polymers

Article
Crystallization of Poly(ε-caprolactone) in
Poly(vinylidene fluoride)/Poly(ε-caprolactone) Blend
Yang Kong, Yangmin Ma, Lele Lei, Xuechuan Wang and Haijun Wang *
Shaanxi University of Science and Technology, Xi’an 710021, Shaanxi, China; kongyang@sust.edu.cn (Y.K.);
mayangmin@sust.edu.cn (Y.M.); 1526875111@qq.com (L.L.); wangxc@sust.edu.cn (X.W.)
* Correspondence: wanghaijun@sust.edu.cn

Academic Editor: Shiao-Wei Kuo

Received: 10 December 2016; Accepted: 24 January 2017; Published: 28 January 2017

Abstract: The crystallization behavior of poly(ε-caprolactone) (PCL) in a poly(vinylidene fluoride)

(PVDF)/PCL blend as well as on a highly orientated PVDF substrate was studied by means of POM,
DSC and TEM. The results show that the miscibility of the PVDF/PCL blend and the spherulitic
morphology of PVDF varies with the blend ratio. For all the compositions, the pre-existing PVDF
crystals accelerated the crystallization of PCL because the PVDF exhibits very strong nucleation
ability toward PCL as reflected by the occurrence of heteroepitaxy and the transcrystallization of PBA
on the PVDF substrate. This is associated with the perfect lattice matching between the PBA and
PVDF crystals.

Keywords: poly(ε-caprolactone); poly(vinylidene fluoride); blend; crystallization

1. Introduction
As a simple and cost-effective way to improve the physical and mechanical properties of polymeric
materials, polymer blending has attracted a broad interest [1–4]. Polymer blends can be miscible,
partially miscible, or immiscible systems, including amorphous/amorphous, amorphous/crystalline
and crystalline/crystalline components. As is known to all, the properties of all of these possible
blends depend strongly on their morphologies and crystal structure. The crystallization behavior
and related morphological control of polymer blends has consequently interested more and more
theoreticians and experimentalists [5–7].
Comparatively speaking, the morphology of the crystalline/crystalline blend is more complicated
than that of the other two systems, because the phase separation structure of this system is always
changing during the sequential crystallization of the two components. It should be noted that the
crystallization kinetics and morphology of crystalline/crystalline blends are far away from being really
understood, though some related works have been published in the literature [8–14]. Less attention
has been paid to the crystallization of the component with a lower melting point (Tm ), particularly in a
partially miscible crystalline/crystalline blend system. This rests on the fact that the crystallization
of the low-Tm component in this special kind of blend is actually affected not only by the miscibility
varying with the composition but also by the pre-existing crystals of the high-Tm component.
In this work, we chose poly(vinylidene fluoride) (PVDF) and poly(ε-caprolactone) (PCL) as the
model system of partially miscible crystalline/crystalline polymer blends. From the measurements of
the cloud point and melting point depression, the PVDF/PCL blend was found to be miscible when
the content of PVDF was less than 30 wt % [15]. Since the difference in the melting points between
PVDF (ca. 167 ◦ C) and PCL (ca. 56 ◦ C) is large, the crystallization of PVDF is always completed before
PCL. So the sequential crystallization of PVDF and PCL corresponds to the phase transition from the
fully amorphous to the amorphous/crystalline, and then to the crystalline/crystalline state. The phase
separation structure of PVDF/PCL was studied by taking into account the influences of the blend

Polymers 2017, 9, 42; doi:10.3390/polym9020042 www.mdpi.com/journal/polymers

Polymers 2017, 9, 42 2 of 8

composition. Moreover, much more attention has been directed to the crystallization and morphology
of the low-Tm component PCL by considering the effect of the presence of the pre-existing crystals of
the high-Tm component PVDF. Finally, the crystallization behavior of PCL on highly orientated PVDF
film was studied by POM and TEM.

2. Experimental Section

2.1. Materials
PCL (Mn = 45,000) and PVDF (Mn = 275,000) were purchased from Sigma-Aldrich Company.
The melting points were measured to be 167 ◦ C for PVDF and 56 ◦ C for PCL. Both of them were used
without further purification.
Blends of PCL and PVDF were prepared by solvent casting using DMF as a mutual solvent
(total concentration was 20 mg/mL). Thin films for POM and SEM observations were prepared by
solution casting on glass slide. The obtained films were heat-treated at 190 ◦ C and then cooled to
predetermined isothermal crystallization temperature. To check the epitaxial behavior of PCL with
PVDF, a double-layered sample was prepared by transferring a thin layer of PCL onto the highly
oriented PVDF substrate. The double-layered sample was heated to 85 ◦ C for 15 min to erase the
thermal history of PCL and then cooled to 30 ◦ C for isothermal crystallization. The highly oriented
PVDF film was prepared through a melt-drawing technique introduced by Petermann and Gohil [16].

