Rate Dependence of Soft PZT Ceramics under Electric Field Loading

Dayu Zhou, Marc Kamlah and Dietrich Munz

Forschungszentrum Karisruhe, Institut fr Materialforschung II, D-7602 1 Karisruhe, Germany
ABSTRACT
Polarization and longitudinal strain of the commercial soft PZT piezoceramic PlC 1 5 1 were measured as a function of
amplitude and frequency of an AC electric field. The range of frequencies considered was selected in the quasi-static range
from 0.01Hz to 1 .0 Hz. The electric field was selected as triangular loading. Besides the standard hysteresis loops for
polarization (P) and strain (S) versus electric field (E), strain versus polarization curves (S-P curves) were plotted in
separate diagrams. It was shown that both polarization and strain were frequency dependent. The coercive field increased
with the loading frequency. Furthermore, a significant hysteresis was observed for S-P curves at a loading frequency below
1 Hz. At a frequency of I Hz, however, the S-P plots were nearly close to an idealized parabolic curve without hysteresis. A
tentative explanation shall be given for these observations in terms ofthe rate effects ofthe domain switching process.
Keywords: soft PZT, polarization, strain, rate dependence, domain switching

1. INTRODUCTION
Lead zirconate titanate (PZT) piezoelectric ceramics provide excellent electromechanical properties that make them very
attractive for applications in electromechanic and electroacoustic transducers. Important applications are actuators, active
damping, precision positioning, structure control, and noise control [1].

Two basic types of polycrystalline PZT are distinguished, they are commonly called "soft" and "hard". In general, highvalent substituents induce soft piezoceramic behavior, whereas lower-valent ones induce hard behavior. Soft ferroelectrics
have lower coercive fields, higher hysteretic loss, higher susceptibilities and piezoelectric constants, compared to hard
types. Furthermore, the electromechanical coupling of soft materials is more pronounced than that predicted by the LaudauDavonshire phenomenology theory. The extra contributions are believed to be due to domain dynamics [2].
It is well known that PZT ceramics in the tetragonal phase state have two kinds ofdomain structures: 1 800 domains and 900
domains. Strong electric fields (higher than E) induce switching of the 180 domains and the reorientation of 90 domains

(ferroelectric switching), 90 domains reorientation can also be induced by stresses (ferroelastic switching). 1 80 domain
reversal does not contribute to the induced strain, only 90 rotation does, whereas the I 80 domain reversal contributes
mainly to the polarization [3].
Strong forces and large strains are required for many applications. This results in the operation of actuators at high stresses

and electric fields, where they show strong non-linearity and hysteresis induced by domain switching processes in the
material. Since non-linearity and hysteresis limit the performance, it is important to take the non-linear response and
hysteresis into consideration, when selecting materials and designing devices.

Constitutive responses of ferroelectric materials under uniaxial stress and electric field loading have been studied by many
researchers. Important experimental works concerning non-linear electromechanical coupling phenomena was carried out
by Cao and Evans, Schufele and Hrdtl, and Lynch [4, 5,6]. In their work, however, the influence of the loading rate on
the induced strain and polarization was not discussed.

It was supposed that the investigation of strain vs. polarization (S-P) curves can help to understand the domain switching
process in the ferroelectric materials. Schmidt and Kuwata et al. reported S-P plots of tetragonal structure PLZT(6.25/50/50)
ceramics and Pb(Mg113Nb213)03 relaxors respectively [7, 8]. However, the frequency dependence of S-P curves was not
presented in their work.

64

Smart Structures and Materials 2001: Active Materials: Behavior and Mechanics, Christopher S. Lynch,
Editor, Proceedings of SPIE Vol. 4333 (2001) 2001 SPIE 0277-786X/01/$15.00

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In this paper, systematic P-E, S-E and S-P investigations have been performed at various frequencies and maximum fields.
It was expected that such investigations would provide a better understanding of domain dynamics in ferroelectrics.

2. EXPERIMENT
All measurements were performed using the initially unpoled commercial material PlC 1 5 1 (Pt Ceramic, Lederhose,
Germany). The material is a kind of Pb(Ni113Sb213)03-PbTiO3-PbZrO3 ternary phase system including about 2-3% of
Pb(Ni113Sb2i3)03 in the vicinity ofthe morphotropic phase boundary ofPZT in the tetragonal range. The material properties

are listed in Table. I.

