Composites Science and Technology 192 (2020) 108108

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Composites Science and Technology

journal homepage: http://www.elsevier.com/locate/compscitech

Fabrication of Poly(vinylidene fluoride)/Multiwalled carbon nanotube

nanocomposite foam via supercritical fluid carbon dioxide: Synergistic
enhancement of piezoelectric and mechanical properties
Dawei Xu , Huili Zhang , Lian Pu , Li Li *
State Key Laboratory of Polymer Materials Engineering, Polymer Research Institute of Sichuan University, Chengdu, 610065, China

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

Keywords: The fabrication of poly(vinylidene fluoride) (PVDF) based foam with complicated three-dimensional (3D) ge­
Polyvinylidene fluoride ometry and excellent piezoelectric property remains great challenge worldwide. In this study, microcellular
Multiwalled carbon nanotube PVDF/multiwalled carbon nanotube (MWCNT) nanocomposite foaming part was fabricated by supercritical
Supercritical carbon dioxide
carbon dioxide (scCO2) bead foaming technology. With the assistance of the ball milling, the good dispersion of
Bead foaming
Piezoelectric property
MWCNT particles in PVDF matrix was achieved, which promoted the heterogeneous nucleation and enhance­
ment effects of MWCNT on PVDF, resulting in the formation of more unique and denser cells, e.g. from 3.4 � 105
cells/cm3 of pure foam to 1.7 � 106 cells/cm3 of the composite foam when MWCNT content was 1.5%, and high
compression strength, i.e. 3.1 MPa with 1.5% MWCNT at 10% compressive strain, about 1.1 MPa higher than
that of pure foam. During the bead foaming process, the induced crystallization effect of MWCNT as well as the
plasticizing and squeezing effect of scCO2 on PVDF matrix contributed to the increase of the β-phase crystal in
PVDF matrix, thus endowing the composite foaming part with good piezoelectric property, i.e. 6.5 V of output
voltage under periodic compression, which lightened 4 LEDs and made the foaming part had wide potential
application in smart electronic field.

1. Introduction 11 (PA11), polyvinylidene fluoride (PVDF) and their composites have

With the rapid development of modern industry and advanced
technology, smart equipment and portable devices, which can response
sensitively to the environment effect, are now attracting more and more
attentions [1–3]. Piezoelectric material is one of the important smart
materials, and has been widely applied to plenty of fields, ranging from
electric actuators and sensors to energy harvesters [4–7]. Once suffering
external force, the piezoelectric material would deform in some direc­
tion, making the polarization phenomena occurred inside, meanwhile,
positive and negative electric charges accumulated on its opposite sur­
faces, thus converting mechanical energy into electric energy [8].
Piezoelectric material has experienced great developments in quartz
crystals, piezoelectric ceramics, organic polymers and composites.
Considering the high cost of quartz crystals [9] and the harm of the
plumbum element in piezoelectric ceramics for human living [10], more
and more attentions have been turned to polymers and their composites,
and lead-free soldering, high performance as well as functionalization
have become the hotspots in recent years. Polymers including polyamide
been widely applied in the fields of underwater acoustic measurement,
pressure sensor, ignition and detonation for their flexibility, low density,
low impedance and high piezoelectric constant [11–15]. Especially
PVDF, who possesses five crystalline phases, is the most popular mate­
rial to be studied [16–18].
Among the five crystalline phases of PVDF, α phase with non-polarity
is most stable and common, while polar β phase with oriented dipole
moments endows PVDF with high electroactive property including py­
roelectric, piezoelectric and ferroelectric properties [19–22]. Accord­
ingly, how to obtain more β phase become the hot research topics. Plenty
of methods have been developed, e.g. cold drawing, the most commonly
way to effectively align PVDF molecular chains and induce the trans­
formation of α phase to β phase [23,24]; melting crystallization at high
pressure or high cooling rate [25,26]; blending with conductive fillers
[27,28]; etc.
Porous materials show unique advantages in practical piezoelectric
applications for their special repeated compression-recovery perfor­
mance and charge distribution at the cell interface after polarization,