2.2. Measurements
A JEM GEOL-100CX electron microscope operated at 100 kV, a Field Emission Scanning Electron
Microscope (Hitachi S-4800, Japan) operated at 2.0 kV and an OLYMPUS BH-2 optical microscope
were used for TEM, SEM and optical microscopy observation, respectively. For SEM, the films were
immersed for 24 h in chloroform at room temperature to etch away PCL. Etching was necessary
because the lamellar bundles of PVDF were buried in PCL and almost invisible. After etching, the
lamellar morphologies of PVDF emerged. Thermal analysis was measured by means of differential
scanning calorimetry (DSC) using the DSC-2000 equipped with an Intracooler system.

3. Results and Discussion

Figure 1 shows the blend composition effect on the phase separation and the crystallization of
PVDF and PCL. Figure 1(a1,b1,c1) show the morphologies of 70/30, 50/50 and 30/70 PVDF/PCL
blends at 150 ◦ C, at which temperature the crystallization of PVDF has been completed but PCL is still
in the melt state. In the 70/30 blend shown in Figure 1(a1), the PVDF-rich phase was continuous and
the PCL-rich phase domains were finely dispersed within the PVDF-rich phase, indicating that the two
components are immiscible in PVDF-rich compositions. In addition, the phase separation morphology
indicated that the mechanism of nucleation and growth governs the development of phase separation
of the 70/30 mixture (see Supplementary Materials). In the 50/50 blend, PVDF was still immiscible
with PCL and the two components formed bicontinuous phases (see Figure 1(b1) and Supplementary
Materials). In the 30/70 blend shown in Figure 1(c1), the PVDF component formed uniform spherulites
with increased ring spacing and the melt of PCL was expelled into the interspherulitic, interfibrillar or
interlamellar regions of the PVDF spherulites. The open spherulitic morphology of PVDF observed
here can be often found in its miscible blend with other low-Tm crystallizable blends, suggesting that
PVDF is miscible with PCL in PCL-rich compositions. These findings are in accordance with the report
of Jo et al. [15]. However, it should be noticed that some open PVDF spherulites could be observed
within the PCL-rich phase in the 70/30 and 50/50 blends, suggesting that the PCL-rich phase also
contains small amounts of PVDF and the two components are miscible in the PCL-rich phase.
Polymers 2017, 9, 42 3 of 8
Polymers 2017, 9, 42 3 of 8

Figure 1.1.POM
POMimages
imagesof of
(a1–a4) 70/30,
(a1–a4) (b1–b4)
70/30, 50/50
(b1–b4) and and
50/50 (c1–c4) 30/7030/70
(c1–c4) PVDF/PCL blends.
PVDF/PCL The blend
blends. The
samples were first cooled ◦ C for the crystallization of PVDF and then quenched to
blend samples were first from 190from
cooled to 150190 to 150 °C for the crystallization of PVDF and then
30 ◦ C to crystallize PCL.
quenched to 30 °C to crystallize PCL.

