Polymer Testing 28 (2009) 875–885

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Characterisation

Compatibility and characteristics of poly(butylene succinate)

and propylene-co-ethylene copolymer blend
Hung-Yi Tsi a, Wen-Chin Tsen a, Yao-Chi Shu a, Fu-Sheng Chuang a, *, Chien-Chung Chen b
a
Department of Polymer Materials, Vanung University, Chung-Li, Tao-Yuan 320, Taiwan, ROC
b
Graduate Institute of Biomedical Materials and Engineering, Taipei Medical University, Taipai 250, Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Propylene-co-ethylene elastomer resin (PER) has been blended into biodegradable
Received 23 June 2009 poly(butylene succinate) copolymer (PBS) by a melt-blending process to develop a novel
Accepted 6 August 2009 semi-biodegradable thermoplastic elastomer. The PBS/PER blends displayed good
compatibility in the range 70/30 > PBS/PER > 30/70 according to analyses by DSC, DMA
Keywords: and the Couchman method. Although the PBS/PER blends displayed compatibility, SEM
Blends
analyses of most of the PBS/PER blends revealed two-phase structures including sea-island
Compatibility
and irregular fiber-shaped morphologies, except for PBS/PER (70/30). PBS/PER (60/40) and
Poly(butylene succinate) copolymer
Propylene-co-ethylene elastomer PBS/PER (50/50) display low tensile strength due to large sea-phase and irregular fiber-
shaped morphologies, even though they have good compatibility. PBS/PER (70/30)
apparently exhibited a single phase by SEM and showed the best compatibility by DSC and
DMA. Furthermore, the tan d, elongation and initial moduli of the PBS/PER blends were
seen to increase with increasing PER content, indicating that the toughness and shock
resistance of PBS are improved by incorporating PER into the composition.
Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction synthesis and/or modification have been too time-

The rapid growth of plastics production is considered as
a serious source of environmental pollution. Biodegradable
polymers offer one way of reducing this source of envi-
ronmental pollution, and have been used in packaging and
plastic products. Although biodegradable polymers have
good biodegradability and biocompatibility, their
mechanical and thermal properties as thermoplastic elas-
tomers (TPEs), such as shock absorbance, impact strength,
tensile strength and thermal resistance, have hitherto been
inadequate. Therefore, there has been much interest in
modifying their properties by the synthesis and/or
modification of biodegradable polymers such as poly
(3-hydroxyalkanoate), poly(lactic acid), poly(butylene
succinate), and so on [1–6]. However, the methods of
* Corresponding author. Tel.: þ886 3 4515811x51652.
E-mail address: ymj0826@mail.vnu.edu.tw (F.-S. Chuang).
consuming and/or uneconomical for the commercial
production of novel biodegradable polymers.
BionolleÒ is available in many grades from Showa
Highpolymer, Japan. Of these, BionolleÒ-1001 is a poly(-
butylene succinate) copolymer (PBS) and is soft and strong,
closely resembling linear low-density polyethylene, but is
biodegradable in compost or moist soil, in fresh water with
activated sludge, and in sea water. PBS has excellent
biodegradability and tensile strength, but its impact, shock
absorbance and toughness properties are lower than those
of engineering TPEs because it is designed to have the
characteristics of plastic materials [6]. Ethylene-co-
propylene copolymer (EPR) and ethylene-propylene diene
copolymer (EPDM) are often added to materials such as
polypropylene (PP) and polyethylene (PE) in order to
improve their impact strength, shock resistance, and
toughness [7–9]. VersifyÒ, from Dow Chemical Company, is
a TPE that consists of propylene-co-ethylene copolymer
resin (PER), which differs from EPR in its propylene content.

