ARTICLE IN PRESS

Journal of Electrostatics 65 (2007) 182–188

www.elsevier.com/locate/elstat

Pyroelectric conversion—Effects of P(VDF–TrFE) preconditioning on

power conversion
Lia Kouchachvili, Michio Ikura
CANMET Energy Technology Centre-Ottawa (CETC-O), Natural Resources Canada, 1 Haanel Drive, Ottawa, Ont., Canada K1A 1M1
Received 22 July 2005; received in revised form 1 July 2006; accepted 23 July 2006
Available online 11 September 2006

Abstract

Large amounts of low-grade heat are emitted from various industries and wasted into the environment. This heat energy can be used as
a free source for pyroelectric power generation. We first discuss the principle of pyroelectric conversion based on the differences in crystal
structures of copolymer. Then we discuss the pyroelectric conversion of waste heat using copolymer films containing 60% vinylidene
fluoride (VDF) and 40% trifluoroethylene (TrFE) and the impact of the preconditioning of the pyroelectric films on the net power
output. We discovered that the pre-polarization (poling) of pyroelectric films has a significant beneficial effect by decreasing internal
conduction during power conversion. This in turn increased net power output. We were able to reach 95–165 J/L of copolymer used in
each cycle even including the internal leakage. We also showed it is critically important to operate the power conversion near the phase
transition where electron discharge is the highest.
Crown Copyright r 2006 Published by Elsevier B.V. All rights reserved.

Keywords: Pyroelectric conversion; Waste heat; Poling; Resistivity; P(VDF–TrFE)

1. Introduction It utilizes the charge–voltage characteristics (displacement

Large amounts of low-grade heat are wasted at pulp and
paper mills, steel works, petrochemical plants, glass
manufacturers and electric power stations. However, due
to the high cost of energy recovery and the lack of
promising technologies, low-grade heat is normally dis-
charged to the environment. When the temperature of a
heat source is low, the amount of available heat for useful
work is also low, i.e., inherently limited Carnot cycle
efficiency. Further, equipment for improved heat utiliza-
tion becomes bulky and the cost of installation becomes
prohibitive. Nevertheless, the need and opportunity exist
for converting waste heat to usable electricity. Existing
technologies such as the organic Rankine cycle cannot
function well below 80 1C [1]. Pyroelectric conversion
technology could meet this challenge.
Olsen et al. [2] developed a pyroelectric conversion cycle
and in this paper it will be referred to as the Olsen Cycle.
Corresponding author.
E-mail address: mikura@nrcan.gc.ca (M. Ikura).
versus applied electric field) of pyroelectric materials at
different temperatures and voltages to achieve heat-to-
electric power conversion. Pyroelectric films used in their
study were a copolymer of 60% vinylidene fluoride (VDF)
and 40% trifluoroethylene (TrFE), 60/40 P(VDF–TrFE).
Pyroelectric copolymers belong to a specific subgroup of
dielectrics. Dielectrics fall in two groups: symmetric and
nonsymmetric. Dielectrics without a center of symmetry
exhibits piezoelectricity, i.e., charge generation upon
stressing the material. Piezoelectric material can be
nonpyroelectric or pyroelectric. As the name suggests,
pyroelectric materials responds to change in temperature
that causes internal strain which in turn results in electrical
charging on the material surface.
Pyroelectricity has been observed in different crystals
and ceramics [3]. In the early 1970s, it was discovered that
poly (vinylidene fluoride) (PVDF) is pyroelectric [4]. PVDF
is a semicrystalline high-molecular-weight polymer of a
repeat unit (–CH2–CF2–) whose structure is essentially
head to tail, i.e. –CF2(–CH2–CF2–)n–CH2–, and has
typically 50% amorphous content. Its simple formula