Figure 1(a2–a4,b2–b4,c2–c4)
Figure 1(a2–a4,b2–b4,c2–c4)show show thethe crystallization
crystallization of PCLof inPCL
the in the 50/50
70/30, 70/30, and 50/50 andblends,
30/70 30/70
blends, respectively, when the samples were cooled
◦ to 50 °C. For the 70/30
respectively, when the samples were cooled to 50 C. For the 70/30 blend, it was difficult to observe the blend, it was difficult to
observe the crystallization
crystallization of PCL in theofPVDF-rich
PCL in thephase PVDF-rich
because phase because
of the of the lowofresolution
low resolution the opticalofmicroscopy.
the optical
Therefore, the crystallization of PCL in the PCL-rich phase in the 70/30 blend has been paidhas
microscopy. Therefore, the crystallization of PCL in the PCL-rich phase in the 70/30 blend been
greater
paid greater attention. As shown in Figure 1(a2), the crystallization
attention. As shown in Figure 1(a2), the crystallization of PCL occurred in the interspherulitic region of PCL occurred in the
interspherulitic
in the PCL-rich phase regionorinthe
theinterfacial
PCL-rich region
phase or the interfacial
between region phase
the PVDF-rich between andthe thePVDF-rich phase
PCL-rich phase.
and the PCL-rich phase. Subsequently, the crystallization of PCL
Subsequently, the crystallization of PCL proceeded within the PVDF spherulites in the PCL-rich phase proceeded within the PVDF
spherulites
(see in theFor
Figure 1(a3)). PCL-rich
the 50/50 phase
blend,(see Figure
it was found 1(a3)).
that For the 50/50 blend,
the crystallization of PCLit wasstill found
occurred that the
in the
crystallization of
interspherulitic PCL still
region and occurred in the interspherulitic
then proceeded in the PCL-rich phase region(see andFigure
then proceeded
1(b2)). It was in the PCL-rich
noticed that
phase (see Figure 1(b2)). It was noticed that the PCL started to crystallize
the PCL started to crystallize in the PVDF-rich phase after its complete crystallization in the PCL-rich in the PVDF-rich phase
after its
phase (seecomplete
the white crystallization
circles in Figure in the PCL-rich
1(b4)). phase (see
This indicated thethe
that white
PCLcircles in Figure
was probably 1(b4)).inThis
located the
indicated that the PCL was probably located in the interlamellar regions
interlamellar regions of the PVDF in the PVDF-rich phase and the crystallization of this part of the PCL of the PVDF in the
PVDF-rich phase and the crystallization of this part of the PCL was confined
was confined [17]. The crystallization of the PCL in the 30/70 blend was similar to that in the PCL-rich [17]. The crystallization
of the PCL
phase in the in 70/30
the 30/70andblend
50/50 was similarAs
blends. to seen
that in inthe PCL-rich
Figure phasethe
1 (c2–c4), in the 70/30 and 50/50
crystallization blends.
of the PCL
As seen in Figure 1 (c2–c4), the crystallization of the PCL occurred in the
occurred in the interspherulitic regions and then proceeded in the interfibrillar or interlamellar regions. interspherulitic regions
and then
For aproceeded in the interfibrillar
better understanding or interlamellar
of the morphological regions.
details of the PVDF/PCL blend systems, a further
For a better understanding of the morphological
study of the internal structures of PVDF spherulites is necessary. Figure details of the 2PVDF/PCL
shows the SEM blendmicrographs
systems, a
further study of the internal structures of PVDF spherulites
of the spherulitic morphologies of the 70/30 blend melt-crystallized at 150 C. Figure 2a,b is necessary. Figure
◦ 2 shows theshows
SEM
micrographs of the spherulitic morphologies of the 70/30 blend
the spherulitic morphologies of PVDF in the PVDF-rich phase. As seen in Figure 2a or Figure 2b, melt-crystallized at 150 °C. Figure
2a,bPVDF
the shows the spherulitic
spherulite morphologies
is composed of PVDF
of the twisting in thebundles
lamellar PVDF-rich that phase.
are viewedAs seen in Figure
alternately 2a or
edge-on
Figure 2b, the PVDF spherulite is composed of the twisting lamellar
and face-on. In addition, the arrangement of the lamellae is very tight. Figure 2c,d show the spherulitic bundles that are viewed
alternately edge-on
morphologies of PVDF andinface-on. In addition,
the PCL-rich phase. As the seen
arrangement
in Figure of thethe
2c,d, lamellae
open PVDF is very tight. Figure
spherulites are
2c,d show the spherulitic morphologies of PVDF in the PCL-rich
well dispersed in the PCL-rich phase. Some of PVDF spherulites grew into corals, indicating thatphase. As seen in Figure 2c,d, the
a
open PVDF spherulites are well dispersed in the PCL-rich phase.
large amount of the PCL component was located in the intraspherulitic region. However, the other Some of PVDF spherulites grew
into corals,
PVDF indicating
spherulites that ainto
just grew large amount
sheaves due of to
thethePCLlackcomponent was located in the intraspherulitic
of raw materials.
region. However, the other PVDF spherulites just grew into sheaves due to the lack of raw materials.
Polymers 2017, 9, 42 4 of 8
Polymers 2017, 9, 42 4 of 8

Figure 2. SEM images of (a,b) PVDF-rich phase and (c,d) PCL-rich phase in the 70/30 PVDF/PCL
Figure 2. SEM images of (a,b) PVDF-rich phase and (c,d) PCL-rich phase in the 70/30 PVDF/PCL
blend
blend crystallized at 150
crystallized at 150 ◦°C.
C. The
The PCL
PCL component
component has
has been etched away.
been etched away.

