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NASA / CR- 1998-208708

Properties of PZT-Based Piezoelectric

Ceramics Between-150 and 250°C

Matthew W. Hooker

Lockheed Martin Engineering & Sciences Co., Hampton, Virginia

National Aeronautics and

Space Administration

Langley Research Center Prepared for Langley Research Center

Hampton, Virginia 23681-2199 under Contract NAS1-96014

September 1998
p_

_, _ i-i_i_,i_ I_i_i
¸_ii._il,k_ -I-i i_i_iIi_IL ,_
 Abstract

The properties of three PZT-based piezoelectric ceramics and one PLZT electrostrictive ceramic were
measured as a function of temperature. In this work, the dielectric, ferroelectric polarization versus
electric field, and piezoelectric properties of PZT-4, PZT-5A, PZT-5H, and PLZT-9/65/35 were measured
over a temperature range of-150 to 250°C. In addition to these measurements, the relative thermal
expansion of each composition was measured from 25 to 600°C, and the modulus of rupture of each
material was measured at room temperature. This report describes the experimental results and
compares and contrasts the properties of these materials with respect to their applicability to intelligent
aerospace systems.

Keywords: piezoelectric, PZT, PLZT, temperature

InWoducfion

The term piezoelectricity refers to the relationship between pressure and electricity that exists within a
unique family of materials. Piezoelectrics are materials that either output a voltage when subjected to a
mechanical stress or exhibit a dimensional change when an electric field is applied. These two behaviors
are referred to as the direct and indirect modes of operation respectively [1-2]. Both modes of
piezoelectric operation are currently being utilized in modem aerospace systems in such diverse
applications as vibration cancellation and optical positioning [3-5]. Because these materials have the
ability to sense and respond to changes in their environment, they are often referred to as "smart" or
"intelligent" materials [6].

The primary applications of piezoelectric technologies in fixed-wing aircraft include the active control
of boundary layers along leading edges [7], the suppression of internal cabin noise [8], and the
elimination of panel flutter [9] and tail buffeting [10]. This technology is also being applied in
helicopters to eliminate the vibrations present in rotor blades [ 11-13].

In addition to the aeronautical applications of intelligent structures, piezoelectric technologies are also
being developed for use in spacecraft systems. In recent years, satellite systems have become smaller and
lighter to reduce the cost of launching the payloads into orbit. As spacecraft masses have been reduced,
however, the elimination of vibrational disturbances has become a critical design issue. Since many of
the scientific instruments aboard these spacecraft require precision pointing to perform their intended
functions, the spacecraft must be mechanically stable for the payloads to function as designed. As such,
methods of incorporating intelligent structures to minimize jitter in spacecraft structures has become a
critical area of research and development in the aerospace community [14-15].

Piezoelectric materials are typically incorporated into aerospace structures by either applying a patch-
style device to the surface of the structure [16-17] or by embedding the device into a graphite-epoxy
composite structure [18-20]. In each instance, distributed networks of sensors and actuators are used to
sense and nullify vibrational disturbances. Similarly-controlled systems are also being developed for use
in space-based instruments to actively position optical components [21]. These control systems typically
include a position sensor that locates the optical component and a piezoelectric drive mechanism which
positions the optic based on real-time feedback from the position sensor.

Because of the wide range of operating conditions for the systems under development, careful
consideration must be given to the selection of piezoelectric materials. This is particularly important
 when selectingmaterialsfor use in systemsthat will be exposedto a wide range of operating
temperatures. To addresstheseconcerns,
thedielectric,ferroelectric,andelectro-mechanical
properties
of four PZT-based materialswereevaluated
overa temperature rangeof -150to250°C.Additionally,the
thermalexpansion propertiesweremeasuredfrom25 to 600°C,andthemoduliof ruptureweremeasured
at room temperature.This reportdescribes the experimentalresultsandcomparesandcontraststhe
propertiesof thematerialsevaluated
withrespecttotheirapplicabilitytointelligentaerospace
systems.

