Polymer Degradation and Stability 206 (2022) 110182

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Polymer Degradation and Stability

journal homepage: www.journals.elsevier.com/polymer-degradation-and-stability

Low-shrinkage biodegradable PBST/PBS foams fabricated by microcellular

foaming using CO2 & N2 as co-blowing agents
Kun Xue , Peng Chen , Can Yang , Zhimei Xu , Ling Zhao , Dongdong Hu *
a
State Key Laboratory of Chemical Engineering, Shanghai Key Laboratory of Multiphase Materials Chemical Engineering, School of Chemical Engineering, East China
University of Science and Technology, Shanghai 200237, China

A R T I C L E I N F O A B S T R A C T

Keywords: Poly (butylene succinate-butylene terephthalate) (PBST) displays favorable foamability with the supercritical
Poly (butylene succinate-butylene tere­ CO2 as the blowing agent, but the foams behave serious shrinkage behavior. In this work, a serious of fully
phthalate) biodegradable PBST/poly (butylene succinate) (PBS) microcellular foams with low volume shrinkage ratio were
Poly (butylene succinate)
fabricated with the co-blowing agent of CO2 & N2. The presence of PBS can not only improve the rheological
Microcellular foaming
CO2 & N2
behavior, crystallization and mechanical properties to alleviate shrinkage process, but also play the role of
Low-shrinkage nucleating agent to promote cell nucleation. With the increasing content of PBS, the cell size of the foam de­
creases from 25.0 μm to 7.03 μm, the cell density increases from 8.84×108 to 3.19×1010 cells/cm3 and the
volume shrinkage ratio reduces from 62.10% to 47.81%. Furthermore, it is demonstrated that the introduction of
N2 can inhabit the shrinkage behavior of PBST/PBS foams effectively. With the introduction of 12 MPa CO2 and
8 MPa N2, the volume expansion ratio of PBST/PBS10 microcellular foam can achieve 10.6-fold with good
dimensional stability.

1. Introduction Polymer foams exhibit excellent impact resistance, higher stiffness-

With the rapid development of polymer materials, biodegradable
materials have played an increasingly important role in the rapid
development of polymer materials, such as polylactic acid (PLA), poly­
caprolactone (PCL) and polybutylene succinate (PBS), which mainly due
to their favorable biodegradability, biocompatibility, and non-toxicity
[1–5]. However, the aliphatic biodegradable polyesters
above-mentioned have high production costs and poor mechanical
property. To interchange the degradability and application perfor­
mances, the copolymerization of aromatic units and aliphatic units is an
effective solution to maintain the good mechanical properties and
favorable biodegradability. Therefore, as the most representative
biodegradable copolymers, poly (butylene adipate-co-terephthalate)
(PBAT) and poly (butylene succinate-butylene terephthalate) (PBST)
have attracted more and more attention. PBST is synthesized by the
polycondensation of 1,4-butanediol (BDO), succinic acid (SA), and ter­
ephthalic acid (TPA) [6]. PBST displays better barrier properties of ox­
ygen, carbon dioxide and water vapor than that of PBAT [7], and shows
better biodegradability which is closer to a fully bio-based biodegrad­
able polyester [8].
to-weight ratio, and excellent thermal insulation property [9], which
have been widely used in industry, agriculture, transportation, aero­
space and oil adsorption [10]. As one of the burgeoning research hot­
spots, microcellular foams have excellent performance while consuming
less material and energy. Compared with traditional blowing agents,
more and more related scholars utilized N2 or supercritical CO2 as the
blowing agent, which is due to their nonflammability, environmental
benignity, and low cost. Unfortunately, PBST foams have serious
shrinkage problems due to its weak stiffness with CO2 as the blowing
agent [11]. As for the problem of easy shrinkage, the similar phenom­
enon exists in many materials with strong toughness but weak stiffness,
such as TPU, LDPE, TPEE and PBAT [12–18]. If the blowing agent escape
from the cell faster than the air permeate into the foam, the shrinkage
behavior will occur. We have reported three methods which can address
the shrinkage problem of foams: utilizing the co-blowing agent,
increasing the open-cell content and improving the stiffness of polymer
matrix [17]. Among them, utilizing the co-blowing agent is considered
the most cost-effective method, especially the mixture of CO2 and N2
[19]. Xu et al. have fabricated anti-shrinkage, high-elastic, and strong
thermoplastic polyester elastomer foams with CO2 & N2 as the blowing

* Corresponding author.
E-mail address: hudd@ecust.edu.cn (D. Hu).