Next, the effect of the pre-existing PVDF spherulites on the crystallization of PCL was further
Next, the effect of the pre-existing PVDF spherulites on the crystallization of PCL was further
investigated. One possible scenario is that the crystallization rate of PCL will be accelerated due to
investigated. One possible scenario is that the crystallization rate of PCL will be accelerated due to
the nucleation effect of PCL crystals induced by PVDF crystals. Another possible scenario is that the
the nucleation effect of PCL crystals induced by PVDF crystals. Another possible scenario is that the
crystallization of PCL will be inhibited if the pre-existing PVDF crystals have no nucleation ability.
crystallization of PCL will be inhibited if the pre-existing PVDF crystals have no nucleation ability.
Figure 3 shows the crystallization of PCL at 30 °C after the complete crystallization of PVDF at 100
Figure 3 shows the crystallization of PCL at 30 ◦ C after the complete crystallization of PVDF at 100 ◦ C in
°C in the 70/30 PVDF/PCL blend. The PCL-rich phase is located in the central region and surrounded
the 70/30 PVDF/PCL blend. The PCL-rich phase is located in the central region and surrounded by the
by the PVDF-rich phase. As seen in Figure 3a,b, the crystallization of PCL occurs along the border
PVDF-rich
between the phase. As seen in
PVDF-rich Figure
phase 3a,b,
and the crystallization
PCL-rich of PCL of
phase. Because occurs
the along
high the border between
nucleation density,thea
PVDF-rich phaselayer
transcrystalline and of
PCL-rich
PCL came phase.
intoBecause of the high nucleation
being. Subsequently, density, a transcrystalline
the transcrystalline layer
layer kept growing
of PCL
in came into
the PCL-rich being.
phase Subsequently,
until colliding with the the
transcrystalline
PCL spherulites.layerThe
keptformation
growing of in the
the transcrystalline
PCL-rich phase
until colliding
layer with the
of PCL clearly PCL spherulites.
indicates The formation
that the pre-existing PVDF of crystals
the transcrystalline layer ofeffect
have a nucleation PCL clearly
on the
crystallization of PCL. Figure 4 shows DSC cooling traces of PVDF/PCL blends at 10 °C/min of
indicates that the pre-existing PVDF crystals have a nucleation effect on the crystallization (a)PCL.
and
Figure 4 shows DSC cooling traces of PVDF/PCL blends at 10 ◦ C/min (a) and the subsequent melting
the subsequent melting behavior at 10 °C/min (b). As shown in Figure 4, both the crystallization and
melting at 10 ◦ C/minof
behaviortemperatures (b).
theAsPVDF
shown in Figure 4,
component inboth thethe
any of crystallization
PVDF/PCL blendsand melting temperatures
were lower than neatof
the PVDF component in any of the PVDF/PCL blends were lower than neat PVDF,
PVDF, which suggests that some degree of miscibility exists for all compositions. In addition, the which suggests that
some degree oftemperature
crystallization miscibility exists
of PCLfor in
allits
compositions.
blends with In addition,
PVDF the crystallization
was higher temperature
than neat PCL, indicatingof
PCL the
that in its blends with
pre-existing PVDFcrystals
PVDF was higher than neat
promoted PCL, indicatingofthat
the crystallization PCL.the pre-existing PVDF crystals
promoted the crystallization of PCL.
Polymers 2017, 9, 42 5 of 8

Polymers 2017, 9, 42 5 of 8
Polymers 2017, 9, 42 5 of 8

Figure 3. Crystallization of PCL at ◦°C

Figure 3.
Figure 3. Crystallization
Crystallization of PCL at 30 30C°C for (a) 2 min, (b) 5 min, (c) 10 min
for (a) 2 min, (b) 5 min, (c) 10 10and
min(d)and
min 20 min
and (d)after
(d) the after the
20 min
20 min after the
crystallization of PVDF at◦ 100 °C in PVDF/PCL (70/30) blend.
crystallization of PVDF at 100 °C in PVDF/PCL
crystallization of PVDF at 100 C in PVDF/PCL (70/30) blend. (70/30) blend.