0304-3886/$ - see front matter Crown Copyright r 2006 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.elstat.2006.07.014
 ARTICLE IN PRESS
L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188
hides a host of interesting properties, one of which is a
number of crystal forms. It exhibits at least four crystalline
phases (a, b, g and d) [5]. The stereochemical manner in
which monomers are linked together defines polymer’s
chain configuration. In the melt or in the solution, polymer
chains have randomly coiled shapes (conformations) but
when cooled it forms many phases. The high piezoelectric
and pyroelectric responses of PVDF are associated with the
polar b phase [6].
PVDF melts at about 170–200 1C, depending on poly-
meric form and crystallization temperature, and when
cooled from the melt without external stresses it crystallizes
in the form of spherulites of the nonpolar a phase.
The b phase is not usually produced from the melt
since that requires high pressures or epitaxial techniques,
but is obtained by mechanical deformation or electrical
poling [6,7].
The introduction of TrFE monomer into the VDF chain
affects the structural stability of the crystals significantly.
Copolymer P(VDF–TrFE) with VDF content between 50
and 80 mol% forms a ferroelectric b phase directly upon
crystallization from the melt without any further stretching
and shows higher piezoelectricity than PVDF [8]. Thus,
polar b phase transforms to nonpolar a phase upon heating
across the phase transition temperature. The temperature
and electric field dependent property of pyroelectric
materials can be used to convert heat to electricity as
described by Olsen et al. [2].
2. Pyroelectric conversion cycle
The electrical energy production cycle (the Olsen cycle)
may be described in terms of the charge–voltage behavior
of a ferroelectric material. Fig. 1 shows a hysteresis loop
of a typical pyroelectric copolymer at two different
temperatures.
Charge
Tlow
A
D
B 3. Experimental
C Thigh
Volts
Fig. 1. Copolymer hysteresis curves and Olsen cycle.
183
The direction of the path (either clockwise or counter-
clockwise) determines whether electrical energy is produced
or dissipated. When voltage is applied to a ferroelectric
material and is cycled isothermally, the material’s natural
response is to follow a counterclockwise loop as indicated
by the broad white arrows in Fig. 1. Electrical input is
dissipated as Joule heating, which is equal to the hysteresis
loop area [2].
The pyroelectric generator exploits the fact that, by
removing the isothermal constraint, it is possible to reverse
the direction in which the loop is cycled thus enabling the
production of electrical energy from heat [2]. Point A
corresponds to a fully polarized film at high voltage and
low temperature.
Electric power is discharged from the film as it is heated
from (A–B). This corresponds to the transformation of
crystal structure in the film from polar b phase (point A) to
nonpolar a phase (point B). After reaching at high
temperature (point B), further discharge can occur by
reducing the external voltage (B–C). This brings the energy
state of the film to point C. The film is then recharged at
low voltage while cooling (C–D). This change occurs as the
crystal structure retransforms from nonpolar (a) to polar
(b) phase under a certain electric field. The energy state of
the polarized film at low temperature and low voltage
corresponds to point D in Fig. 1. After reaching the low
temperature (point D), the material is further recharged by
increasing the externally applied voltage (D–A) and the
energy state of the film returns to point A. Thus, the
electrical cycle can be realized in a clockwise manner,
which is opposite to the Joule heating direction, and net
electrical energy appears as indicated by the shaded area in
Fig. 1 [9]. The essential concept of the Olsen cycle is to
control external voltage (bias voltage) in synchronization
with the temperature change to convert heat to electricity.
This operation requires electrical input but the electrical
output exceeds the electrical input required for the power
conversion cycle. The net electrical output originates from
the conversion of heat to electrical energy that occurs
within the pyroelectric copolymer. The shaded area in
Fig. 1 is expressed in Joules, and therefore dividing the
value of the shaded area by a cycle time will give power
output in Watts. The faster the cycling, the more power
output the system generates by converting heat to electric
power.
3.1. Film preparation
The pyroelectric film was prepared using 60/40
P(VDF–TrFE) pellets. The pellets were pressed into a
25 mm film in two stages at 200 1C for 5 s; initial pressing
required 1275 kg/cm2 to flatten the pellets but subsequent
ones were done at 650 kg/cm2 to obtain the targeted 25 mm
thickness. A thin aluminum electrode was vacuum depos-
ited on both sides of the film. Subsequently electrical leads
 ARTICLE IN PRESS
184 L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188
were attached and high DC voltage (1000 V) was applied to
the film at room temperature. This burned the defects and
ensured no premature short circuit would occur between
the aluminum electrodes during film poling (pre-polariza-
tion) and experiments.
The film was then sandwiched between brass shims
(25 mm). The brass shim was electrically insulated to avoid
short circuit between its surface and the electrical leads.
Initial polarization of the film was done as follows. The
film assembly was immersed in a hot water bath at 95 1C
and a DC voltage was applied. It was gradually increased
to 1000 V (25 MV/m electric field) and kept at this voltage
for approximately 40–50 min. During the pre-polarization
of a pyroelectric film, it is imperative to increase the voltage
gradually in order to avoid repeated short circuiting that
ruins the usefulness of the pyroelectric film by leaving
charred fragments at the short-circuited sites. The film was
gradually cooled to room temperature and then the voltage
was removed.
3.2. Measuring circuit
Fig. 2 is a simplified measuring circuit used in power
conversion measurements. KEPCO operational power
supply (BOP1000M) was used to control bias voltage on
the pyroelectric film. We measured output and input
current to/from the pyroelectric film using resistor R1.
Resistor RD was used as a divider to protect the
measurement instrument. Resistor R2 was used to measure
operating voltage. Again resistor RL served as a voltage
divider to protect the measurement channel. The selection
of these resistors was based on the consideration for signal
input limit settings and measurement precision.
Pyroelectric current Ip is given by
dP dT f
I p ¼ Af ¼ Af p , (1)
dt dt
Power supply
Pyroelectric film
VH VL
RL
RD
R2
R1
Fig. 2. Simplified measuring circuit.
where t is the time (s), Af the film surface area (cm2), P the
polarization (mC/cm2), p the pyroelectric coefficient (mC/
cm2 K), and Tf the film temperature (K). As shown in
Eq. (1), the pyroelectric current depends on three
parameters: film surface area, rate of temperature change
and pyroelectric coefficient.
The overall net power output Np from a pyroelectric film
can be calculated as follows:
  