https://doi.org/10.1016/j.polymdegradstab.2022.110182
Received 23 August 2022; Received in revised form 16 October 2022; Accepted 17 October 2022
Available online 19 October 2022
0141-3910/© 2022 Elsevier Ltd. All rights reserved.
K. Xue et al.
agent [20].
Furthermore, improving the stiffness is also an effective way. There
are a multitude of modification methods which can improve the overall
properties of polymers, such as: chain extension [21–23], blending [24],
inorganic particle filling [25] and cross-linking [26]. Particularly,
blending is widely used and the improvement is significant. In our
previous work, PBAT/PBS foams were successfully prepared with the
volume expansion ratio above 18-fold which showed the good dimen­
sional stability [27]. Chen et al. have prepared stable PBST/PLA foams
with a cell density of 3.5 × 1010 cells/cm3 and the volume expansion
ratio is over 17-fold [11]. In addition, more and more blending systems
are applied to the field of oil-water separation in recent years. For
instance, the foams fabricated by the composite of PLA/PBS possess
ultra-low density and positive oil adsorption [28]. Similarly, the
blending system of PVDF/PMMA can be used to manufacture the ul­
tralight and hydrophobic foams with outstanding heat-insulation and
oil-adsorption performances [10].
In the field of foaming, the compatibility of blended samples is very
important. Nofar have reported the bead foaming behavior of PLA/PBST
system [29]. The cell morphology is not optimistic and the dispersed
phase particles can be observed in the cell wall. As one of the most
discussed biodegradable materials, PBS can be produced by poly­
condensation of SA and BDO, which are bio-renewable resources and
also used to synthesis PBST [30,31]. Therefore, the melting-blending of
PBST and PBS could possess great research value.
In this work, PBST and PBS were blended to produce foams with
good cell morphology and dimensional stability. Firstly, the rheological
behavior, non-isothermal crystallization and mechanical properties of
PBST/PBS blends were investigated to evaluate the foamability. Then,
the foaming behavior of PBST/PBS blends with CO2 as blowing agent
was estimated; finally, the effect of the co-blowing agent (CO2 & N2) on
the cell morphology and dimensional stability of PBST/PBS10 foams
were evaluated.
2. Experimental section
2.1. Materials
PBST (TS159) was obtained from Sinopec Yizheng Chemical Fiber
Fig. 1. Schematic procedure of PBST/PBS microcellular foam.
2
Polymer Degradation and Stability 206 (2022) 110182
Co., Ltd. with a density of 1.26 g/cm3. PBS (TH803S) was provided by
Blue Ridge Tunhe Chemical Industry Co., Ltd, with a density of 1.26 g/
cm3 and a melt flow rate of 13 g/min (190 ◦ C, 2.16 kg). CO2 (purity:
99.99 wt%) and N2 (purity: 99.99 wt%) were purchased from Air Liq­
uide Shanghai Co., Ltd.
2.2. Sample preparation
The pellets of PBST and PBS were pre-dried in a blast oven at 50 ◦ C
for 5 h, and then placed in a vacuum oven at 60 ◦ C for 8 h. Subsequently,
the fully dried PBST and PBS were mixed according to a certain mass
ratio (90/10, 80/20, 70/30, 60/40, 50/50), and then added to a twin-
screw extruder (Nanjing Giant SHJ-20, with a diameter of 20 mm and
an aspect ratio of 30) for melt-blending to obtain PBST/PBS blends. The
process of melt-blending was displayed in Fig. 1. The samples were
denoted as PBST/PBS10, PBST/PBS20, PBST/PBS30, PBST/PBS40, and
PBST/PBS50 according to the PBS content in the blends, respectively.
Namely, PBST/PBS10 represented the mass fraction of PBS in the blend
was 10 wt%.
The temperature of the six temperature zones of the extruder (from
the hopper to the die) was set to 105-140-140-140-135-135 ◦ C, where
the main engine speed is 180 rpm, the feeder speed is 20 rpm, and the
pelletizing speed is 20 rpm.
2.3. Rheological properties
The rheological properties of all the samples were conducted by
small-amplitude oscillatory (SAOS) tests on a HAKKE rheometer (MARS
III, Thermal Fisher). All the tests were measured with the frequency
ranging from 100 to 0.1 rad/s under N2 atmosphere at the temperature
of 140 ◦ C.
2.4. Differential scanning calorimetry (DSC)
The crystallization and melting process of PBST/PBS blends were
investigated by using DSC (204 HP, Netzsch, Germany). First, the sample
was heated from room temperature to 140 ◦ C at a heating rate of 10 ◦ C/
min and held for 5 min to eliminate the thermal history. Then, the
