Piezoelectricity in polyvinylidenefluoride

G. M. Sessler

TechnischeHochschuleDarmstadt,6100 Darmstadt, WestGermany

(Received21 September1981;acceptedfor publication25 September1981)

A review of the physicalpropertiesof polyvinylidenefiuoride (PVDF) with particular emphasison its

piezoelectricactivity is givenand the applicationsof this materialare discussed.
PVDF is a semicrystalline
polymerwhosecrystallinedomainsappearin four differentforms.Theseformsmaybe interconverted by the
applicationof heat,electricalfields,and pressure.Thermal polingor coronapolingwill orientthe molecular
dipoles
in thecrystalline
partsandthusyielda permanent
polarization.
Thispolarization
causes,
bymeans
of
differences
in the dielectricand elasticproperties
of the amorphous and crystallineparts,the piezoelectricity
of PVDF. The piezoelectricconstantd a] reachesvaluesof about 35 pC/N at room temperature.At
decreasingtemperatures a dropof d 3]andd 3ais observed. Comparedto otherpiezoelectric materials,PVDF
has suchuniquepropertiesas flexibility,ruggedness, availabilityas thin films, and low acousticimpedance,
but a somewhatsmallerelectromechanical couplingfactor. Applicationsof PVDF are in transducers for
audiofrequency,ultrasonic,underwater,andelectromechanical useandin pyroelectric andopticaldevices.

PACS numbers: 43.88.Fx, 77.60. + v

INTRODUCTION polarization are explained in Sec. III. In Sec. IV, mod-

els of the piezoelectric activity in PVDF are reviewed,
The piezoelectric effect in quartz and in some other
followed in Sec. V by a listing of the piezoelectric and
materials was discovered in 1880 by Curie and Curie. z
pyroelectric constants. In Sec. VI, the ferroeleetric
However, practical applications based on this dis-
properties of this polymer are briefly surveyed. A
covery did not come until Langevin suggested the first
comparison of PVDF with other piezoelectric materials
piezoelectric transducer in 1918.a In the following
is then given in Sec. VII. Finally the applications of
decades, piezoelectric activity was found in a number
PVDF, with emphasis on the electroacoustic devices,
of natural and synthetic single-crystal materials and
the effect was widely utilized? The discovery in 1947 are reviewed in Sec. VIII, and the conclusions are
drawn in Sec. IX.
that a ceramic substance, namely bariumtitanate, can
be made piezoelectric by poling was followed by the I. STRUCTURE OF PVDF
detection of a very strong effect in lead zirconate
titanate (PZT). This material has since been the pre- PVDF is a semicrystalline polymer consisting of
ferred piezoelectric ceramic. The development of longchain molecules with the repeat unit CFaCHa. Its
theory and applications up to 1950 is authoritatively molecular weight is about 10• corresponding to 2000
treated in Mason's book on piezoelectric crystals, 4 repeat units or an extendedlengthof 0.5 x 10-4 cm.x•
while the later developments are described in review Chain defectsof the headto head (CF2followedby CFa)
articles. s
lO:m
Although the piezoelectric properties of another FO
group of materials, namely polymers, were already
investigated8 in 1924, it was not until the work of
Fukada in the 1950's and 1960's that this topic re-
ceived attention.? The breakthrough came in 1969,
when Kawai discovered the strong piezoelectric effect
in polyvinylidenefluoride (PVI)F). 8 As Fig. 1 illus- • __ Z FORMIIPVDF
• 11•1 N ooPVF
trates, PVDF exhibits considerably stronger piezo-
electric activity than other polymers. This behavior
•
PVLO
NyLon
/A
1,1%/FNMA
is, at least in part, related to its high dielectric con- '"" P0iy,ui-o
/
slant. ø The discovery of the piezoelectric and later of • phone
•
the pyroelectric properties zøof PVDF and the early use
of this material in a number of applications• sparked
extensive research and development activities in the
11•
1 FEP/c•PE
/ Polycarbonate
mid- and late 1970's. Some of the results of this work
have been reviewed in the past few years. •2-•?
0 ?• 10
In the present article, a survey of the PVDF work SPECIFIC
DIELECTRIC
C;011STANT
[1000Hz]
with particular emphasis on the piezoelectric activity
of this material and the related applications is at-
tempted. In Sec. I, the morphology of the various
FIG. 1. Piezoelectric d constant as function of dielectric per-
crystalline forms of PVDF and the conversions between
rnittivity. Abbreviations: PVC (polyvinylchloride), PAN
these forms are discussed. This is followed in Sec. II
(polyacrylonitrite), PVF (polyvinylfiuouride), PMMA ( poly-
by a short review of some of the physical properties of methylmethacrylate), FEP (fiuorinated ethylenepropylene),
this material. The polingmethods and the resultant and PE (polyethylene).
9

1596 J. Acoust.Soc.Am. 70(6), Dec. 1981 0001-4966/81/121596-13500.80 ¸ 1981 AcousticalSocietyof America 1596

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 drawing
and the tail to tail (CH2 followedby CH2)typesoccur FormI I•1 ' .{Form
Ill (¾){
in a few percent of the sequences.•s The material con-
sists of about 50• lameliar crystals which are of the
order of 10 -s cm thick and up to 10-s cm long. The h
• high-
temperoture
ønnealin.•/l
high-pr. sure
{ castingfrom
crystals are embedded in an amorphous phase which
has supercooled liquid properties with a glass-transi-
tion temperature T, of about -40 ø C when measured
quenching
at low frequencies. A molecule typically extends
HMPTA I • / /
through several crystalline and amorphous regions. cost{•fr•/ {sto•c•iing //
The repeat unit has a dipole moment of 7.56 x 10 -zs C
cm or 2.27 D.
......
orowm
g acetone
• ]]•/
IForm
/
high-temperoture
onneoling
Presently, four crystalline forms of PVDF are pling
known.•6 These are referred to as forms I, II, TTT,
andII• (occasionallycalledform IV) or /3, cx,y, and
• paling
{For,
m
Ilp
I
ap(5), respectively. The crystalline structurexsof
these forms, when projected onto a plane normal to the FIG. 3. Production and conversion of the crystal forms of
molecular axis, is shown in Fig. 2. The identity and PVDF. is
the structure of the various forms has been studied
by infrared transmission and x-ray scattering experi-
ments.
symmetric, polar crystal. This form is less known
than the other forms but has been the subject of some
Form I has an all-trans (planar zigzag) conforma-
recent studies. •-•s
tionTMwith slight deflections from repeat unit to repeat
unit. All chains are oriented essentially parallel to the The different crystal forms may be obtained from the
b axis of the unit cell with the dipoles pointing in the melt or from solutions and they can also be intercon-
same direction, resulting in a noncentrosymmetric verted. •s'• Some of the known procedures are shown
crystal. The component of the dipole moment parallel in Fig. 3. For example, forms I, II, and HI may be
to the b axis is 2.1 D. obtained by casting from different solutions, forms II
Form H has a trans-gauche-trans-gauche' (TGTG') and HI by cooling from the melt, and form II• by poling
form II at fields in excess of 1 MV/cm.
conformation•'øwith individual chains arranged to yield
a centrosymmetric unit cell. Thus an antipolar crystal PVDF films are often uniaxially or biaxially stretched
results. While the repeat unit has a dipole moment of or rolled ("elongated,
.... drawn,.... oriented") to improve
1.2 D perpendicular to the b axis and 1.0 D parallel to their mechanical or electrical properties or to effect a
the b axis, the overall crystal is nonpolar. conversion from one form to another. For example,
stretching form H samples will generate form I materi-
Form Hphas the same conformationz' as form H and al since the molecular chains of form I are more ex-
follows from this form by rotation of every second
chain such that all chains are aligned. The unit cell
tended than those of form II. In many cases, the sam-
pies are uniaxially stretched to a 4:1 draw ratio.
is thus noncentrosymmetric and the crystal is polar.
Larger uniaxial stretching beyond the "natural draw
The resulting polarization is x64/7 that of form I or
1.3D. ratio" (where the neck formed upon extension starts
to move along the specimen) up to draw ratios of 7:1
Form HI has a TsGTsG'conformation.•'•' The mole- will yield an enhancement of the mechanical and elec-
cular chains are packed in parallel in the noncentro- trical properties. 's'•'v