* Corresponding author.
E-mail address: powerlily@scu.edu.cn (L. Li).

https://doi.org/10.1016/j.compscitech.2020.108108
Received 13 November 2019; Received in revised form 8 February 2020; Accepted 2 March 2020
Available online 3 March 2020
0266-3538/© 2020 Elsevier Ltd. All rights reserved.
D. Xu et al.
which can contribute to the superb piezoelectric performance. To obtain
porous PVDF composites, hard template, sol-gel and solution methods
were developed [29–31]. However, by using these methods, the regular
pore shape and uniform pore distribution are quite difficult to be ach­
ieved, and the manufacturing process is time-consuming and sophisti­
cated. Therefore, developing a facile and efficient strategy to obtain
PVDF part with superior cell structure is still a challenge and urgent
need.
Supercritical carbon dioxide foaming (SCF) technology is one of the
most preferable approaches to produce the controllably and homoge­
neously microporous materials due to its simplicity, economic afford­
ability and greenness. Therefore, recent years, supercritical carbon
dioxide (scCO2), which has good compatibility with PVDF matrix at high
pressure and temperature, has been widely introduced into the prepa­
ration of PVDF based porous materials. During the foaming process, the
cell growth was considered as a micro-extensional process, thus effec­
tively increasing β phase of the matrix [32–34]. Simultaneously, the
compact and uniform cell structure obtained by SCF technology
endowed the product with more stable electric response behavior and
better compressive strength. However, ascribing to the long adsorption
time of PVDF for CO2, the present porous PVDF obtained via SCF tech­
nology is almost limited to two-dimensional products, e.g. film and thin
sheet. Three-dimensional (3D) porous PVDF parts, which might have
wider applications, are seldom to be reported.
Bead foaming is a special technology to prepare 3D porous products
with large and complex shape as well as high expansion ratio and pre­
cision [35]. Different from the traditional foaming process which only
refers to the bubble nucleation, growth and solidification, the bead
foaming includes the processes of bead expansion, squeeze and interface
sintering. But the present sintering temperature usually comes from the
pressurized water vapor, so is limited to 120–180 � C and only suitable
for the polymer materials with low glass transition temperature and low
melting point, e.g. expandable polystyrene (EPS) [36], expanded poly­
ethylene (EPE) [37] and expanded polypropylene (EPP) [38], rather
than PVDF.
Accordingly, in this paper, a confined mold assisted batch bead
foaming technology by using scCO2 as both physical blowing agent and
plasticizer was developed to fabricate three-dimensional (3D) porous
PVDF based parts. And to further improve the cell structure and elec­
trical properties of the final part, MWCNT, one of the widely used
conductive nanofillers for its high aspect ratio and large electron-rich
surface, was utilized. The good dispersion of MWCNT was achieved
via co-milling MWCNT particles and PVDF cryogenic ground powders,
and PVDF/MWCNT composite beads were prepared on a twin-extrusion.
The dispersion of MWCNT in PVDF matrix, the crystal structure of the