crystallization process was recorded at a cooling rate of 10 ◦ C/min to
K. Xue et al.
20 ◦ C. Finally, the sample was heated to 140 ◦ C with 10 ◦ C/min to study
the melting behavior.
The relatively crystallinity χc of pure PBST and PBST/PBS blends
samples were calculated by Eq. (1):
ΔHm
χc = ( ) (1)
1
ΔHm0 2
Wf + ΔHm0 1 − Wf
where ΔHm is the measured enthalpy of melting, ΔH1m0 and ΔHm0 2
are the
theoretical enthalpy of melting for 100% crystalline PBST (121.7 J/g)
and PBS (110.3 J/g) [30,32]. Wf is the weight fraction of the PBST in the
PBST/PBS blends.
2.5. Mechanical properties
The standard splines for neat PBST, PBS, and PBST/PBS blends were
prepared by using a micro injection molding machine (SZS-20, Wuhan
Ruiming Experimental Instrument Co., Ltd.). The injection temperature
and pressure were set to 150 ◦ C and 0.6 MPa. The injection time and
cycle time were 2 and 20 s, respectively. All the splines were placed at
room temperature for 24 h to relieve internal stress before the me­
chanical property tests.
According to the standard of GB/T 1040.3–2006, all the splines were
tested on a double-column desktop electronic universal material testing
machine (Instron 3367). The tensile speed was set to 50 mm/min, and
each sample was tested at least 5 times to obtain the average value.
2.6. Batch foaming process
The pelletized PBST/PBS blend samples were first dried in a vacuum
oven at 60 ◦ C for 12 h, and then were hot-pressed into square pieces of
10 mm×10 mm×2 mm for foaming. The batch foaming process of all
samples was carried out in an autoclave with CO2 as the blowing agent,
as shown in Fig. 1. The saturation pressure was 20 MPa with a saturation
time of 1 h at the foaming temperature ranging from 70 to 105 ◦ C. When
conducting the foaming experiments with mixed blowing agents, N2
with a certain pressure (4, 8, 12, and 16 MPa) was first introduced into
the autoclave to saturate for 0.5 h, and then introduced into a certain
pressure of CO2 (16, 12, 8 and 4 MPa) into the chamber to saturate for
another 1 h at 20 MPa. Finally, the foams were obtained by the rapid
depressurization method.
2.7. Cell morphological analysis
According to the standard ASTM D792–00, the apparent density of
the foam, ρf, can be calculated by the Eq. (2):
a plateau region, which is consistent with the characteristics of Newtonian
ρf = ρ (2)
a + w − b water
where a and b are the mass of the foamed sample and that of the copper
mesh in water, respectively. w is the total mass of the sinker and the
foamed sample immersed in water together, and ρwater is the density of
water.
The volume expansion ratio RV is calculated by the Eq. (3):
ρ0
RV = (3)
ρf
where ρ0 and ρf are the densities of polymer and the foamed samples,
respectively.
The foamed samples were quenched after cooling in liquid nitrogen
for 10 min, and the fracture surface was sprayed with platinum to
enhance its electrical conductivity. The cell morphology of the fracture
surface was observed by field emission electron microscopy (Nove
NanoSEM450, FEI). The SEM images can be analyzed with the Image Pro
Plus software (Media Cybernetics) to obtain the average cell size l and
cell density N0, which are evaluated by Eq. (4) and Eq. (5), respectively:
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Polymer Degradation and Stability 206 (2022) 110182
∑
li ni
l= ∑ (4)
ni
where ni is the number of cells with a diameter li in the SEM photograph.
( n )32
N0 = × RV (5)
A
where n is the number of cells in the SEM photograph, and A is the area
of each photograph.
2.8. Shrinkage behavior of foams
The shrinkage process of foams was investigated by measuring the
curve of expansion ratio versus time (shrinkage curve). After rapid
pressure relief and cooling, the foamed sample was quickly taken out
from the autoclave, and then measured its density and calculate the
volume expansion ratio RV, which was recorded as the initial RV. Sub­
sequently, the density of the foamed sample was repeatedly measured at
certain time intervals, and the shrinkage curve of foams was finally
obtained.
RV0 − RVt
VSR = (6)
RV0
where VSR represents the shrinkage rate. Rv0 and Rvt are the volume
expansion ratio of polymer at the initial time and the aging time t [19].
3. Results and discussion
3.1. Rheological properties of PBST/PBS blends
The storage modulus G’, complex viscosity η* and loss factor tan(δ)
were measured as a function of ω at 140 ◦ C for pure PBST, PBS and