Table 1. Physical properties of the PIC151 soft PZT ceramic material
Resistivity (Qm)
1011

E / Curie temperature (C)

2400

250

d33

450

22.8

e: relative permittivity d: charge constants [x10'2 mV'] g: voltage constants [x103 VmN']

The specimens of 5 x 5 x 1 5 mm3 in dimension were cut from bulk ferroelectrics and all surfaces were polished. The upper
and bottom surfaces of the specimens with an area of 5 x 5 mm2 were electroded with silver. The high voltage is supplied by
a bipolar high-voltage power supply. A triangular wave was applied with a maximum amplitude of 2 kV/mm. The loading
frequency was selected in the quasi-static range from 0.01Hz up to 1Hz.
All samples were immersed into a bath of electronic liquid in order to avoid arcing.

The polarization vs. electric field (P-B) hysteresis loops were measured using a Sawyer-Tower circuit. A I OpT capacitor is

placed between the specimen and ground. The voltage on this capacitor is measured by an electrometer at an input
resistance of 1O'4Q.

For butterfly longitudinal strain vs. electric field (S-B) hysteresis loops, a linearly variable displacement transducer (LVDT)
connected to an AC measuring bridge was used.

A computer equipped with an AD/DA data acquisition board and the Dasylab software package were used to control the
high-voltage power and plot the measuring signal. To avoid electrical damage to the computer, a customized isolated DC
input/output signal conditioning module was applied to isolate the computer from high voltage.

3. RESULTS AND DISCUSSION

3.1 P-E & S-E Curves as a Function of Electric Field Amplitude and Frequency
The responses ofP-E and S-B curves under different electric amplitudes and frequencies are shown in Figures 1(a)-1(c) and
Figures 2(a)-2(c), respectively.
These figures clearly demonstrate a strong frequency dependence of P-B and S-B curves. At the electric field amplitude of 2

kV/mm and 1 .5 kV/mm, the familiar polarization and butterfly curves were observed at 0.01 Hz and 0. 1 Hz, and the
coercive field at 0.01 Hz is about 1 kV/mm. In addition, the coercive field (Er) was found to be frequency dependent and to
increase with increasing measuring frequency. The frequency dependence of E in ferroelectric materials has been known
for many years, including unmodified crystals and thin films [9, 10].

For the loading frequency of 1 Hz, polarization and strain were not saturated at the maximum electric field amplitude. For
example, about 62.5% of the maximum polarization and 72.3% of the maximum strain were induced after unloading from
+1- 1.5 kV/mm; and about 16.7% of the maximum polarization and 35.4% of the total strain were induced after unloading
from +1-2 kVlmm.

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65

(a)

(b)

(c)

Figure 1 . Polarization vs.electric field (P-E) curves for initially unpoled PICI5I soft PZT ceramic material as obtained at a
maximum AC drive amplitude of: (a) 2, (b) 1 .5, (c) 1kV/mm. 0.01 Hz A- 0. 1 Hz -* I Hz.

E(KVImm)

(a)

5oc5

075100

E(KV/mm)

(b)

E(KV/rrn)

(c)

Figure 2.Strain vs. electric field (S-E) curves for the initially unpoled PIC15I soft PZT ceramic material as obtained at a
maximum AC drive amplitudeof: (a)2,(b) 1.5,(c) 1kV/mm. 0.01HzA 0.1Hz * 1Hz.

Recently, Viehiand and Chen reported experimental results about the frequency dependence of initially polarized
O.7Pb(Mg113Nb213)03-O.3PbTiO3 soft ferroelectric material [9, 10]. Their results showed that when the electric field
amplitude was higher than E in our case by two times, typical P-E and S-E curves of ferroelectrics were observed from low
frequency (0.01Hz) to high frequency (1Hz). Only the coercive field increased with increasing frequency. However, the
phenomenon of incomplete saturation of polarization and strain at high loading frequency was not detected. The different
results obviously have to be attributed to the varying chemical compositions of the materials.