0142-9418/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2009.08.004
876 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885
VersifyÒ-3401 has low density, high softness, as well as
good impact strength, shock absorbance, and elasticity.
Thus, PER can be used to improve the shock absorbance,
impact strength, and toughness of plastics.
Accordingly, in the work described herein, PER has been
mixed with PBS by a simple and economical melt-blending
method in order to improve the shock absorbance, tough-
ness, and elongation of PBS. The PBS/PER blend has been
studied with a view to developing a novel, semi-biode-
gradable TPE for reducing the source of waste pollution. We
have investigated the effects of the characteristics of PBS
and PER on the phase transition, compatibility, shock
absorbance, and tensile strength of PBS/PER blends.
Furthermore, the relationships between the morphology of
blends, compatibility and tensile strength are discussed on
the basis of scanning electron microscopy (SEM) images.
2. Experimental
2.1. Blending and sample preparation
The poly(butylene succinate) (PBS) used was Bion-
olleÒ-1001 from Showa Highpolymer Co. Ltd., a thermo-
plastic polyester with biodegradation properties. As
a thermal plastic elastomer (TPE), we used VersifyÒ-3401
from Dow Chemical Co. Ltd., a propylene-co-ethylene
copolymer resin (PER) with a 25% ethylene content. The
PBS and PER pellets were dried in a vacuum oven at 80  C
for 24 h prior to use. The PBS/PER blends were mixed at
190  C for 5 min in a Brabender plastograph, the twin-
rotary mixer of which was set to operate at a speed of
30 rpm. The compositions of the mixtures of PBS/PER
ranged from 90/10 to 10/90 (wt/wt). For comparison
purposes, pure PBS and PER were also melt-blended
under the same processing conditions in the Brabender
plastograph. After blending, the blends were injection-
moulded by means of an injection press at 190  C with
a mould temperature of 50  C. The injection mould was
a standard dumbbell-shaped tensile bar (ASTM D 638 ISO
527-2) of dimensions 25  4  1 mm3.
2.2. Measurements
2.2.1. DSC
DSC measurements were made using a Perkin–Elmer
Pyris-1 DSC with an ice-water and liquid-nitrogen cooler.
Indium was used to calibrate the temperature and heat of
fusion. The mass of all specimens used for the measure-
ments was roughly 5 mg. The initial scan of the specimens
proceeded from 150 to 250  C at a rate of 10  C/min in
a nitrogen atmosphere. The melt-quenched scans of the
specimens were similar to their initial scans. First, the
specimens were heated to 250  C and held at this temper-
ature for 1 min to eliminate their thermal histories. They
were then quenched to 150  C at a rate of 100  C/min.
Subsequently, the thermograms of the specimens were
obtained by heating at a rate of 10  C/min from 150 to
250  C. The annealed samples were prepared in the same
way as for the quenched scans. They were firstly heated to
250  C and held at this temperature for 1 min to eliminate
their thermal histories; they were then quenched to 10  C
at a rate of 100  C/min, at which temperature they were
maintained until thermal equilibrium was reached. There-
after, the thermograms of the samples were obtained at
a heating rate of 10  C/min. The DSC thermograms of the
annealed samples were measured only above room
temperature under various annealing conditions. Figs.3 and
4 show the various annealing conditions.
2.2.2. DMA
The storage moduli (E0 ) and loss tangents (tan d) of the
individual components and blends were measured by
dynamic mechanical analysis (Perkin–Elmer DMA7e). Test
data were acquired in tensile mode from 100 to 100  C at
a scan rate of 10  C/min and a frequency of 1 Hz.
2.2.3. SEM
Scanning electron microscopy (SEM) analysis was
applied in order to observe the morphologies of the blends.
SEM was performed with a TESLA-B340 scanning electron
microscope. Test samples were sputter coated by exposing
them to a gold ion beam using a PELCO S.C. 6 at a current of
25 mA for 40 s.
2.2.4. Tensile strength
The tensile strengths of the blends were evaluated with
a tensile machine (MTS Qtest-5) in conjunction with
material-testing software (TestWorkÒ4). The tensile
strength tests were performed at 25  C with a relative
humidity of 60  5%. The crosshead speed was set at
50 mm/min using a 5 kN load cell.
3. Results and discussion
3.1. Phase transition and compatibility
Semi-crystalline polymers possess amorphous and
crystalline phases, each of which has a phase transition
region, i.e. glass transition temperature (Tg) and melting
temperature (Tm). The phase transition regions were
determined by DSC and DMA to reveal the miscibility and
compatibility of the polymer blends. It is generally accepted
that a miscible polymer blend is homogeneous and usually
displays a single Tg between those of the pure components,
whereas a compatible blend still reveals both Tgs, although
these eventually shift towards one another.
The thermograms of the PBS, PER, and PBS/PER blends
in the initial and melt-quenched scans feature several
endothermic regions, as shown in Figs. 1 and 2. The melt-
quenched scans of all samples were examined in order to
eliminate their thermal histories and to determine their
compatibilities. Table 1 lists the characteristic temperatures
of their glass transition regions. All glass transition
temperatures (Tgs) reported herein were determined by the
half heat capacity (1/2 Cp) of the glass transition region.
3.1.1. DSC analyses of PBS and PER
The first endothermic regions for PBS and PER, as shown
in Table 1, appear at 31 to 40  C and are associated with
the glass transition region resulting from the amorphous
phase. The initial scan Tg values (Tg-1) of PBS and PER are
about 36  C. The first endothermic regions for PBS and
 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885 877

20 PER in the melt-quenched scan appear at 28 to 41  C

PBS
and 30 to 38  C, respectively, as shown in Table 1. The Tg
PER
values from the melt-quenched scan (Tg-2) for PBS and PER
PBS/PER(10/90)
are seen to be around 33 and 34  C, respectively, which
25
are slightly higher than their Tg-1 values due to phase
Heat Flow Down

PBS/PER(20/80)

PBS/PER(30/70) mixing between the crystalline and amorphous phases

PBS/PER(40/60) during the melt-quenching process. Examining the widths
30
of the Tg regions (Tgw) of PBS and PER, reveals an obvious
PBS/PER(50/50)
distinction between the initial and melt-quenched scans, as
PBS/PER(60/40)
shown in Table 1. The Tgw-1 (Tgw of the initial scan) and Tgw-2
35 PBS/PER(70/30)
(Tgw of the melt-quenched scan) of PBS are 6.85  C and
13.25  C, respectively, while the Tgw-1 and Tgw-2 values of
PBS/PER(80/20)

PBS/PER(90/10) PER are both at around 8  C. This result reflects the large
40
amount of amorphous PER, the molecular chains of which
-100 0 100 200 adopt a highly random coil structure. Therefore, the Tgw-2 of
Temperature(°C) PER does not increase when this material is subjected to the
melt-quenching process; on the contrary, the Tgw-2 of PBS is
Fig. 1. The initial scanning DSC thermograms of PBS, PES and PBS/PER blends. greatly increased because the molecular chains of PBS
possess a high degree of crystallinity, which is lost to an
amorphous phase during the melt-quenching process.
10 The endothermic characteristics of the crystal phase are
12 PBS
also seen in the DSC thermograms, as shown in Figs. 1 and
PER 2. The endothermic characteristics and enthalpies of the
14 PBS/PER(10/90)
crystal phases are listed in Tables 2 and 3. The initial and
Heat Flow Down

PBS/PER(20/80)

16 PBS/PER(30/70)
melt-quenched thermograms of PBS exhibit one large
PBS/PER(40/60) endothermic peak at around 120  C, i.e. its melting
18 temperature, in both the initial scan, TmB1–1, and in the
PBS/PER(50/50)
20 melt-quenched scan, TmB2–1. The initial scan thermogram
PBS/PER(60/40)
of PER features two small melting peaks at around 54  C
22 PBS/PER(70/30) (TmE1–1) and 103  C (TmE1–2). However, TmE1–1 disappears in
24 PBS/PER(80/20) the melt-quenched scan, while TmE1–2 still appears at about
100  C, as shown in Figs. 1 and 2. The endothermic
PBS/PER(90/10)
26 behavior of TmE1-1 is perhaps associated with destruction of
fragmentary crystals or enthalpy relaxation. In order to
-100 0 100 200 verify the endothermic behavior of TmE1–1, PER was further
Temperature (°C) subjected to various annealing treatments. The PER ther-
Fig. 2. The melt-quenched scanning DSC thermograms of PBS, PES and PBS/
mograms showed no obvious change after annealing at
PER blends. 50  C for a long period; however, after annealing at 70  C

Table 1
Temperature and capacity of glass transition region in the initial and melt-quenched scans of PBS, PER and PBS/PER blends.