PBST/PBS blends, as shown in Fig. 2. Fig. 2(a) presents the G’ curves of
all samples. It can be seen that the G’ of pure PBST is lower than that of
pure PBS, and the difference of G’ at low angular frequencies is more
obvious, which indicates that PBST has lower melt elasticity than PBS.
The G’ of PBST/PBS blends increases with the content of PBS, and the
enhanced melt elasticity can be attributed to the relaxation process of
the dispersed phase under shearing [33]. Subsequently, when the con­
tent of PBS is over 30%, the G’ of PBST/PBS blends is higher than pure
PBS, especially in the low frequency region. This abnormal phenomenon
may be due to the transesterification of PBST and PBS at high temper­
ature [34]. Fig. 2(b) illustrates the complex viscosity η* curves of pure
PBST, PBS and PBST/PBS blends. In the low frequency region, the η* of
PBST is smaller than that of PBS, and both of them have a Newtonian
fluid with linear chain structure [35]. Furthermore, the addition of PBS
significantly increases the viscosity of the blends, which may be attrib­
uted to the entanglement of two different segments in the system [36].
The loss factor tan(δ) of the polymer can also effectively reflect the
foamability of the polymer [37]. The tan(δ) curves of PBST, PBS and
PBST/PBS blends are displayed in Fig. 2(c). It can be observed that the
tan(δ) of PBST/PBS blends decreases with the increasing content of PBS.
This phenomenon is similar with the change of G’, which is because the
tan(δ) represents the change in the elastic response of the polymer.
The Cole-Cole diagram not only can analyze the long-chain branched
structure of the polymer, but also can investigate the compatibility of
two phases in the polymer blend system. It has been reported that when
the phase-separated structure appeared in the blend system, the Cole-
Cole curve will show two arcs or the end of the curve will rise obvi­
ously [38]. Fig. 3 behaves Cole-Cole curves of each PBST/PBS blend
sample. As shown in Fig. 3, the Cole-Cole curves of PBST/PBS10,
PBST/PBS20 and PBST/PBS30 only show one arc, which means that
there is only one relaxation mechanism in these blend systems. How­
ever, the Cole-Cole curves of the other samples with higher PBS content,
K. Xue et al.
Fig. 2. Dynamic shear rheological properties as a function of the angular frequency for pure PBST, PBS and PBST/PBS blends.
Fig. 3. Cole-Cole plots of PBST/PBS blends
*η’ and η’’ represents the real part and imaginary part of the complex viscosity
(η), respectively.
show a second arc or an upward end, which means a second relaxation
mechanism that belongs to the dispersed phase. This result indicates the
compatibility of PBST and PBS becomes poorer with increasing PBS
4
Polymer Degradation and Stability 206 (2022) 110182
content in the PBST matrix. This phenomenon is also similar with the
changing trends of storage modulus G’, complex viscosity η* and loss
factor tan(δ).
3.2. Crystallization and melting behavior of PBST/PBS blends
To evaluate the effect of PBS on the thermal behaviors of PBST
blends, DSC was applied to measure the crystallization and melting
process of PBST/PBS samples. Fig. 4 shows the DSC curves of pure PBST,
PBS and PBST/PBS blends with the cooling and heating rate of 10 ◦ C/
min. Table 1 lists the corresponding thermal performance parameters. It
can be observed from Fig. 4(a) that the introduction of PBS can accel­
erate the crystallization process of PBST. Herein, no obvious crystalli­
zation peak appears for pure PBST at a cooling rate of 10 ◦ C/min. In our
previous work [11], pure PBST showed a broad crystallization peak
around 40.5 ◦ C at a cooling rate of 5 ◦ C/min. For the PBST/PBS blends, a
crystallization peak around 52 ◦ C appears at a cooling rate of 10 ◦ C/min,
indicating that the existence of PBS promotes the crystallization of PBST
in the PBST/PBS blends. It is noteworthy that the degree of crystallinity
(χc) has a significant increase in the blends compared with the pure
PBST. It is because the dispersed phase of PBS can be used as a nucle­
ation site for the heterogeneous crystallization of PBST, enhancing the
non-isothermal crystallization of PBST during the cooling process.
Interestingly, when the content of PBS increases to 50 wt%, the crys­
tallization temperature (Tc) is higher than that of pure PBS. The addition
of PBST also can significantly promote the crystallization of PBS, and the
K. Xue et al. Polymer Degradation and Stability 206 (2022) 110182

