The Journal of Supercritical Fluids 184 (2022) 105555

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The Journal of Supercritical Fluids

journal homepage: www.elsevier.com/locate/supflu

Structure disorder observation of fluoropolymers composed of vinylidene

fluoride and tetrafluoroethylene in supercritical CO2 using time-resolved
small- and wide-angle X-ray scattering
Kohei Yamanoi a, b, 1, Satoshi Shibuta c, 1, Atsushi Shiro a, Masao Noumi b,
Melvin John F. Empizo a, Marilou Cadatal-Raduban a, d, Nobuhiko Sarukura a,
Keiko Nishikawa e, f, Takeshi Morita e, *
a
Institute of Laser Engineering, Osaka University, 2-6 Yamadaoka, Suita, Osaka 565-0871, Japan
b
Technology and Innovation Center, Daikin Industries, LTD., 1-1, Nishi-Hitotsuya, Settu, Osaka 566-8585, Japan
c
Department of Physics, College of Humanities and Sciences, Nihon University, 3-25-40, Sakurajosui, Setagaya, Tokyo 156-8550, Japan
d
School of Natural Sciences, Massey University, Albany, Auckland 0632, New Zealand
e
Department of Chemistry, Graduate School of Science, Chiba University, Chiba 263-8522, Japan
f
Toyota Physical & Chemical Research Institute, Nagakute, Aichi 480-1192, Japan

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• Vinylidene fluoride and tetrafluoro­

ethylene copolymers were synthesized.
• SC CO2 was applied as an SC fluid Compression molding
for WAXS
Process of structure disorder
stimulus to synthesized fluoropolymers. copolymer with
VdF:TFE = 5:5
• Time-resolved mesoscopic structural
changes in fluorocopolymers were
investigated. Melt molding copolymer with
• Little change in fluoropolymer crystal­ for time-resolved SAXS VdF:TFE = 8:2

linity was observed after SC CO2

application. 0 400 800 1200
• Higher vinylidene fluoride content SC CO 2 application time / s

enhanced tolerance to SC CO2 stimulus. Higher VdF ratio Tolerance Enhancement

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

Keywords: Fluoropolymers have a growing range of applications in many industries. Neat fluoropolymers and fluorinated
Fluoropolymer copolymers were prepared via the suspension polymerization method with entire mass ratio of vinylidene
Supercritical CO2 fluoride (VdF) and tetrafluoroethylene (TFE). Supercritical CO2 was applied as a fluid stimulus to the fluo­
Small-angle X-ray scattering
ropolymers. An increase in structural disorder was investigated using time-resolved small-angle X-ray scattering
Wide-angle X-ray scattering
(SAXS). The SAXS change induced by the stimulus proceeded more slowly with increasing VdF ratio of the
Vinylidene fluoride
Tetrafluoroethylene copolymer, suggesting that the higher VdF content contributes to the tolerance of microvoid formation and the
corresponding onset of breakdown in the polymer material. The degree of crystallinity of the fluoropolymers was
evaluated using wide-angle X-ray scattering, showing the degree of crystallinity was similar before and after the

Abbreviations: VdF, vinylidene fluoride; TFE, tetrafluoroethylene; PVdF, poly(vinylidene fluoride); PTFE, poly(tetrafluoroethylene); polyVdF–TFE, poly(vinyli­
dene fluoride-co-tetrafluoroethylene); SC, supercritical; CO2, carbon dioxide; SAXS, small-angle X-ray scattering; WAXS, wide-angle X-ray scattering; XRD, X-ray
diffraction; SWAXS, SAXS/WAXS.
* Corresponding author.
E-mail address: moritat@faculty.chiba-u.jp (T. Morita).
1
KY and SS contributed equally