II. PHYSICAL PROPERTIES

I
A number of measurements of the elastic and di-
electric constants of PVDF and their frequency and
temperature dependencies have been reported in the
literature.•6, 28-34

The temperature dependence of the elastic com-

pliances sx• and s•.•.and of the dielectric permittivity
of oriented form I PVDF, measured at 0.3 Hz, is
shown in Fig. 4 together with the temperature depen-
dencies of the electromechanical couplingfactors k3xand
k s• which will be discussed in Sec. V. A strong de-
IIp III crease of the 1/s curves occurs at the glass-transition
temperature T, where peaks of the loss curves are also
FIG. 2. Crystalline structure of forms I(fi), II(
10catedfs Suchtemperature dependenciesof the com-
and III(•) of PVDF projected onto the a-b plane of the unit pliances and loss factors are found inall stretched and
cell. Fluorine atoms are shown as large circles, carbon unstretched form I and form II materials. x• The fre-
atoms as small circles, and hydrogenatoms are omitted. quency dependence of the compliance has not been well

1597 J.Acoust.
Soc.Am.,Vol.70,No.6, December
1981 G.M.Sessler:
Piezoelectricity
inpolyvinylidenefluoride1597

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 documented but a decrease of, perhaps, a factor of two corona poling,ssthe nonmetalized or one-sided meta-
is expected when going from 10 Hz to 100 MHz. "9 lized sample.is subjected to a corona discharge from
a needle electrode at a distance of a few centimeters.
The Poisson's ratios /•., and /•s, at room temperature A charge builds up on the film which causes a high
were determinedas functions of the roll ratio for films
field in the sample volume. This field aligns the di-
elongated by rolling from 1.5 to 4.5 their original
polaf chains even at room temperature.
lengths.s4 While /•s, rises from 0.37 for the nonrolled
film to 0.7 for films subjected to a roll ratio of 4.5, For thermal poling, the polarization achieved de-
/•., falls over the same interval from 0.35 to 0.25. The pends on the applied field and on poling temperature
temperature dependenceof/•s, has been derived from and poling time. For long enough poling times, the
that of the electromechanical coupling factor and is polarization is only a function of the poling field while
assumed to rise with temperature from values of about the poling temperature affects merely the rate at which
0.2 below T• to the above-mentioned values at room the polarization builds upSS;the polarization achieved
temperature.'4'•'9'sø's•"ss under such conditions is, for applied fields up to about
2 MV/cm, proportionalto the field? 'ss For higher
The dielectric permittivity Essof form I PVDF is also
plotted in Fig. 4. It shows a somewhat similar depen-
fields, a maximumpolarizationof about2 gC/cm•' is
reached. • For corona poling, the polarization is small
dence on temperature as the mechanical compliances
if the field due to the corona charge is below 1
with a strong rise around the glass-transition tempera-
MV/cm. s4's• For higher fields, the polarization rises
ture.
sharply and assumesa saturationvalue•4 of about12
The frequency dependence of the permittivity of form •C/cm 2.
I and form II PVDF films is depicted in Fig. 5. It is
The dipolaf alignment during either poling process
seen that dispersion ranges exist around 0.1 and 10?
occurs by reorientation of the randomly oriented crys-
Hz. In the audio-frequency range, the permittivity is
talline regions in the field direction. This process
reasonably independent of frequency and amounts to
does not involve a reorientation of the crystallites as a
about 14 for the poled form I material. The drawn
whole since, as explained above, neighboring crystals
samples showa considerably higher permittivity than
are interconnected by the long molecular chains and
the undrawn ones; this has been attributed to the orien- thus hindered in their motion. The reorientation is
tation of the crystal lamellae. '8
rather caused by chain rotation about the C-C-chain
axis. In cases where the chain axis has a component
III. POLING AND POLARIZATION
normal to the electrodes only an incomplete alignment
is attainable. Furthermore, only discrete directions
The commercially available PVDF film consists
of orientation, spacedat 60ø increments, are possible
usually of antipolar form II material. In order to make
for a given chain.4ø As will be discussed in Sec. VI,
this material piezoelectric, a sequence of processes
the reorientation of the molecular chains in PVDF can
as illustrated in Fig. 6 has to be performed.
be described by a ferroelectric model.
The film is first uniaxially stretched at 60ø to 65 øC
to 3 to 5 times its original length whereby the material If the poling is performed at fields up to 1 MV/cm,
the buildup of the polarization is affected by the injec-
recrystallizes in form I. Subsequentannealing of the
clamped sample at 120 øC heals the damage incurred tion of real charges.4•-4s In particular, thermal poling
with a blocking positive electrode results in samples
during stretching and stabilizes the film. The poling
can be performed either by a thermal or by a corona showing only weak piezoelectric activity, i.e., weak
polarization. It was also demonstrated that poling at
procedure. For thermal poling,8 the sample is first
electroded and then subjected to a field of 500 to 800 relatively low fields yields samples in which the piezo-
kV/cm at 90ø to 110 ø C for about an hour. This will and pyroelectric activity is greatest on the side which
partially align the dipoles in the crystalline regions in
the field direction. Subsequent cooling to room tem- 1500-
500-
perature under the applied field stabilizes the polar 1Hz lkHz 1HHz 16Hz
alignment resulting in a permanent polarization. For

i 20[
\
\

1/S., 1/Sz2,
6Po
k:n,k:n,ø/o
FIG. 4. Temperature depend- lO-
ence of the elastic compli-
ancessll ands22, the dielec-
k33
- 0.3
Hz tric constant ½33and the coup-
k - lkH'z ling constants k 31and k 33for
stretched form I PVDF. The

/•, 3•
_0.3
Hz films were stretched
150 øC and poled for 2 h at
110øCand 1 MV/cm. 3•
5.1:1 at

FIG. 5.
FREQUENCY
6
(Hz).••.

Frequency dependence of dielectric permittivity for

o
Tg•..t•,, øC
,I nondrawn form II (a) film and drawn and poled form I (•)
-lOO -60 0 •0 film. 29

1598 J. Acoust. Soc. Am., Vol. 70, No. 6, December 1981 G. M. Sessler'Piezoelectricity
in polyvinylidenefluoride 1598

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 faces the positively biased electrode while poling at
fields in excess of 1.7 MV/cm at 70ø C is necessary
to produce a uniform polarization. 4s-4• ELON6ATION
HANNEALIN6
'HEVAPORATIO
i_•THERI4A
65 'C, •, TIMES 120'C, 2•,HRS.
ICLAMPED}
OF ELECTRODES 600 KV/cm,
105'C, l,Orain

The uniformity of the polarization was directly mea-

sured with the thermal-pulse and the pressure-pulse
methods. These methods arc.based on the evaluation
of changes in the surface potential of poled films due
CORONA
HEVAPORA
l, HVlcm
R.T., 60 s
OFELECTRODE(SI

to the expansion of the sample causeribs,the diffusion

FIG. 6. Processing of form II PVDF to yield piezoelectric
of thermal energy or by the propagation of a pressure film.
pulse, respectively.48'47Older thermal-pulse experi-
ments in PVDF • indicate an almost uniform polariza-
tion in 25-/•m samples poled at fields of about 300
kV/cm. Very recent pressure-pulse measurements49 Models of the piezoelectric effect in PVDF are based
on 85-/•m thick films polarized thermally at 200 kV/cm on the assumption that the material consists of a
disclosed, however, the existence of a nonuniform crystalline and an amorphous phase with the two
polarization concentrated close to the positive elec- phases differing in their dielectric and elastic proper-
trode. This agrees with the above-discussed results ties. s•'-s4 The material is further assumed to be po-
of piezoelectric- and pyroelectric-activity measure- larized with the polarization consisting either of aligned
ments. For samples corona-charged for a few seconds, dipolar chains in the crystalline and perhaps the sur-
the polarization is found to be in the center of the sam- rounding amorphous parts and of real charges at the
ple with field-compensating real charges at the po- boundaries of the polarization zones. The piezoelec-
larization-zone boundaries. tricity in such a material may be due to several ef-
fectsS•:
These results allow some important conclusions about
the physics of the poling phenomenon. The effect of the (a) The dielectric constants of the crystalline and
blocking electrode and the concentration of the polariza- amorphous parts have different strain dependence. In
tion near the positive electrode indicate that space- the presence of a polarization, this yields a piezoelec-
charge injection plays a role in low-field poling. Al- tric effect of the material (electrostrictive contribu-
though the details are not clear, it appears that real tion).
charges enhance the field in the vicinity of the positive (b) The elastic constants of the crystalline and
electrode which, in turn, causes an increase of the amorphous parts are different. In a polarized sample,
polarization in this region. 4s While in this picture the this yields a strain dependence of the polarization and
space charge is only important during formation of the thus contributes also to the piezoelectric activity
polarization, a recent model•9'søassumes such charges (dimensional contribution).
to be also instrumental for the permanence of the
dipolar alignment. This concept is based on the ob- (c) The crystalline parts have an intrinsic piezoelec-
servation of a weak orientational stability of the dipole tricity due to the strain dependence of their polarization
alignment and its stabilization by trapped charges. (crystal contribution).
A recent theory based on the above assumptions has
IV. MODELS OF THE PIEZOELECTRICITY OF PVDF
been numerically evaluated with the result that the pie-
The piezoelectric properties of PVDF can be charac-
terized by a piezoelectric matrix. If written for the 30-
d constants,s this matrix is for the film poled without
d33
stretching s• 25