nanocomposite, the foaming behavior as well as the piezoelectric per­
formance and compression property of the final foaming parts were
studied.
2. Experimental
2.1. Materials
PVDF granules (FR906) with density of 1.79 g/cm3, molecular
weight of ~300000 g/mol and melting temperature of 172 � C were
purchased from Suzhou Tao Lian Plasticizing Co., Ltd, China. MWCNT
(NC7000) with average diameter of 9.5 nm and average length of 1.5 μm
was supplied by Nanocyl S.A., Belgium. CO2 with 99.5% purity was
provided by Chengdu Taiyu Gas., China.
2.2. Preparation of PVDF/MWCNT nanocomposite beads
PVDF granules were first cryogenic ground into powders, then mixed
with MWCNT particles on a planetary ball-milling equipment (QM-3P,
Nanjing Nanda Instrument Plant., China) at 500 rpm for 3 h. After that,
the mixture was melt extruded on a TSSJ-25/33 co-rotating twin-screw
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Composites Science and Technology 192 (2020) 108108
extruder (Chenguang Research Institute of Chemical Industry, China)
with a rotation rate of 30 rpm and processing temperature of 185 � C.
PVDF/MWCNT nanocomposite beads were obtained via granulating and
drying the extrusion strip. PVDF/MWCNT nanocomposite beads pre­
pared via simple mechanical blending without ball milling were used as
contrast sample. The MWCNT content in the nanocomposite beads was
0, 0.5 wt%, 1.0 wt%, 1.5 wt% and 2.0 wt% respectively.
2.3. Preparation of PVDF/MWCNT nanocomposite foaming part
PVDF/MWCNT nanocomposite beads were firstly filled into a
stainless-steel mold with micro nozzles. Then, the mold was put into a
high pressure autoclave (Beijing Century Senlang Experimental Appa­
ratus Co., Ltd, China) to be saturated with CO2 at 40 � C and 7 MPa for 1
h. After that, the autoclave was rapidly heated to above 160 � C within
30 min, and then fast depressurized (10 MPa/s) and put into ice-water
bath to obtain PVDF foaming part. The mol of scCO2 was calculated
using appropriate PVT data from saturation pressure, saturation tem­
perature and vessel volume. The sketch map of the preparation process
of PVDF and PVDF/MWCNT beads, foaming beads as well as foaming
parts was shown in Fig. 1.
2.4. Characterization
The dispersion of MWCNT particles in PVDF matrix and the cell
morphology of the PVDF foaming parts were observed using Inspect
Scanning Electron Microscopy (SEM) instrument (JSM-5900LV, JEOL
Co., Ltd., Japan) at 10 kV. Nano Measurer software was used to calculate
the average cell diameter and cell density (N, number of cells per unit
foamed polymer volume). Before test, sample was fractured in liquid
nitrogen and sputtered with a conductive gold coating. N was deter­
mined using Equation (1) [39],:
� 2 �32
N¼
nM
(1)
A
where n is the number of cells in SEM micrograph, A is the area of the
micrograph and M is the magnification factor.
The CO2 adsorption of the composites were measured according to
the following steps. The PVDF and PVDF/MWCNT composite beads
were firstly dried in an oven for about 6 h, and then placed in a high-
pressure vessel under 7 MPa at 40 � C for 1 h. After the quickly
reducing pressure, the swelled samples were immediately taken out and