https://doi.org/10.1016/j.supflu.2022.105555
Received 4 January 2022; Received in revised form 14 February 2022; Accepted 16 February 2022
Available online 25 February 2022
0896-8446/© 2022 Elsevier B.V. All rights reserved.
K. Yamanoi et al.
stimulus. Time-resolved and in-situ SAXS/WAXS measurements were carried out on the copolymer with a ratio of
VdF:TFE = 8:2 as the copolymer having the highest VdF content studied here.
1. Introduction
Fluoropolymers have increasing applications in many industries. The
fluoropolymers composed of vinylidene fluoride (VdF) and tetrafluoro­
ethylene (TFE) show excellent properties in chemical resistance, me­
chanical strength, hydrophobicity, thermal stability, low surface
energies, low coefficients of friction, and low dielectric constants [1–4].
In the viewpoint of chemical bonding, these excellent properties are
predominantly caused by the electronic structure of the fluorine (F)
atom and the stable carbon–fluorine (C–F) covalent bonding. Further­
more, the unique intramolecular and intermolecular interactions be­
tween the polymers’ fluorinated segments and the main chains of the
polymers contribute to the advantageous properties of the fluoropol­
ymers composed of VdF and TFE [5].
Considering their structure and composition, fluoropolymers are
classified as partially fluorinated polymers or perfluoropolymers.
Partially fluorinated polymers contain F and hydrogen (H) atoms in their
chemical structures, whereas perfluoropolymers only contain F atoms.
For example, poly(vinylidene fluoride) (PVdF) is a highly processable
and mechanically strong partially fluorinated polymer, whereas poly
(tetrafluoroethylene) (PTFE) is a chemically robust and heat-resistant
perfluoropolymer. A copolymer composed of VdF and TFE is thus ex­
pected to exhibit the desirable properties of high chemical resistance,
thermal stability, and mechanical strength, combining the characteris­
tics of both the partially fluorinated polymer PVdF and the per­
fluoropolymer PTFE.
PVdF and the derived fluoropolymers have been already used as
membrane fibers for applications related to water distillation [6–8].
Among their different applications, the copolymers composed of VdF
and TFE are valuable for their uses related to the packing and linings of
high-pressure vessels. This is because the Young modulus of PVdF is one
order of magnitude larger than that of PTFE, whereas the PTFE is rela­
tively rubbery [9,10]. Thus, the Young’s moduli of these fluoropolymers
have been systematically used to evaluate their pressure tolerance under
various conditions. Although PVdF and PTFE both appear to endure
high-pressure environments, their breakdown begins at the microscopic
level and manifests as distortions, as well as the irreversible stretching or
compression of the molecular chains in the fluoropolymers. Conse­
quently, the ability to directly observe the microscopic morphology of
the material is essential in evaluating the onset of fluoropolymer dam­
age. The stretching and compression of molecular bonds during the
application of high-pressure carbon gases have been observed in several
polymers using attenuated total reflection infrared (ATR-IR) spectros­
copy [11]. Thurecht et al. utilized high-pressure nuclear magnetic
resonance (NMR) to investigate the effects of swelling on the linear
low-density polyethylene under supercritical (SC) carbon dioxide (CO2)
conditions [12].
The small-angle scattering (SAS) of neutrons and X-rays is one of the
most effective methods to study the structure on the mesoscopic length
scale. Marigo et al. have investigated the lamellar structure that consists
of both amorphous and crystal phases in the perfluorinated copolymers
of tetrafluoroethylene using the small-angle X-ray scattering (SAXS)
[13]. The SAXS method has been used to clarify the stressed or stretched
bulk PVdF along with PVdF fibers and sheets, showing deformation of
the crystalline and amorphous phases in PVdF [14–16]. Tang et al. have
analyzed the deformation of PTFE during stretching and its
radiation-induced morphological transformation [17]. However, the
structural changes on the mesoscopic length scale induced by stimuli
using the SAS method have not been reported for copolymers composed
of both VdF and TFE.
The SC CO2 is widely applied to various green and sustainable
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The Journal of Supercritical Fluids 184 (2022) 105555
process applications, such as alternative chemical extraction media, heat
exchangers, fine particle synthesis, sterilization, and surface cleaning
[18–27]. Furthermore, it is well known that the SC CO2 has the higher
chemical activity than nonpolar SC fluids due to the quadrupole moment
of the CO2 molecule. In this study, an SC CO2 treatment was applied as
an SC fluid stimulus to fluoropolymers. The fluoropolymers of PVdF,