dT f
N p ¼ V a I m ¼ V a ðI p þ I f Þ ¼ V a pAf þ If , (2)
dt
where Va represents the external voltage applied across the
pyroelectric film, Im the total current, Ip the pyroelectric
current, and If. the film leakage current. When the film
temperature is kept constant as practiced during the poling
process, there is no pyroelectric current Ip and thus, the
total current Im is equal to the film leakage current If. The
total current Im is determined by measuring a voltage drop
across R1. Thus, when the pyroelectric film goes through
A–B–C current discharging path as described using Fig. 1,
it generates power. According to the measurement config-
uration shown in Fig. 2, the current flows from the ground
side towards the film to complete the current loop and the
voltage reading will register negative. Thus, according to
the convention used in this paper, when the pyroelectric
film acts as a power generator, Np values will be negative,
but this is simply a matter of convention. Conversely,
positive Np indicates that the pyroelectric film is being
recharged by either lowering temperature at low voltage or
raising external power supply voltage at low temperature
(path C–D–A).
The cumulative pyroelectric conversion output Wp (J)
according to Olsen cycle as described above is given by
Z Z Z
dT f
W p ¼ N p dt ¼ V a pAf dt þ V a I f dt. (3)
dt
3.3. Temperature cycling
The temperature cycling was achieved by manually
immersing the film assembly in hot and cold water baths
repeatedly. We mainly used water in the current series of
experiments. However, for examining the film performance
at higher than 100 1C, we used a water (50%) and
propylene glycol (50%) mixture. Due to the difficulties in
immersing the film in the hot or cold bath at precise
intervals, the cycling period varied a little.
4. Experimental results and discussion
4.1. Resistivity and poling process
It is known that copolymer resistivity is highly dependent
on temperature [6,10]. When temperature increases, resis-
tivity decreases and the internal conduction increases. This
has a detrimental effect during pyroelectric conversion,
 ARTICLE IN PRESS
L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188 185

because increased leakage current decreases the net output 14

while pyroelectric films are discharging, i.e., generating 12
V=30MV/m
power.

Total current (µA)

10
As the poling process proceeds at constant temperature V=34MV/m
and electric field, resistivity increases and thus the leakage 8 V=37MV/m
current If decreases. Since the pyroelectric film is not going 6
through the phase transition stages and is not developing 4
any output current Ip ¼ 0. In this case the total current
2
Im ( ¼ Ip+If) and the leakage current If are equal. The
decreasing rate of total current is fairly rapid initially but it 0
0 50 100 150 200 250
slows down as the poling process approaches completion.
Time (min)
It appears the poling process is slow. The total current
reaches a steady value asymptotically and it stabilizes after Fig. 4. Effect of field strengths on polarization time at 94 1C.
about 3 h. We considered this as the completion of the
poling process. Fig. 3b gives the film resistivity calculated
from the data in Fig. 3a.
Poling duration, temperature and voltage all affect the electric field. In theory, when a pyroelectric film
film polarization. Fig. 4 plots the total current Im across polarizes completely, there should be virtually no
the resistor R1 at 94 1C at different electric fields. leakage current as the film is transformed to a ‘perfect’
It shows the higher the electric field the shorter the insulator. However, the presence of localized impurities
polarization time. The total current decreases with time and mechanical defects created during film assembling
but the decrease rate is dependent on the strength of makes the actual film somewhat imperfect, and all these
factors contribute to prolonging polarization time and
residual total current.