Experimental Procedure

Materials Evaluated

The properties of three piezoelectric materials and one electrostrictive composition were measured
between -150 and 250°C. The piezoelectric materials evaluated in this work were commercially-
produced PZT-4, PZT-5A, and PZT-5H ceramics. The electrostrictive materials, PLZT-9/65/35, were
produced by tape casting powders synthesized by the solid state reaction of PbO, La203, ZrO2, and TiO 2.
All of the ceramics used in this study were obtained in an unelectroded and unpoled condition and
possessed density values that were at least 95% of theoretical density. Prior to testing, gold electrodes
were sputtered onto the major surfaces of each specimen.

Initially, the room temperature (25°C) dielectric, ferroelectric, and piezoelectric properties of each
composition were determined. Once the initial room temperature evaluations were complete, the
properties of each composition were then measured between -150 and 250°C. The specific details of each
measurement are described below.

During the thermal tests, each specimen was placed in an environmental chamber with a temperature
sensor located in close proximity to the test article. Throughout this investigation, multiple specimens of
each composition were tested at each condition, and the average value of each property was determined.

Dielectric and Ferroelectric Measurements

The dielectric constant (K), dissipation factor (tan 8), and electrical resistivity of each composition
were measured at frequencies of 100 Hz, 1 kHz, 10 kHz, and 100 kHz using an HP 4284A LCR meter.
From this data, the Curie point (To) of each specimen exhibiting a maximum dielectric constant between -
150 and 250°C was determined.

Next, the ferroelectric polarization versus electric field (P-E) properties of each composition were
measured at 1 Hz using a Sawyer-Tower circuit. The P-E properties of the soft piezoelectric materials
(i.e., PZT-5A and PZT-5H), as well as the electrostrictive specimens, were measured in an unpoled
condition. However, because the hard piezoelectric ceramics (i.e., PZT-4) are not initially polarizable at
room temperature, these specimens were poled at 100°C prior to testing. The properties of these
materials were tested in the polarized state in order to accurately simulate the polarization state of the
materials as they would be used in practice.
i"¸ ,

Piezoelectric Measurements

The piezoelectric coefficients of each composition were measured in accordance with published
standards [22-23]. The various specimen geometries and electrode patterns necessary for determining the
piezoelectric coefficients for radial, transverse, and longitudinal modes of operation are shown in Figure
1. The circular ceramics used in this work were 25.4 mm in diameter and 250 to 380 gm thick. The
rectangular specimens had dimensions 2 mm x 2 mm x 7.5 mm.

(c)

Dimensional / l > 2.5 w, t l > 3.5 w, t d > 10 t

requirements [ - - -

1c33,K_, D ks1, K_T D kp, KT, D

Used for / D
determination of I. $33' SE SI_' S_1 Qm
d33, g33 d31, g31

Figure 1. Specimen geometries and polarization directions associated with the measurement of radial, transverse,
and longitudinal piezoelectric properties.

The resonance properties of the poled piezoelectric specimens were measured using an HP 4194A
Impedance Analyzer. The effective electromechanical coupling coefficient, k_, of the radial test
specimens was then calculated using the resonance/antiresonance method described by the relation [23]:

(1)

where fro andf_ refer to the frequencies of minimum and maximum impedance, respectively. In addition to
the kaf values, the planar coupling coefficient, k, for each composition was determined using the
procedures described in references 22 and 23.

The piezoelectric coefficients for the transverse (k31, dsl , and g3_) and longitudinal (k3s, dss, and g33)
modes of operation were determined by measuring the resonance properties of the thickness-poled and
length-poled ceramics, respectively. The coefficients describing the transverse mode of operation were
calculated using the following relations:

3
 ....... _ . vV.?S-- _

k3_ = A
I+A (2)

rcf_
where A - ---- tan
2f. 2 fm
(3)

(4)

d31 m k314_OK3S1E1
(5)

d31
g31 - (6)
EoK 3

The coefficients for the longitudinal mode of operation were calculated using the relations:

k33 =J_fmtan Jr(f"-f")

(7)
V2f. 2 f.