PTFE, and copolymers composed of both VdF and TFE were synthesized
through the suspension polymerization method with entire range of
polymerization ratios. The stimulus-induced structural changes of the
copolymers were investigated using time-resolved SAXS measurements.
The wide-angle X-ray scattering (WAXS) method was utilized to analyze
changes in the crystallinity of the fluoropolymers induced by the stim­
ulus. Furthermore, the time-resolved and in-situ SAXS/WAXS (SWAXS)
measurements were carried out on the copolymer with a ratio of VdF:
TFE = 8:2, which was selected as the copolymer having the highest VdF
content studied here.
2. Experimental
2.1. Material preparation
PVdF, PTFE, and the copolymer poly(vinylidene fluoride-co-
tetrafluoroethylene), abbreviated as poly(VdF–TFE), with different
mass ratios (w/w) of VdF (–CH2–CF2–) and TFE (–CF2–CF2–) were pro­
vided by Daikin Industries, Ltd. The polymers were synthesized using
the suspension polymerization method; this procedure is similar to that
reported in Ref. [28]. The ratios used for the poly(VdF–TFE) synthesis
were set at VdF:TFE = 8:2, 6:4, 5:5, 4:6, and 3:7. Considering the
structure control in the synthesis, the prepared poly(VdF–TFE) was
classified as a random copolymer.
To obtain a sample that was appropriate for the WAXS measure­
ments, the synthesized polymer powder was formed into pellets (see
Fig. 1a) via the compression molding method. The polymer powder was
placed in cylinders under pressurizing at 10–60 MPa and heating at
temperatures from 200◦ to 380◦ C with adjusting the conditions to pre­
vent void formation in the material and to maintain sample uniformity.
For the SAXS, ultra-SAXS (U-SAXS), and SWAXS measurements, the
synthesized polymer powder was formed into a rod of 3 mm in diameter
Fig. 1. (a) Sample pellet prepared by compression molding for WAXS mea­
surements. (b) Sample rod of 3 mm in diameter prepared by melt molding for
time-resolved SAXS, U-SAXS, and SWAXS measurements. Disk of 0.6 mm in
thickness indicated by red arrow was used for the SWAXS measurements. L-
shaped tool is an M3-hexagonal wrench included for scale.
K. Yamanoi et al.
(Fig. 1b) via the melt molding method. The polymer powder was melted
by heat treatment for the molding process and then solidified by cooling.
The polymer was passed through 3-mm-diameter stainless steel die with
a heat treatment at 300 ◦ C.
2.2. Combined SAXS and U-SAXS
The combined SAXS and U-SAXS measurements were performed
using the BL19B2 station at SPring-8 of the Japan Synchrotron Radiation
Research Institute (JASRI). The scattering signals were acquired using a
two-dimensional semiconductor detector (PILATUS 2 M, Dectris). The
distance from the sample to the detector was set at 3107 and 41,000 mm
for the SAXS and U-SAXS measurements, respectively. Considering the
long path length of U-SAXS measurements, the X-ray energy was set at a
high value, 18.0 keV, (λ = 0.0689 nm, λ: wavelength). The exposure
time was adjusted to 60 and 300 s for the SAXS and U-SAXS measure­
ments, respectively. The observable q-region was evaluated to be
0.0580–2.91 nm− 1 for the SAXS and 0.00440–0.200 nm− 1 for the U-
SAXS, where q is the scattering parameter defined by 4πsinθ/λ (2θ:
scattering angle). The absorption correction was examined using the
absorption factor, μl (μ: linear absorption coefficient, l : sample thick­
ness), determined using the direct-beam monitoring apparatus implan­
ted in the beamstop. The background intensity was subtracted by
background measurement using the relation of I = Iobserved ∙exp⁡(μl ) −
Ibackground , where Iobserved is the experimentally observed intensity with
the sample polymer and Ibackground is the experimentally measured
background intensity. For the SAXS measurements in this study, the
correction of absorption and background was performed in the same
manner. The SAXS and U-SAXS signals were normalized using the cali­
bration factor determined from the standard glassy carbon
measurements.
2.3. Time-resolved SAXS
The time-resolved SAXS measurements were carried out on the poly
(VdF–TFE) with ratios of VdF:TFE = 5:5 and 8:2 using the BL19B2 sta­
tion at SPring-8 of the JASRI. To effectively extract the scattering signal
from the supercritical fluid and polymer system, the X-ray energy was
set to be the value of 18.0 keV, (λ = 0.0689 nm); this value is higher
than that used in a typical SAXS experiment. The scattering signals were
acquired using a two-dimensional semiconductor detector (PILATUS
2 M, Dectris). The sample-to-detector distance was set to 3107 mm. The
acquisition interval and exposure time were set to 20 and 10 s, respec­
tively. During the measurements, the SC CO2 treatment was kept at a
constant temperature and pressure of 60 ◦ C and 10 MPa, respectively.