At the electric amplitude of 1 kV/mm, which is about the coercive field of soft PZT PlC 151 ceramics, the residual
polarization and strain decreased very fast with increasing loading frequency. At I Hz, most of the strain was induced
during the unloading process (see Figure 1(c) and Figure 2(c) ). In the work of Viehland and Chen, it was also reported
that the frequency dependence ofpolarization and strain was most pronounced at the coercive field oftheir material.

3.2 s-P Curves as a Function of Electric Field Amplitude and Frequency

The strain vs. polarization (S-P) curves under different electric field amplitudes and frequencies are shown in Figures 3(a)
3(c).

The frequency dependence of S-P curves is nearly the same for various field amplitudes. At 0.01 Hz and 0.1 Hz, significant
hystereses were observed in the S-P curves, however, when the loading frequency was up to 1 Hz, approximately parabolic
S-P curves were found.

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-0.4

-0.3

-0.2

-0,1

0,0

0.1

0.2

P(CIm)

(c)

(b)

(a)

Figure 3. Strain vs. polarization (S-P) curves for the initially unpoled PIC15 1 soft PZT ceramic material as obtained at a maximum AC
0.01 Hz,* 0.1 Hz, * 1 Hz.
drive amplitude of: (a) 2, (b) 1.5, (c) 1 kV/mm,

3.3 Discussion of the Frequency Dependence of S-P Curves

Kruger and Gerthsen studied the domain switching process in rhombohedral-phase (Pb,La)(Zr,Ti)03-ceramics. Their results
showed that this kind of ceramics exhibited polarization switching by two successive 71/109 domain processes, which
was idealized as two successive 900 domain wall motion processes. Polarization reversal was primarily determined by 900
domain reorientation [1 1, 12J.
Experimental results obtained by Schmidt confirmed that the polarization changes of tetragonal-phase PLZT-ceramics were
caused almost exclusively by 900 domain wall motions [7].
In order to investigate the frequency dependence of S-P curves in detail, P-E and S-E curves at 2 kV/mm were plotted in the

same diagram in this paper. Furthermore, the changes of polarization and strain as a function of the electric field were
compared (polarization values were multiplied by a factor of 4 for better comparison.). Then, a tentative explanation was
given in terms of the domain switching process. The results for 0.01 Hz and 1 Hz are illustrated in Figure 4 and Figure 5,
respectively.

B
b

-0,4

(a)

-0,3

-Q2

-0.1

0,0

(31

0,2

0,3

0,4

P(an

I I - --
**+-+--4+I

I
I

JL

C,cI I

(b)

(c)

Figure 4. Response of polarization and strain as a function of the electric field of +1- 2 ky/mm, 0.01 Hz.

(a) history of strain and polarization as reponse to electric field loading, (b) strain vs. polarization (S-P) curve, (c) proposed domain
switching process. (A-B-C-D-E-F-G, history of strain; a-b-c-d-e-f-g, history of polarization)

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67

At points A and a, the electric field is zero. The specimen has a residual strain of 0.27% and a residual polarization of O.33CIm2. As shown in Figure 4(c) at points A and a, most of the domains are aligned along the previous direction of
electric field loading, while a small part ofthe domains relax and gradually change their polarization direction to the initial

state before poling [13]. With the application of a positive electric field (opposite direction of polarization), both
polarization and strain begin to decrease. At point B, the strain reaches its minimum value, however there is still some
residual polarization. At point b, the electric field has reached the value that is usually called coercive field (here about I
kV/mm for PlC I 5 1). Now, the polarization is zero, whereas the strain is higher than its minimum value. Since the strain
and polarization do not reach their minimum values simultaneously, a hysteresis can be observed in the corresponding S-P
curves.

The domain switching process at 0.01 Hz shall now be discussed in terms of Figure 4(c). According to the results given by
Schmidt and KrUger [7, 1 1 , 12], most of the domains undergo a 900 switching from points A and a to B for the first time,
but there are still some domains remaining at the previous poling direction. Hence, the polarization is still negative and the
strain reaches its minimum value at point B, but it is not zero. From point B to b, part of the domains experiences a second
9O reorientation, domains with opposite poling direction make the net polarization to be zero, but the strain has already
started to increase. From point b, most of the domains undergo a 900 switching for the second time. At points C and c,

nearly all the domains have been aligned to the direction of a positive electric field. Both polarization and strain are
saturated. The domain switching process of the following sequence of D, d-E-e-F, f-G, g is nearly same, just the direction is
opposite.