0 0 0 0 d• 0
20

d•=
0 0 0 d•0 • .
• d• d• 0 0 15
/d31 -30

If the material is poled after uniaxial stretching, the

piezoelectric matrix ist?'•t d3h
-10

• 0 0 0 d•s
0 0 T•d32 0"
d•:s•0 0d,4
0• .
d•, d• 0 0
-oo
TEHP, 'C •

The piezoelectric constants of PVDF are expected to

depend on such parameters as temperature, crystal-
FIG. 7. Temperature dependence of the piezoelectric and py-
linity, stretch ratio, and poling conditions. They have roelectric constants of stretched form I PVDF. The films
been the subject of numerous theoretical and experi- were stretched 5.1:1 at 1 50øC and p61ed for 2 h at 11 0øC and
mental studies.
1 MV/cm.31d33is negative.

1599 J. Acous•.$oc.Am.,Voi. 70, No.6, December

i98i G.M. Sessler:Piezoelectricity
in polyvinylidenefluoride 1599

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 TABLE I. Piezo- andpyroelectriccoefficientsof PVDFat roomtemperature.
3•
Conditions of
Sample Drawing Poling (2 h) Ps 1/s•
Undrawn Drawn øC- % øC-- kV/cm pC/N • percent p C/m2K GPa

110- 1000 5.3 5.3 -13.6 3 3 4.4 13 1.6

9.8 2.2 -14.8 2.8 4.5 14 2.7
II• 167-350 11O-lOOO
16.8 5.8 7.8 1.7
II• 167- 350 165-1000
1 O0 - 500 4.2 4.2 -11.1 2.7 1.8 3.8 1.6
I 100-400 120-1000 17.9 0.9 -27.1 8.3 10.3 12.6 30 3.8
I 75 -400 165-1000 37 7.2 14.7 2.1
III 15O - 900 4.9 4.9 -13.3 3.5 5.3 16 1.6
III 100-400 110-500 19 7.8 9.6 3.6

zoelectric constantsd• or e• so obtainedare in good the form I material shows roughly twice the ds, and dss
agreement with experimental datails It follows that for values of the form II} material. This corresponds
all constants the dimensional contribution predomi- closely to the factor 4/7 discussedabove. The
nates. In case of the transverse effect (ds,,ds2or stretched material has a small ds•.constant. This
es,, es2)the dimensionalcontributionis proportionalto anisotropy between the 1 and 2 directions is well-
a Poisson's ratio gin.. Thus a large part of the trans- known. '•' The electromechanical coupling factors listed
verse constants is affected by the magnitude and tem- in Table I reach up to about 0.15; kssvalues up to 0.20
perature dependenceof the have been reported in the literature. •'s
The present theoretical models should, however, only Since kssfor a particular samplealways exceedsks,
be seen as approximate descriptions of the piezoelectric it is reasonable to assume that the primary piezoelec-
behavior of PVDF with many of the details still to be tric activity is the longitudinal effect and that the trans-
worked out. In particular, the effect of neutralizing verse effect is due to lateral contraction of the film and
counter charges•4 and the contribution of those parts of determinedby Poisson'sratio /•s,.TMThis view is also
the amorphousphaseneighboringthe crystals'6 are not supported by the temperature dependenciesof ks, and
yet well understood. There is, however, a consensus kss shownin Fig. 4. While kssfor PVDF, as for crystal-
emerging that the piezoelectricity of poled PVDF is line materials, is almost independent of temperature,
essentially due to the electric moment of the crystal- /% exhibitsa rise with temperature. The increase of
line regions ils ks, is causedby a correspondingtemperature de-
pendenceof/%, which is believed to rise from 0.2 at
The pyroelectric activity of PVDF has the same ori-
temperatures
belowT, to 0.7 it temperatures
aboveT,
gin as its piezoelectricity. l•nile the latter is due to a
(see above).'4
strain dependence, the former is caused by a corres-
pondingtemperature dependence.The relation of the The temperature dependence of the piezoelectric and
two effects can be expressedby the ratio of the (hydro- pyroelectric constants of stretched form I PVDF is de-
.

static) piezoelectric constant to the pyroelectric co- picted in Fig. 7. The strong increase of ds, with tem-
efficient, whichfollowsfrom theory'• as 0.005øK perature is readily explained from the relation
cm 2
ks,=ds,(%s,,)-•/2.
Since, according to Fig. 3, ks,, œss,and su all rise
V. PIEZOELECTRIC AND PYROELECTRIC
with temperature, ds, has to increase too. A similar
CONSTANTS
reasoning holds for dss, while ds• is practically tem-
A number of detailed experimental investigations of perature independent. The hydrostatic piezoelectric
the piezoelectric and pyroelectric constants of PVDF constant follows from

have been published recently. '6'•8's"s' The measured

-ds•, =ds, +ds2+dss.
constants are strongly dependent on crystal form,
stretch ratio, and poling conditions. The pyroelectric coefficient Ps has a relatively weak
temperature dependence. Comparison with ds•shows
Values of the piezo- and pyroelectric coefficients of
that the ratio ds•,/ps is temperaturedependent
and, at
PVDF together with some other constants are given in
room temperature, by about a factor of two smaller
Table I. All measurements were taken at room tem-
than the above-mentioned value predicted from simple
perature. The table shows that the d constants of the
theory.
undrawn samples are about the same for the three
forms althoughthe polarization of form II• is smaller Of particular importance for practical applications
than that of form I. The relatively high activity of the of PVDF is the thermal long-term stability of the
form II• sample is due to the higher field used for its piezoelectric and pyroelectric effects in this ma-
poling. For the stretched films and equal poling fields, terial. '4'•"•'•ø At room temperature the constants are

1600 J. Acoust.Soc.Am., Vol. 70, No. 6, December1981 G.M. Sessler:Piezoelectricityin polyvinylidenefluoride 1600

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 either stable•ø or only subject to a slight decay• over o

periods of a year or more. At elevated temperatures, •.••.• _ U•IIAXIAL

the decay is more pronounced. Typical results for the
piezoelectric activity of uniaxially stretched films con- -o.2
raining a mixture of form I and form II crystals are
shown in Fig. 8. While the data at 60 ø to 88 ø C can be :
described by a single activation energy of 1.2 eV, the
-o.f,
decay at 102 ø C exhibits a more complicated behavior
which suggests additional relaxation mechanisms. For LOG(t, min.) .