The SC CO2 was loaded from the outside of the beam line hutch using a
high-pressure apparatus specifically designed for this study; this allowed
for the time-resolved signals to be acquired from the initial state (at time
zero) after the stimulus began. The prepared rod-shaped polymer sample
was cut to form a disk with a thickness of 1.00 ± 0.02 mm for the time-
resolved SAXS measurements (0.98 and 1.02 mm in thickness for VdF:
TFE = 5:5 and 8:2, respectively) using a fine cutter. The observable q-
region was determined to be 0.0580–2.91 nm− 1.
2.4. SWAXS
The time-resolved and in-situ SWAXS signals were acquired using the
SWAXS apparatus set at the BL-6A station of the Photon Factory (PF) of
the High Energy Accelerator Research Organization (KEK), Tsukuba,
Japan [29]. During the SWAXS measurements, the X-ray absorption
factors of the samples were measured simultaneously using an in-situ
beam monitoring apparatus with a silicon photodiode device [29,30].
The wavelength of the X-rays used was set to λ = 0.150 nm. The tem­
perature and pressure were kept constant at 60 ◦ C and 10 MPa,
respectively. The scattering signals were measured using the
3
The Journal of Supercritical Fluids 184 (2022) 105555
two-dimensional semiconductor detectors of PILATUS 1 M (Dectris) and
PILATUS 100 K (Dectris) for the SAXS and WAXS measurements,
respectively. The distance from the sample to the detectors for the SAXS
and WAXS measurements was set to be 1446 and 254 mm, respectively.
For the SAXS measurements, the exposure time and interval were set at
10 and 120 s, respectively. The exposure time and interval for the WAXS
measurements were set at 60 and 120 s, respectively; these values were
used to take into account the difference in scattering intensity between
the SAXS and WAXS measurements. The prepared rod-shaped sample
was cut to form a disk with a thickness of 0.6 mm for the SWAXS
measurement using a fine cutter, as shown in Fig. 1b.
2.5. Sample holder
An SC fluid sample holder was used for the time-resolved SAXS and
SWAXS measurements. The sample holder was made of the titanium
alloy (Ti–6Al–4V). A pair of single crystal diamond disks of 5.0 mm in
diameter and 0.70 mm in thickness (type Ib, Sumitomo Electric In­
dustries, Ltd.) were used as the X-ray scattering window. The diamond
disks were sealed to the cell body by applying stress from the outside to
the inside using a hand-made gold O-ring. The sealing system permits
the high-pressure experiments under keeping the sample thickness
constant. A K-type thermocouple (class I, Chino Co.) and a compact
strain gage (PGL-A, Kyowa Electronic Instruments Co., Ltd.) were used
to measure the temperature and pressure, respectively. The measure­
ment system is suitable for SAXS experiments at temperatures of up to
350 ◦ C and pressures of up to 40 MPa, including in high-temperature SC
conditions.
2.6. WAXS
The WAXS measurements were performed using a Rigaku SmartLab
X-ray diffractometer. The X-rays of copper (Cu) Kα radiation
(λ = 0.1542 nm) was used as the probe under a 40 kV tube voltage and a
40 mA tube current. The scanning conditions were as follows: step size,
0.02◦ ; step speed, 10◦ /min; scattering angle 2θ range, from 5◦ to 60◦ ;
and scanning resolution, 0.0002◦ . For 4 h, the polymer samples were
subjected to an SC CO2 environment at a temperature and pressure of
60 ◦ C and 10 MPa, respectively. The degree of crystallinity for each
polymer was determined using the profile fitting software provided by
Smartlab Studio II before and after the SC fluid treatment. The observed
WAXS signals were deconvoluted into broad curves (amorphous phase
contribution) and sharp diffraction patterns (crystal part contribution).
The degree of crystallinity was calculated from the ratio of the inte­
grated values in each region.
3. Results and discussion
3.1. Mesoscopic structure by SAXS and U-SAXS
The fundamental information on the polymer structure on the
mesoscopic scale was obtained using the combined SAXS and U-SAXS
signals. Fig. 2 shows the SAXS and U-SAXS profiles of the copolymers
with ratios of VdF:TFE = 3:7, 4:6, 5:5, 6:4, and 8:2. As shown in Fig. 2,
the first peak positions gradually shifted to the higher q-region as the
VdF ratio increased. The peak positions for VdF:TFE = 3:7 and 8:2 were
observed around q = 0.1 nm− 1 (63 nm in real space) and q = 0.3 nm− 1
(21 nm in real space), respectively. It is suggested here that the periodic
structure of the copolymers on the mesoscopic scale, and possibly its
lamella morphology, becomes more compact and tightened as the VdF
ratio becomes higher in the copolymer.
3.2. Mesoscopic structural change by time-resolved SAXS
As described previously, PVdF has an advantage in mechanical
strength, compared with PTFE. Furthermore, SC CO2 has the higher
K. Yamanoi et al. The Journal of Supercritical Fluids 184 (2022) 105555