Fig. 4. Crystallization behaviors of pure PBST, pure PBS and PBST/PBS blends.

Table 1
Thermal properties of pure PBST, PBS and PBST/PBS blends.
Sample Tc(◦ C) Tcc(◦ C) Tm(◦ C) χc(%)
PBST / / 109.2 8.2
PBST/PBS10 51.3 / 109.5 23.7
PBST/PBS20 52.0 / 114.4 25.0
PBST/PBS30 52.3 / 114.7 25.3
PBST/PBS40 53.4 / 114.8 25.9
PBST/PBS50 84.7 116.8 26.7
PBS 73.8 102.1 116.9 27.3

*Tcc: The temperature of cold crystallization peak.

crystallization temperature of PBS has been increased from 73.8 ◦ C to

about 84.7 ◦ C. In this case, the PBST chain disperses in PBS matrix in a
melt state at about 80 ◦ C, and the chain movement is strong, which is
conducive to the rearrange of the PBS molecular chain at the cooling
process, increasing the crystallization temperature of the PBS. In
PBST/PBS50 blend, PBS is most likely continuous phase while the
dispersed phase is PBST.
In addition, the presence of PBS also affects the melting behavior of Fig. 5. Tensile mechanical properties of pure PBST, PBS and PBST/PBS blends.
the blend system, as illustrated in Fig. 4(b). The PBST/PBS blends have a
narrower melting temperature interval and a more obvious melting peak
than PBST, and the melting temperature (Tm) is higher than that of pure Table 2
Tensile mechanical properties data of pure PBST, PBS and PBST/PBS blends.
PBST. In our previous work, the molecular chains of PBST were arranged
in a disorderly manner, and could not be rearranged in time at a cooling Sample Tensile strength Elongation at break Tensile modulus
(MPa) (mm/mm) (MPa)
rate of 10 ◦ C/min [11]. Therefore, the partially melted crystals of PBST
may crystallize again, and these new formed crystals will also melt, PBST 25.1 ± 1.3 11.1 ± 0.3 67.9 ± 4.1
resulting in a longer melting range and a wider melting peak of PBST. PBST/ 23.5 ± 0.7 10.7 ± 0.1 78.4 ± 10.1
PBS10
Furthermore, the existence of PBS not only can accelerate the crystal­
PBST/ 21.3 ± 1.1 10.0 ± 0.2 89.3 ± 8.5
lization of PBST and improve the perfection of PBST crystals, but also PBS20
avoid the recrystallization of PBST molten crystals during the heating PBST/ 18.1 ± 0.6 9.3 ± 0.2 106.8 ± 5.7
process, so that shorten the melting temperature range. PBS30
PBST/ 16.3 ± 0.6 8.6 ± 0.2 121.5 ± 9.4
PBS40
3.3. Mechanical properties of PBST/PBS blends PBST/ 29.5 ± 1.7 5.5 ± 0.2 291.0 ± 17.0
PBS50
The tensile properties of pure PBST, PBS and PBST/PBS blends are PBS 33.2 ± 0.9 1.8 ± 0.2 440.8 ± 12.8
summarized in Fig. 5 and Table 2. It can be seen that the tensile strength
and tensile modulus of pure PBS are 33.2 MPa and 440.8 MPa, respec­
blends. When the dispersed phase in the blend system is distributed in
tively, while those of pure PBST are 25.1 MPa and 67.9 MPa, suggesting
the polymer matrix, the tensile modulus strongly depends on the tensile
that PBS has stronger rigidity than PBST. On the contrary, the elongation
modulus of the matrix phase. Compared with PBS, PBST has stronger
at break of PBST is 1110%, which is much higher than 180% of PBS,
toughness, so the elongation at break of PBST/PBS blends decreases with
indicating that the toughness of PBST is better than PBS.
the increasing content of PBS. The similar phenomenon has been re­
The tensile modulus of the PBST/PBS blends is between the values of
ported in the biodegradable polyester systems of PBAT/PBS [17],
PBST and PBS, and increases with the increment of PBS. From Fig. 5, the
PBS/PBAT [32], and PLA/PBAT [39].
tensile modulus of blends is close to that of PBST. This phenomenon is
Interestingly, the tensile strength of the blended samples shows a
also a typical feature of the phase morphology of “droplet-matrix”

