPEE (80/20) and PLA/TPEE
(80/20)—containing a small amount of reactive compatibilizer ADR, were prepared and subjected
to annealing to obtain the highly crystallized samples. The main aim of the paper is to research the
combined influences of crystallinity and reactive compatibilizer ADR on micro-morphology, tensile
property, and heat resistance of the immiscible PLA/TPEE blends. The PLA/TPEE sample in glassy
state was obtained by quenching, and annealing was performed to the quenched samples to obtain
crystallized PLA/TPEE samples with high crystallinity. For the quenched PLA/TPEE sample in glassy
state, annealing the sample above its glass transition temperature (around 60 ◦ C) mainly involved the
isothermal cold crystallization process of PLA in that the amorphous solid structure transformed into
a highly crystallized solid structure [18]. Hence, in order to fully understand the effects of annealing
and ADR on the crystallization behavior of PLA matrix, first, isothermal cold crystallization kinetics
of PLA/TPEE blends with various ADR loadings were researched by using DSC measurement in
the temperature range of 80–86 ◦ C. Then, the combined effects of annealing and ADR loading on
crystalline structure, tensile performance, heat resistance, and micro-morphology of the PLA/TPEE
samples were studied by using differential scanning calorimetry (DSC), wide angle X-ray diffraction
(WAXD), tensile test, vicat softening temperature (VST), and scanning electron microscope (SEM)
observation, respectively. Finally, the differences in tensile fracture behaviors among the quenched
and annealed PLA/TPEE samples with and without ADR were discussed.

2. Materials and Methods

2.1. Materials
PLA resin (4032D) was commercial available from Natureworks LLC (Minnetonka, MN, USA).
Its density (ρ) and melting flow rate (MFR) were 1.25 g/cm3 and 5.3 g/10 min (190 ◦ C under 2.16 kg load),
respectively. TPEE resin (4056) was purchased from Dupont (Wilmington, DE, USA) (ρ = 1.17 g/cm3 ,
and MFR = 6.0 g/10 min (190 ◦ C under 2.16 kg load)). The multifunctional exipode oligomer (Joncryl
ADR 4370s, abbreviating as ADR in this paper) purchased from BASF (Ludwigshafen, Germany) was
used as reactive compatiblizer. Its molecule weight and exipode equivalent weight were 6800 and
285 g/mol, respectively.

2.2. Sample Preparation

Raw materials were placed in a vacuum oven at 50 ◦ C for 12 h at least to remove moisture before
each processing step. ADR was used as received.
PLA/TPEE blends with and without ADR were obtained by melt blending in an internal mixer
(XS-60, Shanghai Kechuang Plastic Machinery Equipment Co., Ltd., Shanghai, China) at 190 ◦ C with
a rotor speed of 50 rpm for 10 min. The mass ratio of PLA/TPEE blend was set as 80:20 in weight
fraction. The obtained PLA/TPEE/ADR ternary blends with different content of ADR (0.5 and 1.0 phr)
were denoted as PLA/TPEE/ADR (80/20/0.5) and PLA/TPEE/ADR (80/20/1.0).
Quenched PLA/TPEE/ADR specimens for mechanical property measurements were prepared
as follows: the obtained blends were molded under 210 ◦ C with a pressure of 15 MPa within 8 min
using a hot press, and then the melts in mold were quickly transferred into a cold press attached
to a water cooling system and quickly cooled down to ambient temperature with a cooling rate of
around 100 ◦ C/min under 15 MPa. Finally, quenched sheets with 1 mm thickness were obtained.
The dumbbell shaped specimens were cut from the sheets for the following tests.
Crystalline PLA specimens were prepared as follows: a part of the quenched specimens were
annealed in an oven for different time (holding time ranged from 0 to 60 min) under 80 ◦ C to obtain the
crystallized specimens with varying crystallinity. In the paper, it has to be noted that the specimens with
a holding time of 0 min refer specifically to the quenched (as-molded) specimens without annealing.
The samples were kept at room temperature for 72 h prior to testing.
Polymers 2016, 8, 417 4 of 16

2.3. Differential Scanning Calorimetry (DSC) Analysis

Crystallization behavior of the samples was investigated using a TA Instruments Q100 series
(TA Instruments, New Castle, DE, USA) under nitrogen atmosphere with a flow rate of 50 mL/min.
In order to research the isothermal cold crystallization behavior of the samples, each sample
(around 5 mg) was first heated quickly to 200 ◦ C and held at 200 ◦ C for 4 min to erase its thermal history;
then quenched down to 30 ◦ C at a rate of 50 ◦ C/min; and finally, heated again quickly to a preset
crystallization temperature (Tc = 80, 82, 84 and 86 ◦ C, respectively) at 200 ◦ C/min, and kept at the set
temperature for enough time to crystallize completely. The exotherm of each sample was recorded.
The isothermal crystallization kinetics parameters of polymers can be obtained by the well-known
Avrami equation, as shown in Equation (1).

X(t) = 1 − exp(−ktn ), (1)

where t denotes the real time of crystallization. X(t) is related to the relative crystallinity at time t.
k stands for the Avrami rate constant, and n is the Avrami exponent depending on the nucleation
mechanism and crystal growth pattern.
According to the obtained isothermal DSC thermograms, X(t) is the ratio of the area of the
exotherm up to time t (Qt ) divided by the area of the total exotherm (Q∞ ):
Rt
Qt (dH/dt) dt
X (t) = = R0t (2)
Q∞
0 ( dH/dt ) dt

where Qt is the heat generated at time t, and Q∞ is the heat generated at infinite time. dH/dt refers to
the rate of heat evolution.
Taking the Avrami equation double logarithmic form, Equation (2) can be transformed to
Equation (3).
log[−ln(1 − X(t))] = nlogt + logk, (3)

The crystallization half-time (t1/2 ), defined as the time required to reach half of the final
crystallinity, can be calculated according to Equation (4).

t1/2 = (ln2/k)1/n , (4)

Meanwhile, the crystallinities of the quenched and annealed specimens were obtained by using
DSC measurement, the testing conditions were as follows: each sample was heated directly to 200 ◦ C at
a scan rate of 10 ◦ C/min from 30 ◦ C. Cold crystallization enthalpy (∆Hcc ) and fusion enthalpy (∆Hm )
shown in the heating scan were recorded. The crystallinity (Xc ) of each specimen was calculated by
Equation (5).
|∆Hcc + ∆Hm |
Xc = (5)
Φ × |∆Hm ∗|

where ∆Hcc and ∆Hm are cold crystallization enthalpy and melting enthalpy of the PLA samples,
∗ refers to the melting enthalpy of 100%
respectively; Φ stands for the mass fraction of PLA and ∆Hm
crystalline PLA, which is reported to be 93 J/g [19].

2.4. Wide Angle X-Ray Diffraction (WAXD)

Wide angle X-ray diffraction (Bruker D8 ADVANCE, Karlsruhe, Germany) was employed to
evaluate the crystalline structure of the quenched and annealed samples in the reflection mode.
The CuKα radiation (λ = 1.54 Å) was operated at 40 kV and 40 mA. Data were recorded in the range of
5◦ ≤ 2θ ≤ 50◦ with a scan speed of 2◦ /min.
Polymers 2016, 8, 417 5 of 16

2.5. Vicat Softening Temperature (VST) Analysis

The VST of the quenched and annealed samples were investigated using a thermal deformation
and VST tester (Chengde Jiande Detection Instrument Co., Ltd., Chengde, China). The test was
conducted according to Standard GB/T 1633–2000 with a heating rate of 120 ◦ C/h and a load of 1000 g.
For each formulation, pairs of specimens were tested until the VST values of the two specimens
did not differ by more than 2 ◦ C. The average value of the VST was then calculated.

2.6. Tensile Tests

The tensile tests were done by using an intelligent electronic tensile testing instrument (XLW,
Jinan Lan-Guang Mechanical and Electrical Technology Co., Ltd., Jinan, China) with a crosshead
speed of 50 mm/min and a gauge length of 30 mm. The samples were stored at rest for 72 h at room
temperature before testing. Each value is the average of five valid tests.

2.7. Micro-Morphology of the Samples

The micro-morphology of the samples was examined using scanning electron microscope (SEM)
(S-3500N, Hitachi, Tokyo, Japan). The samples were immersed in liquid nitrogen for enough time and
then broke quickly to obtain the cryo-fractured surfaces. The cryo-fractured surfaces of the samples
were sputtered with gold powder in order to achieve better SEM observations. An acceleration voltage
of 10 KV was used for the SEM examination. The magnification was 3000 times.

