Polymer Testing 23 (2004) 791–796

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Analysis Method

Vibrational spectrum of PVDF and its interpretation

Ye. Bormashenko, R. Pogreb, O. Stanevsky, Ed. Bormashenko

Laboratory of Polymer and Composite Materials, The College of Judea and Samaria, The Research Institute, Ariel 44837, Israel
Received 26 February 2004; accepted 1 April 2004

Abstract

IR spectra of poled and non-poled PVDF films were studied. Non-poled extruded samples were annealed and
cooled at different cooling rates. Then, FTIR spectra of all samples were taken under scanning with different
diaphragms. It was found that the spectra and their interpretation depend strongly on the scale of the scanning pro-
cedure for both poled and non-poled films. Scanning by a diaphragm with a diameter D close to the size of b-phase
domains d reveals the presence of the b-phase in the annealed non-poled PVDF, whereas spectra obtained with a
‘‘large’’ diaphragm (D4d) do not show discernable peaks inherent to the b-phase. Cooling rate influence on the
b-phase contents is strong. When the diameter of the diaphragm D and size of crystalline c inclusions are of the same
magnitude, peak splitting is observed in the poled PVDF.
# 2004 Elsevier Ltd. All rights reserved.

Keywords: PVDF; a; b; c; d-phases; IR spectrum; Thermal history; Boled; Splitting of peaks; Cooling rate

1. Introduction the a- and b-phases, with the a fraction increasing with

In 1969, Kawai discovered a significant piezoelectric
effect in PVDF [1]. Since then, extensive studies have
been made on the piezoelectricity of PVDF. Excellent
mechanical properties, high continuous use of tempera-
ture and strong piezoelectricity made possible various
scientific and industrial applications of PVDF. PVDF
was applied widely as an ultrasound transducer in non-
destructive evaluation and medical ultrasound [2–4]. At
the same time, the essence of piezoelectricity in PVDF
is not still clearly understood.
It was shown that PVDF exhibits at least four crys-
talline phases, known as a, b, c, and d [5]. The apolar
a-phase predominates at melt-crystallization below 160
v
C. The oriented polar b-phase is normally obtained by
drawing of a-phase films at temperatures between 70
v
and 100 C. The unoriented b-phase may be obtained
by crystallization from dimethylformamide (DMF) or
dimethylacetamide solutions at temperatures below
v obtained by different groups in Table 1.
70 C [6]. Higher temperatures result in a mixture of


Corresponding author. Tel.: +972-3-906-6134; fax: +972-
3-906-6834.
E-mail address: edward@ycariel.yosh.ac.il (E. Borma-
shenko).
temperature increase. The polar c-phase may be
obtained from both solution and melt-crystallization at
v
temperatures above 160 C or by annealing a-phase
v
samples between 175 and 185 C. The d-phase, a polar
version of the a-phase, may be obtained by polarizing
of the a-phase in the strong electric fields. All these
phases differ structurally: b-phase (which is responsible
for piezo- and pyro-electrical properties of PVDF) pre-
sents all trans-TTT planar zigzag structure while a- and
d-phases present trans-Gauche TGTG0 sequences.
T3GT3G0 conformational structure is inherent for
c-phase [8,9].
The vibrational spectrum of PVDF gives valuable
information about the structure of PVDF, and it has
been under intensive investigation recently [5,8–10]. A
theoretical approach to the vibrational-mode analysis
of b-phase was performed by Li [11,12]. We have sum-
marized the experimental and theoretical results
In spite of significant efforts directed to interpret-
ation and calculation of the IR spectrum of PVDF, the
literature data are contradictory. For example, the
absorption peaks at 778 cm1 related by Gregorio and
Capitao to c-phase and 855 cm1 assigned by the same
researchers to a-phase, were not revealed by other

0142-9418/$ - see front matter # 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2004.04.001
792 Y. Bormashenko et al. / Polymer Testing 23 (2004) 791–796