5
K. Xue et al. Polymer Degradation and Stability 206 (2022) 110182

trend of first decreasing and then increasing. Although the tensile resistance for cell nucleation and growth.
modulus of the blended samples increases and the elongation at break Due to the high diffusion rate of CO2 and the weak stiffness of PBST
decreases, the blended samples still show stronger toughness and [15], the foam prepared by PBST have serious shrinkage problem. The
weaker rigidity. Therefore, the slight increase in stiffness of the blended shrinking process of PBST foam at 85 ◦ C and 20 MPa is shown in Fig. S3
samples and the premature fracture of the splines could result in a of Supplementary Materials. Fig. 7 shows the changes of the expansion
decrease in the tensile strength of the samples when the content of PBS ratio of various foams prepared by pure PBST and PBST/PBS blends at
lower 40 wt%. However, when the content of PBS is 50 wt%, the tensile 85 ◦ C and 20 MPa CO2. Herein, the foams of PBST and PBST/PBS blends
strength and tensile modulus of the blended samples are greatly have serious shrinkage problem, and the expansion ratio continues to
improved. This could be due the compatibility of PBST with PBS be­ decrease with time. After almost 6 h, the volume shrinkage ratio of the
comes weaker, and leading to the mechanical properties of the blended foams reached 65.65% (PBST/PBS10), 62.10% (PBST), 49.40%
samples began to move closer to the PBS phase, further indicating that (PBST/PBS20), 48.80% (PBST/PBS30) and 47.81% (PBST/PBS40). It
PBS is the continuous phase while PBST is the dispersed phase in PBST/ can be easily observed the volume shrinkage ratio of PBST/PBS foams
PBS50 blend. decreases with the increasing content of PBS except PBST/PBS10. This is
mainly due to the crystallinity and rigidity of the blended samples were
improved with the increment of PBS. First, Li et al. have reported that
3.4. Foaming behavior of PBST/PBS blends with CO2
the increase in crystallinity helps to reduce the CO2 diffusion rate,
thereby alleviate the shrinkage process of foams [41]. Fig. S6(a) displays
The supercritical CO2 foaming of pure PBST and PBST/PBS blends
the XRD pattern of various PBST/PBS foams. According to Fig. S6(a), the
were carried out at 20 MPa with different foaming temperatures. The
typical diffraction peaks of PBST/PBS foams become narrower with the
SEM images of samples foamed after shrinkage are summarized in the
increasing content of PBS, which indicating that the introduction of PBS
Fig. S1 of Supplementary Materials. It can be found from Fig. S1, the
is helpful to promote the growth of crystal size. Besides, the mechanical
foaming window of PBST is wider and the cell structure of PBST foams is
properties of polymers are related to the degree of crystallinity [42], and
uniform, indicating PBST possesses excellent foamability. However, the
the stronger stiffness can also slow down the shrinkage rate of foams
problem of cell burst and coalescence in PBST/PBS foams is more serious
[12]. As for the PBST/PBS10 foam, the similar phenomenon has been
with the increment of PBS. Especially, the cell morphology of PBST/
reported in our previous work. The larger expansion ratio means that the
PBS50 is so poor and there is almost no complete cell structure, so that
cell wall will be weaker, thereby accelerating the rate of CO2 escape
the data of cell diameter and cell density cannot be obtained, as shown in
from the cell.
Fig. S2. This is mainly due to the compatibility of PBST with PBS will
Fig. 8 shows the cell morphologies of samples foamed at 85 ◦ C after
become worse with the increase of PBS content. And the foaming tem­
shrinkage. The presence of PBS is a significant factor which can influ­
perature window of PBST/PBS50 is closer to that of pure PBS
ence the foaming behavior of PBST/PBS blends. In totally, the intro­
(110–120 ◦ C) since PBS plays the role of continuous phase in this blend.
duction of PBS results in that the cell density of the foam increases and
In our previous work, we have reported the open-cell structure of foams
the cell diameter decreases. Herein, PBS phase could act as a hetero­
is easy to generated in blend systems, which is because the phenomenon
geneous nucleation site to accelerate the nucleation of bubbles. This
of cell coalescence is very serious around the dispersed phase [18].
phenomenon is very common in the system of polymer blends, such as
The data of initial volume expansion ratio are illustrated in Fig. 6 to
LDPE/LLDPE [13], LLDPE/LDPE [43], PBAT/PBS [17], PBST/PLA [18]
explain the foamability of pure PBST and PBST/PBS blends. It can be
and PLA/PBAT [29]. As we all know, the nucleation of cells can be
observed from Fig. 6, PBST has the largest volume expansion ratio and
divided into homogeneous and heterogeneous nucleation. The later
the widest foaming temperature window, but the foamability of PBST/
often occurs in heterogeneous systems such as blends and inorganic
PBS weakens with the content of PBS. This is mainly due to the addition
particle-filled systems, and the energy barrier of heterogeneous nucle­
of PBS promotes the crystallization and increases the degree of crystal­
ation was much lower than homogeneous nucleation [44].
line, although the Tm of PBST and PBST/PBS blends is relatively close.
In order to better understand the heterogeneous nucleation effect of
Generally, formed crystals will hinder the dissolution and diffusion of
PBS on the foaming process of the blended samples, the cubic cell model
CO2 [40], which is not conducive to the nucleation and growth of
was used to calculate the cell size of each shrinkable foam material
bubbles. Therefore, pure PBST has a wider melting range and slower
before shrinkage. The schematic of cubic cell permeation model is
crystallization, which leads to sufficient dissolution of CO2 in the poly­
mer matrix and could provide sufficient driving force and smaller

Fig. 6. Initial expansion ratio of pure PBST, PBS and PBST/PBS blends foams Fig. 7. Effect of PBS contents on the dimensional stability of PBST/PBS foams
(20 MPa CO2). (85 ◦ C, 20 MPa CO2).

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K. Xue et al. Polymer Degradation and Stability 206 (2022) 110182

Fig. 8. SEM images of pure PBST and PBST/PBS blends foams after shrinkage at 85 ◦ C
(a) PBST, (b) PBST/PBS10, (c) PBST/PBS20, (d) PBST/PBS30, (e) PBST/PBS40.