1
$3_ = (8)
4pf _l 2

s35- (9)
l - k_3

d33 = k334EoK3S3E3 (10)

d33
g33 -- (11)
EoK 3

All of the symbols used in equations 1-11 are defined in Table 1.

4
 Table1.Definition
ofsymbols
usedinthedetermination
ofpiezoelectric
coefficients.

Symbol Definition Units

d31 Transverse strain constant m/V

d33 Extensional strain constant m/V

D (superscript) At constant electric displacement

E (superscript) At constant electric field

f. Frequency of minimum impedance nz

Frequency of maximum impedance Hz

g31 Transverse voltage constant Vm/N

g33 Extensional voltage constant Vm/N

Transverse coupling coefficient

1% Extensional coupling coefficient

k ff Effective electro-mechanical coupling coefficient

k Planar coupling coefficient

P

Dielectric constant

1
Specimen length m

Sll, $33 Elastic compliance constants m2/N

E0 Permittivity of free space, 8.85 x 10 -12 F/m

P Density kg/m 3
 Thermal Expansion Measurements

The thermal expansion properties of unelectroded, unpoled specimens with dimensions 25 mm x 4

mm x 3 mm were measured from 25 to 600°C using a Linseis model L75 dilatometer. All of these tests
were performed in an argon atmosphere using a heating rate of 2°C/min. Once the measurements were
complete, the relative change in length, A1/10,for each material was calculated.

Mechanical Testing

The flexural strength of each composition was measured at room temperature using a four-point bend
test. In this work, unelectroded and unpoled ceramics with dimensions of 38 mm x 6 mm x 4 mm were
tested to failure. All of the mechanical testing was performed using a load rate of 0.25 mm/min and inner
and outer span lengths of 17 and 34 ram, respectively. Once all of the tests were complete, the Modulus
of Rupture (MOR) of each specimen was calculated using the relation [24]:

MOR = 3P(L - a)
2bd 2 (12)

where P is the mechanical load required to break the specimen, L is the outer span distance, a is the inner
span distance, b is the width of the bar, and d is the depth of the bar. Between five and ten specimens of
each composition were tested, and an average MOR value was calculated for each composition.

Experimental Results

Room Temperature Properties

As shown in Table 2, all of the materials evaluated in this work possessed room-temperature dielectric
constants ranging from 1100 to 5000. Additionally, each of the piezoelectric compositions exhibited Ec
and PR values in excess of 5.5 kV/cm and 12.9/.tC/cm 2, whereas the electrostrictive possessed E c and PR
values of 2.5 kV/cm and 1.1 pC/cm 2, respectively.

After the initial dielectric and ferroelectric measurements were performed, additional materials of each
composition were poled and tested. The piezoelectric specimens exhibited k ff values ranging from 0.49
to 0.53, with the highest values exhibited by the PZT-5H ceramics. The PZT-5H ceramics also exhibited
the highest d31and d33 values followed by the PZT-5A and PZT-4 compositions, respectively. Because of
the cubic nature of the PLZT-9/65/35 crystal structure, these materials do not exhibit strong resonance
properties, and therefore, the calculation of piezoelectric coefficients for these materials yields negligible
values.