Table 1 Thickness of Kynar films was 40 lm, and poled films

Vibrational mode wavenumbers (cm1) of PVDF 25 lm. Spectral study of the non-poled PVDF films
Band Phase Group and Assignment
was preceded by a standardization treatment, i.e., by
v
(cm1) vibrational annealing at 150 C for 1 h. According to E1 Mohajir
mode and Heymans, at this annealing temperature, most of
the thermomechanical history of the samples is erased
483 c 9
without altering their shape [13]. Annealing was carried
489 a 9
out by use of the laboratory press, Specac (P/N 15011/
511 b CF2 bending 8,9
530 a CF2 bending 8 25011), equipped with heated plates and automatic
615 a CF2 bending and 8,9 temperature controller. Then, non-poled samples were
skeletal bending cooled by ‘‘slow’’ and ‘‘rapid’’ cooling. Slow cooling
678 Polymer chain 9 was performed in the press with an average speed of
defects due to 0.1 K/min, and rapid cooling was realized by immedi-
head-to-head, ate immersion of the annealed samples into ice cold
tail-to-tail lin- water.
kages
766 a CF2 bending and 5,8,9
scelete bending 2.2. Experimental technique
778 c CH2 rocking 5
795 a CH2 rocking 5,8,9 The IR absorption spectrum of the PVDF films was
812 c CH2 out-of- 5,9 studied with the optical bench used by the authors pre-
plane wag viously for the investigation of laser-induced changes in
834 c 5 the absorption spectra of polymers and presented in
840 b or c CH2 rocking 5,8,9 Fig. 1. Spectra were taken by FTIR spectrometer under
855 a CH out-of-plane 5 sample-scanning using an iris diaphragm with a vari-
deformation able diameter [14]. A step of the scanning procedure
976 a CH out-of-plane 5,9
was 50 lm. Moving of the samples was carried out
deformation
1234 c CF out-of-plane 9,11,12
with a precise XYZ translator. A FTIR spectrometer
deformation Bruker 22 allowed spectral measurements in the band
1279 b CF out-of-plane 9,11,12 400–8000 cm1 (1.25–25 lm) with an accuracy of better
deformation than 1 cm1. All spectral measurements were done at
room temperature.

3. Observations and results

groups [5–9]. Gregorio and Capitao classify the strong
peak at 840 cm1 as inherent to c-phase, whereas other
investigators assign it to b-phase [5–9]. Theoretical
vibrational-mode analysis performed by Li leads to the
conclusion that only modes which are located in the
region 1020–1330 cm1 may be responsible for the
spontaneous polarization [11,12]. However, this infer-
ence contravenes experimental data obtained by other
investigators [8,9].
We applied first time scanning FTIR spectrometry
to PVDF films with a well-defined thermal history.
Change of the scale of the scanning procedure gave
valuable information about absorption spectra of
PVDF films and their conformational structure.
2. Experimental
2.1. Materials and films preparation
Two grades of PVDF were used in this work. We
performed our experiments with non-poled PVDF films
(trademark Kynar) supplied by Westlake Plastics Inc,
and poled PVDF supplied by Precision Acoustics Ltd.
3.1. Investigation of the absorption spectrum of the
non-poled PVDF
Fig. 2 presents the spectra of non-poled PVDF
samples annealed according to the aforesaid procedure
and cooled slowly. Absorption peaks at 1234 and
1279 cm1 are located in the band of PVDF strong
absorption, so we depict in Fig. 2 spectra, which lie
within 480–860 cm1 (fingerprint region for crystalline
phases of PVDF). Curve B presents the typical
spectrum obtained with a diaphragm of 5 mm (‘‘large’’
diaphragm), and curves A and C present spectra
obtained when the diameter of the diaphragm was 500
lm (‘‘small’’ diaphragm). First of all, we notice that
measurement with a diaphragm of 5 mm gives the same
result at every step of scanning, that is why we present
one spectral curve only (curve B). This spectrum is
innate to the a-phase of PVDF. Well-known peaks of
the a-phase located at 488, 532, 615, 766, and 795 (see
Table 1) could be recognized very distinctly. The peak
at 855 cm1 assigned by Gregorio and Capitao to the
a-phase is seen clearly as well.
 Y. Bormashenko et al. / Polymer Testing 23 (2004) 791–796 793

Fig. 1. Optical bench used for spectral measurements.