1.6
10
10

1.2
5 VdF:TFE
10
VdF:TFE = 5:5
8:2
720 s
0.8 600 s
480 s
360 s
6:4 240 s
0
10 180 s
120 s
5:5 60 s
0.4 40 s
20 s
4:6 0s

10 3:7
10 10 10
0 0
scattering parameter q (nm ) 0 0.2 0.4 0.6
q (nm )
Fig. 2. Combined SAXS and U-SAXS profiles for poly(VdF–TFE) with ratios of
VdF:TFE = 8:2, 6:4, 5:5, 4:6, and 3:7. Fig. 3. Time-resolved SAXS intensities for poly(VdF–TFE) with ratio of VdF:
TFE = 5:5 during SC CO2 stimulus from its initial state (blue circle) to that
observed after a stimulus of 720 s in duration (red circle).
chemical activity compared with nonpolar SC fluids due to the quad­
rupole moment of the CO2 molecule. This study was focused on
analyzing poly(VdF–TFE) with a relatively high VdF proportion (not
neat PVdF) due to the possibility that it would exhibit the desirable
property of resilience to the SC CO2 exposure. The ratio of VdF:TFE VdF:TFE = 8:2
= 8:2 had the highest VdF content of the poly(VdF–TFE) materials 0.12
studied here. As a comparison, poly(VdF–TFE) with the ratio of a VdF:
TFE = 5:5 was also investigated to establish the possible VdF content 720 s
600 s
dependence on the tolerance to the SC CO2 treatment. 480 s
Fig. 3 shows the SAXS change for poly(VdF–TFE) with a ratio of VdF: 360 s
TFE = 5:5 during the SC CO2 stimulus. The SAXS intensities were 240 s
significantly increased by the stimulus. The SAXS increase was observ­ 180 s
0.08 120 s
able only in the relatively smaller-angle region. The peak position 60 s
observed in the SAXS measurements gradually shifted toward the low-q 40 s
region with increase in the application time; this indicates that the 20 s
formation of microvoids, structural disordering of the periodic structure, 0s
and swelling induced by the SC CO2 led to structural expansion on the
mesoscopic scale, as has been previously reported in the literature [10, 0.04
31–33]. The SAXS increase became slower and was almost saturated
around 720 s after the stimulus started, although the saturation time will
depend on experimental conditions, such as sample thickness, pressure,
and temperature.
Fig. 4 shows the SAXS change for the poly(VdF–TFE) with a ratio of
VdF:TFE = 8:2 during the SC CO2 stimulus. The aspects of SAXS change 0
for the poly(VdF–TFE) with a ratio of VdF:TFE = 8:2 were analogous to
those of the 5:5 poly(VdF–TFE); namely the significant increase in SAXS
0 0.2 0.4 0.6
intensities, the low-q shift, and the smaller change in the higher-q re­ q (nm )
gion. However, the SAXS increase at the lower q-region around q
Fig. 4. Time-resolved SAXS intensities for poly(VdF–TFE) with ratio of VdF:
= 0.1 nm− 1 was observed as much smaller than that for the 5:5 poly
TFE = 8:2 during SC CO2 stimulus from its initial state (blue circle) to that
(VdF–TFE). The rate of SAXS increase remained constant at 720 s after observed after a stimulus of 720 s in duration (red circle).
the stimulus started, indicating much slower change in the 8:2 poly
(VdF–TFE) compared with the 5:5 poly(VdF–TFE).
proceeded even after 1200 s of SC CO2 treatment, whereas the increase
Fig. 5 shows the changes in the SAXS intensities for poly(VdF–TFE)
in the case of the 5:5 poly(VdF–TFE) was saturated after around 600 s of
with a ratio of VdF:TFE = 5:5 and 8:2 as a function of the SC CO2
treatment. On the basis of the SAXS and combined SAXS/U-SAXS results,
application time. As shown in Fig. 5, the evaluation of the intensity in­
it is suggested that the characteristics such as the shortened-periodic
crease for the 8:2 poly(VdF–TFE) was much slower than that of the 5:5
morphology caused by the higher VdF content is one of the origins of
poly(VdF–TFE). The SAXS increase for the 8:2 poly(VdF–TFE) gradually
tolerance enhancement to SC CO2 stimulus.