6
 Table 2. Room temperature (25°C) dielectric, ferroelectric, and piezoelectric properties of PZT-based ceramics.
L5 ¸

Property Units PZT-4 PZT-5A PZT-5H PLZT-9/65/35

K (1 kHz) --- 1400 1600 3400 5000
tan 8 (lkHz) --- 0.05 0.02 0.02 0.06

Ec kV/cm 14.4 11.8 5.5 2.5

PR gC/cm 2 31.0 23.0 12.9 1.1
PSA_ [xC/cm 2 40.1 27.7 19.5 20.8

ko_f --- 0.49 0.50 0.53 ---

1% --- 0.54 0.56 0.59 ---

d33(xl0-12) m/V 225 350 585 ---

g33(x10-3) Vm/N 8.5 16.6 12.5 ---
lq3 --- 0.35 0.53 0.59 ---

d31(xl0 -12) m/V -85 -190 -265 ---

g3_(xl 0-_) Vm/N -7.5 - 13.7 -8.5 ---
1%1 --- 0.22 0.40 0.36 ---

Density g/cm _ 7.6 7.7 7.4 7.3

Dielectric and Resistive Properties

As shown in Figure 2, all of the materials evaluated in this work exhibited their lowest dielectric
constant values at -150°C, and as the temperature was increased the dielectric constant of each
composition also increased. The dielectric constants of the PZT-4 and PZT-5A ceramics increased
steadily as a function of temperature with neither possessing a Curie point in the temperature range
evaluated in this study. The other two materials evaluated, PZT-5H and PLZT-9/65/35, exhibited Curie
points within the -150 to 250°C range. The PZT-5H ceramics possessed a T value of 180°C at each
e

frequency, whereas the PLZT-9/65/35 materials exhibited To properties typical of a relaxor ferroelectric
(i.e., varying with frequency). In this instance, the temperature at which the maximum dielectric constant
was observed increased from 72 to 91°C as the measurement frequency increased from 100 Hz to 100
kHz.

The dissipation factors for each material were also found to be dependent upon both the temperature
and measurement frequency. As shown in Figure 3, the tan _ values for PZT-4 were approximately 0.05
over the entire temperature range when measured at 10 and 100 kHz. At 100 Hz and 1 kHz, however, the
dissipation factor began to increase at 125 and 150°C, respectively. The tan 6 values for PZT-5A were
also found to be relatively constant when measured at frequencies of 100 Hz, 1 kHz, and 10 kHz.
However, at 100 kHz the dielectric loss was significantly higher over the entire temperature range.

Unlike the previous two materials discussed, the PZT-5H and PLZT-9/65/35 ceramics exhibited
maximum tan _ values at each measurement frequency which correspond to their respective Curie points.
In both instances, the dissipation factors were found to increase with increasing measurement frequency
as seen in Figures 3 (c) and 3 (d).

7
 4000 4000

(a) PZT-4 lOOHz \ /j (b) PZT-5A

C.)
3000

2000
100 kHz
lkHz
10kHz
!'°
• 2000 10 kHz

o1,,_ 1000

0 J I J I 0 I r I I
-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

16000

14000 (c) PZT-5H 12000 _ 100 Hz \

100Hz
12000
lkHz
8000 10 kHz \
o 10000 10kHz
100 kHz .
8000 100 kHz • 6000

112 5/35

]::tJ
-g

2o0o1
0/ I I I I 0-1 f I [
-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

Figure 2. Dielectric constant versus temperature data for (a) PZT-4, (b) PZT-5A, PZT-5H, and (d) PLZT-9/65/35.

8
 1.5
0.05

(a) PZT-4 (b) PZT-5A

0.04

100Hz / 0.03
t_ 10 kHz

0.02
0.5
\7 kHz
0.01
100Hz
, 1 100 kI-Iz _
0 I I I I
-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

0.2 0.2

(c) PZT-5H (d) PLZT-9/65/35

0.15 0.15
10kHz A

_ \/ \_00_
0.1 °_ 0.1
lO_\ / \
1 kI-Iz \ ._._ "
0.05 0.05

0 I f I ] 0
-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

Figure 3. Dissipation factor (tan 6) versus temperature data for (a) PZT-4, (b) PZT-5A, PZT-5H, and (d) PLZT-
9/65/35.

9
 As shown in Figure 4, the resistivity of the PZT-4 ceramics remained relatively constant between -150
and 50°C. However, as the temperature was further increased the resistivity was found to decrease
significantly. For example, the resistivity measured at 100 Hz decreased from 10 9 _-_-cm at 50°C to less
than 107 _"_-cm at 250°C. The PZT-5A ceramics were also found to possess a resistivity on the order of
10 9 _'_-cm at -150°C when measured at 100 Hz. Although the resistivity of the PZT-5A specimens was
found to decrease with increasing temperature, these materials did not exhibit the sharp decrease in
resistivity exhibited by the PZT-4 ceramics as the measurement temperature exceeded 50°C.