Curve B does not supply clear evidence about the
presence of the b-phase in the sample. The curve shows
weak and undecipherable peaks of the b-phase only.
The situation changed dramatically when the same
sample was scanned with a diaphragm of 500 lm
(curves A and C). Curve C demonstrates peaks
inherent for a-phase only, whereas curve A demon-
strates two distinct peaks inherent for the b-phase at
511 and 840 cm1. From 20 spectra taken continuously
under scanning of the sample, at least one shows
pronounced peaks of the b-phase. It is reasonable to
suggest that the sample comprises inclusions of the
b-phase dispersed in the a-phase. The peak disappears
on the next scanning step, hence the characteristic size
of b-inclusions is estimated as d  100 lm . Typical
dimensions of such inclusions according to Gregorio
and Capitao are also something near 100 lm.
Thus, it could be concluded that spectral data and
their correct interpretation depend strongly on the
diameter of diaphragm D, which must be compared to
the typical dimensions of the b-phase inclusions d.
When condition D4d is fulfilled (curve B) we obtain
an averaged spectrum, which demonstrates very slight
peaks of the b-phase. In the case of D  d (curves A
and C) the spectrum depends strongly on the dia-
phragm location under the scanning procedure. When
the diaphragm spans a domain of the b-phase, we
observe strong peaks inherent for it (curve A); and
when it does not, we recognize no presence of the
b-phase (curve C).
Fig. 3 presents spectral data taken when a rapidly
cooled sample was under investigation. It could be
recognized that the peaks innate to the b-phase were
strengthened very significantly in the rapidly cooled
PVDF films compared to the slowly cooled samples.
Curve B taken with a diaphragm of 5 mm demon-
strates the distinct peak of the b-phase at 840 cm1,
and the peak of the b-phase at 511 cm1 is recognized
as well. All spectra measured under scanning with a
diaphragm of 500 lm demonstrate peaks at 840 cm1:

Fig. 2. Absorption spectrum of annealed and slowly cooled non-poled PVDF. Spectra A and C were taken with a diaphragm of
500 lm, spectrum B measured with a diaphragm of 5 mm.
794 Y. Bormashenko et al. / Polymer Testing 23 (2004) 791–796

Fig. 3. Absorption spectrum of annealed and rapidly cooled non-poled PVDF. Spectra A and C were taken with a diaphragm of
500 lm, spectrum B measured with a diaphragm of 5 mm.

some of them demonstrate more sharp peaks (curve A)
and some of them relatively weak ones (curve C). It
could be concluded that cooling rate is important for
the formation of domains of b-phase in the PVDF
films.
A very similar situation was observed when poled
PVDF films were studied under the same FTIR scan-
ning: measurement with a diaphragm of 5 mm gives the
same result at every step of scanning, so we depict in
Fig. 4 only one curve B taken with a ‘‘large’’ dia-
phragm. A very strong peak at 880 cm1 is common
for a-, b- and c-phases, and could not be used for their
identification. Absorption peaks inherent for the
a-phase (488 and 765 cm1) and b-phase (507 cm-1) are
recognized. It is worth noting that the b-phase peak is
shifted slightly from its location in the non-poled
samples. We will show that variation of the scanning
scale reveals the presence of the c-phase.
First of all, we want to give special attention to the
peak at 600 cm1, which was not discussed by previous
investigators. This peak makes its appearance in the
spectra of PVDF membranes comprising a substantial
fraction of the b-phase [9]. The samples under investi-
gation demonstrate strong piezoelectric properties,
hence they also obviously contain a considerable frac-
tion of the b-phase. Thus, it is reasonable to relate the
absorption peak at 600 cm1 to the b-phase.
The spectrum taken with a ‘‘large’’ diaphragm
demonstrates a broad and strong peak located between
830 and 840 cm1. This peak is interpreted variously
by different investigators [5–9]. It was related both to
the b-phase and c-phase of PVDF. We believe that
scanning with a diaphragm of 500 lm sheds new light
on the nature of this peak. Some of the spectra taken
with a ‘‘small’’ diaphragm are very similar to the spec-
tra obtained with the ‘‘large’’ one. But some of them