Two successive 900 domain switching processes have been used by Lynch to explain the phenomenon of negative strain
with reference to the initially unpoled state in his experiments [6]. Even though we did not observe negative strains, the
minimum strains in our experiments were close to zero. In our interpretation, this also indicates the occurrence of two-step
900 domain switching processes.

At a low loading frequency of 0.01 Hz, there is enough time for the two-step 900 domain switching to take place. In
addition, polarization switching in the tetragonal-structure PZT ceramics (such as PlC 1 51 in our experiments) is caused
almost exclusively by 900 domain wall motions according to Schmidt, Kruger and Gerthsen [7, 11, 12]. So in case of
Figure 4, some 1 800 domain reversals may also have happened, however, only the contribution of two-step 900 domain
switching can be detected.

The domain switching process was also studied at the loading frequency of 1 Hz. The results are illustrated in Figure 5.

JJ

I I++*--+--*

B,b** I

JJ

44+4+4+- +
C,c
,

(a)

(b)

(c)

Figure 5. Response ofpolarization and strain as a function ofthe electric field at +1- 2 ky/mm, i Hz.

(a) history of strain and polarization in response to electric field loading, (b) strain vs. polarization (S-P) curve, (c) proposed domain
switching process (A-B-C-D-E-F-G, history ofstrain; a-b-c-d-e-f-g, history of polarization).

At points A and a, the material has a negative residual polarization and strain. When a positive electric field is applied to the
specimen, the strain reaches its minimum value at points B and b. At the same time the net polarization is zero, so a nonhysteretic and nearly parabolic S-P curved was detected at 1Hz.

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The domain switching process at I Hz shall now be discussed in the light of Figure 5(c). According to Uchida and Iketa, the
rate of I 80 domain reversal is faster than that of 900 domain reorientation [1 4]. Experimental results reported by Tsurumi
et al. also indicated that the velocity ofthe 900 domain wall motion was relatively low [1 5]. At a loading frequency of 1 Hz,

some domains still keep in their negative polarization direction from points A and a to points B and b, even though the
electric field strength at points B, b is as higher than 1.5 kVlmm, which is much higher than the coercive field at 0.01 Hz.
At the same time, a small number of domains have completed their I 80 reversals and changed their polarization directions
to the positive direction of the electric field. The number of domains with opposite polarization directions is same, so the
net polarization of the sample is zero. At points C and c, only some of the domains have finished their second-time 900
reorientation, as a result of which the strain and polarization are not saturated. Some domains will begin or continue their

switching during the unloading process, more polarization and strain will be induced. At points D and d, the residual
polarization and strain are higher than for 0.01 Hz since the time is not sufficient for some 90 domains to switch back to
their initially unpoled direction (see Figure 2(a) ). However, after removal of the electric field, our experimental results
show that the residual polarization and strain induced at 1 Hz will decrease very fast in the begining several seconds and
eventually become stationary. The final residual polarization and strain are lower than those at 0.01 Hz.

4. SUMMARY
Response of polarization and strain under AC electric field loading with different amplitudes and frequencies was studied
for the PlC 1 5 1 soft PZT ceramic material. Besides the standard hysteresis loops of polarization (P) and strain (S) versus
electric field (E), strain versus polarization curves (S-P curves) were plotted in separate diagrams at the same time. It was
shown that both polarization and strain were frequency dependent. The coercive field was found to increase with increasing
loading frequency. At 1 Hz, polarization and strain were not saturated at the maximum electric field amplitude, part of them
will be induced during the first period of the unloading process. A significant hysteresis was observed for the S-P curves at
0.01 and 0.1 Hz, whereas a nearly parabolic S-P curve was detected when the frequency was up to 1Hz. The two successive
90 domain switching processes were used to explain the experimental phenomena. The relatively slow reorientation
velocity of 90 domains compared to 1 80 domains was supposed to be the reason of the experimental results.

5. ACKNOWLEGEMENT
The support by the Deutsche Forschungsgemeinschaft is greatly acknowledged and the authors would also like to give
thanks to Mr. A. Frhlich for useful discussions.

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