3. Results and Discussion

3.1. Isothermal Cold Crystallization Kinetics

Isothermal cold crystallization behaviors of the PLA/TPEE (80/20) samples with and without
ADR were investigated by DSC measurement. Figure 1 showed the relationship between relative
degree of crystallinity (X(t)) and isothermal time (t) of the samples at different crystallization
temperature (Tc = 80, 82, 84 and 86 ◦ C, respectively). All the curves showed a sigmoid dependence
on isothermal time. The sigmoid curves moved to the left with increasing Tc , indicating that time
to reach the maximum crystallinity for PLA blends decreased under higher Tc . The dependences of
crystallization half-time (t1/2 ) on Tc and ADR loading had been further discussed in succession by
calculating from isothermal crystallization kinetics of the PLA/TPEE blends.
The representative plots of log[−ln(1 − X(t))] versus logt for the PLA/TPEE blends were shown in
Figure 2. The curves consisted of two parts: the first crystallization stage and the second crystallization
stage. It was found that in the first stage logt linearly depended on log[−ln(1 − X(t))]. At the second
stage, an obvious roll-off at longer times was observed, indicating that the existence of a secondary
crystallization which resulted from the spherulite impingement in the later stage of the crystallization
process at a longer crystallization time. Hence, the linear regimes were chosen to determine the
exponent n and k of the samples according to Equation (3). The calculated crystallization kinetics
parameters were listed in Table 1.
Usually, the value of n should be an integer between 1 and 4 for different nucleation mechanisms
and crystal growth modes. As shown in Table 1, the values of n were in the range of 2.2–2.5 for the
PLA/TPEE sample at crystallization temperatures ranged from 80 to 86 ◦ C. It was an average value of
various nucleation mechanisms, and growth dimensions occurred simultaneously in the crystallization
process. As a result, the Avrami exponent n was not a straightforward integer.
Due to the existence of TPEE domains, it can be inferred that the nucleation type of PLA in the
blends should predominantly be heterogeneous nucleation and its growth dimension should be 2D
growth. By contrast, the values of n were also kept between 2.3 and 2.5 for the PLA/TPEE/ADR
samples at the same crystallization temperatures. It meant that the incorporation of ADR has little
effect on the crystallization mechanism of PLA matrix.
Polymers 2016, 8, 417 6 of 16
Polymers 2016, 8, 417 6 of 16
Polymers 2016, 8, 417 6 of 16

(a) 1.00 (b)

1.00
(a) 1.00 (b)
1.00

0.75 0.75
0.75 0.75

(%)
(%)

(%)
(%)

0.50 0.50

X(t)
X(t)

0.50 PLA/TPEE 0.50 PLA/TPEE/ADR

X(t)
X(t)

PLA/TPEE
(80/20) PLA/TPEE/ADR
(80/20/0.5)
(80/20) o (80/20/0.5)
o
0.25 80o C 0.25 80o C
0.25 80
82oCC
o 0.25 80
82oCC
o

82
84oCC
o 82
84oCC
o

84
86oCC
o 84
86oCC
o
0.00 0.00
0.00 86 C 0.00 86 C
0 5 10 15 0 5 10 15 20
0 5 10 15 0 5 10 15 20
t (min) t (min)
t (min) t (min)

1.00 (c)
1.00 (c)

0.75
0.75
(%)
(%)

0.50
X(t)

0.50 PLA/TPEE/ADR
X(t)

PLA/TPEE/ADR
(80/20/1.0)
(80/20/1.0)
o
0.25 80o C
0.25 80
82oCC
o

82
84oCC
o

84
86oCC
o
0.00
0.00 86 C
0 5 10 15 20 25 30
0 5 10 15 20 25 30
t (min)
t (min)
Figure 1. Relative crystallinity (X(t)) vs. crystallization time (t) in the isothermal cold crystallization
Figure 1. Relative
Figure crystallinity
1. Relative (X(t))
crystallinity (X(t))vs.
vs.crystallization
crystallizationtime
time (t)
(t) in
in the
the isothermal coldcrystallization
isothermal cold crystallization
process for PLA blends: (a) PLA/TPEE (80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c) PLA/TPEE/ADR
process for PLA
process blends:
for PLA (a) PLA/TPEE
blends: (a) PLA/TPEE (80/20); (b)(b)
(80/20); PLA/TPEE/ADR
PLA/TPEE/ADR(80/20/0.5);
(80/20/0.5); (c) PLA/TPEE/ADR
PLA/TPEE/ADR
(80/20/1.0).
(80/20/1.0).
(80/20/1.0).

1 (a) 1 (b)
1 (a) 1 (b)

0
0
0
0
log(-ln(1-X(t)))

log(-ln(1-X(t)))
log(-ln(1-X(t)))

log(-ln(1-X(t)))

-1
-1 -1
-1
PLA/TPEE PLA/TPEE/ADR
PLA/TPEE
(80/20) -2 PLA/TPEE/ADR
(80/20/0.5)
-2 (80/20) -2 (80/20/0.5)
-2 o o
80 C 80 C
o o
80
82 CC
o -3 80
82 CC
o
o -3 82
o
-3 82
84 CC 84 CC
o o

-3 o
84
o
84
86 CC 86 CC
o o
o
-4 o
86 C -4 86 C
-4
-4 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0 1.5
-0.5 0.0 log t 0.5 1.0 -1.0 -0.5 0.0 log t 0.5 1.0 1.5
log t log t
1 (c)
1 (c)

0
0
log(-ln(1-X(t)))

-1
log(-ln(1-X(t)))

-1

-2 PLA/TPEE/ADR
-2 PLA/TPEE/ADR
(80/20/1.0)
(80/20/1.0)
-3 o
-3
80 C
o
80
82 CC
o
o
-4 82
84 CC
o
o
-4 84
86 CC
o
o
86 C
-5
-5 -0.5 0.0 0.5 1.0 1.5
-0.5 0.0 log t 0.5 1.0 1.5
log t
Figure 2. Plots of log[−ln(1 − X(t))] vs. logt of the representative samples isothermally crystallized at
Figure 2. Plots of log[−ln(1 − X(t))] vs. logt of the representative samples isothermally crystallized at
Figure Plots of log[−ln(1
the 2.predetermined − X(t))] vs.(a)logt
temperatures: of the representative
PLA/TPEE (80/20); (b) samples isothermally
PLA/TPEE/ADR crystallized
(80/20/0.5); (c)
the predetermined temperatures: (a) PLA/TPEE (80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c)
at the predetermined
PLA/TPEE/ADR temperatures: (a) PLA/TPEE (80/20); (b) PLA/TPEE/ADR (80/20/0.5);
(80/20/1.0).
PLA/TPEE/ADR (80/20/1.0).
(c) PLA/TPEE/ADR (80/20/1.0).
Polymers 2016, 8, 417 7 of 16

Table 1. Data of isothermal cold crystallization kinetics for PLA/TPEE/ADR blends.

Sample T c (◦ C) Crystallization induction time (tinduce , min) n k × 103 (min−1 ) t1/2 (min)
80 8.7 2.5 5.9 6.9
PLA/TPEE 82 4.1 2.4 17.8 4.7
(80/20) 84 2.8 2.3 39.9 3.4
86 1.9 2.2 84.0 2.6
80 10.3 2.5 2.0 10.1
PLA/TPEE/ADR 82 6.5 2.5 4.9 7.0
(80/20/0.5) 84 4.8 2.5 13.1 5.0
86 2.7 2.3 26.3 4.0
80 11.5 2.3 2.7 11.2
PLA/TPEE/ADR 82 9.0 2.3 4.0 9.4
(80/20/1.0) 84 5.5 2.4 6.1 7.0
86 3.3 2.5 9.7 5.6