I I
biaxially stretched material, the decay rates are some- 3
what smaller. Another study'4 indicates a more pro-
nounced decay for form I films than for form II films.
FIG. 8. Isothermaldecayof piezoelectricd31constantof 25
A review of the stability data for PVDF shows that, for •m thick uniaxially oriented PVDF films. The material con-
applications where a slight drop (20%) over periods of raineda mixture of form I and form II crystals. 6o
a year is tolerable or where such a drop can be elimi-
nated by annealing of the material, the useful tempera- light weight, relatively low acoustic impedance, and
ture range extends up to about 80 ø C. low Q. The material is also available in thin films and
in large sheets and is inexpensive to produce. Most
Vl. FERROELECTRICITY of these properties, which are typical of polymeric
substances, contrast sharply with those of the conven-
Numerous studies have indicated that PVDF shows tional piezoelectric materials. PVDF thus offers a
ferroelectric behavior: its polarization can be re- welcomed alternative in many applications as will be
versed by a strong external electric field and applica- shown in Sec. VIII.
tion of a sinusoidally varying field yields hysteresis
of such quantities as the electric displacement or the
A comparison of some of the physical properties of
PVDF with those of other piezoelectric materials is
piezoelectric constants.'ø'4ø's6'm'6•'
given in Table II. It is evident from the table that the
The results of a typical experiment of this kind are d•t constant and the pyroelectric coefficient of PVDF
plotted in Fig. 9. Shownis the dependenceof the esx are considerably smaller than the corresponding con-
constant on electric field during slow cycling of the lat- stants of the ceramic PZT. However, because of the
ter. For fields smaller than40 MV/m peak-to-peak, relatively small dielectric constant of PVDF, its g
esxfollows the field with small phase lag, i.e., the constant is high and the electromechanical coupling
response is sinusoidal. If the field is increased, a factors k3, and k3sreach values of 16% and 20%, re-
hysteresis loop develops. For peak fields of 120 MV/ spectively.
m, the reinanent esxconstant present after removal of
Although PVDF has almost an order-of-magnitude
the field is almost as large as the maximum es, value.
The hysteresis loops are observed in the temperature
lower d constants than PZT, the field strength that can
be applied to the polymer without danger of depolariza-
range from -100 ø to + 100 øC, but the coercive field
tion is about 100 times greater. •5 Since in transducer
significantly decreases with increasing temperature. •'
applications the strain is proportional to the d constant
The ferroelectric polarization inPVDF has been ex- and the field, the maximum strain achievable with
plained by a cooperative model assuming the molecular
dipoles to have two or more orientations available to
them.ss Actually, a six-orientation model with poten- e31(mC/m2)
tial-energy minima spaced 60ø apart is needed to ac-
count not only for the observed polarization hysteresis
but also for infrared hysteresis data and for field-in-
---
EolMV/m)
120
ß
-0.-'oo ,/I
duced structural changes seen in x-ray pole figures. • 80 /', n_[•
The 60ø spacing of the orientational sites corresponds
to the essentially hexagonal cross section of the unit
cell. If the free energy of the crystal is calculated and
minimized, a set of equations follows which can be
solved to obtain the polarization. Good agreement be- -120-80 i,( 80 12,_•,.0
E (MY/m)
tween the predictions of this relatively simple model
and the experimental data was found.

VII. COMPARISON OF PVDF WITH OTHER

PIEZOELECTRIC MATERIALS

PVDF differs in many respects from the more con-

ventional crystalline and polycrystalline piezoelectric
materials.•4 In particular, PVDF is characterizedby FIG. 9. Plot of e31constant measured on a form I PVDF sam-
ple during applicationof a sinusoidalfield E of frequency10-s
suchpropertiesas flexibility, ruggedness,softness, Hz. Temperature is 20øC.S•

1601 J.Acoust.
$oc.Am.,Vol.70,No.6, December
1981 G.M.Sessler:
Piezoelectricity
inpolyvinylidenefluoride1601

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 TABLE II. Piezoelectric, pyroelectric, and other constantsof PVDF and someother materials15
(PVF: Polyvinylfluoride,
PZT: leadzirconatetitanate,BaTiO3:bariumtitanate,TGS:triglycine
su•fate).

Material Density Dielectric Piezoelectric constants Pyroelectric Coupling

constant coefficient factor
d g
g cm'3 pC/ N 10'3Vm/N • C/ m2K percent

PVDF 1.76 11 20(d3•) 200(g3•) 40 16

PVF 1.38 5 1(d3,) 20(g3,) 10 3

PZT-5 7.75 1700 171(d3•) 11(g3•) 60-500 34

BaTiO3 5.7 1700 ß 78(d31) 5(g31) 200 21

Quartz 2.66 4.5 2(dl•) 50(g•) ß" 9

TGS 1.7 50 ...... 350 ....

PVDF transducers is ten times larger than for ceramic signal is appliedbetweenthe electrodesof the plane
systems. This advantageis of importance in numerous polymer film shownin Fig. 10(a), the film vibrates in
the transverse direction and the coupling to the sur-
applications.
rounding medium is weak. Better coupling can be
Amongthe drawbacks of PVDF are its relatively poor achievedby the arrangementshownin part (b) of the
electrical stability which is in part due to mechanical figure, wherethe film has a cylindrical curvature and
relaxation. This makes long-term measurements of is clamped at its two straight edges. Due to the shape
weak signals somewhatproblematic. Also, the service of the film, the transverse motion is now converted
temperatureof PVDF is limited to about80ø C. In into a pulsar'ragvibration which strongly couples to the
these respects, ceramic transducer materials are surrounding medium.
much superior.
Based on this principle, audio-frequency micro-
VIII. APPLICATIONS phones, headphones,and tweeters have been built and
Some of the most important applications of PVDF are commercialized. • As an example, a cross section of a
in electroacoustic and electromechanical transducers. headphoneof this kind is illustrated in Fig. 11. In this
•ne lower-frequencydevices(operatingbelow1 MHz) transducer, the 8-•m thick PVDF membraneis placed
are mostly based on the excitation of flexure modes over a polyurethane-foam backing which gives the film
by means of the transverse piezoelectric effect. As is the desired curvature and also provides sufficient
well-known from the analysis of conventional piezo- mechanical damping to suppress undesirable reson-
electric transducers, this allows it to reach relatively ances. Since a thin PVDF film of large area is used,
high sensitivites. In the upper ultrasonic range, ex- such transducers have a relatively high capacitance
ploitation of the longitudinal piezoelectric effect is (about 0.1 •F)and yield without step-up transformer
more advantageous. for 3-V signal voltage a sound-pressure level of 100 dB
in an artificial ear. Furthermore, the frequency re-
Apart from such applications, the uses of the pyro-
sponse is excellent and the distortion low.
electric effect of PVDF are also important, but of
lesser interest in the context of the present paper. A simplification of such transducers is possible by
Still other applications of this material, for example, the use of self-supporting, preshaped mem-
those based on its nonlinear optical properties, have branes? '•'6g'vø The performance of such transducers
not yet achieved comparable significance. is characterized by particularly low distortion.s2'7•
The emphasisin the following will therefore be on the The sensitivity of PVDF transmitters has recently
piezoelectric applications of PVDF with the pyroelec- been improved by the use of multilayer systems. In one
tric and other applications only discussed briefly. An design, two PVDF films are arranged and energized
overview of some of the applications of PVDF is given in a way that their acoustic output doubles relative to
in Table IH.
that of a single-film transducer? • Such systems re-
A. Audio-frequencytransducers quire only 1 V to achieve a sound-pressure level of
100 dB and might therefore be of interest for telephone
As explained above, PVDF transducers for audio-
applications.
frequency applications are generally based on the
transverse piezoelectric effect. While the well-known Another improvement of the foam-backed and self-
bimorph and unimorph principles TMhave been used for supported transducers was achieved by utilizing a rigid
the designof PVDF transducers,TM the flexibility of film support? •'• A microphone of this kind with a
this material makes possible the very advantageous point support in the center of the membrane is shown in
arrangement • illustrated in Fig. 10. If an electrical Fig. 12. The PVDF film is statically deflected by the

1602 J. Acoust.
Soc.Am.,Vol.70, No.6, December
1981 G.M. Sessler:
Piezoelectricity
inpolyvinylidenefluoride 1602

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 TABLE III. Applications of PVDF.