4
K. Yamanoi et al.
4
VdF:TFE = 5:5
peak intensity change
3 assigned to the Miller indices of (100) and (110), respectively [34]. As
VdF:TFE = 8:2
2 3.4. XRD peak position change
1 around 20◦ , which can be associated with the XRD peak for (110) of
0 400 800 1200
SC CO 2 application time (s)
Fig. 5. Changes in SAXS intensities at peak position for poly(VdF–TFE) with
ratios of VdF:TFE = 5:5 and 8:2 as a function of SC CO2 application time. Initial
position at 0 s was normalized to 1 on the vertical axis.
3.3. Crystal structure by WAXS
Fig. 6 shows the WAXS signals for PVdF, PTFE, and poly(VdF–TFE)
with the ratios of VdF:TFE = 3:7, 4:6, 5:5, 6:4, and 8:2. The signals were
acquired for the polymers before and after the SC CO2 treatment stim­
ulus as static measurements. The X-ray diffraction (XRD) for the PVdF
was observed at 17.8, 18.4, 20.1, 25.6, 36.0, and 37.2◦ , which were
assigned to be the Miller indices of (100), (020), (110), (120), (200), and
(210)/(040) in an α-phase PVdF, respectively. As shown in Fig. 6, the
WAXS signals for PVdF remained in the same manner after the SC CO2
Fig. 6. WAXS for PVdF, PTFE, and poly(VdF–TFE) with ratios of VdF:TFE = 3:7, 4:6, 5:5, 6:4, and 8:2 before and after SC CO2 treatment stimulus. Curves labeled
“before” and “after” indicate before and after SC CO2 application, respectively.
5
The Journal of Supercritical Fluids 184 (2022) 105555
stimulus. In contrast with PVdF fibers that change their structure from
α-phase to β-phase under the application of stress [14–16], the crystal
structure of PVdF was maintained in the same manner after the SC CO2
stimulus. The XRD for PTFE was observed at 18.0 and 31.6◦ , which were
shown in Fig. 6, transitions in the crystal structure of PTFE, PVdF, and
poly(VdF–TFE) were not detected after the SC CO2 stimulus was applied.
The XRD pattern for the 8:2 poly(VdF–TFE) exhibited the peak
PVdF at 20.1◦ . As the TFE ratio increases, the peak position observed for
the 8:2 poly(VdF–TFE) at around 20◦ gradually shifted toward the XRD
for (100) of PTFE at 18.0◦ ; the lower angle shift indicates the expansion
of the dominant crystal structure. Fig. 7 shows the dominant peak po­
sition for the polymers including the change before and after the SC CO2
stimulus. As shown in Fig. 7, the 8:2 poly(VdF–TFE) showed the XRD at
the higher angle region, even though the polymer is a copolymer
composed of both VdF and TFE. This result indicates that the copolymer
with the higher VdF ratio has specifically tightened crystal structure.
The peak positions were seen to be maintained even after the stimulus
for the homopolymers and copolymers.
3.5. Degrees of crystallinity
The enhancement of the XRD height corresponds to further ordering
the crystal structure. Using the WAXS, the degrees of crystallinity were
determined for the polymers studied here before and after the SC CO2
stimulus. The evaluation procedure of the degree of crystallinity for the
K. Yamanoi et al. The Journal of Supercritical Fluids 184 (2022) 105555

Fig. 7. Dependence of VdF:TFE ratios on dominant XRD peak positions before

and after SC CO2 treatment stimulus. Labels of “before” and “after” indicate
before and after SC CO2 treatment, respectively.

typical ratios is shown in Fig. 8. The procedure for all of the polymers
studied here is shown in Fig. S1. The degree of crystallinity and differ­
ence between before and after the SC CO2 stimulus are listed in Table 1.
The WAXS signals were deconvoluted into broad curves (representing
the amorphous phase contribution) and sharp diffraction patterns
(representing the crystal phase contribution). The degree of crystallinity
was calculated from the ratio of the integrals of the amorphous phase
and crystal phase contributions. Although the degrees of crystallinity
were similar before and after the stimulus, a slight increase after the
stimulus was identified in all the polymers studied here. Considering the
enhancement of the crystallinity induced by the SC CO2 treatment, it is
suggested that the SAXS increase shown in Figs. 3 and 4 is related to the
enhancement of structural disorder in the amorphous phase area. On the
basis of the present SAXS and WAXS investigations presented here, it is
proposed that a key feature for the enhanced tolerance is considered as
structural shortening on both the mesoscopic and microscopic length
scales due to polymerization with the higher VdF ratio in the copolymer.
For semicrystalline polymers, little penetration by the SC CO2 fluid is
observed in the crystalline phase, whereas the degree of swelling in the
amorphous phase part is relatively dominant. High-pressure NMR
studies indicate that the high-pressure condition affects the chain
mobility in the amorphous region of semicrystalline polymers [12,
37–39]. The present results depicting the difference in the observed
structural changes between the amorphous phase and crystalline part
are consistent with the literature knowledge.