The resistivity of the PZT-5H materials was also found to decrease with increasing temperature. In
this instance, however, the resistance reached a minimum value at the Curie point and increased as the
test specimen was heated to 250°C. A resistance minimum corresponding to the Curie temperature was
also observed for the PLZT-9/65/35 ceramics. As previously noted, this material is a relaxor ferroelectric
and therefore the temperature of minimum resistance was found to increase from 72 to 91°C as the
measurement frequency increased from 100 Hz to 100 kHz.

1.E+10 1.E+10
100 Hz
(b) PZT-5A
1_ (a) PZT-4
lkHz
_l.E_8 _1.E_8
10kHz
°_

-_l.E_6 100 kHz

-_l.E_6

1 .E+04 J I I f 1.E_4 I I I I
-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

1.E+10 1.E+10

(c) PZT-5H 100Hz

l.E_8 1 kHz _1.E_8

._l.E_6 _I.E_6

_ 1.E+04 1.E_4

(d) PLZT-9/65/35
1.E+02 I I I I 1.E_2 I I I f

-200 -100 0 100 200 300 -200 -100 0 100 200 300
Temperature (C) Temperature (C)

Figure 4. Resistivity versus temperature data for (a) PZT-4, (b) PZT-5A, (c) PZT-5H, and (d) PLZT-9/65/35.

Ferroelectric Polarization versus Electric Field Properties

As shown in Figures 5 (a) to 5 (c), all of the piezoelectric ceramics evaluated in this work possessed
maximum remanent polarization values between 0 and 50°C, indicating that the highest induced
polarization states occur near room temperature. For each composition tested, the PR values were lowest

10
 at -150°Candincreased until a maximumvaluewasreached.As thetemperature
wasfurtherincreased
beyondthetemperature at whichthemaximumvaluewasobserved, thePRvaluesof eachcomposition
decreasedsteadilyoverthebalance of thetemperature
range.

Aspreviouslymentioned, theresistivityof thePZT-4materialsdecreased asthematerialswereheated

beyond50°C.Because of this decrease
in resistance,
calculationof thePRvaluesat temperaturesabove
120°Cindicatesanincreasethatis dueto theconductivenatureof thesematerialsathigh temperatures.
Theincrease in thePRandPSAT valuesabove120°Cis illustratedin Figure5 (a). As thetemperature
was
further increased, the applicationof high electricfields ultimatelyled to the breakdownof these
specimens. Therefore,P-Edataforthismaterialwasnotcollectedabove160°C.

Unlike the PZT-4specimens,the PZT-5Aceramicswerepolarizableover the entiretemperature

range.Asshownin Figure5 (b),thePRvaluesfor thiscomposition
increased
from2 gC/cm2at-150°Cto
a maximumvalueof 25gC/cm2at25°C.Asthetemperature wasfurtherincreasedto 250°C,thePRvalues
decreasedto 20gC/cm2.

As shownin Figures5 (c) and5 (d), the PRvaluesfor bothPZT-5HandPLZT-9/65/35reached

maximumvaluesnear25°Candthendecreased steadilywith increasing
temperature
until thematerialno
longerexhibiteda ferroelectrichysteresis.Eachof theselattercompositions
exhibitedparaelectric
P-E
behaviors
ateachmeasurement temperatureabovetheirrespectiveTcvalues.

Thecoercivefieldvaluesfor eachcomposition werealsofoundtoexhibitamaximumvalueandthen

decrease with increasingtemperature.As seenin Figures5 (a) to 5 (d),the maximumcoercivefield
valueswerefoundto occurbetween-100and-50°C.As wasnotedin theP, behaviors, theEc valuesfor
thePZT-5HandPLZT-9/65/35 materialsdecreased
to zeroattheirrespectiveCuriepoints,indicatingthat
the ferroelectricdomainsarenot spontaneously
reversibleandthata remanent polarizationstatecannot
beinducedabovethattemperature.