Application References

A. Audio-frequency transducers
Microphones 11, 13, 32, 66-74
Noise-canceling microphones 68, 75
Telephone transmitter 76
Bimorph transducers 75, 76
Headphones 11, 66, 77, 78
Loudspeakers(tweeters) 11, 14, 79- 81
Accelerometer 81
Medical sensors 14, 82
B. Ultrasonic and underwater transducers
Ultrasonic transmitters and receivers 83
Bulk-wave transducers 14, 26, 84
Nondestructive testing transducers 14, 26, 85
Stack transmitters 86, 87
Rayleigh- and Lamb-wave devices 26, 88- 91
Delay lines 89- 92
PVDF-MOSFET 93
Imaging arrays 26, 93, 94
Hydrophones 67, 95- 100
Light modulator 101
Variable-focus transducer 102
Anti-fouling transducer 103

C. Electromechanical transducers and devices

Phonograph cartridge s 11, 81
Contactless switches 37, 67, 104, 105
Telephone dial 105
Typewriter and computer keyboard 106
Bimorphs 107, 108
Display device 108
Light shutter 108
Optical fiber switches 108, 109
Air flow fan 108
Variable-focus mirrors 108, 110, 111
Mechanical transformer 65
Coin sensor 112
Impact detector 113

D. Pyroelectric and optical devices

Infrared detectors 67, 114
Intrusion detector 64
Vidicons 115, 116
Laser-beam profile system 67
Infrared-to-visible converter 67
Photocopying machine 117
Optical second harmonic generator 10
Reflectivity detector 118

support and assumes a tent shapewhich guarantees its cylindrical element having a laterally omnidirectional
linear operationf •'v4 Advantagesof such microphones radiation pattern. n'•9 Providing the latter systems
compared to elastically or self-supported structures with horn loading improves the frequency response.so
are the well-defined geometry of the membrane which The piezoelectric effect in PVDF has also been used
is importantfor reproduciblemicrophonesensitivity, in accelerometers of very simple design.s• An exam-
the goodmechanicaland thermal stability, andthe ple of an experimental transducer, shown in Fig. 13,
possibility to vary the membrane tension and to con- consists of a mass and a ringshaped PVDF element
trol damping by the membrane support. which is only 2 mm long and 5 mm in diameter. An
Other audio-frequency transducers with PVDF mem- almost flat frequency response up to 10 kHz is achieved
branes are the above-mentioned bimorph microphones with a sensitivity about equal to that of conventional
ceramic accelerometers.
which consist of two oppositely polarized films con-
nectedin series,•s'vsnoise-cancelingmicrophones Of potential future interest are also medical sensors
based either on a gradient principle vs or utilizing two which consist simply of PVDF tapes that can be at-
independentfoils to reject vibrational noise,ssand tached to the human body to monitor heart beat, breath-
high-frequency loudspeakers (tweeters) consisting ing, and blood-circulation sounds at low acoustic or
either of a full spherical PVDF element •4 or of a infrasonic frequencies. TM The fact that such PVDF

1603 J.Acoust.
Soc.Am.,Vol.70,No.6,December
1981 G.M.Sessler'
Piezoelectricity
inpolyvinylidenefluoride
1603

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 Z SOUND WAVE PVDF- MEMBRANE '

CAVITY--
• POINT
SUPPORT
Y/ METAL
ELECTRODE '"•'

I \
I
• • , /INNER
ELECTRODE) P
PIEZO -POLYMER FOIL

(a) (b)
• •i [/•--CASE
(GROUND)
FIG. 10. (a) Transverse motion of plane piezopolymer ele-
ment. (b) Conversion of transverse motion into pulsating mo-
tionby useof cylindricalelement
withclamped
y-direction
edges.ll
INSULATION
/ --'7-- ø
transducers can be made large and thus of high capaci-
tance simplifies amplification requirements. Recently, FIG. 12. Cross-sectional view of microphone with rigidly
more sophisticated transducers with receiving •nd supportedP VDF membrane.71
transmitting function have actually been used for medi-
cal examinations. = faithful impulse response.

B. Ultrasonic and underwater tramducer$ Rayleigh waves or Lamb waves may be excited on
PVDF sheets by interdigital electrodes. At room tem-
The ultrasonic and underwater applications of PVDF perature, these waves propagatealong the polymer
are mostly based on the longitudinal piezoelectric ef- films up to frequencies of about 1 MHz, in the cryogenic
fect. This effect is of useful magnitude up to frequen- temperaturerangeup to higher frequencies.ss'SøUnder
cies of at least 500 MHz at room temperature and up certain conditions, the attenuation is low enoughto al-
to 9 GHz at 1.5 ø K. 8s The Q factors of PVDF are be- low use of the PVDF film as a delay line. s9-9•' To avoid
tween 10 and 100 in the low MHz range with a loss the attenuation in the polymer, .the waves can also be
maximum at about 5 MHz. •'8'x•'ø'•'x coupled into other materials. 9ø
Several approaches to the generation and detection Another interesting application is the so-called
of ultrasonic waves with PVDF have been described. POSFET, a combinationof a PVDF transducerwith a
Of relatively simple design are bulk-wave trans- MOSFET amplifier as shownin Fig. 157 In this de-
ducers.•4'•e'84 An example is shownin Fig. 14: a vice, a single sheet of the polymer is bondedby an
cylindrical PVDF sheet is properly mounted to excite epoxy layer to the surface of a MOSFET wafer. The
concentric ultrasonic waves, for example, in water. lower PVDF electrode is a layer deposited onto the
Similar transducers have been the subject of extensive silicon oxide. Source and drain of the MOSFET are
theoretical and experimental studies with such quanti- n-type regions diffused into the p-type silicon wafer.
ties as insertion and dieIectric losses investigated.•e The small section of the lower electrode close to
Possible applications of such transducers are the mea- source and drain constitutes the gate while the remain-
surement of ultralow attenuation of liquids, the de- der of the electrode acts as a collector of the charge
tection of particles or bubbles in flowing liquids,TMand produced by the piezoelectric response of the PVDF
nondestructive testing. ss film to an incident acoustic wave. A linear arrayof 34
such elements has been built and evaluated. os Due to
To increase the acoustic power output, multilayer
the low Q of PVDF it has a bandwidth of 6 MHz. The
transmitters have been built in which adjacent layers
array serves as a prototype of a system to be de-
are oppositely poled.s•'• For such transducers, the
veloped for medical imaging.
frequencyof the thicknessresonanceis lowered, which
can be advantageous. The acoustic power generated by Another recently designed•'6multielement imaging
these and other PVDF transducers is significantly array utilizing a PVDF transmitter is illustrated in
less than that of ceramic transmitters. However, ad-
vantages of the PVDF transducer are the flat fre-
quency responsebelow resonancewhich results in a
f-
/HOUSING
o•PENSION BOARD

o o,
RING
BASE
•MASS

•..-PVDF- ELEMENT
..•... EARPAD
,''/•,-----•DIAPHRAGM OUTPUT
TERMINALS

•• (PIEZO-POLYMER
FOIL}
•POLYuRETHANE IASE

FRAMEWORK FOAM BACKING

FIG. 11. Cross-sectional view of PVDF headphone. FIG. 13. Schematic cross section of accelerometer. 81

1604 J.Acoust.
Soc.Am.,Vol.70,No.6, December
1981 G.M.Gessler:
Piezoelectricity
inpolyvinylidenefluoride
1604

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 the inside of the hull of a sailboat and excited at fre-