3.6. Time-resolved and in-situ SWAXS

In this study, the SAXS change induced by the SC CO2 stimulus was
investigated using time-resolved measurements. The static WAXS mea­
surements were conducted using a laboratory X-ray diffractometer with
a goniometer and reflective optics to permit the quantitative determi­
nation of the degree of crystallinity of a polymer. The SAXS and WAXS
signals discussed above were not acquired as simultaneous observations.
Time-resolved and in-situ SWAXS investigation was examined for the 8:2
poly(VdF–TFE), which was selected as a typical polymer possibly having
the highest tolerance property developed in the present stage.
Fig. 9 shows the SWAXS signals under SC CO2 stimulus of 60 ◦ C and
10 MPa. As shown in Fig. 9a, the significant increase in SAXS intensities
and the gradual low-q shift were observed; the changes in SAXS were the
same manner as the observation shown in Fig. 4. The observed change in
the SAXS was faster than that shown in Fig. 4 due to difference in the Fig. 8. Evaluation procedure of degree of crystallinity at typical VdF/TFE ra­
sample thickness. The equilibrium time is comparable to study focused tios. WAXS intensities were deconvoluted into broad curves (amorphous phase
on the swelling kinetics of semicrystalline polymer under a SC CO2 contribution) and sharp diffraction patterns (crystal phase part). Black solid
condition with the different pressure and temperature by in-situ optical lines, black dotted lines and red dotted lines represent experimental data,
observation [40]. As shown in Fig. 9b, the peak position in WAXS deconvoluted fitting, and total fitted results, respectively. Labels of “before”
and “after” represent before and after SC CO2 application, respectively.
remained around the same q-value. This is evidence that the crystalline
part is stable even when subjected to the SC CO2 treatment stimulus. As
also shown in Fig. 9b, a decrease in the WAXS intensities around q

6
K. Yamanoi et al. The Journal of Supercritical Fluids 184 (2022) 105555

Table 1
Degrees of crystallinity for PVdF, PTFE, and poly(VdF–TFE). Labels of “before”
(a) SAXS
and “after” represent before and after SC CO2 application, respectively. 80 80
VdF:TFE (w/w) Degree of crystallinity (%) 12 min
10 min
Before After Difference (After – Before) 60 min
10:0 (PVdF) 42.4 43.0 0.6 8 min
8:2 36.4 39.5 3.1
60

I(q) (arb. units)

6:4 44.6 46.5 1.9 60 6 min
5:5 54.1 56.1 2.0
4 min
4:6 62.0 63.5 1.5
3:7 65.8 68.4 2.6 40
0:10 (PTFE) 48.9 49.2 0.3 2 min

= 12 nm–1 was observed under application of the SC CO2 condition. The 40 0 min
20 after CO2
deconvolution analysis for the 8:2 poly(VdF–TFE) shown in Fig. 8 sug­
initial state
gests that the shoulder peak around q = 12 nm–1 could be generated by
the amorphous phase contribution. Therefore, the profile change in­
dicates an enhancement of the degree of crystallinity in the polymer. 0
The time-resolved WAXS observations are consistent with the results 20 0 0.2 0.4 0.6
obtained via static measurements, which indicates an increase in the q (nm )
0 min
degree of crystallinity by 3.1% as listed in Table 1.
Fig. 10 shows the change in the mesoscopic periodic length, Lmeso­
scale, as a function of the SC CO2 application time. The periodic length
was estimated from the q-values of the SAXS peak position using the
relation Lmesoscale = 2π/q. The peak position was carefully determined 0
via a fitting analysis using the Gaussian function. Although the satura­ 0 1 2 3 4
tion time for the 8:2 poly(VdF–TFE) was not identified in Figs. 4 and 5, q (nm )
the expansion and saturation process were clearly observed in the time-
resolved signals due to thinner sample used (0.6 mm in thickness). As
shown in Fig. 10, the value of Lmesoscale changed from 25.8 nm at 0 min
to 27.1 nm after a 10-min-application time. The result indicated a 5.0%
b) WAXS
expansion of the periodic structure on the mesoscopic scale induced by 10000
SC CO2 application. After the saturation time of ~10 min, the change in
the periodic length plateaued even while subject to a continuing SC CO2 initial state
exposure. The significant expansion and saturation of the change were
similarly observed for the periodic length change in the 5:5 poly
(VdF–TFE) discussed in Fig. 3.
8000