25 60

(a)PZT-4 : /

15 40 _o

30
20
10
. Ec r 50_
20
J / PR and PSAT increases
5 - _# above 120°C due to 10

decrease in resistivity
0 I I I I I I I I I 0
-200 -150 -100 -50 0 50 100 150 200 250 300
o
Temperature (C)

Figure 5. Coercive field (Ec), remanent polarization (PR), and saturation polarization (Ps^T)versus temperature
properties of (a) PZT-4, (b) PZT-5A, (c) PZT-5H, and (d) PLZT-9/65/35.

11
 : • :.L, • :,i• ::i_,:;!:ii•;_:_'?i:!! ¸

20 35
PSAT
30
(b) PZT-5A f_-----I_
15
25

20 "_
10
V

15
5 10

I [ P I I I I I [ 0
-200-150-100-50 0 50 100 150 200 250 300
Temperature (°C)

20 25
(c) PZT-5H
20
15

10

10 _

0 0

-200 -150-100 -50 0 50 100 150 200 250 300

Temperature (°C)

20 25

15 (d) PLZT-9/65/35 20

15 -_
> 10

5
0 0

-200-150-100-50 0 50 100 150 200 250 300

Temperature (°C)

Figure 5 (continued). Coercive field (Ec), remanent polarization (PR), and saturation polarization (PsAT)versus
temperature properties of (a) PZT-4, (b) PZT-5A, (c) PZT-5H, and (d) PLZT-9/65/35.

12
 In addition to the graphs summarizing the ferroelectric hysteresis properties of each composition from
-150 to 250°C, typical examples of the P-E behaviors of each composition at -150, -75, 0, 25, 100, and
250°C are shown in Figures 6 to 9. As previously discussed, each composition exhibits a very low
polarization of -150°C, and as the temperature increases, the hysteresis loops of the three piezoelectric
compositions exhibit typical square (PZT-4 and PZT-5A) or rounded (PZT-5H) ferroelectric hysteresis
behavior near room temperature.

As shown in Figures 6 (a) and 6 (b), the PZT-4 ceramics exhibited somewhat asymmetric hysteresis
behavior below -50°C. However, all of the P-E loops collected above this temperature were symmetric
about each axis. Symmetric hysteresis loops were obtained at every temperature for the soft piezoelectric
ceramics evaluated herein.

The PLZT-9/65/35 ceramics also exhibited low polarization properties at -150°C. However, as
r previously observed in Figure 5 (d), the maximum E c and PsAr values for this composition were obtained
near -50°C. At this temperature, these materials exhibit a P-E behavior that is very similar to those of the
piezoelectric ceramics near room temperature. As these specimens were further heated to 25°C, the
remanent polarization and coercive field values decreased significantly, and a slim-loop ferroelectric
behavior was observed at room temperature (see Figure 9 (d)).

13
 40 P (#C/cm 2)
o 40 T P (ILtC/cmZ)
(a) - 150°C
30
(b) -75 C 3o
/
20

10
E (kV/cm)
I
I
-30 10 20 30
30

-20 - • 20 "

-30 -30

-40 -40

40- P (ktC/cm 2)
(C) 0°C

20
(d) 25°C
10

'_'_v'_,r_'
l , o ,1 , ,
iE (kV/cfm) S
I J I

30

-30 __ 2_40 = 0 30

40
(e) 100°C

IE (kV/cm)
F
i I
20

-30 -20 I10 10

-40

Figure 6. Typical ferroelectfic polarization versus electric field (P-E) properties of PZT-4 ceramics at (a) -150°C,
(b) -75°C, (c) 0°C, (d) 25°C, (e) 100°C, and (f) 150°C.

14
 35 P (_C/cm 2) 35- P (_C/cm z)
(a) -150°C (b) -75°C
25 25

15 15

E (kV/cm) 5 "
,E (kWc_
"__7 I
-20 - 10 -5 10 20 lO 20

-15 -15

-25 -25

-35 -35

35 P Q.tC/cm 2)
(c) 0°c

jEv/cm /
25

iE (kV/cm) i_

-25
"20__35 _ 20
-35

(e) 100 ° 35 q- P (btC/cm z) 35 P (_C/cm z)

IE (kWcm) I r I I I

-35 _
o -35

Figure 7. Typical ferroelectric polarization versus electric field (P-E) properties of PZT-5A ceramics at (a) -150°C,
(b) -75°C, (c) 0°C, (d) 25°C, (e) 100°C, and (f) 250°C.