measured on a Mettler AE240 analytical (with the accuracy of �10 μg).
Each sample was tested five times.
X-ray diffraction (XRD) patterns were collected on DX-1000
diffractometer (DanDong FangYuan instrument Co., Ltd. China). The
samples were continuously scanned from 10� to 30� at a rate of 0.2� /min
with the accelerating voltage of 40 kV and the electric current of 35 mA,
respectively.
Fourier transform infrared (FT-IR) spectra were carried out on a
Nicolet 6700 IR spectrometer (Thermo Scientific Company, USA) from
4000 cm 1 to 750 cm 1 at 4 cm 1 resolution and 32 scans with ATR
mode or transmission mode. The relative β phase fraction (F(β)) was
estimated according to Lambert-Beer law, which can be expressed as
Equation (2) [40],:
Xβ Aβ
FðβÞ ¼ ¼ (2)
Xβ þ Xα ðKβ =Kα ÞAα þ Aβ
where Xα and Xβ represent the crystallinity of α and β phase, respec­
tively; Aα and Aβ are the absorbance at 766 cm 1 and 840 cm 1,
respectively; Kα and Kβ are the adsorption coefficients at the corre­
sponding wavenumber, Kα ¼ 6.1 � 104 cm2 mol 1 and Kβ ¼ 7.7 � 104
cm2 mol 1.
Differential scanning calorimetry (DSC) analysis was recorded on a
D. Xu et al.
Fig. 1. Scheme of the preparation of PVDF and PVDF/MWCNT beads, foaming beads and parts.
TA-Q20 differential scanning calorimeter (TA Instrument, USA) from 40
�
C to 200 � C at a heating rate of 10 � C under a nitrogen atmosphere flow
of 50 ml/min. The corresponding degree of the crystallinity (χ c) was
calculated according to the Equation (3) [41],:
ΔHf
χc ¼ � 100% (3)
ΔHc
where ΔHf is the melting enthalpy of the measured PVDF sample, ΔHc
represents the melting enthalpy of PVDF with 100% crystallinity, which
is about 105 J/g.
The piezoelectric performance was evaluated by a periodic impact­
ing test with a linear motor (NTI AG HS01–37 � 166) as the impact
source. The open-circuit voltage and short-circuit were collected on a
Keithley 6514 system electrometer and an SR570 low noise current
amplifier, respectively.
The compression properties of the sample with 30 mm diameter and
10 mm thickness were tested on an Instron 5567 universal testing
Fig. 2. SEM images of the dispersion of 2% MWCNT in PVDF matrix without (a-1, a-2, a-3) and with (b-1, b-2, b-3) ball milling.
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Composites Science and Technology 192 (2020) 108108
machine (Instron, USA) at room temperature with a crosshead speed of
10 mm/min. After reaching 10% compressive strain, the sample was
recovered with the same rate. Five specimens were tested for each group
and the average values were calculated.
3. Results and discussion
3.1. Dispersion of MWCNT in PVDF matrix
The dispersion and morphology of MWCNT influenced the foaming
and final electrical and mechanical properties of PVDF matrix. Fig. 2
showed the SEM images of the nanocomposite with 2% MWCNT pre­
pared with and without the assistance of the ball milling. As well known,
MWCNT is a kind of nanofiller with large specific surface area and aspect
ratio. When dispersed in polymer matrix, MWCNT particles are prone to
closely clustering together for their great specific surface energy, thus
bringing negative effects on foaming properties of the matrix and
D. Xu et al. Composites Science and Technology 192 (2020) 108108