Code Initial scan Melt-quenched scan

(the first scan) (the second scan)

Tgi-1a ( C) Tg-1c ( C) Tge-1a ( C) Cp-1d (J/g  C) Tgw-1e Tgi-2b ( C) Tg-2c ( C) Tge-2b ( C) Cp-2d (J/g  C) Tgw-2e DCpf
PBS 39.32 35.96 32.47 0.028 6.85 41.26 33.38 28.01 0.052 13.25 0.024
PBS/PER (90/10) 38.53 36.05 33.05 0.029 5.48 37.36 34.36 31.29 0.063 6.07 0.034
PBS/PER (80/20) 39.67 36.34 32.70 0.037 6.97 38.16 34.93 31.44 0.061 6.72 0.024
PBS/PER (70/30) 39.43 35.55 31.32 0.045 8.11 37.56 34.59 31.28 0.055 6.28 0.010
PBS/PER (60/40) 38.65 36.71 32.42 0.034 6.23 37.61 34.33 31.03 0.064 6.58 0.030
PBS/PER (50/50) 40.39 36.26 30.29 0.040 10.1 37.39 34.62 30.71 0.065 6.68 0.025
PBS/PER (40/60) 39.09 35.21 30.57 0.035 8.52 36.44 33.87 31.89 0.056 6.55 0.021
PBS/PER (30/70) 40.54 35.33 30.45 0.038 10.09 39.12 34.85 30.18 0.056 8.94 0.018
PBS/PER (20/80) 37.87 36.21 31.92 0.036 5.95 38.63 36.46 31.53 0.050 7.1 0.014
PBS/PER (10/90) 38.83 35.96 32.77 0.041 6.06 39.39 35.7 31.87 0.052 7.52 0.011
PER 39.67 35.24 31.49 0.055 8.18 38.04 34.64 30.72 0.058 8.32 0.003
a
Tgi-1 and Tge-1: initial and end temperature of glass transition region at the initial scan.
b
Tgi-2 and Tge-2: initial and end temperature of glass transition region at the melt-quenched scan.
c
Tg-1and Tg-2: the temperature of glass transition region at the initial scan and melt-quenched scan, which are determined by the half heat capacity
(1/2 Cp) of glass transition region.
d
Cp-1 and Cp-2: the half heat capacity of glass transition region at the initial scan and melt-quenched scan.
e
Tgw-1 and Tgw-2: the widths of Tg region at the initial scan and melt-quenched scan, which are respectively (T1ge  T1gi) and (T2ge  T2gi).
f
DCp ¼ Cp-2  Cp-1.
878 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885

Table 2
The endothermic characteristics and enthalpy of crystal phase in the initial scans of PBS, PER and PBS/PER blends.

Code Endothermic characteristics and enthalpy of crystal phase in the initial scans
TmB1–1 ( C) HmB1–1 (J/g) TmB1–2 ( C) HB1–2 (J/g)
PBS 121.54 16.6 – –
TmE1–1 ( C) HmE1–1 (J/g) TmE1–2 ( C) HmE1–2 (J/g)
PER 54.62 1.3619 103.43 1.1582
TmBE1–1 ( C) HmBE1–1 (J/g) TmBE1–2 ( C) HmBE1–2 (J/g) TmBE1–3 ( C) HmBE1–3 (J/g)
PBS/PER (10/90) 51 1.232 102.11 0.497 119.71 0.758
PBS/PER (20/80) 52.55 1.2883 101.72 0.277 118.31 1.3
PBS/PER (30/70) 54.25 1.3832 102.56 0.176 119.49 2.422
PBS/PER (40/60) 53.9 1.2576 101.32 0.127 119.31 4.776
PBS/PER (50/50) 52.2 0.8047 101.43 0.134 119.98 5.471
PBS/PER (60/40) 52.54 1.3378 100.21 0.097 120.48 6.039
PBS/PER (70/30) 53.06 0.5921 – – 120.5 5.672
PBS/PER (80/20) 52.32 0.6031 102.22 0.102 120.47 9.490
PBS/PER (90/10) 51.02 0.1263 101.48 0.087 121.32 9.943

for 2–24 h, the TmE1–1 disappeared and a new Tg-like
endothermic region appeared at about 75  C, as illustrated
in Fig. 3. Notably, the temperature of this Tg-like endo-
thermic region did not increase as the annealing temper-
ature was increased, whereas the enthalpy associated with
the melting peak at about 100  C increased with the
annealing time. After annealing at 100  C for a long period,
the TmE1–1 and Tg-like endothermic regions disappeared,
and a large endothermic peak appeared at about 109  C,
which is close to the TmE1–2 temperature, as shown in
Fig. 4. Moreover, the endothermic peak has larger enthalpy
than TmE1–2, and increases with increasing annealing time.
Therefore, the large peak seen after annealing at 100  C for
a long period is considered as the PER crystal melting peak
resulting from TmE1–1 merging with TmE1–2. Accordingly,
the Tg-like endotherm is a result of crystal melting.
Furthermore, the position and magnitude of the Tg-like
endotherm do not increase linearly with the logarithm of
the annealing time, so the TmE1–1 peak is not due to
enthalpy relaxation [10,11]. Thus, the TmE1–1endotherm is
due to melting of fragmentary crystals which results in the
temperature of TmE1–1 being lower than TmE1–2. The
endothermic behavior of TmE1–2 is due to large and
complete crystal melting.
Tables 2 and 3 display the crystal enthalpy (Hm) of the
PBS and PER melting peaks in the initial and melt-
quenched scans. The TmB1–1 and TmB2–1 enthalpy values
(HmB1–1 and HmB2–1) are much higher than the TmE1–1, TmE1–
2,and TmE2–2 enthalpy values (HmE1–1, HmE1–2, and HmE2–2).
These results reveal that PBS has a higher degree of crys-
tallinity than PER. Moreover, the crystalline phases of PBS
and PER are diminished following the melt-quenching
process; on the contrary, their amorphous phases are
increased. Accordingly, PBS and PER have a semi-crystalline
structure comprising crystalline and amorphous phases.
Moreover, the PBS and PER enthalpy values in the melt-
quenched scan are lower than those in the initial scan, and
the degree of decrease for the PBS enthalpy values
following the melt-quenching process is larger than that
for PER. This is because PBS is a thermoplastic with a high
degree of crystallinity, whereas PER is a thermoplastic
elastomer copolymer with low crystallinity.
DSC analysis of PBS and PER revealed a two-phase
structure comprising crystalline and amorphous regions;
these phases are mixed by the melt-quenching process.
This phase mixing is readily apparent from the Tgw and
heat capacity of Tg (Cp) values. Table 1 shows that the Tgw of
PBS following the melt-quench was greatly increased, but
that the Tgw of PER remained at about 8.3  C. Because PBS
has a high degree of crystallinity whereas that of PER is
low, the former undergoes a lot of mixing between the
crystal and amorphous phases during the melt-quenching
process. The values of Tgw-2 and heat capacity in the second
scan (Cp-2) of PBS are, therefore, increased by the melt-
quenching process due to the increase in the amount of
amorphous phase, as shown in Table 1. Furthermore, the

Table 3
The endothermic characteristics and enthalpy of crystal phase in the melt-quenched scan of PBS, PER and PBS/PER blends.