Fig. 4. Absorption spectrum of poled PVDF. Spectrum A was taken with a diaphragm of 500 lm, spectrum B with a diaphragm
of 5 mm.
 Y. Bormashenko et al. / Polymer Testing 23 (2004) 791–796 795

Fig. 5. Splitting of poled PVDF absorption peak. Curve A taken with a diaphragm diameter of 500 lm, curve B with a diaphragm
diameter of 5 mm. Presence of b- and c-phases is recognized.

(on the average two spectra from every 20 measure-
ments) bring to light a spectrum given by the curve A
(Fig. 4).
The peak under discussion splits into two distinct
peaks located at 831 and 837 cm1 (see Fig. 5, which
presents the splitting of the peak on a larger scale). We
propose an interpretation of this splitting, correlating
with the data obtained by other investigators: the peak
at 837 cm1 we relate to the b-phase, and peak at 831
cm1 we assign to the c-phase of PVDF. Gregorio and
Capitao noted that the peak, which is located close to
831 cm1, strengthened when the fraction of the
c-phase in the sample increased, so this peak is obvi-
ously assigned to the c-phase [6]. At the same time,
most investigators relate the peak at 837 cm1 to the
b-phase. The situation becomes clear if we conclude
that the sample of poled PVDF comprises small
domains (d  100 lm ) of the c-phase distributed in
the b-phase. When condition D4d is met we obtain an
averaged spectrum, which demonstrates a broad peak,
that integrates peaks of b- and c-phases (curve B in
Fig. 5). This peak splits to the separated ones in the
case of D  d, when the diaphragm covers the domain
of the c-phase (curve A).
The same splitting is seen in the far IR between 480
and 490 cm1 (see Fig. 6). The broad integral peak at
488 cm1 in curve B splits into two separated peaks in
the curve A: 492 cm1 assigned to the a-phase and
483 cm1 related to the c-phase. Such a splitting
disappears on the next scanning step. Thus, we con-
clude that the poled PVDF sample under investigation
contains inclusions of the c-phase dispersed in the
matrix blend comprising b- and a-phases. As to
c-phase inherent peaks, it is worth noting that we did
not reveal the absorption peak at 788 cm1 assigned by
Gregorio and Capitao to the c-phase [6].

Fig. 6. Splitting of poled PVDF absorption peak. Curve A taken with a diaphragm diameter of 500 lm, curve B with a diaphragm
diameter of 5 mm. Presence of a- and c-phases is recognized.
796 Y. Bormashenko et al. / Polymer Testing 23 (2004) 791–796
4. Conclusions
1. Spectra of poled and non-poled PVDF and their
interpretation depend strongly on the diameter of
the diaphragm used for a spectral measurement.
2. Presence of b-phase inclusions of an average size
d  100 lm in the a-phase matrix of non-poled
PVDF is revealed with a ‘‘small’’ diaphragm D,
when D  d.
3. Splitting of the absorption peaks is shown for poled
PVDF under measurement with a ‘‘small’’ diaphragm.
4. Cooling rate is important for the formation of the
b-phase in the non-poled PVDF.
5. The absorption peak at 600 cm1 is identified as
belonging to the b-phase, and the absorption peak
at 855 cm1 as belonging to the a-phase.
Acknowledgements
The work was supported by the Israel Ministry of
Absorption. The authors are grateful to Professor
Michael Zinigrad for his continuous support of our
research activity.
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