The crystallization half-time (t1/2 ) and crystallization induction time (tinduce ) [20] of the
PLA/TPEE and PLA/TPEE/ADR samples at different crystallization temperature (Tc = 80, 82, 84 and
86 ◦ C) were also listed in Table 1. It was shown that tinduce and t1/2 of the PLA/TPEE (80/20) sample
was 8.7 and 6.9 min under 80 ◦ C, respectively. As the cold crystallization temperature increased to 86 ◦ C,
tinduce and t1/2 of the PLA/TPEE (80/20) sample shortened to 1.9 and 2.6 min, respectively. It was
attributed to the fact that the elevated temperature was helpful for enhancing the macromolecule chain
mobility and arrangement ability, leading to an improvement in cold crystallization rate of PLA matrix.
Furthermore, compared to the PLA/TPEE (80/20) sample, tinduce and t1/2 of the PLA/TPEE/ADR
(80/20/x) samples tended to prolong at the same crystallization temperature. For example, when Tc
was 80 ◦ C, tinduce and t1/2 increased from 8.7 and 6.9 min for the PLA/TPEE (80/20) sample up to
11.5 and 11.2 min for the PLA/TPEE/ADR (80/20/1.0) sample. It indicated that the incorporation
of ADR impeded the cold crystallization ability of PLA matrix. The depression of crystallization
ability can be ascribed to the restraining in PLA segment reorganization in the presence of ADR.
Multiple epoxide groups on ADR reacted with terminal –COOH groups and terminal –OH groups
on PLA and TPEE chains leading to the formation of extended and branched chains [10]. The chain
extension/branching results are complex. Besides the formation of PLA-ADR-TPEE copolymers,
the generation of PLA-ADR-PLA and TPEE-ADR-TPEE is inevitable when ADR is melt blended with
PLA/TPEE blend. The SEC measurement’s result showed that the molecule weights of PLA and TPEE
increased largely with the incorporation of a small amount of ADR [10]. The increase in molecule
weight, as well as the formation of long branched chains, would enhance macromolecular chain
entanglement and significantly limit the regular arrangement ability of PLA segments and chains
in amorphous solid, especially when the cold crystallization process was held in a relatively lower
temperature (close to Tg ). Thereby, the crystal growth of PLA matrix was retarded in this situation.
As a result, the overall crystallization rate of the samples showed a decrease with the incorporation of
ADR at crystallization temperatures ranging from 80 to 86 ◦ C.
It was known from the crystallization kinetics analysis of the PLA/TPEE/ADR blends that the
isothermal cold crystallization ability of the PLA/TPEE samples was retarded to some extent when
ADR increased from 0 to 1.0 phr. However, the semi-crystallized PLA/TPEE/ADR samples still could
be obtained by appropriately prolonging the crystallization time. In the subsequent experiments,
the quenched samples were annealed at 80 ◦ C in order to obtain the crystallized samples. The combined
effects of annealing and ADR loading on crystalline structure, tensile performance, heat resistance,
and micro-morphology of the PLA/TPEE samples have been researched and discussed.

3.2. Effect of Annealed Time on Crystallinity of PLA/TPEE/ADR Samples

Plots of annealed time vs. crystallinity (Xc ) of the PLA/TPEE/ADR (80/20/x) samples annealed
at 80 ◦ C are shown in Figure 3. It was found that crystallinity of the samples increased markedly
Polymers 2016, 8, 417 8 of 16

while increasing
Polymers 2016, 8, the
417 annealed time due to the cold crystallization of PLA matrix during the annealing 8 of 16
process. It was consistent with the isothermal cold crystallization kinetics results. As seen in Figure 3,
3, the annealed
the annealed timestimes to reach
to reach the maximum
the maximum crystallinity
crystallinity for the
for the PLA/TPEE
PLA/TPEE (80/20),PLA/TPEE/ADR
(80/20), PLA/TPEE/ADR
(80/20/0.5)
(80/20/0.5) and
and PLA/TPEE/ADR (80/20/1.0)
PLA/TPEE/ADR (80/20/1.0) samples
sampleswere
were30, 30,
40 and 40 min,
40 and respectively.
40 min, Then,Then,
respectively. the
crystallinities of
the crystallinities of the
the samples
samples kept
kept almost
almostconstant.
constant.As Aswe weknow,
know,thetheannealed
annealedtimetimetotoreach
reachthe
the
maximum crystallinity should consist of induced time and crystallization
maximum crystallinity should consist of induced time and crystallization time. With the incorporation time. With the
incorporation
of ADR, the annealed of ADR,
time the annealed
to reach time to reach
the maximum the maximum
crystallinity showed crystallinity
an obvious showed
increaseandue
obvious
to the
increase due to the fact that the chain extension and branched reactions among
fact that the chain extension and branched reactions among PLA, TPEE, and ADR impaired the cold PLA, TPEE, and ADR
impaired the
crystallization cold crystallization
ability ability of the PLA matrix.
of the PLA matrix.

40

30
Xc (%)

20

10 PLA/TPEE (80/20)
PLA/TPEE/ADR (80/20/0.5)
PLA/TPEE/ADR (80/20/1.0)

0
0 10 20 30 40 50 60

Annealing time (tanneal) (min)

3. Crystallinity (Xc )(Xvs. annealed time of PLA/TPEE/ADR ◦ C.

Figure
Figure 3. Crystallinity c) vs. annealed time of PLA/TPEE/ADR(80/20/x) samplesannealed
(80/20/x) samples annealedatat80
80°C.

Moreover,
Moreover, the maximum
the maximum crystallinity
crystallinity of the of the PLA/TPEE
PLA/TPEE samplessamples also decreased
also decreased with the
with the increasing
increasing of ADR loading. As shown in Figure 3, while the annealed time reached
of ADR loading. As shown in Figure 3, while the annealed time reached to 30 min, Xc of the PLA/TPEE to 30 min, Xc of
the PLA/TPEE (80/20) sample increased from 4% for the quenched
(80/20) sample increased from 4% for the quenched PLA/TPEE sample to the maximum value PLA/TPEE sample to theof
maximum value of 40%. A similar result was also reported by Harris et al. [14]. It was confirmed that
40%. A similar result was also reported by Harris et al. [14]. It was confirmed that annealing of both
annealing of both nucleated and neat PLA samples at 80 °C increased the crystallinity of PLA to its
nucleated and neat PLA samples at 80 ◦ C increased the crystallinity of PLA to its maximum level
maximum level of around 42%. However, with increasing ADR loading, the maximum Xc of the
of around 42%. However, with increasing ADR loading, the maximum Xc of the PLA/TPEE/ADR
PLA/TPEE/ADR (80/20/0.5) and PLA/TPEE/ADR (80/20/1.0) samples dropped down to 36% and 34%,
(80/20/0.5) and PLA/TPEE/ADR (80/20/1.0) samples dropped down to 36% and 34%, respectively.
respectively. The reduction in the maximum crystallinity could also be explained by the fact that the
The reduction in the maximum crystallinity could also be explained by the fact that the extended chain
extended chain and branched reactions among PLA/PLA/ADR and PLA/TPEE/ADR reduced the
andregularity
branched of reactions among
PLA chains andPLA/PLA/ADR and PLA/TPEE/ADR
weakened their regular arrangement ability. reduced the regularity of PLA
chains and weakenedWAXD
Meanwhile, their regular arrangement
measurement ability.
was conducted to investigate crystal structures of the
quenched and annealed PLA/TPEE/ADR blends. WAXDtopatterns
Meanwhile, WAXD measurement was conducted investigate
of thecrystal
quenchedstructures of the
and annealed
quenched and annealed
PLA/TPEE/ADR PLA/TPEE/ADR
(80/20/1.0) samples were blends.
presentedWAXD patterns
in Figure 4. of
Asthe quenched and
a comparison, theannealed
WAXD
PLA/TPEE/ADR (80/20/1.0)
patterns of the quenched andsamples
annealedwere presented
PLA/TPEE in Figure
(80/20) samples4.wereAs also
a comparison,
presented inthe WAXD
Figure 4.
patterns
In order to obtain the fully annealed samples, the quenched PLA/TPEE (80/20) and PLA/TPEE/ADR4.
of the quenched and annealed PLA/TPEE (80/20) samples were also presented in Figure
In order to obtain
(80/20/1.0) the fully
samples had annealed
been heldsamples,
at 80 °C the quenched
for 30 and 40 min,PLA/TPEE (80/20)
respectively. Asand
seenPLA/TPEE/ADR
in Figure 4, the
quenchedsamples
(80/20/1.0) PLA/TPEE/ADR
had been(80/20/1.0) ◦ C for as
held at 80sample, 30well
and as 40the
min,quenched PLA/TPEE
respectively. As seen(80/20) sample4,
in Figure
the showed
quenched a broad dispersing diffraction
PLA/TPEE/ADR peak, indicating
(80/20/1.0) sample, as that the as
well samples were almost
the quenched amorphous
PLA/TPEE with
(80/20)
very low crystallinity. However, two strong reflections located at 16.4°
sample showed a broad dispersing diffraction peak, indicating that the samples were almost and 18.7° were observed in
the WAXD
amorphous pattern
with veryof thecrystallinity.
low PLA/TPEE/ADR (80/20/1.0)
However, twosample
strongannealed
reflectionsat 80 °C for at
located 40 16.4 ◦
min, as well
and as ◦
18.7
wereinobserved
that of theinPLA/TPEE
the WAXD(80/20)patternsample
of theannealed at 80 °C for(80/20/1.0)
PLA/TPEE/ADR 30 min. It was confirmed
sample annealedthat at
crystal
80 ◦ C
modification of the annealed PLA/TPEE and PLA/TPEE/ADR samples could
for 40 min, as well as in that of the PLA/TPEE (80/20) sample annealed at 80 C for 30 min. It was be◦assigned to disorder
α form that
confirmed of PLA, named
crystal α′ form. By
modification ofusing WAXD, PLA/TPEE
the annealed DSC, and infrared spectroscopy (IR)samples
and PLA/TPEE/ADR measurements,
could be
Zhang et al. found that, dependent on Tc,0 the disorder α′ and order α modification of PLA were
assigned to disorder α form of PLA, named α form. By using WAXD, DSC, and infrared spectroscopy
formed at a low temperature range (Tc < 100 °C) and high temperature range (Tc > 120 °C), respectively
(IR) measurements, Zhang et al. found that, dependent on Tc , the disorder α0 and order α modification
[21,22]. It was found that the two strong diffraction peaks between the two samples showed distinct
of PLA were formed at a low temperature range (Tc < 100 ◦ C) and high temperature range (Tc > 120 ◦ C),
shifts in the 2θ positions. In the case of PLA sample annealed at 140 °C, the two strong reflections
located at 16.7° and 19.1°, which were characteristic reflections of α modification. However, the two
Polymers 2016, 8, 417 9 of 16