Code Endothermic characteristics and enthalpy of crystal phase in the melt-quenched scans
TmB2–1  C HmB2–1 (J/g)
PBS 119.87 13.184
TmE2–1  C HmE2–1 (J/g) TmE2–2  C HmE2–2 (J/g) TmE2–3  C HmE2–3 (J/g)
PER – – 102.9 0.7012 – –
TmBE2–1  C HmBE2–1 (J/g) TmBE2–2  C HmBE2–2 (J/g) TmBE2–3  C HmBE2–3 (J/g)
PBS/PER (10/90) – – 102.05 0.803 119.91 0.803
PBS/PER (20/80) – – 101.55 0.394 119.31 1.356
PBS/PER (30/70) – – 101.38 0.203 119.83 2.684
PBS/PER (40/60) – – 98.82 0.303 119.98 4.298
PBS/PER (50/50) – – 98.20 0.312 120.46 4.949
PBS/PER (60/40) – – 100.01 1.215 120.99 5.981
PBS/PER (70/30) – – 100.02 1.124 120.50 7.244
PBS/PER (80/20) – – 97.62 1.581 120.98 9.906
PBS/PER (90/10) – – 100.81 0.807 121.32 10.410
 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885
Heat Flow Down
4hr
8hr
24hr
40 60 80 100 120
Temperature(°C)
Fig. 3. PER DSC thermogram under 70  C annealing treatment for 2, 4, 8 and
24 h.
Tgw-2 and Cp-2 values of PER are close to Tgw-1 and Cp-1,
respectively. This is because PER is an elastomer with a low
degree of crystallinity and hence a large entropy value;
therefore, during the melt-quenching process it retains
a large amorphous phase content, and so its state is similar
to that during the initial scan.
3.1.2. DSC analyses of the PBS/PER blends
In Section 3.1.1, it was established that PBS and PER
display Tg region from 41 to 28  C. The initial and melt-
quenched scans of PBS/PER blends feature one Tg region
from 40 to 30  C, as shown in Table 1. On this basis, the
PBS/PER blends might be considered as miscible because
they display one Tg value at about 35  C in the DSC
analysis. However, this result is not unequivocal because
PBS and PER exhibit Tg values in the same region. Actually,
a lower limit of the utility of glass transition temperature
determination in ascertaining polymer–polymer misci-
bility applies to blends composed of components having
equal or similar Tgs (<20  C difference), whereby resolu-
tion of the two Tgs by the discussed techniques is not
Heat Flow Down
40 60 80 100 120
Temperature(°C)
Fig. 4. PER DSC thermogram under 100  C annealing treatment for 2, 4, 8
and 24 h.
879
possible [12]. Furthermore, the PBS/PER blends display two
almost independent melting temperatures in DSC analysis
and a two-phase morphology in their SEM images, attrib-
utable to discrete PER and PBS, as illustrated in Figs. 1 and 2
and Section 3.3.
2hr The thermograms of PBS/PER blends at above room
temperature feature several endothermic regions in the
first scan, indicating that the blends have at least one
melting temperature, as shown in Fig. 1. For all of the PBS/
PER blends, the first melting peak in the initial scan, TmBE1–1,
is seen at about 52  C, as shown in Table 2. The TmBE1–1
enthalpies increase with increasing amount of PER, and the
maximum enthalpy value of TmBE1–1 is seen for PBS/PER (30/
70). However, the TmBE1–1 peaks disappear following the
140 melt-quenching process, as shown in Fig. 2. Therefore, the
TmBE1–1 is also considered as melting of fragmentary crys-
tals, because its endothermic temperature and behavior are
similar to PBS TmE1–1. The second endothermic peak of the
PBS/PER blends in the first scan, TmBE1–2, appears at around
100  C, except in the case of the PBS/PER (70/30) blend, as
shown in Fig. 1. The second endothermic peak of the PBS/
PER blends in the melt-quenched scan, TmBE2-2, appears in
the range 98–102  C, as shown in Fig. 2. The third endo-
thermic peaks of the PBS/PER blends in the first and second
scans, TmBE1–3 and TmBE2–3, appear at about 120  C, as shown
in Tables 2 and 3. Considering the melting temperatures for
PER and PBS, as illustrated in Section 3.1.1, the second and
third endothermic peaks for the PBS/PER blends at around
100 and 120  C can be ascribed to the Tms of PER and PBS,
respectively. Notably, PBS/PER (70/30) does not give rise to
a TmBE1–2 peak at 100  C, but a peak (TmBE2–2) at around
100  C is seen again in the melt-quenched scan. This result
may possibly be ascribed to the blend undergoing spinodal
decomposition resulting in phase separation during the
melt-quenching process. Subsequently, both the PER and
PBS phases exhibit, respectively, crystal nucleation and
growth; thus, PBS/PER (70/30) displays TmBE2–2 and TmBE2–3
peaks attributable to PER and PBS crystals, respectively.
Actually, since PBS/PER (70/30) was a homogeneously
mixed phase before the melt-quenching process (with
excellent compatibility), there must have been rapid cool-
ing in the spinodal region in order for the phase separation
to develop. As the cooling temperature in the melt-
quenching process was lower than the equilibrium melting
temperatures of PER and PBS, both the PER and PBS phases
2hr
could crystallize. Thus, while PBS/PER (70/30) displays
excellent compatibility following the melt-blending
process based on the melting behavior of the blend, it partly
4hr
separates into PBS and PER crystals after the melt-quench-
ing process due to spinodal decomposition.
8hr
The enthalpy values of the PBS/PER blends reflect their
degree of compatibility. PBS/PER (70/30) has a low
24hr enthalpy (HmBE1–3) relative to PBS/PER (80/20) and PBS/
PER (60/40) in the third peak because the uniformly
dispersed phase of PBS/PER decreases the degree of crys-
tallinity of the PBS phase, indicating that the blend has
140 excellent compatibility, as shown in Table 1. The enthalpies
of the third peaks of the PBS/PER blends in the initial scan,
HmBE1–3, and of the third peaks in the melt-quenched scan,
HmBE2–3, are decreased with increasing PER content.
However, the enthalpies do not display a linear
880 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885
relationship because of interfacial action between PBS and
PER in the PBS/PER blends. Furthermore, the enthalpies of
the second peaks of the PBS/PER blends, HmBE1–2, are lower
in the initial scan than the HmBE2–2 values (the enthalpies
of the second peaks in the melt-quenched scan) and again
do not display a linear relationship. The results indicate
that the PBS/PER blends are compatible and that PBS/PER
(70/30) has the best compatibility. Because the PBS/PER
blends present a degree of compatibility and both PBS and
PER phases are dispersed in them, the PBS/PER blends
display two crystallisation temperatures, that is, TmBE2–2
and TmBE2–3 which is respectively the crystallisation
temperature of PBS and PER.
The compatibility of blends can also be determined from
the heat capacity (Cp) of the Tg region. According to the
classical thermodynamic theory of binary polymer
mixtures[13–15], the glass transition temperatures are
largely unaffected by the excess mixing entropies. Hence,
the model derived by Couchman [13,14] applies, which may
be rewritten as follows:
X Z Tg
Mi DCpi dln T ¼ 0 (1)
Tgi
i ¼ 1;2
where Mi is the mass fraction of each component, and DCpi
is the heat capacity increment of the glass transition region
of each component, J/g  C. Tgi ( C) is the glass transition
temperature of each component, and Tg is the glass tran-
sition temperature of the blend. The Tgi must be converted
into Kelvin (K) for the calculation of the Tg of the blends, as
otherwise it may be negative (minus degrees Celsius).
For binary polymer mixtures, integration of Eq. (1)
yields:
   