comprehensive properties of the final foaming part. Obviously, without chains, thus constructing more β-phase PVDF [42,43].
any external force or pretreatment, long-tubular MWCNT particles in
PVDF matrix presented plenty of aggregations on the fracture interface
3.3. Foaming behaviors of PVDF/MWCNT nanocomposite beads
(Figs. 2 a-1, a-2, a-3) due to the poor interactions between MWCNT and
PVDF and the strong surface effect among MWCNT particles. Once
Supercritical CO2 was used as physical blowing agent to get well-
suffering the strong impact force of the ball milling, the length of
dispersed PVDF/MWCNT nanocomposite foaming beads and the rela­
MWCNT was greatly shortened, from ~1.5 μm to ~0.3 μm, making more
tive foaming behaviors were investigated. Usually, CO2 adsorption in
polar groups in MWCNT exposed and thus enhancing the interactions
polymer matrix could play plasticization effect on polymer molecular
between MWCNT and PVDF, finally improving the dispersion of
chains, thus having great impact on the foaming states. Fig. 4 showed
MWCNT in PVDF (Figs. 2 b-1, b-2, b-3), i.e. the aggregations of MWCNT
the effects of MWCNT loading on the CO2 adsorption under 7 MPa at 40
remarkably decreased and most MWCNTs homogenously attached on �
C within 1 h and the foaming ratio of the composite beads. Obviously,
the surface or just embedded in PVDF matrix. In this way, the whole
the CO2 adsorption of PVDF was greatly influenced by MWCNT, and was
section was connected by well-dispersed MWCNT particles.
decreased with the increase of MWCNT loading, from 3.8% (0%
MWCNT) to 2.5% (2.0% MWCNT). This might be due to the weak in­
3.2. Effect of MWCNT on crystalline structure of PVDF teractions between MWCNT and CO2 as well as the induced crystalli­
zation effect of MWCNT on PVDF matrix. The former made CO2 scarcely
XRD and FTIR were utilized to further investigate the influence of attached to MWCNT particles, while the later limited the movement of
MWCNT on the crystallization behavior of PVDF. As shown in XRD PVDF molecular chains, thus greatly constricting the entrance of CO2
patterns (Fig. 3a), the characteristic peaks, respectively representing and reducing its adsorption concentration in matrix. The reduced
(020) and (021) planes of the α -form crystallinity of PVDF matrix, physical blowing agent and the enhanced melt strength of the matrix
appeared at 2 θ ¼ 18.3� and 26.6� . While the typical diffraction peak of β with the introduction of MWCNT surely resulted in the decrease of
phase appeared at 2 θ ¼ 20.3� , corresponding to (110) and (200) planes. foaming ratio, from 7.6 to 6.4 with MWCNT content increasing from 0%
It could be obviously seen from the figure that with the increase of to 2.0%.
MWCNT content, both the peak intensity of α phase and β phase To clarify the effect of MWCNT on foaming behaviors more intui­
evidently enhanced, meaning that the crystallinity of PVDF increased. tively, SEM images and cell size distribution of PVDF and PVDF/
This could be attributed to the heterogeneous nucleation ability of ho­ MWCNT foaming parts were shown in Fig. 5, and the average cell
mogeneously dispersed MWCNT nanofillers, which effectively induced diameter and cell density were listed in Fig. 6. On account of the great
the interfacial crystallization of PVDF molecules. influences of the inter- and intra-bead bonding force on the
To further identify the content of different crystal phase, the corre­
sponding FT-IR spectra were revealed in Fig. 3b. The vibration peak at
around 766 cm 1 was attributed to the α phase of PVDF generated from
the framework vibration of CF2, while the vibration peak corresponding
to β phase appeared at around 840 cm 1, attributing to the in-plane
rocking vibration of CF2. In case of incorporating MWCNT, the vibra­
tion peak of α phase just had a slight change, but the strength of β-phase
peak clearly increased. The relative β-phase fraction of pure PVDF and
PVDF/MWCNT were calculated by using equation (2), i.e. 30.7%,
34.7%, 36.9%, 40.8% and 43.2%, respectively, with the increase of
MWCNT content, implying that the addition of MWCNT induced the
formation of more β-phase PVDF. This could be attributed to the
nucleating effect of MWCNT, which altered the crystallization behaviors
of PVDF. At the boundary of MWCNT and PVDF, electrostatic in­
Fig. 4. CO2 adsorption content and foaming ratio of PVDF and PVDF/
teractions were formed between the functional groups of MWCNT and
MWCNT beads.
the CF2 dipoles of PVDF, inducing the formation of more stretched PVDF