respectively [21,22]. It was found that the two strong diffraction peaks between the two samples
showed
Polymersdistinct
Polymers 2016, 8,
2016, shifts in the 2θ positions. In the case of PLA sample annealed at 140 ◦ C, the two9strong
8, 417
417 of 1616
9 of
reflections located at 16.7◦ and 19.1◦ , which were characteristic reflections of α modification. However,
◦ and
reflections
thereflections werewere
two reflections
were found at 16.4°
found 16.4° and
at 16.4
and 18.7° in ◦WAXD
in
18.7°18.7 in WAXD
WAXD pattern of
ofthe
pattern
pattern of PLA
thethe sample
PLA
PLA sample
sample annealed
annealed
annealed atat80
at80°C,
80 ◦ C,
°C,
which
which
which were
were
were attributed
attributed
attributed α0α′
to
toto α′modification.
modification.
modification.In In addition,
addition,ititwas
Inaddition, wasconfirmed
confirmedby
confirmed bythe
theauthors
authorsthat a amixture
that
that a mixture
mixture
of
of of α
α and and
α and 0
α α′α′ phases
phases
phaseshad had formed
hadformed in
formedininPLAPLA matrix
PLAmatrix while
matrixwhile the
whilethe samples
the samples crystallized in the
samples crystallized in the temperature
the temperature
temperature range
range
range
from
from
from 100100
100 to
to to120120◦
120C. °C.
°C. It revealed
It Itrevealed from
revealedfrom Figure
fromFigure 4 that
Figure44that the
thatthe isothermal
theisothermal cold
isothermal cold crystallization
cold crystallization of the
crystallization of the quenched
the quenched
quenched
PLA/TPEEsamples
PLA/TPEE
PLA/TPEE sampleswith
samples withand
with and without
andwithout ADR
without ADR happened
happened while
ADR happened while the
thesamples
sampleswere
samples wereannealed
were annealed
annealed atatat
8080 °C.
80 ◦ C.
°C.
After
After
After being
being
being fully
fully
fully annealed,
annealed,
annealed, the
thethe highly
highly
highly crystallized
crystallized
crystallized PLA/TPEE
PLA/TPEEand
PLA/TPEE and PLA/TPEE/ADR
andPLA/TPEE/ADR blends
PLA/TPEE/ADR blends with
blends with α′
with α′ α0
phases
phases were
were obtained.
obtained.
phases were obtained.

(b) PLA/TPEE/ADR (80/20/1.0)

(a) PLA/TPEE (80/20) (b) PLA/TPEE/ADR (80/20/1.0)
(a) PLA/TPEE (80/20)

Annealed for 40min

Annealed for 40min
Intensity

Intensity
Intensity

Intensity
Annealed for 30min
Annealed for 30min

Quenched Quenched
Quenched Quenched

10 20 30 40 50 10 20 30 40 50
10 20 o 30 40 50 10 20 o 30 40 50
2θ ( ) 2θ ( )
o o
2θ ( ) 2θ ( )

Figure 4. WAXD patterns of the quenched samples and the annealed samples held at temperature of
Figure
Figure 4. WAXD
WAXD
4. (a) patterns
patterns ofof
thethequenched
quenchedsamples
samplesand
andthe
theannealed
annealed samples
samples held
held at
at temperature
temperature of
of
80 °C, PLA/TPEE (80/20) samples; (b) PLA/TPEE/ADR (80/20/1.0) samples.
◦
80 °C, (a) PLA/TPEE (80/20) samples; (b) PLA/TPEE/ADR (80/20/1.0)
80 C, (a) PLA/TPEE (80/20) samples; (b) PLA/TPEE/ADR (80/20/1.0) samples. samples.
3.3. Effects of ADR and Crystallinity on Tensile Performance, Heat Resistance, and Micro-Morphology of the
3.3.3.3. Effects
Effects
PLA/TPEE of of
ADRADR and
and
Samples CrystallinityononTensile
Crystallinity TensilePerformance,
Performance,Heat
HeatResistance,
Resistance,and
and Micro-Morphology
Micro-Morphology of
of the
the
PLA/TPEE
PLA/TPEE Samples
Samples
Tensile performance, crystallinity, and VST of the quenched PLA/TPEE samples were shown in
Tensile
Tensile
Figure performance,
5. performance, crystallinity,
crystallinity, andVST
and VSTofofthe
thequenched
quenchedPLA/TPEE
PLA/TPEE samples
samples were
were shown
shownin in
Figure
Figure 5. 5.

Figure 5. Data of tensile performances, Xc and VST of quenched PLA/TPEE/ADR (80/20/x) blends.
Figure 5. Data of tensile performances, Xc and VST of quenched PLA/TPEE/ADR (80/20/x) blends.
Figure 5. Data of tensile performances, Xc and VST of quenched PLA/TPEE/ADR (80/20/x) blends.
AsAs Figure
Figure5 showed,
5 showed, the
thetensile
tensileductility
ductilityof
ofthe
thequenched
quenched PLA/TPEE samplesimproved
PLA/TPEE samples improved greatly
greatly
with theAs
with incorporation
the incorporation
Figure ofof
5 showed, ADR.
ADR. Compared
Compared
the tensile totothe
ductility ofquenched
the quenched
the PLA/TPEE
quenchedPLA/TPEE
PLA/TPEE (80/20)
(80/20) sample
sample
samples without
without
improved ADR,
ADR,
greatly
thewith
elongation
the elongation at break of the
at breakofofADR.
the incorporation quenched
the quenched
ComparedPLA/TPEE/ADR
PLA/TPEE/ADR (80/20/0.5)
to the quenched(80/20/0.5)
PLA/TPEE sample
sample reached
(80/20)reached
sample250%,250%, having
having
without ADR,
increased
increased
the byby
290%
elongation at (64%
290% (64%
break for the
for
of thethequenched
quenchedPLA/TPEE).
quenched While
PLA/TPEE). While
PLA/TPEE/ADR ADRloading
ADR
(80/20/0.5)loading
sample further
further increased
increased
reached upup
to to
250%, having
1.0increased
phr,phr,
1.0 thethe
elongation
byelongation
290% (64%at at
break
break kept
for the steady.
kept steady.Meanwhile,
quenched PLA/TPEE).the
Meanwhile, the tensile
tensile
While strength
ADR loadingofthe
of thePLA/TPEE
PLA/TPEE
further samples
samples
increased up to
increased from 39.9 to 42.8 MPa with increasing ADR addition from 0 up to 1.0 phr, because
1.0 phr, the elongation at break kept steady. Meanwhile, the tensile strength of the PLA/TPEE samples ADR as
a chain extender increased the molecular weight of PLA and therefore increased
increased from 39.9 to 42.8 MPa with increasing ADR addition from 0 up to 1.0 phr, because ADR as the strength with
a chain extender increased the molecular weight of PLA and therefore increased the strength with
Polymers 2016, 8, 417 10 of 16