M1 DCp1 ln Tg =Tg1 þ M2 Cp2 ln Tg =Tg2 ¼ 0 (2)
For convenience, Eq. (2) can be rearranged to:
 
M1 DCp1 lnTg1 þ M2 DCp2 lnTg2
Tg ¼ exp (3)
M1 DCp1 þ M2 DCp2
Subscripts 1 and 2 denote PBS and PER, respectively. The
values of DCp and Tg of each component were determined
by DSC analyses with a Perkin–Elmer Pyris 1 instrument.
The DCp and Tg values for the PBS/PER blends were deter-
mined in the same way as for PBS and PER. The DCp and Tg
values are designated as Cp-1 and Tg-1 in the initial scan and
as Cp-2 and Tg-2 in the melt-quenched scan, and are listed in
Table 1. Using Eq. (3) and the measured data, the Tg values
of the polymer blends have been calculated and are pre-
sented in the same figure as the experimental values, as
shown in Fig. 5. The theoretically calculated Tg values are in
good agreement with the experimental values, with the
PER/PBS blends of the different compositions showing only
deviations within 1  C between the experimental and
calculated values in their initial scans. For the melt-
quenched scans, the blends in the composition range 70/
30 > PBS/PER > 30/70 again show deviations within 1  C,
but the other samples show deviations greater than 1  C.
Accordingly, the blends with compositions in the range 70/
30 > PBS/PER > 30/70 are considered to have good
compatibility. Moreover, the degree of compatibility is
reflected in the Tg heat capacity values. The Cp-2 values of
the PBS/PER blends are higher than their Cp-1 values due to
the melt-quenching process, as shown in Table 1. The DCp
(Cp-2  Cp-1) value of PBS/PER (70/30) is the lowest, indi-
cating that this blend has the best dispersive state. In other
words, the PBS/PER (70/30) blend displays the highest
compatibility of all of the samples. The morphologies of
these blends will be presented in Section 3.3.
3.2. Dynamic mechanical analysis
Dynamic mechanical analysis (DMA) not only provides
information on mechanical characteristics and the
temperature of phase transition, but also on the miscibility
or compatibility of blends. Fig. 6 reveals that the storage
modulus (E0 ) values of PBS and PER show a slight decrease
below 35  C, indicating that this temperature region
corresponds to a glassy state. Subsequently, the E0 values of
PBS and PER decrease by about one and three orders of
magnitude, respectively, in the region 35 to 0  C, corre-
sponding to the glass transition temperature (Tg) region (a
leathery state). In the region 0–50  C, the E0 value shows
little diminution (a plateau region), reflecting a rubbery
state. Fig. 6 shows that the E0 value of PBS is higher than
that of PER, which is especially so in the rubbery state
region. According to the DSC and DMA results, PBS is
a semi-stiff plastic material with a high degree of crystal-
linity, whereas PER is a soft rubber material with little
crystallinity.
Below 35  C, the E0 values of most of the PBS/PER
blends are located between those of PBS and PER, and
differ only within one order of magnitude. This is because
the blends below 35  C are in a glassy state displaying
ideal elastic deformation. In the region of 35 to 0  C, the
E0 values of the PBS/PER blends decrease sharply by more
than one order of magnitude, reflecting a leathery state.
The E0 values of the blends in the region 0–50  C, which
display a rubbery state, are seen to decrease with
increasing PER content. A high E0 value in the rubbery state
implies that a polymer possesses high hardness and
crystalline character; on the contrary, a low E0 value reveals
low hardness and amorphous character. The E0 value
decreases by more than two orders of magnitude when the
PER/PBS blends have PER contents above 50 wt%. Accord-
ingly, the blends with PER contents above 50 wt%
display elastic characteristics. Notably, the E0 value of PBS/
PER (70/30) is similar to that of PBS/PER (90/10), as shown
in Fig. 6, indicating that it has good compatibility relative
to the other blends. The DMA tests of all of the blends
ended at around 90  C, implying that this temperature is
close to their melt-flow region. In fact, the Tms of the
blends were seen at about 100  C by DSC. Furthermore, in
the DMA tests, PBS, PER, and the PBS/PER blends displayed
similar temperature regions for their glass, leather, and
rubber states, indicating that they have similar phase
transition regions.
The loss tangent peak (tan d peak) indicates a loss of
energy accompanying the motion of segments. Thus, the
temperature of tan d (Ta) corresponds to Tg and is located in
the Tg region. Table 4 shows that the Ta values of PBS and
PER appear at about 17 and 15  C, respectively. These Tgs
 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885 881