15
 20 •P (p.C/cm_ 20 V (ktC/cm 2)
(a) - 150°C (b) -75°C
15 15

10 lO

5
E (kV/cm) E (kV/cm) __

-15 -I0 -5 5 10 15
-5
-15 _ -5 _ 5 10 15
-I0 !
-i0

-15 -15

-20

20 20
(c)O°C (d) 25°C
15 15

E (kWcm) E (kV/cm)
I I I q

-15 - -5 -5
° 15
-15 -10
/° 5 -5 15

-10 -

-20 -20

p (_tC/cm 2)

e lOOOC o25oo
5

jE (kWcrm) l

15

-10 -
-15 -_ 5 10 15 -15 H
-15

-20 -20

Figure 8. Typical ferroelectric polarization versus electric field (P-E) properties of PZT-5H ceramics at (a) -150°C,
(b) -75°C, (c) 0°C, (d) 25°C, (e) 100°C, and (f) 250°C.

16
 25- P (gC/cm 2)

25
t
P QaC/cm 2)
(a) - 150°C 20- (b) -75°C 20
15
15
10 10

E (kV/cm) 5 E (kWcm) __5

-15 -10 -5 -5
'
-15 --i0 " -5 -5 15
-10 - -10
-15 - -15
-20 - -20
-25 -25

25 P (p.C/em 2)
25 T P (/'tC/cm2)
(c) 0°c 20

15

10

FE (kWcrm) I E (kWcm)
I I I _ • f I I
15
-15 -10 /-5 -10 -J/ 5 10 15
i
15
j /-

J 2!
-10

-15

-25 - -25

25 P (g.C/cm 2) 25 P (u.C/cm 2)
(e) 100°C (f) 25o°c 20
15

5
t 15

10

E (kV/cm) 5
E (kWcm)
I r I I

5 10 15 -15 -10 -5 -5
-15 5 10 15
-10 -10
-15 -15
-20 -20
-25 -25

Figure 9. Typical ferroelectric polarization versus electric field (P-E) properties of PLZT-9/65/35 ceramics at (a) -
150°C, (b) -75°C, (c) 0°C, (d) 25°C, (e) 100°C, and (f) 250°C.

17
 Piezoelectric Properties

As previously mentioned, the PZT-5H ceramics exhibited the highest piezoelectric properties (i.e., kff,
k, Id311, and d33) at room temperature, followed by the PZT-5A and PZT-4 materials, respectively. When
cooled to -150°C, the k_ and k values of each composition remained relatively constant. The 10311 and
d33 values for PZT-4 also remained relatively stable over this temperature range. The d constants for the
PZT-5A and PZT-5H ceramics, however, decreased to approximately 50% of their room temperature
values when cooled to -150°C.

When heated to 250°C, the electro-mechanical coupling coefficients of PZT-4 and PZT-5A decreased
from their room temperature values, whereas the d constants for these materials increased over this
temperature interval. The properties of the PZT-5H specimens exhibited similar trends when heated
above room temperature. However, in this instance the specimens no longer exhibited measurable
resonances above 170°C, thereby indicating that the specimens had been thermally de-poled.

As shown in Figure 10 (a), each of the piezoelectric compositions possessed a k ff value ranging from
0.45 and 0.55 between -150 and 150°C. Above 150°C, the k_ value of each composition began to
decrease, with the PZT-5H ceramics becoming completely de-poled at 170°C. The PZT-4 and PZT-5A
specimens both exhibited minimum ko_ values at 250°C. In this work, minimum ko_ values of 0.38 and
0.44 were obtained at 250°C for the PZT-4 and PZT-5A ceramics, respectively.