25 4.2. Effect of polarization on energy conversion

The effect of leakage current on the power output during

20
the Olsen cycle is illustrated in Fig. 5. The negative side of
Total current (µA)

this graph corresponds to the current from the film

15
(discharging legs A–B and B–C in Fig. 1) and the positive
side to the current into the film (charging legs C–D and
10 D–A in Fig. 1). When the film is not well polarized the
leakage current during the Olsen cycle is large (Fig. 5a) and
5 net power output is small (Fig. 5b). The power output is
obtained by multiplying the total current Im and operating
0 voltage Va.
0 100 200 300 If poling process is properly completed and the leakage
(a) Time (min) current is minimized, the current flow from the pyroelectric
film significantly increases (Fig. 5c), and the power output
11.8 from the Olsen cycle increases as well (Fig. 5d).
11.7 Fig. 6 shows the cumulative power output from an
identical film but with and without proper polarization.
11.6
One peak-to-peak interval represents one Olsen cycle.
Log resistivity

11.5 The power output is expressed as the energy density

11.4
of pyroelectric copolymer used in casting the film.
Fig. 6 shows that the net output for each Olsen cycle
11.3 increases by about 35% when the film is properly pre-
11.2 polarized.
11.1
4.3. Effect of raising control voltage and film failure
11
0 100 200 300 When the high limit of the control voltage was increased
(b) Time (min) up to 27.6 MV/m, the film failed only after four cycles.
Fig. 3. (a) Total current Im across pyroelectric film during poling at 95 1C Figs. 7a and b illustrate the film’s failure. Fig. 7b illustrates
and 20 MV/m, and (b) increase in 60/40 P(VDF–TrFE) resistivity that as long as film could withstand the high control
calculated from (a). voltage, the Olsen cycle output was very high.
 ARTICLE IN PRESS
186 L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188

100 60
leakage current
3 4 40

Power output (mW)

Total current (µA)

50
20

0 0

-20
-50
1 2
-40

-100 -60
35 35.5 36 36.5 37 37.5 35 35.5 36 36.5 37 37.5
(a) Time (s) (b) Time (s)

100 60
Leakage current is
minimized

Power output (mW)

Total current (µA)

50
20

-20
-50

-100 -60
22.5 23 23.5 24 22.5 23 23.5 24
(c) Time (s) (d) Time (s)

Fig. 5. Olsen cycle at 6.7 MV/m (charge) and 20 MV/m (discharge), temperatures 55 and 100 1C. (a) Olsen cycle without proper polarization. Arrow 1
indicates discharging by increasing temperature from Tlow to Thigh; Arrow 2 indicates discharging by reducing voltage from Vhigh to Vlow at Thigh; Arrow 3
indicates charging by decreasing temperature from Thigh to Tlow; Arrow 4 indicates charging by increasing voltage from Vlow to Vhigh at Tlow. (b) Power
output corresponding to (a), (c) Olsen cycle after proper film polarization, and (d) power output corresponding to (c).

0
beneficial to increase the high side of control voltage as
70J/L
reported here, the film assembly must be rugged enough to
-500
Cumulative output (J/L)

withstand the short circuit.

-1000
4.4. Temperature
-1500
It is clear that the wider the temperature difference
-2000 between the film assembly and the heat source tempera-
95J/L
tures, the higher the rates of heat transfer, and thus larger
-2500
the pyroelectric output. Further, the pyroelectric conver-
0 20 40 60 sion cycle should be operated near the phase transition
Time (s) temperature where the pyroelectric material undergoes
polar-to-nonpolar conformation change resulting in huge
Fig. 6. Effect of film pre-polarization on the cumulative output.
charge/discharge of electrons. In addition, there is also a
suitable operating temperature as the low temperature
limit.
Date [11] reported that the relationship between applied
electric field and the phase transition temperature Tp of 52/
Upon disassembling the film we found there was a short 48 P(VDF–TrFE). Tp can be correlated by using a Clausius
circuit between the leads and brass shim that was used to Clapeyron equation:
encase the film. There were a few charred spots along the
electrical leads and the electrode surfaces. Although it is dT p =dE ¼ DP T p =L,
 ARTICLE IN PRESS
L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188 187