-32 -32

-33 -33

-34 -34

-35 -35

-36 -36

Tg ( C)
T g ( C)
-37 -37

o
o

-38 -38

-39 Initial scan -39 melt-quenched scan

-40 experimental -40 experimental

calculated
calculated
-41 -41

-42 -42
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
PER (wt%) PER (wt%)

Fig. 5. Experimental (using Eq. (3)) and calculated Tgs of polyblends. PER% is the weight fraction PER in the binary mixtures of PBS/PER blends.

are clearly close to each other, which is consistent with the
results of the above DSC analysis. Furthermore, the tan d
value (E00 /E0 ) of PER is higher than that of PBS, indicating
that the loss modulus (E00 ) of the propylene-co-ethylene
(PER) segments exceeds that of the butylene succinate
(PBS) segments in the Tg region, that is, the motion of the
PER macromolecular chains incurs a larger loss of energy
than that of PBS in the Tg region. This is because PER has
rubber characteristics, whereas PBS is more plastic.
Furthermore, a high tan d value indicates that a material
has good shock or impact resistance, equating to charac-
teristics of softness and toughness. The tan d values of our
PBS/PER blends were seen to increase with increasing PER
content, as shown in Table 4. This result indicates that the
characteristics of PBS were gradually transformed from
plastic to rubber. Accordingly, the softness, toughness, and
shock absorbance of PBS are improved by the addition of
108
107
PER. Furthermore, a small peak appeared at about 50  C in
the loss tangent of PER and the PBS/PER blends with 50 wt%
PER content, which may be attributed to crystalline char-
acter, as shown in Fig. 7. Therefore, the loss tangent peak at
around 50  C is associated with fragmentary crystals in
accordance with the earlier DSC results. Accordingly, the
small endothermic peak at 50  C in the DSC thermograms
of PER is due to melting of fragmentary crystals. The loss
tangent curves of PBS/PER blends with high PER contents
are similar to that of PER, as shown in Fig. 7, indicating that
the blend characteristics are close to that of PER, especially
for PBS/PER (10/90). Notably, however, the tan d value of
PBS/PER (10/90) is higher than that of PER, indicating that
PBS/PER (10/90) has the highest shock or impact resistance
due to the effect of PBS reinforcement, as shown in Table 4.
DMA is useful for the determination of polymer blend
miscibility because Ta corresponds to Tg. Two independent
Tgs generally indicate immiscibility of binary polymer
mixtures. Fig. 7 indicates that the PBS/PER blends only
exhibit one Ta value between 13 and 22  C. Accordingly,
the PBS/PER blends should be considered as miscible
polymer blends; however, this result is again not
unequivocal because for the determination of miscibility
the DMA technique is also limited by the Tgs of PBS and PER

Table 4
E'(Pa)

Loss tangent (tan d) peak.

106
Code tan d Ta ( C) DTa ( C)
PBS PBS 0.126 15.77 89.12
PBS/PER(90/10) PBS/PER (90/10) 0.178 20.89 85.33
105 PBS/PER(70/30) PBS/PER (80/20) 0.183 21.65 85.41
PBS/PER(50/50)
PBS/PER(30/70) PBS/PER (70/30) 0.260 20.99 65.55
PBS/PER(10/90) PBS/PER (60/40) 0.274 19.79 80.62
PER PBS/PER (50/50) 0.542 15.78 68.73
104 PBS/PER (40/60) 0.604 16.42 70.77
-100 -50 0 50 100 PBS/PER (30/70) 0.602 13.79 72.68
PBS/PER (20/80) 0.773 15.22 65.51
Temperature (°C)
PBS/PER (10/90) 0.891 19.39 68.22
PER 0.835 14.25 56.11
Fig. 6. Storage modulus (E0 ) of PBS, PER and PBS/PER blends.
882 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885
being too close to each other. Furthermore, the Ta values of
the PBS/PER blends are lower than those of PBS and PER,
except for PBS/PER (30/70), which can be attributed to the
blends having a two-phase binary morphology, resulting in
a large free volume. Therefore, the blends are compatible.
Although the applicability of DMA for the determination
of miscibility is limited, the degree of compatibility of
blends can be determined by the width of the tan d peak
(DTa). In Table 4, it can be seen that the DTas of PBS and PER
are 89 and 56  C, respectively, while those for the PBS/PER
blends are located in the region 85–65  C. The DTa values
for the PBS/PER blends decrease with increasing PER
content, indicating that they are compatible due to the
effect of the even blending of PBS and PER. Notably, DTa of
the PBS/PER (70/30) blend has a relatively low value among
the blends, further indicating that this blend has excellent
compatibility, in agreement with the results in Section 3.1.
3.3. Morphologies of the blends
According to the DSC and DMA results, the blends with
compositions in the range 70/30 > PBS/PER > 30/70 display
better compatibility than the other blends, with PBS/PER
(70/30) showing the best compatibility. Fig. 8 shows that
most of the PBS/PER blends consist of two distinct phases (a
sea-island morphology) comprising a dispersed phase
(island-phase) and a continuous phase (sea-phase) (Fig. 8
(a), (b), and (e)–(i)). The PER island-phase in the PBS-rich
blends such as PBS/PER (90/10) (Fig. 8 (a)) is dispersed in
the PBS sea-phase. Similarly, in PER-rich blends such as
PBS/PER (10/90), the PBS island-phase is dispersed in the
PER sea-phase (Fig. 8 (i)). The PER component in the sea-
island morphology of PBS-rich blends such as PBS/PER (90/
10) and PBS/PER (80/20) is dispersed as spherical particles
of diameters 3–10 mm, as shown in Fig. 8 (a) and (b). PBS/
PER (70/30) displays an apparently singular phase (close to
a homogeneous morphology), as shown in Fig. 8 (c). PBS/
PER (60/40) displays an irregular fiber shape, as shown in
Fig. 8 (d). When the PER content in the blends exceeds
50 wt%, the sea-island morphology of the PBS-rich blends is
reversed to form a sea-island morphology of PER-rich
2.5
2.0
1.5
Tan d
PBS
1.0 PBS/PER(90/10)
PBS/PER(70/30)
PBS/PER(50/50)
PBS/PER(30/70)
PBS/PER(10/90)
0.5 PER
0.0
-100 -50 0 50
Temperature (°C)
Fig. 7. Loss tangent (tan d) of PBS, PER and PBS/PER blends.
blends. Therefore, PBS/PER (50/50) displays a mixed
morphology including both sea-island and fiber-shape
regions. When the PBS/PER blends have PER contents
between 60 and 90 wt%, the PBS is in the form of a spherical
dispersed phase of particle size in the region of 0.8–75 mm
and the PER forms a continuous phase, as shown in
Fig. 8(f)–(i). The relationships between the morphology and
tensile strength are further discussed in Section 3.4.
The sizes of spherical particles (island-phase size) in the
sea-island morphologies are increased as the concentration
of the island-phase is increased, as shown in Fig. 8. For
example, the island-phase size in the sea-island
morphology of PER-rich blends increases with increasing
the PBS content (Fig. 8e–h). Examining the island-phase
size for the PBS and PER binary mixtures, it can be seen that
the PER island-phase in the PBS-rich blends consists of
larger spherical particles than the PBS island-phase in the
PER-rich blends at the same concentration of the island-
phase. Thus, the particle sizes in PBS/PER (90/10) and PBS/
PER (10/90) are 3–4 mm and 0.8–3 mm, respectively, as
shown in Fig. 8(a) and (i). This may be due to the different
diffusion rates of the chains in the process of nucleation
and growth. Because PER is a thermoplastic elastomer and
has high entropy, the PER macromolecular chains in the
PBS-rich blends assemble at a high diffusion rate, resulting
in the formation of large spherical particles.
On the basis of early DSC and DMA results, PBS/PER binary
blends have been considered as compatible; however, the
SEM images of most of our PBS/PER blends reveal two-phase
morphologies composed of sea-island and irregular fiber
shapes, except for PBS/PER (70/30). This is because all single-
phase polymer blends with compatibility would reveal areas
rich in one component or another, a condition necessitated
by the size of polymer molecules and the geometrical
constraints imposed by covalent linking in the chain-like
macromolecules. The SEM images of most of our PBS/PER
blends display areas rich in one component, such as the sea-
island morphologies composed of areas rich in PER spherical
particles dispersed in the PBS continuous phase. Therefore,
the PBS/PER binary blends described herein are considered
as compatible as opposed to miscible. In fact, most polymer
blends are compatible rather than miscible; indeed,
compatibility of a polymer blend is more useful than its
miscibility. Moreover, the SEM analysis also verified that the
PBS/PER (70/30) blend with an apparently singular phase
had the best compatibility, in accordance with the analyses
by the Couchman method, DSC, and DMA.
3.4. Tensile strength
Compatibility and morphology are associated with the
components of polymer blends, and these in turn deter-
mine the tensile strength. Accordingly, the compatibility,
morphology, and composition affect the tensile strength
of PBS/PER blends. Table 5 lists the tensile strengths of all of
the samples.
The PER component in the PBS/PER blends is favorable for
100 elongation, but it diminishes the stiffness of the blends.
Furthermore, the initial moduli of the PBS/PER blends
decrease with increasing PER content, indicating that the PER
component improves the softness of the PBS/PER blends. The
H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885 883