PVDF- BAND quencies of 5 or 24 kHz. It was found that the acoustic

radiation emanating from these transducers prevents
FIG. 14. Ultrasonic transducer for the deposition and growth of marine life on the hull.
generation of concentric ultrasonic To achieve such antifouling action, only a small frac-
waves in the low MHz range. tion of the hull has to be covered by transducers.
C. Electromechanical transducers and devices
• H2
o Electromechanical PVDF transducers are mostly
low-frequency devices and are therefore almost ex-
clusively based on the transverse piezoelectric ef-
Fig. 16. The individual elements are defined by gold fect. The first devices of this kind to be suggested
strips deposited on an epoxy substrate. Proper choice were phonographcartridges. '"a• Utilizing 1 x2 mm
of the input signals to the elements yields a line focus
strips of PVDF as transducing elements, a high-
of the emitted sound which is converted to a spot focus
compliance vibrating system of high resonance fre-
by the cylindrical lens. The spot can be scanned along quency is obtained. The 45-kHz frequency response
a line, two-dimensional imaging is obtained by linear makes such cartridges suitable for the playback of
motion of the system. The array is operated at about CD-4 records.
2 MHz. Advantages of using PVDF instead of ceramic
material are large bandwidth and wide-angie response. An obvious application of PVI)F is in contactless
switches."'•'xø4'xøs These have potentialuse in tele-
PVDF elements have repeatedly been used in hydro-
phone dials, typewriters, calculators, computer-input
phones.•'•s-'øø The advantagesof such transducers terminals, etc. The operation of piezoelectric switches
as compared to ceramic systems are their nearly flat such as the one shown in Fig. 18 depends on the length
frequency response up to the resonance frequency and expansion of the PVDF film due to the pressure created
their high acoustic transparency due to the close im- by a push button. The maximum deflection is deter-
pedance match with the surrounding water. Sensitivi- mined by the elastomer layer but may also be con-
ties range from about 100 /•V/Pa for 1-kHzbandwidth trolled by a snap disk which guarantees tactile feedback
bender-type transducers 94to about I /•V/Pa for 5-MHz and a more reproducible electrical output pulse. 'ø•
bandwidthbilaminar systems. •øø The newer develop-
ments are directed toward a miniaturization of these The basic two-film bimorph structure, also used in
transducers with sizes down to about 150/•m. 9s-'øø electroacousticapplications (see above), producesoften
Also based on the close PVDF-water impedance insufficient bending forces. Larger forces may be ob-
tained from multilayer bimorph structures •øs such as the
match is an acousto-optic light deflector which consists
of a PVDF transducer bonded to a polymethyl
one illustrated in Fig. 19. It can be shown that for an
methacrylate (PMMA) parallelepiped.TM Light propa- increase of the number of layers by a factor of N, the
gating in the PMMA block is totally diffracted by the displacement and force are multiplied by factors of
ultrasonic wave at a sufficiently high acoustic level. 1/N andN •', respectively.'øv

Another interesting underwatertransducer'øeis shown A number of electromechanical applications of con-

ventional and multilayer bimorphs were suggested re-
in Fig. 17. A circular PVDF film, mountedat its edge,
is spherically deformed by a pressure difference be- cently.•ø8 Amongtheseare optical displays, light shut-
tween its two surfaces. The deformation generates ters, an optical fiber switch, an air-flow generating
an acoustical focus which can be scanned axially by fan, and variable-focus mirrors. In the optical fiber
variation of the pressure difference. Such variable- switch, for example, a PVDF bimorph is used to shift
an optical fiber from one to another fiber. A second
focus transducers maybe of use in medical ultra-
example are the variable-focus mirrors which are
sonics. In this application, the flexibility of PVDF is
used to advantage. based on several different principles' in one design,uø
a PVDF bimorph with a subdivided electrode is used
A potentially very useful application of PVDF trans- as the mirror; application of a proper voltage dis-
mitters is for the prevention of marine fouling on the
hulls of boats and ships. 'øs In first experiments, film-
WATERTIGHTHOUSING
strip transducers were mounted on test panels or on

,, ',
PVDF 3•01.L
EXPOXY=51.1.
• UPPER
ELECTRODE
,i
EPOXY,i I .........
',
I
LOWER
ELECTRODE BOND •,'/.CYLINORICAL
?'I
PVOFJRTV
,"'"'-.-L
DEPOSITED
'"'"-,J--
J'•"•
ARRAY
•OEPOSITEO
FILM LENS AU FILM
PL(100),SILICON Si02
= 1.51.L

FIG. 16. Schematic cross section of multielement imaging

FIG. 15. Schematic cross section of integrated PVDF-MOS- 26
FoETamplifier. 93 array.

1605 J.Acoust.
Soc.Am.,Vol.70, No.6, December
1981 G.M. Sessler:
Piezoelectricity
inpolyvinylidenefluoride 1605

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 DETECTOR SOURCE -3
-2
-1

I' II 1

v
{',,'• L/SEAL N
• J, ,,,k • I X ,o
POLARIZATION FIG. 19. Multilayer bimorph
ELECTRICFIELD structures: (a) With 2 N layers,
PRESSURE
H • connection to each layer neces-
REDUCTION
P................ • •PVDF-FILN sary and (b) with 2 folded
(b) sheets. 108

POLARIZATION
ELECTRICFIELD

FIG. 17. Schematic view of variable-focus transducer. An interesting potential application of PVDF is in
pyroelectric vidicons used for night surveillance.
tribution to the electrode sections will result in the Here, the infrared radiation from a scene is imaged
onto the PVDF target and generates a voltage pattern
desired curvature. In anotherdesign,•u usedin a
on the other (nonmetalized) side of the film. This can
wave-front correction system, thin glass sheets are
bonded to the PVDFtransducer to improve reflec- be interrogated with a scanning electron beam. PVDF
ridicons have less resolution than the customary
tivity; in this system, the wave-frontdeformationto be
corrected is detected by a photo-diode array and a
triglycine sulfate systems•5 but are of greater sim-
plicity. Experimental'systems have worked satis-
signal is fed back to the mirror to control its curva-
factorily over extendedperiods of time. •'•
ture. In yet anotherimplementation
•ø8multiple layers
of PVDF of different shapes are cemented onto a thin Three other experimental applications of the pyro-
sheet of mirror glass thus allowing to affect its curva- electric activity of PVDF are a laser-beam profiling
ture. In all these applications, the flexibility of PVDF systemwhichconsistsof a 50-elementarray designed
and the fact that one can "cut out" the desired film to determine the power distribution across a parallel
geometry is used to advantage. laser beam, a low-resolutionscanningsystemwhich
converts infrared into visible radiation,• and a photo-
A few other electromechanical-transducer applica-
copyingmachine.n? In the copier, the projectionof a
tions of PVDF deserve to be mentioned. One such de-
visible-light image ontoa PVDF sheet generatesa
vice consists of two oppositely poled PVDF sheets which corresponding
chargedistributionwhichis developed
are forming the sides of a tent.e5 By applyinga voltage, with a toner and then transferred to paper.
the ridge of the tent moves sideways. Suchdevices,
which are capable of performing large amplitudes, can Details on these and other pyroelectric and optical
possibly be usedas mechanicaltransformers to couple PVDF devices may be foundin the literature given in
forces to loads. Another application of PVDF that has Table III.

been suggestedis in coin sensors.u•' Comparedto

corresponding PZT sensors, such devices have two to IX. CONCLUSIONS
three times greater sensitivity and allow simpler Our knowledgeaboutthe material properties of PVDF
geometries. A last electromechanical application of has been greatly enhancedover the past few years.
PVDF to be mentioned is an impact-sensitive device Particularly x-ray and infrared-transmission mea-
which measures the interface pressure in vehicular surements have clarified structural details of the
crashes. •3
crystallineforms andhave led to the identificationof
D. Pyroelectricand optical devices the newform IIp. Suchexperimentswere also instru-
mental for the confirmation of the ferroelectric nature
' The pyroelectric effect in PVDF can be utilized in a
detector such as the one shown in Fig. 20. Here, the of the polarization in PVDF. These findingsled to a
incident infrared radiation is either absorbed in the better understandingof the piezoelectric behavior of
face electrode or in the polymer film and thus causes
this material. It is now generally agreed that the
an electrical signal. Similar detectors are in wide piezoelectricity of PVDF is mainly due to the polariza-
practical use. Another commercialized PVDFdevice tion of the crystalline domains with real charges
is the intrusion detector e4 which senses the infrared playing only a minor role.
radiation from an intruding person and activates an
alarm system.
•v o

PVDF FILM PUSH BUTTON

R

FACE ELECTRODE

POLED PVDF FIL

FOAMED ELECTRODES HEAT SINK
ELASTOMER

FIG. 18. Schematic cross section of contactless switch. 37 FIG. 20. Schematicview of pyroelectricdetector.ll4