shown in Fig. S4, which displays the process of replacing the blowing 3.5. Foaming behavior of PBST/PBS blends with CO2 & N2 co-blowing
agent with air during the aging time. The initial cell size l0 of various agent
shrinkage foamed sample can be determined by the Eqs. (S1)–(S3) in
Supplementary Materials. Combining the results of Figs. 7 and 8, the In order to settle the shrinkage behavior of PBST foams, the reason
initial cell density and cell size of sample foamed at 85 ◦ C and 20 MPa for shrinking was needed to analyze. If CO2 diffuses out of the foam
CO2 were calculated by using the cubic cell model, listed in Table 3. faster than air into the foam, the PBAT foam will display serious
With the increasing PBS content, the cell size decreases from 25.0 μm to shrinkage behavior due to the weak rigid of PBAT can’t support the cell
7.03 μm, and the cell density increases from 8.84×108 to 3.12 × 1010 structure under negative pressure. According to the similar diffusion
cells/cm3. This phenomenon could be caused by the heterogeneous rate of N2 and air, the introduction of N2 can effectively solve the
nucleation of PBS and the enhanced melting-strength. The cell size shrinkage problem of foams. As for the mechanism of foaming behavior
distribution of the foamed samples at the initial time before shrinkage of PBST/PBS blends with CO2 & N2 co-blowing agent, it is similar with
also was calculated by using the cubic cell model, as shown in Fig. S5. utilizing sc-CO2 as the blowing agent. During the foaming process, the
The cell distribution becomes narrower and the cell size decreases with solubility of co-blowing agent decreased with the decreasing pressure,
the content of PBS, especially when the PBS content above 10 wt%. The and the cell would undergo three process: cell nucleation, cell growth
result further clearly shows the heterogeneous nucleation effect of PBS and cell solidification. However, the higher content of N2 are favorable
phase. As shown in Fig. 3, the compatibility of PBST with PBS will for the cell nucleation, which is due to the interfacial tension of N2 is
gradually deteriorate with the increment of PBS, resulting in more stronger than CO2. In this work, the anti-shrinkage effect of CO2 & N2 co-
dispersed phase particles serving as heterogeneous nucleation sites. blowing agent on the foams fabricated by PBST/PBS blends was inves­
Therefore, the increasing content of PBS leads to stronger heterogeneous tigated. It can be seen from Fig. 8 that the PBST/PBS10 foam has the
nucleation effect, and the stronger melting-strength can limit cell highest initial expansion ratio (20.3-fold) and volume shrinkage ratio
growth according to the classical nucleation theory [44]. (65.65%) at 85 ◦ C. Therefore, PBST/PBS10 was selected as the example
to evaluate the effect of N2 on the cell nucleation, bubble growth and the
dimensional stability.
Fig. 9 shows the variation of the volume expansion ratio of PBST/
PBS10 foams with time under different CO2+N2 ratios as blowing agent.
It indicates that with the increase of N2 partial pressure, the initial
Table 3 volume expansion ratio will decrease accordingly while the dimensional
The cell structure of pure PBST and blend polymers (Foaming condition: 85 ◦ C, stability of PBST/PBS10 foam can be improved. The reduction of the
20 MPa). initial volume expansion ratio could be due to the decrease of the sol­
Sample At the initial time After shrinkage ubility. Relevant literature shows that the solubility of polymer to CO2 is
more than 10 times of that to N2, which indicates that with the increase
Cell size Cell density Cell size Cell density
(μm) (1010cells/cm3) (μm) (1010cells/cm3) of N2 content, the solubility of polymer to mixed co-blowing agent is
lower [45,46]. Generally, the gas solubility is one of the most important
PBST 25.0 0.0884 5.63 3.83
PBST/ 21.8 0.164 7.29 1.37
factors which affecting the volume expansion ratio [47,48]. Therefore,
PBS10 the lower solution means weaker driving force of cell growth, and
PBST/ 8.83 1.93 4.38 5.85 leading to smaller volume expansion ratio with the increase of N2 partial
PBS20 pressure [44]. When 12 MPa CO2 and 8 MPa N2 were injected into the
PBST/ 8.36 2.08 4.12 5.99
autoclave, the shrinkage problem of PBST/PBS10 foam was effectively
PBS30
PBST/ 7.03 3.12 3.57 8.54 solved, and the volume expansion ratio after aging time was about
PBS40 10.6-fold.

7
K. Xue et al. Polymer Degradation and Stability 206 (2022) 110182

Table 4
The cell structure of PBST/PBS10 (Foaming condition: 85 ◦ C, 20 MPa).
N2 partial CO2 partial At the initial time After shrinkage
pressure pressure
(MPa) (MPa)
Cell Cell density Cell Cell density
size (1010cells/ size (1010cells/
(μm) cm3) (μm) cm3)

0 20 21.8 0.160 7.29 1.37

4 16 17.2 0.332 6.91 1.52
8 12 6.56 2.38 6.13 2.62
12 8 6.53 2.51 5.73 3.44
16 4 5.12 3.96 4.78 4.83