Fig. 8. SEM patterns of PBS/PER blends.

884 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885

PBS-rich blends, which have PER contents below 20 wt% stress values do not decrease as the PBS content
such as PBS/PER (80/20) and PBS/PER (90/10), display a sea- is increased. Furthermore, the stress of PBS/PER (10/90) is
island morphology consisting of a PER island-phase in a PBS higher than that of pure PER. As mentioned above, this
sea-phase (Fig. 8(a) and (b)). These have ultimate stresses of is because the sea-island morphology of PBS/PER blends
around 26 MPa, which are close to that of pure PBS, but their consists of dispersed island-phase domains of PBS hard
strains are in excess of 450%, higher than that of pure PBS. segments, which reinforce the PER soft phase. Furthermore,
Accordingly, both of these PBS/PER blends retain stresses as shown in Fig. 8(f), PBS/PER (40/60) has the lowest ulti-
close to that of PBS, while allowing greater elongation than mate stress among the PER-rich blends due to the large size
PBS itself. This is because the sea-island morphology of the of its spherical hard phase, even though this blend has good
blends is similar to the morphology of elastomers reinforced compatibility. Accordingly, the effect of morphologies on
with fillers. PBS/PER (70/30), which displays an apparently the tensile strength is more important than the degree of
singular phase, has a high elongation above 600% and a ulti- compatibility in the PBS/PER blends.
mate stress lower than that of pure PBS of about 16 MPa.
Accordingly, the elongation of PBS/PER (70/30) corresponds 4. Conclusions
to elastic characteristics. Thus, a breakage cross-section of
the apparently singular phase under liquid nitrogen PBS/PER blends with compositions (wt/wt) ranging from
quenching presents several narrow strips with orientation 90/10 to 10/90 have been prepared in a twin-rotary mixer by
indicating tough break behavior, as can be seen in Fig. 8(c). the melt-blending process. The PBS, PER and PBS/PER blends
Thus, although PBS/PER (70/30) has a lower PER content than have two-phase structures, displaying glass and crystal
PBS/PER (60/40) or PBS/PER (50/50), it displays greater phase transition regions in their initial and melt-quenched
elongation and strength due to its single-phase morphology, DSC thermograms. The Tg values of all blends are at about
as shown in Table 5. PBS/PER (60/40) displays lower stress 35  C, which is close to those of PBS and PER in their DSC
and strain than the other PBS-rich blends and PBS itself, even thermograms. The PBS/PER blends display independent
though it has good compatibility, because it has an irregular crystal melting region at around 120 and 100  C, except for
fiber-shaped morphology, which results in a more extensive PBS/PER (70/30), the latter displaying the best compatibility.
interface and low adhesion between the PBS and PER. Miscibility and compatibility in the present study have been
Moreover, the morphology has no effect on the toughness of determined by DSC and DMA. Attempts have been made to
elastomers reinforced with the spherical particle fillers, as use both DSC and DMA to determine whether the PBS/PER
shown in Fig. 8(d). The PBS/PER (50/50) blend displays some blends displayed a single Tg, but the methods failed because
sea-phase of large size and irregular fiber-shaped morphol- the Tg of PBS is too close to that of PER. According to tests by
ogies, as shown in Fig. 8(e), which resulted in the lowest the Couchman method, DSC, and DMA, the PBS/PER blends
tensile strength because this morphology has the lowest are compatible, with compositions in the range 70/30 > PBS/
adhesion of the interface between the PBS and PER PER > 30/70 displaying good compatibility and PBS/PER (70/
components. 30) having the best compatibility. Furthermore, the tan d
The PER-rich blends, having PER contents in excess of values of PBS/PER blends in DMA have been found to
60 wt%, displayed high elongations above 600%, but low increase with increasing PER content, indicating that the
ultimate stresses below 7 MPa. The tensile strengths of shock or impact resistance of PBS is improved by adding PER.
PER-rich blends reveal typical characteristics of thermo- Most of the compatible PBS/PER blends SEM display two
plastic elastomers, because they have high PER contents phases in their SEM images, composed of sea-island and
and display a sea-island morphology that is similar to those irregular fiber-shaped morphologies, but PBS/PER (70/30)
of covalently cross-linked elastomers reinforced with displays an apparently singular phase. The compositions of