increased from 39.9 to 42.8 MPa with increasing ADR addition from 0 up to 1.0 phr, because ADR as
a chain extender increased the molecular weight of PLA and therefore increased the strength with
longer chains
Polymers 2016,[23].
8, 417With longer chains, there were more entanglements and interactions among these
10 of 16
polymer chains, making them relatively more stationary. This, in turn, increased the strength of the
PLAlonger
samples.chains [23]. With longer chains, there were more entanglements and interactions among these
polymer chains, making them relatively more stationary. This, in turn, increased the strength of the
As is reported in our previous research [10], the in situ compatibilization mechanism of the
PLA samples.
PLA/TPEE/ADR blends was studied systematically. When ADR was added during the melt blending
As is reported in our previous research [10], the in situ compatibilization mechanism of the
process, the terminal
PLA/TPEE/ADR –COOH
blends group systematically.
was studied and terminal When –OH group
ADR was of added
PLA andduringTPEE reacted
the melt with the
blending
multiple
process, the terminal –COOH group and terminal –OH group of PLA and TPEE reacted with the the
epoxides on ADR. ADR not only played the role of chain extender, but also played
role multiple
of reactive compatibilizer
epoxides on ADR. ADR by forming
not only PLA-ADR-TPEE copolymer,
played the role of chain which
extender, reduced
but also playedthetheinterface
role
energy, improved
of reactive the interface
compatibilizer byadhesion, and thus decreased
forming PLA-ADR-TPEE the dispersed
copolymer, which domain
reduced size. As a result,
the interface
tensile ductility
energy, improvedof the
theblends
interfaceincreased
adhesion, significantly. Similarly,
and thus decreased Racha domain
the dispersed Al-Itry size.
et al.As studied
a result, the
tensile
impact of ductility
ADR onofthe the blends increased
interfacial significantly.
property Similarly,blends
of PLA/PBAT Racha Al-Itry et al.interfacial
[8]. The studied the tension
impact in
of ADR on the interfacial property of PLA/PBAT blends [8].
the modified/compatibilized PLA/PBAT decreased, and formed the PLA-ADR-PBAT copolymer. The interfacial tension in the
modified/compatibilized PLA/PBAT decreased, and formed the PLA-ADR-PBAT
The improvement in mechanical properties also was attributed to the formation of the PLA-ADR-PBAT copolymer. The
improvement
copolymer. Hence,initmechanical
was supposed properties also
that the was attributed
coupling reactiontobetween
the formation
ADR andof the PLA-ADR-PBAT
PLA/TPEE improved
copolymer. Hence, it was supposed that the coupling reaction between ADR and PLA/TPEE
the compatibility of the blends. The compatibilization effect of ADR on PLA/TPEE samples can be
improved the compatibility of the blends. The compatibilization effect of ADR on PLA/TPEE samples
verified by SEM micrographs presented in Figure 6. As shown in Figure 6a, it was found that the
can be verified by SEM micrographs presented in Figure 6. As shown in Figure 6a, it was found that
interface compatibility of TPEE domains and PLA matrix was poor according to the fact that the
the interface compatibility of TPEE domains and PLA matrix was poor according to the fact that the
sizessizes
of TPPE
of TPPE particles were
particles werelarger
larger(around
(around 55 µm)μm) and markeddebonded
and marked debonded interfaces
interfaces existing
existing in thein the
PLA/TPEE
PLA/TPEE (80/20)
(80/20)sample.
sample.However,
However,for forthe PLA/TPEE/ADR
the (80/20/0.5)
PLA/TPEE/ADR (80/20/0.5) andand (80/20/1.0)
(80/20/1.0) samples
samples
(Figure 6b,c),
(Figure duedue
6b,c), to the reactive
to the reactivecompatibility
compatibility of of ADR,
ADR, thetheTPEE
TPEEdomain
domain sizes
sizes markedly
markedly dropped
dropped
down to 1to
down µm or less
1 μm from
or less from5 µm,
5 μm, and
andthe
thephase
phaseinterface becamemuch
interface became muchfuzzier.
fuzzier.

Figure
Figure 6. SEM
6. SEM micrographs
micrographs ofof quenchedPLA/TPEE
quenched PLA/TPEE specimens
specimenswith
withand
andwithout
withoutADR:
ADR:(a)(a)
PLA/TPEE
PLA/TPEE
(80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c) PLA/TPEE/ADR (80/20/1.0).
(80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c) PLA/TPEE/ADR (80/20/1.0).

Although the addition of ADR improved the tensile performance of the PLA/TPEE blends
Althoughthe
obviously, theslow
addition of ADR improved
melt-crystallization rate of the
PLAtensile performance
led to low of(X
crystallinity the PLA/TPEE blends
c) for the quenched
obviously, the slow melt-crystallization rate of PLA led to low crystallinity
PLA/TPEE samples. As shown in Figure 5, the crystallinities of the quenched PLA/TPEE (X c ) for thesamples
quenched
PLA/TPEE
with andsamples.
without As ADRshown
wereinonly
Figure 5, the5%,
around crystallinities
indicating that of the
thequenched
PLA samples PLA/TPEE samples
were almost
withamorphous.
and withoutThe ADRWAXD werepatterns
only around 5%, indicating
presented in Figure that theconfirmed
4 also PLA samples were
the full almost
glassy stateamorphous.
in the
The quenched PLA/TPEE
WAXD patterns samples. As
presented in we knew,4 the
Figure alsoglassy state of PLA
confirmed matrix
the full would
glassy leadin
state to athe
poor heat
quenched
resistance of the quenched PLA/TPEE samples, because of the low glass
PLA/TPEE samples. As we knew, the glassy state of PLA matrix would lead to a poor heat resistancetransition temperature
(around
of the 60 °C)PLA/TPEE
quenched of PLA. samples, because of the low glass transition temperature (around 60 ◦ C)
of PLA. As expected, it was found from Figure 5 that the VST value of each quenched PLA/TPEE samples
with and without ADR was very low (about 60 °C). The poor heat resistance would restrict
As expected, it was found from Figure 5 that the VST value of each quenched PLA/TPEE samples
applications of the PLA/TPEE blends with low crystallinity in elevated temperature environments.
with and without ADR was very low (about 60 ◦ C). The poor heat resistance would restrict applications
It can be seen in Figure 3 that Xc of the PLA/TPEE samples with and without ADR increased
of the PLA/TPEE
significantly blends
with with low
the increase crystallinity
of annealing timein atelevated temperature
80 °C. While environments.
the annealing time reached to 30 min,
It can be seen in Figure 3 that X c of the PLA/TPEE samples
Xc of the PLA/TPEE (80/20) sample increased from 4% for the quenched PLA/TPEE with and without ADRup
sample increased
to a
significantly with the increase of annealing time at 80 ◦ C. While the annealing time reached to 30 min,
maximum value of 40%. Meanwhile, while the annealing time lengthened to 40 min, Xcs of the
Xc ofPLA/TPEE/ADR
the PLA/TPEE(80/20/0.5)
(80/20) sample increased from(80/20/1.0)
and PLA/TPEE/ADR 4% for the quenched
samples also PLA/TPEE sample up to
reached to maximum
a maximum
values of value
36% and of 34%,
40%.respectively.
Meanwhile,Apparently,
while the annealing time lengthened
Xc of the quenched PLA/TPEEtosamples40 min, Xc s be
could of the
markedly increased by annealing treatment. As a result, the highly crystallized PLA/TPEE samples
could be obtained after fully annealed at 80 °C.
Polymers 2016, 8, 417 11 of 16

PLA/TPEE/ADR (80/20/0.5) and PLA/TPEE/ADR (80/20/1.0) samples also reached to maximum

values of 36% and 34%, respectively. Apparently, Xc of the quenched PLA/TPEE samples could be
markedly increased by annealing treatment. As a result, the highly crystallized PLA/TPEE samples
could be obtained ◦
Polymers 2016, 8, 417after fully annealed at 80 C. 11 of 16
Figure 7 presented the influences of annealing and ADR loading on crystallinity, VST, tensile
strength,Figure 7 presentedatthe
and elongation influences
break of annealing and ADR
of the PLA/TPEE/ADR loading samples.
(80/20/x) on crystallinity, VST, tensile
strength, and elongation at break of the PLA/TPEE/ADR (80/20/x) samples.
As Figure 7a showed, when the quenched PLA/TPEE (80/20) had been annealed at 80 ◦ C for
As Figure 7a showed, when the quenched PLA/TPEE (80/20) had been annealed at 80 °C for 30
30 min, its Xc increased from 4% to 40%. The VST of the annealed PLA/TPEE sample increased greatly
min, its Xc ◦increased from 4% to 40%. The VST of the annealed PLA/TPEE sample increased greatly
from 62 to 142 C. The PLA/TPEE/ADR (80/20/0.5) and (80/20/1.0) samples also showed a similar Xc
from 62 to 142 °C. The PLA/TPEE/ADR (80/20/0.5) and (80/20/1.0) samples also showed a similar Xc
◦ C for 40 min, X of the PLA/TPEE/ADR (80/20/1.0)
dependence.
dependence. ForFor example, after
example, annealing
after annealingatat80
80 °C for 40 min, Xccof the PLA/TPEE/ADR (80/20/1.0)
sample increased
sample increased from 5%5%
from toto34%,
34%,and
andits
its VST valueincreased
VST value increasedsignificantly
significantly from
from 57 to57136 136 ◦ C.
to °C.