Figure 4. (a) DSC cooling traces of PVDF/PCL blends at 10 °C/min and (b) subsequent melting
behavior at 10 °C/min.

◦ C/min and (b) subsequent melting

Figure 4.4. (a)
Figure (a) DSC
DSC cooling
cooling traces
traces of
ofPVDF/PCL
PVDF/PCL blends
blends at
at 10
10 °C/min and (b) subsequent melting
behavior ◦ C/min.
behavior atat 10
10 °C/min.

The above POM and DSC results have clearly shown that in the PVDF/PCL blend, the pre-existing
PVDF crystals acted as nucleating agents and could accelerate the crystallization of PCL. Next, the
Polymers 2017, 9, 42 6 of 8

Polymers
The 2017, 9, 42
above POM and DSC results have clearly shown that in the PVDF/PCL blend, 6 the of 8

pre-existing PVDF crystals acted as nucleating agents and could accelerate the crystallization of PCL.
Next, the nucleation
nucleation mechanism mechanism
of PCL onofPVDF PCL on PVDFwas
crystals crystals was investigated
investigated from the perspective
from the perspective of epitaxialof
epitaxial crystallization. Figure 5a shows the different supermolecular structures
crystallization. Figure 5a shows the different supermolecular structures of PCL crystallized on the glass of PCL crystallized
on
andthePVDFglass and PVDF
surfaces, surfaces, On
respectively. respectively. On the glass
the glass substrate substrate
(in the lower-left (incorner
the lower-left
of Figurecorner
5a), PCL of
Figure 5a), PCL crystallized in a spherulitic structure. On the PVDF substrate
crystallized in a spherulitic structure. On the PVDF substrate (in the upper-right corner of Figure 5a), (in the upper-right
corner
the PCLofcrystals
Figureshowed
5a), themuch
PCL crystals
strongershowed muchwith
birefringence stronger birefringence
respect with respect
to the PCL spherulites to theonPCL
formed the
spherulites formed on the glass substrate. In addition, no individual PCL
glass substrate. In addition, no individual PCL crystals could be identified. This implies that the PVDF crystals could be
identified. This implies that the PVDF substrate exhibits strong nucleation
substrate exhibits strong nucleation ability toward PCL. It is documented that α-form PVDF crystals ability toward PCL. It is
documented that α-form
show the monoclinic PVDF
unit cell crystals
with show of
dimensions thea monoclinic
= 4.96 Å, b =unit
9.64cell with
Å and c=dimensions
4.62 Å andof a =crystals
PCL 4.96 Å,
b = 9.64 Å and c = 4.62 Å and PCL crystals show the orthorhombic unit cell
show the orthorhombic unit cell with dimensions of a = 7.47 Å, b = 4.94 Å and c = 17.05 Å [18,19]. with dimensions of a =
7.47
Figure 5b shows an electron diffraction pattern of a PCL/PVDF double layer. As seen in Figureof5b,
Å, b = 4.94 Å and c = 17.05 Å [18,19]. Figure 5b shows an electron diffraction pattern a
PCL/PVDF
the appearance double layer. and
of sharp As seen in Figure reflection
well-defined 5b, the appearance of sharp
spots of both PCL and
andwell-defined
PVDF on thereflection
electron
spots
diffraction pattern confirms that both PCL and PVDF substrate layers are highly both
of both PCL and PVDF on the electron diffraction pattern confirms that PCLIn
oriented. and PVDF
addition,
substrate layers are highly oriented. In addition, the alignment of the [004]
the alignment of the [004] of PCL along the [002] direction of PVDF, as well as the [020] of PCL alongof PCL along the [002]
direction of PVDF,ofasPVDF,
the [020] direction well as the [020]
reflects of PCL
a parallel along thebetween
orientation [020] direction
PCL and of PVDF
PVDF,chains.
reflectsThe
a parallel
special
orientation between PCL and PVDF chains. The special parallel chain orientation
parallel chain orientation of PCL and PVDF can be explained well in terms of a two-dimensional of PCL and PVDF
can bematching.
lattice explainedThe welllattice
in terms of a two-dimensional
distances of the (004)PCL and lattice
(001)matching. The lattice distances of the
PVDF lattice planes are 4.32 and 4.62 Å,
(004) PCL and (001)PVDF lattice planes are 4.32 and 4.62 Å, respectively. The mismatching between them
respectively. The mismatching between them is 6.4%. Furthermore, excellent matching can also be
is 6.4%.
found Furthermore,
between excellent
the lattice matching
distances can alsoand
of the (010) be (020)
found between the lattice distances of the
PCL PVDF lattice planes with a mismatching
(010) PCL and (020)PVDF lattice planes with a mismatching of 3.2%.
of 3.2%.