Fig. 3. XRD patterns (a) and FT-IR spectra (b) of PVDF and PVDF/MWCNT nanocomposites.

4
D. Xu et al.
Fig. 5. Photo of PVDF foaming parts (a) and SEM images of cell structure and cell distribution of PVDF and PVDF/MWCNT foaming parts (b–f). (MWCNT: b: 0; c:
0.5%; d: 1%; e: 1.5%; f: 2%, the cell diameter ranges from 0 to 300 μm).
comprehensive properties of the final product [44], and to get the better
cellular structure and sintering conditions, different foaming tempera­
ture, saturation period and pressure were attempted. Clearly, under
proper foaming condition, i.e. initially saturated in CO2 at 40 � C and 7
MPa for 1 h and then rapidly heated above 160 � C, no obvious inter-bead
gap was obtained in the foamed parts (Fig. 5b–f). For pure PVDF
foaming part (Fig. 5b), cells with various dimension and irregular shape
were formed, originating from the serious cell coalescence and collapse
caused by the relatively low melt strength of PVDF matrix at the cell
growth stage. With the addition of MWCNT, especially when its con­
centration reached or above 1.5%, more uniform and regular cells were
obtained (Fig. 5e–f), demonstrating that the existence of MWCNT took
great effect on the foaming process. The well-dispersed MWCNT parti­
cles could first play heterogeneous nucleation role in PVDF matrix, so
effectively reduced the critical free energy barrier of the cells and
increased the number of cell nucleation; simultaneously enhanced the
strength of the cell walls, thus stabilizing the cell structure and pro­
tecting the cells from deterioration under the stretching force produced
during the process of cell growth. Both impelled the formation of more
uniform and smaller cells, which was reflected in Fig. 5 by the
Fig. 6. Average cell diameter and cell density of PVDF and PVDF/MWCNT
foaming parts.
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Composites Science and Technology 192 (2020) 108108
distribution of cell size becoming more concentrated. More information
on cell could be obtained from Fig. 6, in which the average cell diameter
was observed decreased from 147.2 μm (pure PVDF) to 60.3 μm, and the
cell density of the nanocomposite foaming part increased from 3.4 �
105 cells/cm3 to 3.5 � 106 cells/cm3 when MWCNT loading increased to
2%, further confirming the nucleation and reinforcement effects of
MWCNT.
The enhancement of MWCNT on PVDF cell wall could also be
confirmed from the DSC curves of PVDF/MWCNT bead and foaming
part, as shown in Fig. 7, i.e. both the bead and foaming part with the
same MWCNT content, e.g. 1.5%, showed stronger melting peaks than
those without MWCNT, identifying the increase of the crystallinity of
bead and part with the addition of MWCNT. And the crystallinity was
further improved after scCO2 foaming (from 38.1% to 45.6% for PVDF
and from 39.7% to 46.8% for PVDF/MWCNT), indicating again that the
regularity and arrangement of the molecular chains became more per­
fect under the plasticizing and subsequent extension effects of scCO2
Fig. 7. DSC curves of PVDF and PVDF/MWCNT beads and foaming parts
(MWCNT: 1.5%).
D. Xu et al. Composites Science and Technology 192 (2020) 108108