Figure
Figure 7. Effects
7. Effects of of annealingand
annealing andADR
ADR loading
loading on
onVST,
VST,tensile strength,
tensile andand
strength, elongation at break
elongation of
at break of
PLA/TPEE/ADR (80/20/x) samples: (a) VST; (b) tensile strength; and (c) elongation at break.
PLA/TPEE/ADR (80/20/x) samples: (a) VST; (b) tensile strength; and (c) elongation at break.

The improvement in VST with increasing Xc could be explained by the transformation of the
The improvement
amorphous phase intoincrystal
VST phases in the PLA X
with increasing c could
matrix be explained
during by the transformation
the cold crystallization caused by theof the
amorphous
annealingphase into For
treatment. crystal phases inPLA/TPEE
the quenched the PLA samples,
matrix during the coldwas
the crystallinity crystallization
only around 5%.caused
It by
meant that the PLA matrix (continuous phase) was almost amorphous.
the annealing treatment. For the quenched PLA/TPEE samples, the crystallinity was only around As a result, the heat
5%. resistances of the
It meant that PLA/TPEE
the PLA matrixsamples were poor,phase)
(continuous and their VSTs
was were dominated
almost amorphous. mostly
As by Tg of PLA
a result, the heat
matrix. However, when the quenched PLA/TPEE samples were annealed at 80 °C, a cold
resistances of the PLA/TPEE samples were poor, and their VSTs were dominated mostly by Tg of
crystallization process of PLA matrix happened. An amount of crystal nuclei formed and constantly
PLA matrix. However, when the quenched PLA/TPEE samples were annealed at 80 ◦ C, a cold
grew to form crystalline structures from the amorphous PLA matrix. With the lengthening of
crystallization process of PLA matrix happened. An amount of crystal nuclei formed and constantly
annealing time, the crystals continued to grow in PLA matrix until these crystals fully developed and
grewimpinged
to form crystalline
upon each structures
other. When from thethe
Xc of amorphous
PLA/TPEEPLA samplematrix. With
reached to the
the lengthening
maximum, the of fully
annealing
time,grown
the crystals
crystalscontinued to grow
squeezed each other,inwhich
PLA matrix until
led to the these crystals
formation fully
of physical developedinand
crosslinking impinged
the PLA
uponmatrix.
each other. Whenthe
Meanwhile, Xccold
of the PLA/TPEEofsample
crystallization the PLA reached to the
matrix was maximum,
terminated the due
almost fullytogrown
the huge crystals
steric hindrance resulted from the physical crosslinking. Thus, the significant enhancement
squeezed each other, which led to the formation of physical crosslinking in the PLA matrix. Meanwhile, in the
heat resistance
the cold of the PLA/TPEE
crystallization of the PLA samples
matrixcan be attributed
was terminated to the restraint
almost dueoftomolecular
the huge motion
stericby the
hindrance
formation of firm crystals and physical crosslinking [11,17]. The highly crystallized
resulted from the physical crosslinking. Thus, the significant enhancement in the heat resistance of PLA/TPEE
samples did not show a significant thermal deformation until the environment temperature increased
close to Tm of crystalline PLA. In the elevated temperature range, the physical crosslinking points
Polymers 2016, 8, 417 12 of 16

the PLA/TPEE samples can be attributed to the restraint of molecular motion by the formation of
firm crystals and physical crosslinking [11,17]. The highly crystallized PLA/TPEE samples did not
show a significant thermal deformation until the environment temperature increased close to Tm of
crystalline PLA. In the elevated temperature range, the physical crosslinking points were gradually
destroyed and the crystallized PLA started to fuse, that made the PLA/TPEE samples markedly
Polymers 2016, 8, 417 12 of 16
deform under the external loading. In that case, the VST increased markedly because it was dominated
by Tm (around 168 ◦ C)
were gradually of crystalline
destroyed and the PLA matrix,
crystallized PLAinstead
started of Tg ofthat
to fuse, amorphous PLA phase
made the PLA/TPEE [11].
samples
In Figure
markedly7a, all the
deform underPLA/TPEE (80/20)Insamples
the external loading. with
that case, the VSTand without
increased ADRbecause
markedly showed it was a similar
dominatedofbyVST.
Xc dependence Tm (around 168 °C)it
However, of was
crystalline
found PLA matrix,
that theinstead
maximumof Tg ofvalue
amorphous PLA for
of VST phase [11].
the annealed
In Figure 7a, all the PLA/TPEE (80/20) samples with and without ADR showed a similar Xc
PLA/TPEE/ADR (80/20/0.5) and (80/20/1.0) samples decreased from the maximum VST of 142 ◦ C
dependence of VST. However, it was found that the maximum value of VST for the annealed
for the PLA/TPEE (80/20) sample to 136 ◦ C. It was due to the reduction in the maximum X of the
PLA/TPEE/ADR (80/20/0.5) and (80/20/1.0) samples decreased from the maximum VST of 142 °C for c
PLA/TPEE/ADR
the PLA/TPEE samples
(80/20)(Figure
sample 3)to when
136 °C.ADRIt waswas
dueincorporated
to the reduction as ainchain extenderXthat
the maximum weakened
c of the

the coldPLA/TPEE/ADR
crystallizationsamples ability (Figure
of PLA3)chains.
when ADR was incorporated as a chain extender that weakened
the cold crystallization
In summary, the increase ability of PLA chains.
of crystallinity due to annealing greatly enhanced the heat resistances of
the PLA/TPEE In summary,
samplesthe increase
with of crystallinity
and without ADR. due to annealing
However, it isgreatly enhancedthat
well known the heat resistances of firm
the formation
of the PLA/TPEE samples with and without ADR. However, it is well known that the formation of
crystals and physical crosslinking in polymer matrix would markedly restrain the molecular motion
firm crystals and physical crosslinking in polymer matrix would markedly restrain the molecular
resultingmotion
in embrittlement of the semi-crystalline
resulting in embrittlement polymer polymer
of the semi-crystalline [24]. Hence, it is necessary
[24]. Hence, to research
it is necessary to the
of Xc on
influenceresearch the tensile ductility and strength of the PLA/TPEE samples with
the influence of Xc on the tensile ductility and strength of the PLA/TPEE samples with and and without ADR.
Thewithout
effectsADR.
of annealing and ADR loading on tensile strength and elongation at break of
The effects of(80/20/x)
the PLA/TPEE/ADR annealing and ADR loading
samples on tensile strength
were presented in Figureand7b,c,
elongation at break ofIn
respectively. theaddition,
PLA/TPEE/ADR (80/20/x) samples were presented in Figure 7b,c, respectively. In addition, a
a photograph of the tensile-fractured PLA/TPEE (80/20) and PLA/TPEE/ADR(80/20/x) specimens is
photograph of the tensile-fractured PLA/TPEE (80/20) and PLA/TPEE/ADR(80/20/x) specimens is
shown in Figure
shown 8.
in Figure 8.