N2, Fig. 11 compared the pore size distribution of PBST/PBS10 foams

Fig. 9. Expansion ratio of blends foams under different conditions with CO2 &
N2 co-blowing agent.
Fig. 10 shows the SEM images of PBST/PBS10 foams under different
CO2+N2 ratios after shrinkage, and related cell morphology parameters
of PBST/PBS10 foams in Fig. 10 are listed in Table 4. Similar with
Table 3, Table 4 also presents the calculated cell density and cell
diameter at the initial time under different CO2+N2 ratios. It can be
easily obtained from Table 4, with the increase of N2 partial pressure,
the cell size of PBST/PBS10 foam decreases from 21.8 μm to 5.12 μm,
and the cell density increases from 0.16 × 1010cells/cm3 to 3.96×1010
cells/cm3. It indicates that N2 has stronger nucleating effect, and this
conclusion is similar to our previous work [49]. Fernández-Ronco et al.
have compared the effect of pressurized N2 and CO2 on the rheological
properties of PLA, and the result showed that the amount of N2 required
is less than that of CO2 under the condition of achieving the same
plasticizing effect [49]. Therefore, according to classical nucleation
theory, pure N2 can fabricated more cells than pure CO2 at the similar
interfacial tensions in both systems of polymer/N2 and polymer/CO2
[44].
In order to better understand the cell nucleating effect of introducing
after and before shrinkage. It can be seen from the Fig. 11 that with the
increase of N2 partial pressure, the distribution of cell size becomes
narrower, indicating that the uniformity of cell morphology was
improved. This phenomenon is more obvious in Fig. 11(b). Furthermore,
the effect of N2 on the crystallization property of the same material was
observed by XRD experiments for the first time in this work. Fig. S6(b)
displays the XRD pattern of PBST/PBS10 foams which fabricated by the
CO2 & N2 co-blowing agent at different ratio of CO2/N2. Fig. S6(b) shows
that the max value of typical diffraction peaks becomes stronger with the
increasing content of CO2, which could be caused by the stretch of
polymer during the foaming process [50]. According to Fig. 9, more CO2
content could provide stronger driving force in theory, and the degree of
stretch could be larger. Therefore, it is important to limit the N2 content
in the co-blowing agent, and the application of CO2 & N2 co-blowing
agent is helpful to manufacture microcellular foams with larger vol­
ume expansion ratio and good dimensional stability.
4. Conclusion
In this work, a series of PBST/PBS blends with different PBS contents
were prepared by melt blending for supercritical fluids foaming. With
the increased content of PBS, the improvement of rheological behavior
can limit the cell growth, and PBS can act as the heterogeneous nucle­
ation. Compared with pure PBST, the cell size of the foam decreases from
25.0 to 7.03 μm, and the cell density increases from 8.84×108 to
3.12×1010 cells/cm3 with 40 wt% PBS. Furthermore, higher

Fig. 10. SEM images of PBST/PBS10 foams under different CO2+N2 conditions
(a) 20 MPa CO2, (b) 16 MPa CO2 + 4 MPa N2, (c) 12 MPa CO2 + 8 MPa N2, (d) 8 MPa CO2 + 12 MPa N2, (e) 4 MPa CO2 + 16 MPa N2.

8
K. Xue et al.
Fig. 11. Cell size distributions of PBST/PBS10 foams under different CO2+N2 conditions:
(a) After shrinkage, (b) at the initial time.
crystallinity and stiffness of PBST/PBS blends can be helpful to reduce
the diffusion rate of CO2 escaped from cells and alleviate the shrinking
problem. The volume shrinkage ratio reduces from 62.10% to 47.81%
with the increasing PBS.
The introduction of N2 can facilitate the cell nucleation and solve the
shrinkage problem of PBST/PBS10 foams effectively. With the
increasing partial pressure of N2, the cell size of PBST/PBS10 foam de­
creases from 21.8 to 5.12 μm, and the cell density increases from 0.16 ×
1010 to 3.96 × 1010cells/cm3. With the introduction of 12 MPa CO2 and
8 MPa N2, the volume expansion ratio of PBST/PBS10 microcellular
foam can achieve 10.6-fold, almost without shrinkage behavior. Herein,
the melt-blending of commercial PBST and PBS pellets show the great
foamability with shrinkage problem. Controlling the content of succinic
acid and terephthalic acid in PBST will be another feasible strategy to
control the rheological properties, crystallization properties and foam­
ability of PBST, which is expected to fabricate microcellular foams with
low density and fully-biodegradability by using CO2 & N2 as co-blowing
agent.
Funding
Natural Science Foundation of Shanghai (20ZR1413700), and the
Fundamental Research Funds for the Central Universities.
CRediT authorship contribution statement
Kun Xue: Conceptualization, Methodology, Investigation, Writing –
original draft. Peng Chen: Conceptualization, Methodology, Investiga­
tion. Can Yang: Conceptualization, Methodology, Investigation. Zhimei
Xu: Formal analysis, Supervision, Funding acquisition. Ling Zhao:
Formal analysis, Data curation, Supervision, Writing – review & editing,
Funding acquisition. Dongdong Hu: Conceptualization, Supervision,
Formal analysis, Data curation, Writing – review & editing, Funding
acquisition, Project administration.
Declaration of Competing Interest
The authors declare that there is no conflict of interest.
Data Availability
No data was used for the research described in the article.
9
Polymer Degradation and Stability 206 (2022) 110182
Acknowledgment
The authors are grateful to Natural Science Foundation of Shanghai
(20ZR1413700), and the Fundamental Research Funds for the Central
Universities.
Supplementary materials
Supplementary material associated with this article can be found, in
the online version, at doi:10.1016/j.polymdegradstab.2022.110182.
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