during saturation and cell expansion process. It was worth noting that leading to the transformation of some α phase to β phase. Fig. 9b
phase transformation occurred during the foaming process, making the depicted the different macroscopical bead foaming process. For free
fusion peak of α phase at about 165–170 � C greatly weakened or dis­ foaming process (b-1), PVDF beads were separately expanded and
appeared, while the peak of β phase at about 172 � C enhanced. turned rounded without any external force; while for mold foaming (b-
Fig. 8 showed FT-IR spectra of PVDF, PVDF/MWCNT beads and their 2), the expansion of the beads was limited into a confined space, so more
scCO2 foaming beads and parts, from which the changes of crystal phase intensive squeezing and sintering effects could impose on the beads,
during foaming process and the effect of MWCNT could be further making more α-phase PVDF transformed to β phase and the uniform
analyzed. Obviously, regardless of pure PVDF and PVDF/MWCNT sys­ foaming part formed.
tem, after scCO2 foaming, the intensity of the vibration peak of β phase
at around 840 cm 1 gradually increased, while the peak of α phase at
3.4. Compression properties and piezoelectric responses
around 766 cm 1 presented the reverse change, identifying again that
scCO2 foaming promoted the transformation of α phase to β phase. This
The compressive strength of PVDF and PVDF/MWCNT nano­
could be attributed to the extension of PVDF molecules along the cell
composite foaming parts were shown in Fig. 10. Obviously, the PVDF/
expansion direction after the pressure release [45–47], similar to a
MWCNT foaming parts showed higher compressive strength than that of
mechanical stretching process, which induced the rearrangement of
the pure one, attributing to the higher cell density, more uniform and
PVDF molecular chains and made α phase transform to β phase, espe­
smaller cell size of the nanocomposite parts, as well as the enhancement
cially at higher depressurization and cooling rate, for larger expansion
of the well-dispersed MWCNT on cell wall. The more the MWCNT
force could be exerted on PVDF molecular chains, along with the pro­
loading, the stronger the enhancement of MWCNT and the higher the
motion effect on β phase [48,49]. Noticeably, compared with the free
compressive strength of the foaming part. When MWCNT content
foaming of PVDF and PVDF/MWCNT beads, within the confined foam­
increased to 2.0%, the compressive strength of composite foaming part
ing space of part, stronger squeezing stress was imposed on PVDF and
increased to 3.3 MPa, 1.3 MPa higher than that of the pure foaming part.
PVDF/MWCNT beads during the cell expansion and sintering process,
The compressive curves also indicated the excellent reversibility of the
enhancing the extension of PVDF molecules as well as the friction be­
foam parts, which would provide the superior compressibility and sta­
tween beads and mold, further promoting the formation of β-phase
bility in the periodic piezoelectric process.
crystal, thus increasing the peak intensity of β phase. With the further
Considering the special electrical properties of PVDF/MWCNT and
incorporating of MWCNT, more heterogeneous nucleation spots were
the compression deformation performance of the corresponding foam,
generated and cell walls were strengthened, so induced the additional
the piezoelectric performances of PVDF and PVDF/MWCNT 3D foaming
cell nucleation and expansion and protected the cell structure from
parts were tested via periodic compression, and the acceleration of the
breakdown even at high depressurization rate, making more β phase
linear motor was varied (3, 5 and 7 m/s2). Fig. 11 showed the output
formed, resulting in the sharper β-phase peak. It was more clearly seen
voltage of the foaming parts with different MWCNT concentration and
by calculating the relative β-phase fraction of each sample that the
impacting acceleration. Clearly, increasing both MWCNT content and
β-phase content of PVDF foaming bead and part were 52.9% and 60.1%,
acceleration rate, the peak-to-peak voltages of the foaming part
respectively 22.2% and 29.4% higher than that of PVDF bead (30.7%),
increased. For example, at the acceleration of 3 m/s2, 0.5, 1.0, 2.7 and
and further increased to 59.2% and 70.7% with the addition of 1.5%
4.1 V output voltage were observed for the parts with the MWCNT
MWCNT, respectively 18.4% and 29.9% higher than that of
content of 0, 0.5%, 1.0% and 1.5%, respectively. While with 1.5%
PVDF/MWCNT bead (40.8%).
MWCNT, the output voltage was 4.1, 4.6 and 6.5 V respectively at the
The schematic of the scCO2 foaming behaviors of PVDF beads was
impacting acceleration of 3, 5 and 7 m/s2.
shown in Fig. 9. Fig. 9a concretely expressed the influence of scCO2 on
It should be point out that even for pure PVDF foaming part, the
the molecular chains of PVDF matrix. After the gas immersion stage, the
output voltage could reach approximately 1.0 V at the acceleration of 7
absorbed scCO2 was homogeneously swelled into PVDF molecular
m/s2, higher than that obtained through the traditional melting pro­
chains (a-2). Then, at the stage of the rapid pressure release (a-3), the
cessing [50], due to the plasticizing and squeezing effect of scCO2 in the
saturated scCO2 around PVDF molecular chains was quickly nucleated
confined mold foaming space, which promoted the orientation of PVDF
and expanded, exerting stretching effect on PVDF molecules, thus
molecules and the formation of more β-phase PVDF, as well as the more

Fig. 8. FT-IR spectra of PVDF and PVDF/MWCNT beads, foaming beads and parts.

6
D. Xu et al. Composites Science and Technology 192 (2020) 108108

Fig. 9. Schematic illustration of scCO2 foaming process of the nanocomposite beads. (a: influence of scCO2 on PVDF molecular chains, b: free bead foaming and
mold foaming).