Figure 8. Optical photograph of the tensile-fractured specimens: (a) Quenched PLA/TPEE (80/20)
Opticalwith
Figure 8.specimen photograph of the tensile-fractured specimens: (a) Quenched PLA/TPEE (80/20)
Xc of 4%; (b) Annealed PLA/TPEE (80/20) specimen with Xc of 40%; (c) Quenched
specimen with Xc of 4%;
PLA/TPEE/ADR (b) Annealed
(80/20/0.5) specimenPLA/TPEE
with Xc of (80/20) with Xc of 40%;
specimenPLA/TPEE/ADR
5%; (d) Annealed (c) Quenched
(80/20/0.5)
PLA/TPEE/ADR (80/20/0.5)
specimen with Xc of 36%;specimen
(e) Quenched Xc of 5%; (d) Annealed
withPLA/TPEE/ADR PLA/TPEE/ADR
(80/20/1.0) specimen with Xc of (80/20/0.5)
5%;
specimen(f) with
Annealed
Xc PLA/TPEE/ADR (80/20/1.0) specimen
of 36%; (e) Quenched with Xc of 34%.
PLA/TPEE/ADR (80/20/1.0) specimen with Xc of 5%;
(f) Annealed PLA/TPEE/ADR (80/20/1.0) specimen with Xc of 34%.
As seen in Figure 7b, the tensile strength of the PLA/TPEE (80/20) samples showed a slight
increase with the increase of Xc. For the PLA/TPEE (80/20) samples with ADR, a similar increasing
As trend
seen ofin tensile
Figurestrength
7b, theto tensile strength
the PLA/TPEE of the
(80/20) PLA/TPEE
samples was also (80/20)
observed.samples showed
For example, while a slight
increaseincreasing
with theXincrease of Xc . For the
c of the PLA/TPEE/ADR PLA/TPEE
(80/20/1.0) sample (80/20)
from 5%samples
to 34%, thewith ADR,
tensile a similar
strength increasing
increased
trend offrom 42.8strength
tensile to 44.7 MPa. to The
the moderate
PLA/TPEE enhancement
(80/20) in tensile strength
samples was alsoof the PLA/TPEEFor
observed. samples was while
example,
attributed to the formation of firm crystals and physical crosslinking in the samples with the increase
increasing Xc of the PLA/TPEE/ADR (80/20/1.0) sample from 5% to 34%, the tensile strength
of Xc. Moreover, it was interesting to note that the tensile strength also increased upward slightly
increased from
while ADR 42.8 to 44.7
loading MPa. from
increased The 0moderate enhancement
to 1.0 phr. It was attributed in tensile
to the strength
increased of the
molecular PLA/TPEE
weight
samplescaused
was attributed to the formation of firm crystals and physical crosslinking
by the chain extension reaction between ADR and PLA chains [10]. Hence, the Xc and ADR in the samples with
the increase
showedof X . Moreover,
a csynergistic it was interesting
enhancement to note
on the tensile thatofthe
strength the tensile
PLA/TPEE strength
samples.also increased upward
slightly while Although
ADR loading the increase of Xc enhanced
increased from 0the toheat resistance
1.0 phr. It wasandattributed
tensile strength of increased
to the the PLA/TPEEmolecular
(80/20) samples with and without ADR, it was found from Figure 7c that the tensile ductility of the
weight caused by the chain extension reaction between ADR and PLA chains [10]. Hence, the Xc and
samples showed a significant decrease. For the PLA/TPEE (80/20) sample, the elongation at break
ADR showed a synergistic enhancement on the tensile strength of the PLA/TPEE samples.
Polymers 2016, 8, 417 13 of 16

Although the increase of Xc enhanced the heat resistance and tensile strength of the PLA/TPEE
(80/20) samples with and without ADR, it was found from Figure 7c that the tensile ductility of
thePolymers
samples2016,showed
8, 417 a significant decrease. For the PLA/TPEE (80/20) sample, the elongation 13 of 16 at
break decreased drastically from 64% to 28% while the Xc increased from 4% to 40%. Compared with
decreased
that drastically (80/20)
of the PLA/TPEE from 64% to 28% the
sample, while the Xc increased
elongation at breakfrom 4%PLA/TPEE/ADR
of the to 40%. Compared (80/20/0.5)
with that
of the PLA/TPEE (80/20) sample, the elongation at break
sample decreased from 250% to 146% while its Xc increased from 5% to 36%. However, when of the PLA/TPEE/ADR (80/20/0.5) samplethe
decreased from 250% to 146% while its X c increased from 5% to 36%. However, when the ADR
ADR loading increased to 1.0 phr, the elongation at break of the annealed sample remained almost
loading increased
unchanged. It was apparentto 1.0 phr, thatthe
the elongation
significant at break of
increase of Xthemarkedly
annealedreduced
sample the remained
tensilealmost
ductility
c
unchanged. It was apparent that the significant increase of X c markedly reduced the tensile ductility
of each PLA/TPEE sample. It was due to the fact that the progress of crystallization and increase of Xc
of each PLA/TPEE sample. It was due to the fact that the progress of crystallization and increase of
in the semi-crystalline PLA samples resulted in an increased embrittlement of the samples and hence
Xc in the semi-crystalline PLA samples resulted in an increased embrittlement of the samples and
decreased the tensile ductility. As shown in Figure 8, necking and whitening phenomena occurred
hence decreased the tensile ductility. As shown in Figure 8, necking and whitening phenomena
simultaneously while the PLA/TPEE samples with and without ADR were cold drawn during the
occurred simultaneously while the PLA/TPEE samples with and without ADR were cold drawn
tensile test. Therefore, the tensile deformation mechanism of the PLA/TPEE samples should be
during the tensile test. Therefore, the tensile deformation mechanism of the PLA/TPEE samples
attributed to the crazing with shear yielding mechanism. In general, the generation, development,
should be attributed to the crazing with shear yielding mechanism. In general, the generation,
and termination of
development, andcrazes plays an of
termination important
crazes plays role inantheimportant
toughening roleofin
polymer materials.of
the toughening Furthermore,
polymer
formaterials.
polymer Furthermore,
blends, the interfacial compatibility and dispersed phase sizes
for polymer blends, the interfacial compatibility and dispersed phase sizeshave a great effect on the
initiation and termination of crazes that will directly affect the tensile
have a great effect on the initiation and termination of crazes that will directly affect the tensile ductility of the blends.
Figureof9 the
ductility presented
blends. SEM micrographs of the annealed PLA/TPEE (80/20) samples with and
withoutFigure
ADR 9which had been ◦ C for 40 min, respectively. The PLA/TPEE (80/20)
presented SEM annealed
micrographs at 80 of the annealed PLA/TPEE (80/20) samples with and
samples
without annealed
ADR which for 40had minbeen
showed marked
annealed interface
at 80 °C for debondings due to theThe
40 min, respectively. poor adhesion(80/20)
PLA/TPEE between
PLA matrixannealed
samples and TPEE for domains,
40 min showed as shownmarked in Figure
interface 9a. The poor adhesion
debondings due to the andpoorinterface
adhesiondebonding
between
PLA matrix and
phenomenon wasTPEE also domains,
observedasinshown in Figure 9a.
the quenched The poor adhesion
PLA/TPEE and interface
(80/20) sample (Figuredebonding
6a). It is
phenomenon
well-known thatwas thealso
weaker observed in theregions
interfacial quenched couldPLA/TPEE (80/20) sample
not effectively terminate (Figure 6a). It isofwell-
the growth crazes.
known that the weaker interfacial regions could not effectively terminate
As a result, the cracks would be induced and rapidly develop through the weaker interfacial regions, the growth of crazes. As a
result, the cracks would be induced and rapidly develop through
leading to a poor tensile ductility and low elongation at break for the quenched PLA/TPEE (80/20) the weaker interfacial regions,
leading
sample to a poor
during tensile test.
the tensile ductility
While andthe low elongation
annealed time at increased
break for the to 40quenched
min, thePLA/TPEE
crystallinity (80/20)
of the
PLA/TPEE (80/20) sample increased from 4% for the quenched sample to the maximum value ofthe
sample during the tensile test. While the annealed time increased to 40 min, the crystallinity of 40%.
PLA/TPEE
It was confirmed (80/20) thatsample increased
a stacking effect fromof 4%thefor the quenched
increased sample and
crystallinity to thepoor
maximum value of of
compatibility 40%.
PLA
It was confirmed that a stacking effect of the increased crystallinity and poor compatibility of PLA
and TPEE markedly weakened the tensile ductility of the annealed PLA/TPEE (80/20) sample with
and TPEE markedly weakened the tensile ductility of the annealed PLA/TPEE (80/20) sample with
high crystallinity. Sang Dae Park et al. researched the influences of Xc and loading-rate on the fracture
high crystallinity. Sang Dae Park et al. researched the influences of Xc and loading-rate on the fracture
behavior of PLA [16,17]. It was found that the quasi-static fracture toughness of PLA decreased
behavior of PLA [16,17]. It was found that the quasi-static fracture toughness of PLA decreased while
while its crystallinity increased. It was confirmed by the authors that the quenched PLA sample
its crystallinity increased. It was confirmed by the authors that the quenched PLA sample with Xc =
with
2.7%Xc could
= 2.7% could generate
generate extensiveextensive
multiple crazes multiple in crazes in the region
the crack-tip crack-tip region
under under quasi-static
quasi-static loading.
loading. However, with the increase of X , the formation of multiple
However, with the increase of Xc, thec formation of multiple crazes in the crack-tip region crazes in the crack-tip region waswas
drastically
drastically suppressed.
suppressed. Moreover,
Moreover, the crack
the crackgrowth mainlymainly
growth directlydirectly
propagated through through
propagated the spherulites
the
which formed firmly with each other, resulting in a decrease of the
spherulites which formed firmly with each other, resulting in a decrease of the fracture toughness fracture toughness by increasingby
theincreasing
crystallinity.
the In this paper, In
crystallinity. forthis
the paper,
annealed for PLA/TPEE
the annealed(80/20) PLA/TPEE samples, it could
(80/20) be supposed
samples, it could be that
high Xc and
thesupposed that poor
the high interfacial
Xc and pooradhesion further
interfacial sped up
adhesion cracksped
further growth and greatly
up crack growthweakened
and greatlythe
tensile ductility
weakened the of the annealed
tensile ductility of PLA/TPEE
the annealed samples
PLA/TPEE with samples
high crystallinity.
with high crystallinity.