fillers, as can be seen in Fig. 8(e)–(i). Their SEM patterns the PBS/PER blends not only affect their tensile strengths, but
reveal that the dispersed PBS hard-phase (spherical hard- also their morphologies and compatibility. The PBS/PER
phase) is distributed throughout the continuous PER soft- blends having PER contents in excess of 60 wt% display
phase. The PER-rich blends having PER contents above typical characteristics of thermoplastic elastomers since
70 wt% display greater elongation than pure PER and their they exhibit sea-island morphologies similar to those of
covalently cross-linked elastomers reinforced with fillers.
Table 5 Furthermore, the PBS/PER (40/60) displays the lowest tensile
Tensile strength of PBS/PER blends. strength due to the large particle size of the PBS spherical
hard phase, even though this blend has good compatibility.
Code Initial Ultimate Ultimate
modulus (Mpa) stress (Mpa) elongation (%) Although PBS/PER (70/30) has a lower PER content than the
PBS 400.2 26.2 355
PER-rich blends, it displays elastic characteristics due to its
PBS/PER (90/10) 319.1 25.1 459 excellent compatibility and apparently singular phase.
PBS/PER (80/20) 263.8 26.1 488 Consequently, a cross-section of PBS/PER (70/30) under
PBS/PER (70/30) 183.7 16.5 675 liquid nitrogen quenching displays tough break behavior.
PBS/PER (60/40) 112.5 8.3 351
Furthermore, the initial moduli of the PBS/PER blends were
PBS/PER (50/50) 40.1 2.1 271
PBS/PER (40/60) 10.1 3.3 694 found to decrease with increasing PER content and the blend
PBS/PER (30/70) 10.2 4.3 1035 containing 60 wt% PER was found to display high elongation,
PBS/PER (20/80) 6.2 5.1 1085 indicating that the PER component is favorable for
PBS/PER (10/90) 6.7 7.2 1172
improving the softness and elongation of the PBS/PER
PER 5.1 6.6 979
blends.
 H.-Y. Tsi et al. / Polymer Testing 28 (2009) 875–885
Acknowledgement
The authors would like to thank the National Science
Council of the Republic of China, Taiwan, for financially
supporting this research under Contract No. NSC 94-2216-
E-238-005.
References
[1] S.J. Huang, in: H.F. Mark, M.M. Bikales, C.G. Overberger, G. Menges, J.
I. Kroschwitz (Eds.), Encyclopedia of Polymer Science and
Technology, vol. 2, Wiley, New York, 1985 p. 220.
[2] S.J. Huang, in: G.C. Eastmond, A. Ledwith, S. Russo, P. Sigwalt (Eds.),
Comprehensive Polymer Science, vol. 6, Pergamon, Oxford, 1989 p.
597.
[3] W. Amass, A. Amass, B. Tighe, A review of biodegradable polymers:
use, current developments in the synthesis and characterization of
biodegradable polyester, Polym. Int. 47 (1998) 89.
[4] R.W. Lenz, Starch, poly(lactic acid), and poly(vinyl alcohol) blends, J.
Polym. Environ. 11 (2003) 7.
[5] M.Z. Pang, J.J. Qiao, J. Jiao, S.J. Wang, M. Xiao, Y.Z. Meg, Miscibility
and properties of completely biodegradable blend of poly(propylene
carbonate) and poly(butylenes succinate), J. Appl. Polym. Sci. 107
(2008) 2854.
885
[6] T. Fujumaki, Processability and properties of aliphatic polyesters,
‘Bionolle’, synthesized by polycondensation reaction, Polym. Deg.
Stab. 59 (1998) 209–214.
[7] X.F. Zhang, F. Xie, Z.L. Peng, Y. Zhang, Y.Z. Zhang, Effect of nucleating
agent on the structure and properties of polypropylene/poly
(ethylene–octene) blends, Eur. Polym. J. 38 (2002) 1.
[8] Bassani, L.A. Pessan, E. Hage, Toughening of polypropylene with styrene/
ethylene–butylene/styrene tri-block copolymer: effects of mixing
condition and elastomer content, J. Appl. Polym. Sci. 82 (2001) 2185.
[9] J. Xueliang, Z. Yong, Z. Yinxi, Study of dynamically cured PP/MAH-
g-EPDM/epoxy blends, Polym. Test. 23 (2004) 259.
[10] W.C. Tsen, F.S. Chuang, Phase transition and domain morphology
of siloxane-containing hard segmented polyurethane copolymers,
J. Appl. Polym. Sci. 101 (2006) 4242.
[11] T.C. Chen, T.S. Shieh, J.Y. Chi, Studies on the first DSC endotherm of
polyurethane hard segment based on 4,40 -diphenylmethane diiso-
cyanate and 1,4-butanediol, Macromolecules 31 (1998) 1312.
[12] Olagoke, Polymer–Polymer Miscibility, Academic Press Inc., New
York, 1979, p. 120.
[13] P.R. Chuchman, F.E. Karasz, A classical thermodynamic discussion of the
effect of composition on glass-transition, Macromolecules 11 (1978) 117.
[14] P.R. Chuchman, Compositional variation of glass-transition temper-
atures. 2. Application of thermodynamic theory to compatible
polymer blends, Macromolecules 11 (1978) 1156.
[15] Z.A. Sudradjat, M.T. Razzak, F. Yoshii, K. Makuuchi, Polyblend
CPP and Bionolle with PP-g-MAH as compatibilizer: compati-
bility, J. Appl. Polym. Sci. 72 (1999) 1277.