Fig. 10. Compressive stress-strain curves of PVDF and PVDF/MWCNT foaming parts.

perfect 3D porous structure, thus increasing the electromechanical
coupling and presenting a continuous pathway for load transfer,
consequently leading to the enhanced piezoelectric properties.
With the incorporating of MWCNT, the piezoelectric property of the
foaming part presented a further continuous increase, possibly attrib­
uting to the promoting effect of MWCNT on the formation of more
β-phase PVDF and its unique electrical performance. However, this in­
crease was stopped when MWCNT content reached 2%. Within 2%
content, the MWCNT conductive network was not formed for no electric
resistance was tested, so the β-phase content played the dominant role
on the increased output voltage. While the increased MWCNT particles
on the cell wall (Fig. 12A-C) improved the load transfer and charge
output at the interface of the nanocomposite foam during the process of
the periodic compressing, further enhancing the piezoelectric perfor­
mance. However, when MWCNT content reached 2%, the over intensive
cell structure and the filler network were more inclined to fabricate the
inner conductive network (Fig. 12D), consuming large charges. This
influence might be greater than the increased β-phase content, contrarily
leading to the sharp decline in power generation performance, espe­
cially in the case of the periodic compression.
With the increase of the acceleration rate, larger compressive force
generated and exerted on PVDF foaming part, leading to the bigger

7
D. Xu et al.
Fig. 11. Output voltage of PVDF and PVDF/MWCNT foaming parts.
deformation of the foaming part and the denser MWCNT particles, so
induced more remarkable polarization phenomena and improved the
output voltage. Under 7 m/s2 acceleration rate, the output voltage of the
foaming parts with 1.5% MWCNT reached 6.5 V, which could lighten
four LEDs, each with a forward voltage of 1.5 V, as shown in Fig. 12E.
Fig. 12. SEM images of dispersion of MWCNT on the cell wall (A: pure, B: 0.5% MWCNT, C: 1.5% MWCNT), schematic illustration of structure change in foaming
part during the periodic compression (D) and lighting process of LEDs (E).
8
Composites Science and Technology 192 (2020) 108108
4. Conclusion
By using scCO2 bead foaming technology, PVDF/MWCNT nano­
composite foaming parts with 3D geometry and excellent piezoelectric
properties were successfully fabricated. The homogeneous dispersion of
MWCNT in PVDF matrix was achieved via a simple ball milling mixing
method. Ascribing to the heterogeneous nucleation and the enhance­
ment of the well-dispersed MWCNT particles embedded in or attached to
the cell walls, more unique and denser cells were formed, leading to the
increase of the compressive strength of the foaming parts. Compared
with pure PVDF foaming part, the cell density of the composite foaming
part with 1.5% MWCNT was enlarged from 3.4 � 105 cells/cm3 to 1.7 �
106 cells/cm3 and the cell diameter was correspondingly decreased from
147.2 μm to 82.3 μm, while the compressive strength at 10% strain
enhanced to 3.1 MPa, approximately 55% higher than that of pure PVDF
foaming part (2.0 MPa). More importantly, MWCNT influenced the
crystal behaviors of PVDF especially with the assistance of scCO2, which
plasticized PVDF matrix and further led to the expansion and squeeze of
PVDF molecular chains during the cell growth and bead sintering pro­
cess in the confined part foaming space, thus inducing the trans­
formation of more α-phase PVDF to β phase. In this way, the
piezoelectric performance of foaming part with MWCNT was greatly
improved, and the maximum output voltage reached at MWCNT content
of 1.5%, i.e. 6.5 V, meaning that our PVDF/MWCNT nanocomposite
foaming parts presented the promising future in the electronic
applications.
D. Xu et al.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
CRediT authorship contribution statement
Dawei Xu: Conceptualization, Investigation, Writing - original draft.
Huili Zhang: Methodology, Formal analysis. Lian Pu: Resources, Data
curation. Li Li: Visualization, Writing - review & editing.
Acknowledgements
The authors are gratefully for the financial support from the National
Natural Science Foundation of China (51720105012 and 51721091) and
Sichuan Province (2019ZDZX0018).
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