4. Conclusions SC CO 2 application
from 0 min
Neat fluoropolymers and fluorinated copolymers were prepared 6000
to 12 min
through the suspension polymerization method with the mass ratios of
VdF:TFE = 10:0 (PVdF), 8:2, 6:4, 5:5, 4:6, 3:7, and 0:10 (PTFE). The red : 60 min
fundamental structural information on the copolymers on the meso­
scopic scale was obtained using the combined SAXS and U-SAXS mea­
4000
surements. The SAXS and U-SAXS signals suggested that the periodic
structure on the mesoscopic scale become more shortened with
increasing the VdF ratio in the copolymers. An SC CO2 at 60 ◦ C and
10 MPa was applied as an SC fluid stimulus to the fluoropolymers. The
process of structural disorder on the mesoscopic length scale induced by 2000
the stimulus was measured by the time-resolved SAXS technique. The
SAXS change proceeded more slowly with increasing VdF ratio in the
copolymers. The degrees of crystallinity of the fluoropolymers studied
here were evaluated using the WAXS and peak deconvolution analyses.
0
After the SC CO2 stimulus was applied, the degree of crystallinity and 10 12 14 16 18
peak position in the diffraction patterns were analogous to those before
the stimulus. The time-resolved and in-situ SWAXS investigation was q (nm )
examined for the 8:2 poly(VdF–TFE). The SWAXS signals confirmed the
results of the SAXS and WAXS investigations. The SWAXS result indi­ Fig. 9. Time-resolved and in-situ SWAXS signals for poly(VdF–TFE) with ratio
of VdF:TFE = 8:2 under SC CO2 of 60 ◦ C and 10 MPa. (a) SAXS measurements.
cated 5.0% expansion of the mesoscopic periodic structure by SC CO2
Inset shows SAXS change in early stages of SC CO2 application. Dotted red line
application. On the basis of the present SAXS, WAXS, and SWAXS in­
represents peak position at initial state. (b) WAXS measurements. Shoulder
vestigations, it is proposed that the specific properties such as shortened- peak around q = 12 nm–1 highlighted by green arrow was assigned as being
periodic morphology on the mesoscopic scale and compact crystal from amorphous phase in poly(VdF–TFE) with ratio of VdF:TFE = 8:2, ac­
structure by polymerization with the higher VdF ratio are the origins of cording to deconvolution for 8:2 copolymer shown in Fig. 8.
tolerance enhancement to SC CO2 stimulus.

7
K. Yamanoi et al.
28
saturation
Lmesoscale (nm)
27
expansion
5% expansion
by SC CO 2
26
start CO2 injection
25
0 2 4 6 8 10 12 14 16
application time (min)
Fig. 10. Change in mesoscopic periodic length, Lmesoscale, for the 8:2 poly
(VdF–TFE) as a function of SC CO2 application time. Values of Lmesoscale were
calculated from the time-resolved SAXS profiles obtained from SWAXS mea­
surement shown in Fig. 9. Result at 0 min includes CO2 fluid injection process
due to experimental operation.
Koga and coworkers found that the swelling of polymer materials
and the porosity in polymer induced by SC treatment depend on the
density fluctuation (inhomogeneity of molecular distribution) of SC CO2
[32,33]. The time-resolved investigation presented here should be per­
formed in more detail under different conditions including temperature,
pressure, and density fluctuation.
CRediT authorship contribution statement
Kohei Yamanoi: Investigation, Satoshi Shibuta: Investigation,
Atsushi Shiro: Investigation, Resources, Masao Noumi: Resources,
Project administration, Investigation, Melvin John F. Empizo: Inves­
tigation, Marilou Cadatal-Raduban: Investigation, Nobuhiko Sar­
ukura: Supervision, Funding acquisition, Keiko Nishikawa:
Supervision, Takeshi Morita: Team, Conceptualization, Data curation,
Investigation, Writing- Reviewing and Editing, Project administration,
Funding acquisition.
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.
Acknowledgments
We express thanks to SPring-8 at JASRI for the opportunity to
perform the measurements of time-resolved SAXS and combined SAXS/
U-SAXS. TM and MN would like to express appreciation to Dr. Keiichi
Osaka at JASRI for his helpful support for the time-resolved SAXS and U-
SAXS measurements. We are grateful to PF at KEK for providing the
opportunity to perform the SWAXS measurement. TM expresses appre­
ciation to Prof. Nobutaka Shimizu and the stuff members at PF for their
helpful support for the SWAXS experiment. The authors are grateful to
Mr. Y. Yong, Mr. T. Taniguchi, Ms. V. C. Agulto, Mr. Y. Minami, Dr. Y.
Abe, Dr. M. V. Luong, Dr. J. L. F. Gabayno, and Prof. T. Shimizu for their
helpful support. This work was financially supported by Daikin In­
dustries, LTD. NS and KY express thanks to a JSPS Grants-in-Aid for
Scientific Research (KAKENHI, No. 18K04727), Creation of Research
Platforms and Photon Beam Platform. The authors thank Mr. Jason Hart
for a careful reading of this paper.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
8
The Journal of Supercritical Fluids 184 (2022) 105555
online version at doi:10.1016/j.supflu.2022.105555.
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