Figure
Figure 9. 9. SEM
SEM micrographsofofPLA/TPEE/ADR
micrographs PLA/TPEE/ADR samples
samples annealed
annealedatat80 ◦ Cfor
80°C for4040min:
min:(a)(a)PLA/TPEE
PLA/TPEE
(80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c) PLA/TPEE/ADR (80/20/1.0).
(80/20); (b) PLA/TPEE/ADR (80/20/0.5); (c) PLA/TPEE/ADR (80/20/1.0).

As seen in Figure 7c, while the Xc increased from 5% to 36%, the elongation at break of the
PLA/TPEE/ADR (80/20/0.5) sample decreased from 250% to 146%. Compared with the annealed
PLA/TPEE (80/20) samples with the maximum Xc (40%), the annealed PLA/TPEE/ADR (80/20/0.5)
Polymers 2016, 8, 417 14 of 16

As seen in Figure 7c, while the Xc increased from 5% to 36%, the elongation at break of the
PLA/TPEE/ADR (80/20/0.5) sample decreased from 250% to 146%. Compared with the annealed
PLA/TPEE (80/20) samples with the maximum Xc (40%), the annealed PLA/TPEE/ADR (80/20/0.5)
samples with the maxiumu Xc (36%) showed a higher elongation at break that increased by 421%.
It was clear that the increased brittleness resulting from the increased Xc weakened the ductility
of the PLA/TPEE/ADR (80/20/0.5) samples. However, similar to the quenched PLA/TPEE/ADR
(80/20/0.5) sample (Figure 6b), the annealed PLA/TPEE/ADR (80/20/0.5) samples also presented
a marked improvement in interfacial adhesion and a significant reduction in TPEE domain size,
as shown in Figure 9b. Therefore, compared to the annealed PLA/TPEE (80/20) samples, the annealed
PLA/TPEE/ADR (80/20/0.5) sample kept a higher tensile ductility due to the improved interfacial
adhesion. First, the enhanced interfacial adhesion of the PLA matrix and TPEE domains resulted from
the reactive compatibilization of ADR reduced the interface debonding which was a main form of
interfacial crack growth of polymer blends. Second, the improved interfacial compatibility decreased
the interfacial tension and reduced the TPEE domain size significantly. According to the crazing with
shear yielding mechanism, when content of TPEE remained unchanged, the size reduction of the
TPEE domain certainly led to a significant increase in the number of TPEE particles in PLA matrix,
as indicated in Figure 9. This promoted the massive generation of crazes/shear bands, thereby allowing
for a considerable development of plastic deformation [25,26]. Furthermore, the smaller TPEE particles
and the improved interfacial adhesion also enhanced the yielding ability and shear plastic deformation
of PLA matrix under tensile stress. Therefore, although the PLA/TPEE/ADR (80/20/0.5) samples
with high Xc also exhibited a tendency to craze and prematurely fracture under the tensile stress,
the improved interfacial adhesion and smaller TPEE domains still could effectively terminate the craze
growth and restrain the nucleation and propagation of cracks to some extent, as well as enhance the
yielding ability. As a result, the annealed PLA/TPEE/ADR (80/20/0.5) samples with high Xc showed
a better tensile ductility than the annealed PLA/TPEE (80/20) sample without ADR. Moreover, while
increasing ADR loading to 1.0 from 0.5 phr, the elongation at break of the annealed PLA/TPEE/ADR
(80/20/1.0) sample remained almost unchanged.
As a result, the crystallized PLA/TPEE/ADR blends with excellent heat resistance and high
tensile ductility were obtained by annealing and in situ reactive compatibilization.

4. Conclusions
The combined influences of crystallinity and reactive compatibilizer, ADR on the morphology,
tensile performance, and heat resistance of the PLA/TPEE (80/20) blends were investigated. Annealing
was performed to increase crystallinity of the samples. First, DSC measurement was performed to
research the isothermal cold crystallization behavior and kinetics of the PLA/TPEE/ADR blends.
Then, WAXD, SEM, tensile test, and VST measurements were carried out to research the influences
of crystallinity and ADR loading on the morphology, tensile performance, and heat resistance of the
PLA/TPEE blends. The differences in tensile fracture behaviors among the quenched and annealed
PLA/TPEE samples with and without ADR were discussed in detail. The conclusions obtained are
as follows:

(1) The crystallization kinetics results indicated that the addition of ADR decreased the cold
crystallization rate of the samples because the chain extension and branching effects of ADR
reduced the mobility and arrangement ability of PLA macromolecule segments and chains.
For example, t1/2 of the PLA/TPEE (80/20) sample without ADR was 6.9 min. However,
while increasing ADR loading up to 1 phr, t1/2 of the PLA/TPEE/ADR (80/20/1.0) sample
significantly increased up to 11.2 min. In addition, it was confirmed that the increase in
crystallization temperature could accelerate the cold crystallization of the PLA/TPEE samples
with and without ADR.
(2) With the increasing of ADR loading from 0 up to 1 phr, the maximum crystallinity of the
annealed PLA/TPEE/ADR samples also decreased from 40% to 34%. For the PLA/TPEE
Polymers 2016, 8, 417 15 of 16

sample, its heat resistance enhanced greatly while the crystallinity increased from 4% to 40%.
Meanwhile, the tensile ductility of the crystallized PLA/TPEE sample became very poor (ε = 28%)
due to the embrittlement with increased crystallinity and the incompatibility between PLA and
TPEE. As a comparison, the annealed PLA/TPEE/ADR samples with high crystallinity kept
a higher tensile ductility because ADR improved the interfacial compatibility and refined the
TPEE domains. For example, while the crystallinity increased from 5% up to the maximum
value of 36%, the VST value of the PLA/TPEE/ADR (80/20/0.5) sample markedly increased
from 58 to 136 ◦ C. Meanwhile, the highly crystallized sample still presented a higher tensile
ductility with an elongation at break of 146%. Moreover, the chain extension effect of ADR and
increased crystallinity also presented a synergistic enhancement on the tensile strength of the
PLA/TPEE samples.

Acknowledgments: The authors gratefully acknowledge support from Analytical and Testing Center of Hainan
University. The authors also thank the support from National Natural Science Foundation of China (grant number:
51263007, 51663010), Enterprises-Universities-Researches Integration Project of Hainan Province of China (grant
number: cxy20150023), and Natural Science Foundation of Hainan Province of China (grant number: 514206).
Author Contributions: All authors made contributions to the development of this manuscript and approved the
final manuscript. Sisi Wang contributed to the experimental work and wrote the manuscript; Nai Xu contributed
to the concept, analyses of data, design, and revision of the manuscript; Sujuan Pang and Lisha Pan assisted with
data analyses; Tan Li assisted with the experimental work.
Conflicts of Interest: The authors declare no conflict of interest.

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