1606 J. Acoust.
Soc.Am.,Vol.70, No.6, December
1981 G.M. Sessler:
Piezoelectricity
inpolyvinylidenefluoride 1606

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 Simultaneously, detailed measurements have been llM. Tamura, T. Yamaguchi,T. Oyaba,andT. Yoshimi,J.
performed on the elastic, dielectric, and piezoelectric Audio Eng. Soc. 23, 21 (1975).
constants of PVDF and their temperature and frequency 12y. WadaandR. Hayakawa,Jpn. J. Appl. Phys. 15, 2041
dependencies. The piezoelectric constants are, of (1976).
lSp. Micheron,Rev. Tech. Thomson-CSF10,445 (1978).
course, very dependenton the crystalline form and on 14H.SussnerandK. Dransfeld, ColloidPolym. Sci. 257, 591
the poling process. Since the discovery of the (1979).
piezoelectric effect in PVDF in 1969, these constants lSG. M. Sessler(Ed.), Elec•ets, Topicsin AppliedPhysics,
have been improved by about a factor of six. Further Vol. 33 (Springer-Verlag, Berlin, 1980).
increases can be expected although the rate of progress 1GG.R. Davies, in Physicsof Dielectric Solids1980, Confer-
will probably not be as dramatic as in the past. ence Series Number 58 (The Institute of Physics, Bristol,
1980), pp. 50-63.
PVDF differs in very significant ways from conven- l?M. G. BroadhurstandG. T. Davis, in Electrets, Topicsin
tional piezoelectric materials. For example, it is Applied Physics, Vol. 33 (Springer-Verlag, Berlin, 1980),
available in thin films of considerable size. Thus pp. 285-319.
large-area transducers of high capacitance can be de- lSE. L. Nix, L. Holt, J. C. McGrath, and I. M. Ward, Ferro-
electrics 32, 103 ( 1981 ).
signed which are easy to handle from the standpoint
lSK. Tashiro, H. Todakoro,andM. Kobayashi,Ferroelec-
of amplification. Also, PVDF sheets can be made in trics 32, 167 ( 1981 ).
a wide variety of geometries, both plane and curved, 2øR.Hasegawa,Y. Takahashi,Y. Chatani, and H. Tadokoro,
which is also an advantage in many applications. Other Polym. J. 3, 600 (1972).
examples of the special features of PVDF are its low 21G.T. Davis, J. E. McKinney,M. G. Broadhurst,andS.C.
Q value which results in almost flat transducer re- Roth, J. Appl. Phys. 49, 4998 (1976).
sponses up to the resonance frequencies, and its rela- •2Y. Takahashiand H. Tadokora, Macromolecules13, 1317
( 1980 ).
tively low acoustic impedance which closely matches
23M,A. Bachmann,W. L. Gordon,J. L. Koenig, andJ. B.
that of water and thus allows good acoustic coupling
Lando, J. Appl. Phys. 50, 6106 (1979).
from the polymer into water and vice versa. Finally, 24S.OsakiandT. Kotaka,Ferroelectrics32, 1 (1981).
the maximum strain achievable with this material is 2SA.J. Lovinger, Macromolecules14, 322 (1981).
very large due to its high depolarization field. In all 2GH.J. Shaw,D. Weinstein,L. T. Zitelli, C. W. Frank, R.
these respects PVDF is superior to conventional C. DeMattei, and K. Fesler, Proc. 1980 Ultrason. Syrup.
piezoelectric materials. (IEEE, Piscataway, NJ, 1980).
27E.FukadaandT. Sakurai,Polym.J. 2, 656(1971).
These advantages have stimulated the search for ap- 28H.Ohigashi,J. Appl. Phys.47, 949 (1976).
plications of PVDF in spite of the fact that the size and 29C.M. vander Burgt,G. A. vanMaanen,andJ. W. Vegt,
the thermal stability of its piezoelectric response are Ultrasonics International 1977, Brighton, U.K. (IPC Science
inferior to the corresponding characteristics of ceram- and TechnologyPress, Guildford, Surrey, England, 1977),
ic materials. Some of the applications that have been pp. 500-507.
suggested were put into service over the past few 3øH.Sussner, Phys. Lett. 58A, 426 (1976).
Sip. T. A. Klaase and J. van Turnbout, in Proc. Third In-
years; others will, no doubt, be forgotten. As with tern. Conf. Dielectr. Materials, MeasurementsandAppli-
any new material, PVDF will be used where its advan- cations ( IEE Conf. Publ. 177, 1979), pp. 411-414.
tages count and where its shortcomings canbe tole- 32R.Lerch, "Untersuchungenan Piezo-Polymer-Mikropho-
rated. It appears that PVDF is finding its place in the nen, Darmst1•clter
Dissertation,ISBl•I-3-8102-0526-5
family of useful piezoelectric materials. (1980).
33R. Lerch, Techn. Messen (to be published).
34S.Tasaka andS. Miyata, Ferroelectrics 32, 17 (1981).
ACKNOWLEDGMENTS
35p. D. Southgate,Appl. Phys. Lett. 28, 250 (1976).
The author is grateful to R. Gerhard and J. E. West 3•W. R. Blevin, Appl. Phys. Lett. 31, 6 (1977).
for helpful comments on the manuscript. 37N. Murayama, N. Nakamura, H. Obara, and M. Segawa,
Ultrasonics 14, 15 (1976).
38T. Mizutani, T. Yamaria, andM. Ieda, J. Phys. D: Appl.
Phys. 14, 1139 ( 1981).
lJ. Curie and P. Curie, C. R. Acad. Sci. Paris 91, 294 39D.K. Das Gupta, K. Doughty,andD. B. Shier, J. Electro-
stat. 7, 267 (1979).
(1880); 91, 383 (1880).
2p. Langevin,Brev. Franc. 505,703(1918). 4øR.G. Kepler andR. A. Anderson,J. Appl. Phys.
3W. G. Carly, Piezoelect•4city( McGraw-Hill, New York, 49, 1232 (1978).
1946).
41G.Pfister, M. Abkovitz, andR. G. Crystal, J. Appl. Phys.
4W. P. Mason, Piezoelectric C•,•dstals
and Their Applications 44, 2064 (1973).
to Ultrasonics (Van Nostrand, Princeton, 1950). 4•1•1.
Murayama, T. Oikawa, T. Katto, andK. Nakamura, J.
5D. A. Berlincourt, D. R. Curran, and H. Jaffe, in Physical Polym. Sci.- Polym. Phys. 13, 1033 (1975).
Acoustics, Principles and Methods, editedby W. P. Mason 43H. Sussnerand K. Dransfeld, J. Polym. Sci.: Polym. Phys.
(•Academic, New York, 1964), pp. 169-270. 16, 529 (1978).
6K. R. Brain, Proc. Phys. Soc. (London)36, 81 (1924). 44R.J. Phelan, R. L. Peterson,C. A. Hamilton, andG. W.
?E. Fukada, Ultrasonics 6, 229 (1968). Day, Ferroelectrics 7, 375 (1974).
SH. Kawai, Jpn. J. Appl. Phys. 8, 975 (1969). 4SG.W. Day, C. A. Hamilton,R. L. Peterson,1R.J. Phelan,
9N. Murayama, N. Nakamura,H. Obara, andM. Segawa, and L. O. Mullen, Appl. Phys. Lett. 24, 456 (1974).
Ultrasonics 14, 15 ( 1976 ). 46R. E. Collins, J. Appl. Phys. 51, 2973 (1980).
10j. G. Bergman, J. H. McFee, andG. R. Crane, Appl. 47P.Laurenceau,G. Dreyfus,andJ. ,Lewiner,Phys. Rev.
Lett. 38, 46 (1977).
Phys. Lett. 18, 203 (1971); J. H. McFee, J. G. Bergman,
and G. R. Crane, Ferroelectrics 3, 305 (1972). 48M. G. Broadhurst, G. T. Davis, S.C. Roth, and R. E. Col-