100 instead of the 60/40 we used, his equation is in good

Film's failure
agreement with our measurements [1].
Total current (µA)

50 It must be recalled, however, that as the film temperature

rises, so does the leakage current. Fig. 8 shows the
0 total current across the resistor R1 in Fig. 2 when the
pyroelectric film was discharged at two temperatures: 75
-50 and 101 1C. As mentioned earlier the total measured
current Im is the sum of the pyroelectric current Ip and
-100 the leakage current If. Whereas discharge current at 101 1C
10 12 14 16 18 20 is much larger than that at 75 1C, the leakage current
(a) Time (s) at 101 1C is unacceptably high. Thus, it is critically
0
important to choose the high limit of operating tempera-
ture (Thigh), which in our case lies somewhere between 101
about 165J/L and 75 1C.
Cumulative output (J/L)

-200
We now consider the issue related to the low limit of
operating temperature (Tlow). In an Olsen cycle, the
-400
Film's failure charging of a pyroelectric film occurs at Tlow. The lower
the Tlow the larger the charge current as the pyroelectric
-600
copolymer restores the polar crystal structure during the
charging period (C–D–A) of the Olsen cycle. The principle
-800 of the Olsen cycle as illustrated in Fig. 1 suggests that the
wider the operating temperature difference, the larger the
-1000 net power output. Fig. 9(A) shows that the lower the Tlow,
0 5 10 15 20 25 30 35
the larger the charge current and the smaller the effect of
(b) Time (s)
leakage current.
Fig. 7. (a) Film failure after four Olsen cycles. (b) Power output at
Vhigh ¼ 27.6 MV/m and Vlow ¼ 6.23 MV/m; Thigh ¼ 100 1C, and
Tlow ¼ 50 1C.
5. Conclusion

The pre-polarization (poling) of pyroelectric films has a

30
leakage current
very significant effect on the net power output by
20 pyroelectric conversion. The poling process of a copolymer
10 film was highly dependent on the strength of the electric
field on the film, poling time and temperature. For a
Total current (µA)

0
commercial 60%/40% P(VDF–TrFE) copolymer, satisfac-
-10
101°C 75°C tory pre-polarization was achieved by applying an electric
-20 field of 20–37 MV/m for 2–4 h near 95 1C. The complete
-30 pre-polarization of the pyroelectric film significantly
-40 increased its resistivity.
-50
It was confirmed that well pre-polarized pyroelectric
films had very low internal conduction (leakage) during the
-60
5 10 15 20 25 Olsen cycle and thus had increased net power output.
Time (s) Properly poled pyroelectric films could produce 95–165 J/L
of copolymer used in each Olsen cycle by allowing the
Fig. 8. Total output current Im across R1 at 26 MV/m at 75 and 101 1C. application of high voltage at high temperature while
keeping the leakage current low. This resulted in nearly 2–4
times of output that was achieved previously (40 J/L of
copolymer used) [12].
where E is a bias electric field, DP the polarization change A high heat transfer rate is critically important for
at phase transition point and L the latent heat. Date gives achieving high net power output. High heat transfer rates
L ¼ 1:090E+07 J/m3, T c ¼ 340 K, and DP ¼ 38 mC/m2. allow quickly reaching the phase transition temperature
By integrating this formula using the Date’s values, we can where film discharge is the greatest and returning to low
calculate the shift in transition temperature as the voltage temperature where film charging takes place at minimal
changes. leakage current. Thus, the configuration of the pyroelectric
Although Date’s experiments were limited to a maximum film assembly is another important issue that needs further
electric field of 15 MV/m and his copolymer was 52/48 investigation.
 ARTICLE IN PRESS
188 L. Kouchachvili, M. Ikura / Journal of Electrostatics 65 (2007) 182–188

a b c
2
80
60

Total current (µA)

40
20
0
-20
-40
-60
-80
29 30 31 32 33 34
1 Time (s) 1-charging current
(A) 2-leakage current

a b c
80
60
Power output (mW)

40
20
0
-20
-40
-60
-80
29 30 31 32 33 34
(B) Time (s)

Fig. 9. (A) Output current of three Olsen cycles at three low temperature limits. Curve a: Tlow ¼ 35.5 1C, curve b: Tlow ¼ 45.5 1C, curve c: Tlow ¼ 55.5 1C.
(B) Corresponding power outputs for the three Olsen cycles. (A) and (B). Comparison of three Olsen cycles at three different Tlow temperatures.

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