Figure 5. (a) Optical micrograph shows the morphologies of PCL melt-crystallized at 30 ◦°C on glass
Figure 5. (a) Optical micrograph shows the morphologies of PCL melt-crystallized at 30 C on glass
slide (lower left corner) and PVDF substrate (upper right corner); (b) Electron diffraction pattern of a
slide (lower left corner) and PVDF substrate (upper right corner); (b) Electron diffraction pattern of a
PCL/PVDF double-layered film.
PCL/PVDF double-layered film.

4. Conclusions
4. Conclusions
The miscibility of the PVDF/PCL blend, the spherulitic morphology of the PVDF, and the
The miscibility of the PVDF/PCL blend, the spherulitic morphology of the PVDF, and the
crystallization behavior of the PCL in the PVDF/PCL blend as well as on the highly orientated PVDF
crystallization behavior of the PCL in the PVDF/PCL blend as well as on the highly orientated PVDF
substrate were studied by means of POM, DSC, SEM and TEM. It was found that the miscibility of
substrate were studied by means of POM, DSC, SEM and TEM. It was found that the miscibility
the PVDF/PCL blend varies with the compositions. PVDF and PCL were immiscible in the
of the PVDF/PCL blend varies with the compositions. PVDF and PCL were immiscible in the
PVDF-rich blend but they were miscible in the PCL-rich blend. In addition, the spherulitic
PVDF-rich blend but they were miscible in the PCL-rich blend. In addition, the spherulitic morphology
morphology of PVDF was also affected by the blend ratio. In the PVDF-rich blend, PVDF formed
of PVDF was also affected by the blend ratio. In the PVDF-rich blend, PVDF formed tiny and
tiny and compact spherulites in the PVDF-rich phase and crystallized in an open spherulitic
compact spherulites in the PVDF-rich phase and crystallized in an open spherulitic structure in
structure in the PCL-rich phase. However, only open spherulites of PVDF were formed in the
the PCL-rich phase. However, only open spherulites of PVDF were formed in the PCL-rich blend.
PCL-rich blend. The pre-existing PVDF crystals acted as the nucleation agent for PCL and promoted
The pre-existing PVDF crystals acted as the nucleation agent for PCL and promoted the subsequent
the subsequent crystallization of PCL. In the immiscible PVDF-rich blend, the crystallization of PCL
crystallization of PCL. In the immiscible PVDF-rich blend, the crystallization of PCL occurred at the
occurred at the phase interface and then proceeded within the PCL-rich phase. In the miscible
phase interface and then proceeded within the PCL-rich phase. In the miscible PCL-rich blend, PCL
PCL-rich blend, PCL crystallized first in the interspherulitic region and then in the interfibrillar or
crystallized first in the interspherulitic region and then in the interfibrillar or interlamellar region.
interlamellar region. For all compositions, the nonisothermal crystallization temperature of the PCL
For all compositions, the nonisothermal crystallization temperature of the PCL component in the
Polymers 2017, 9, 42 7 of 8

PVDF/PCL blend was higher than that of neat PCL at the same cooling rate. Finally, the strong
nucleation ability of PVDF crystals toward PCL was further proved by the occurrence of heteroepitaxy
and the transcrystallization of PCL on the PVDF substrate. The electron diffraction results show that
there exists perfect two-dimensional lattice matching between PVDF and PCL crystals.

Supplementary Materials: The following are available online at www.mdpi.com/2073-4360/9/2/42/s1,

Figure S1: Phase separation morphologies in the 70/30 and 50/50 PVDF/PCL blend at 190 ◦ C.
Acknowledgments: The financial support by the National Natural Science Foundations of China (No. 21204045)
and the Natural Science Basic Research Plan in Shaanxi Province of China (No. 2016JM2020) are
gratefully acknowledged.
Author Contributions: Yang Kong performed the experiments and data analysis and wrote the paper.
Yangmin Ma and Xuechuan Wang contributed to data analysis and the editing of the paper. Lele Lei performed
the TEM experiments and analyzed the data. Haijun Wang managed the project as a principal investigator and
designed the experiments.
Conflicts of Interest: The authors declare no conflict of interest.

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