1607 J. Acoust.
$oc.Am.,Vol./O, No.15,Uecember
1981 G.M. Sessler:
Piezoelectricity
in polyvinylidenefluoride 1607

Redistribution subject to ASA license or copyright; see http://acousticalsociety.org/content/terms. Download to IP: 130.83.18.21 On: Tue, 21 Jun 2016 13:55:37
 lins, in 1976 Annual Report, Conf. on Elecfrical Insulation 8•E. Carome, H. J. Shaw, D. Weinstein, andL. T. Zitelli,
and Dielectric Phenomena(NAS, Washington, DC, 1978), Proc. 1979 Ultrason. Syrup. (IEEE, Piscataway, NJ, 1979),
pp. 38-47. pp. 346-349.
86j. G. Linvi11,Tech. Rep. 4834--3, 83-88, StanfordElec-
4SW.Eisenmengerand M. Haardt (to be published). tronic Laboratories (1978).
5øW.Eisenmenger(to be published). 87R. G. Swartz and J. D. Plummet, IEEE Trans. Sonics Ultra-
51E. Fukada and T. Furukawa, Ultrasorties 19, 31 (1981).
son. SU 27, 295 (1980).
•2R. Hayakawaand Y. Wada, Rep. Progr. Polym. Phys. Jpn. 88K.TodaandK. Ikenohira,J. Appl. Phys. 51, 5657(1980).
19, 321 (1976).
8SR.S. Wagers, J. Appl. Phys. 51, 5797 (1980).
53y. Wada and R. Hayakawa, Ferroelectrics 32, 115 (1981).
9øE. Dieulesaint, F. Mattiocco, andD. Royer, C. R. Acad.
•4M. G. Broadhurst, G. T. Davis, J. E. Mc Kinneyand R. E.
Sci. Paris 287, 171 (1978).
Collins, J. Appl. Phys. 49, 4992 (1978).
SlK. Toda and Y. Yamashito, El. Lett. 14, 747 (1978).
•M. G. Broadhurst, F. Micheron, and Y. Wada, Ferroelec-
S2p. Merilainen and M. Luukalla, Electron. Lett. 14, 745
trics 32, III (1981).
(1978).
56M.Tamura, K. Ogasawara,N. Oho, andS. Hagiwara, J. 93R. G. Swartz and J. D. Plummet, IEEE Trans. El. Dev.
Appl. Phys. 45, 3768 (1974).
ED-26, 1921 (1979).
57M.OshikiandE. Fukada, Jpn. J. Appl. Phys. 15, 43 (1976). 94B.Woodward,Proc. 9th Int. Congr.Acoust.Madrid, paper
•SD. K. Das Guptaand K. Doughty, J. Phys. D: Appl. Phys. K40 (1977).
11, 2415 (1978). 95T. D. SullivanandJ. M. Powers, J. Acoust. Soc. Am. 63,
•9L. L. Blyler, G. E. Johnson,andN.M. Hylton, Ferroelec- 1396 (1978).
trics 28, 303 (1980). 9•B. Woodward,Acustica38, 264 (1977).
6øG.E. Johnson,L. L. Blyler, G. R. Crane, and C. Gieniew- •?B. Woodwardand R. C. Chandra, Electrocomput.Sci. and
ski, Ferroelectrics 32, 43 (1981). Tech. 5, 149 (1978).
61T. Furukawa, M. Date, and E. Fukada, J. Appl. Phys. 51, •SK. C. Shotton,D. R. Bacon, andR. M. Quilllain, Ultrason.
1135 ( 1980 ). 18, 123 (1980).
62N. Takahashi andA. Odajima, Ferroelectrics 32, 49 (1981); •D. T. Wilson, R. B. Tancredi, andJ. Callerame, Proc.
T. Takahashi, M. Date, and E. Fukada, Ferroelectrics 32, 1979 Ultrason. Syrup. (IEEE, Piscataway, NJ, 1979), pp.
73.( 1981 ). 506-510.
63M. G. Broadhurst and G. T. Davis, Ferroelectrics 32, 177 løøA.S. DeReggi,S.C. Roth, J. M. Kenney,S. Edelman,and
(1981). G. R. Harris, J. Acoust. Soc. Am. 69, 853 (1981).
64M. G. Broadhurst,S. Edelman, andG. T. Davis, Natl. lø•H. Ohigashi,R. Shigenari, andM. Yokota, Jpn..J. Appl.
Meas. Lab., Natl. Bur. Stand., Washington, DC AD-A079 Phys. 14, 1085 (1975).
649/0 (January, 1980), p. 110. lø2S.D. Bennett and J. Chambers, Electron. Lett. 13, 110
6•J. G. Linvill, Ferroelectrics 28, 291 (1980). (1977).
66W.D. Cragg andN. W. Tester, Elektr. Nachrichtenwesen lø3M. Latour and P. V. Murphy, Ferroelectrics 32, 33
52, 359 (1977). ( 1981 ).
67H. R. Gallanttee and R. M. Quilllain, Marconi Rev. 39, løaM. Quilllain, Electron. Industr. 3, 23 (1977).
189 (1976). lø•C. T. Pearman, J. L. Hokanson,andT. R. Meeker, Ferro-
68H.Naono, T. Gotoh, M. Matsumoto,andS. lbaraki, Audio electrics 28, 311 (1980).
Eng. Soc. Preprint No. 1271 (0-1) (1977). løSH.Ohigashi(private communication).
69G.M. Sessler, in Fortschritte der Alzustilz,DAGA '76 (VDE lø?M. Toda andS. Osaka, Trans. IECE Jpn. E61, 507 (1978).
Verlag, Berlin, 1976), pp. 81-95. løSM.Toda, Ferroelectrics 32, 127 (1981).
?øR.Lerch, J. Acoust. Soc. Am. 66, 952 (1979). lø9T. Ebato, T. Kajiwara, andS. Kobayaski,Electron. Lett.
?•R. Lerch and G. M. Sessler, J. Acoust. Soc. Am. 67, 1379 16, 829 (1980).
(1980). lløS. A. Kokorowski,J. Opt. Soc. Am. 69, 181 (1979).
?2G. M. Sessler and R. Lerch in Fortschritte der Alzustilz, lllT. Sato, H. Ishida, andO. Ikeda, Appl. Opt. 19, 1430
DAGA'80 (VDE Verlag, Berlin, 1980), pp. 799-802. ( 1980 ).
?dR.Lerch, J. Acoust. Soc. Am. 69, 1809 (1981). l•2G. R. Crane, IEEE Trans. SonicsUltrason. SU--25, 393
?aR.Lerch, J. Acoust.Soc. Am. (to be published). (1978).
?•J. F. Sear andR. Carpenter,Electr. Lett. 11, 532 ll3A. S. DeReggi, "Piezoelectric Polymer Transducerfor Im-
(1975). pact Pressure Measurement," Rep. NBS,COM-75-11127 (1975).
?6G.M. Garner, Syst. Tech. 27, 22 (1977). ll4j. H. McFee, J. G. Bergman, and G. R. Crane, IEEE
??P.V. Murphyand G. Maurer, J. AudioEng. Soc. 29, 364 Trans. SonicsUltrason. SU-19, 305 (1972).
(1981). ll•L. E. Garn and E. J. Sharp, IEEE Trans. Parts, Hybrids
?8R.A. Abram, J. Phys. D.: Appl. Phys. 13, 201(1980). Packaging, PHP-10, 208 (1974).
?9K.Hatakeyama, S. Kinoshita,A. Haeno,andT. Asanuma, l•sj. E. Jacobsand S. A. Remily, Infrared Phys. 19, 1
Audio Eng. Soc. Preprint No. 1056 (L-l) (1975). (1979).
8øB.Locanthi,K. Maekawa,K. Sugano,H. Fukura, andS. ll?j. G. Bergman, G. R. Crane, A. A. Ballman, and H. M.
Koyano, Audio Eng. Soc. Preprint No. 1302 (0-3) (1977). O'Bryan, Appl. Phys. Lett. 21, 497 (1972).
81T. Yamamoto
andM. Tamura, "Application
of Piezoelectric llSW. R. Blevin and J. Geist, Appl. Opt. 13, 2212 (1974).
Polymers to Audio Transducers" (unpublished); see also J. llgC. P. Germano, IEEE Trans. Audio Electroacoust.AU-19,
Acoust. Soc. Am. 60, S46 (1976). 6 ( 1971 ).
82K.KobayashiandT. Yasuda,Ferroelectrics
32, 181(1981). 12øW.P. LeungandK. K. Yung, J. Appl. Phys. $0, 8031
83H.Sussner,D. Michas,A. Assfalg,S. Hunklinger,
and K. ( 1980 ).
Dransfeld, Phys. Lett. 45A, 475 (1973); C. Alquie, J. l•'lL. N. Bui, H. J. Shaw, andL. T. Zitelli, IEEE Trans.
Lewiner, and C. Friedman, Appl. Phys. Lett. 29, 69 [1976]. Sonics Ultrason. SU'24, 331 (1977).
84D.Ricketts,J. Acoust.Soc.Am. 68, 1025(1980).

1608 J. Acoust.Soc.Am., Vol. 70, No. 6, December1981 G.M. Sessler:Piezoelectricityin polyvinylidenefluoride 1608

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