Similar trends were also observed in the measured k values. As seen in Figure 10 (b), the kp values of
each composition were between 0.5 and 0.6 over the -150 to 150°C temperature interval. Furthermore,
the k values of the PZT-4 and PZT-5A ceramics decreased to minimum values of 0.40 and 0.48 at 250°C.
Likewise, above 150°C, the kp values for the PZT-5H ceramics decreased sharply to zero near 170°C.

As shown in Figures 11 (a) and (b), each composition exhibited its minimum Ic1311and d33 values at -
150°C. At -150°C, the d constants of the PZT-4 ceramics decreased less than 10% from their room
temperature values whereas the properties of the PZT-5A and PZT-5H compositions declined by
approximately 50% over the same temperature interval. Although PZT-4 ceramics exhibited the most
stable performance between -150 to 25°C, the d33values for this composition are significantly lower than
those of the other two piezoelectric materials near room temperature.

When the materials were heated from 25 to 250°C, the d3_ values of the PZT-4 and PZT-5A ceramics
increased continuously to their maximum values whereas the properties of the PZT-5H ceramics were
more strongly dependent upon the measurement temperature. Specifically, the PZT-4 and PZT-5A
ceramics exhibited maximum d33 values of 360 x 10 _2and 440 x 10 -_2m/V at 250°C whereas the PZT-5H
specimens possessed d33 values on the order of 900 x 10 -12 m/V before being thermally de-poled at
approximately 170°C.

18
 0.7

0.6 (a)

0.5

0.4

0.3
o PZT-4
0.2 [] PZT-5A

0.1 A PZT-5H _x
A
0 I I r I I I

-200 -150 -100 -50 0 50 100 150 200 250 300

O

Temperature (C)

0.7

0.6 (b)

0.5

0.4
_¢
0.3
o PZT-4
0.2 [] PZT-5A
_x
0.1 A PZT-5H
A
0 I I I I I I

-200 -150 -100 -50 0 50 100 150 200 250 300

O

Temperature (C)

Figure 10. Typical (a) effective electro-mechanical coupling coefficient (k_) and (b) planar coupling coefficient (1%)
versus temperature behavior of PZT-4, PZT-5A, and PZT-5H ceramics.

19
 6OO

0 PZT-4 (a)
500
[] PZT-5A _
A PZT-5H A Az_
400
t'-I
A
300

200

100

-200 -150 -100 -50 0 50 100 150 200 250 300

Temperature (°C)

(b)
800 [] PZT-5A A A
1°°°t o zT_4
_, 600

400

200
0/ [ I I I I [ "lJllllllcIIIIIIIl_f

-200-150-100 -50 0 50 100 150 200 250 300

Temperature (°C)

Figure 11. Typical (a) d31 and (b) d33versus temperature behavior of PZT-4, PZT-5A, and PZT-5H ceramics.

20
 Thermal Expansion

As shown in Figure 12, all of the piezoelectric specimens evaluated in this study showed some
evidence of a phase transformation between 25 and 600°C. The PZT-4 specimen exhibited a change in
the rate of expansion at approximately 310°C, whereas the PZT-5A and PZT-5H ceramics exhibited
similar changes at 350 and 170°C respectively.

For the PZT-5H material, the temperature at which the rate of expansion changes correlates strongly
with the To value of this composition. Although dielectric constant data was not obtained at temperatures
greater than 250°C for the PZT-4 and PZT-5A ceramics, the thermal expansion data shown in Figure 12
provides a strong indication of the Curie points of these materials.

The PLZT-9/65/35 ceramics exhibited the largest thermal expansion of the materials tested. In this
case, a change in the rate of thermal expansion was observed at approximately 275°C. This result
suggests that a phase transformation other than the one indicated by the dielectric constant measurements
takes place at this temperature.

0.5

PZT-4
0.4"

...... -sA / .l
.... Pzr-sH 7 /" I
,-, 0.3 "_'PLZT-9/65/35 / tl "I

0.2

0.!

0
0 lO0 200 300 400 500 600
Temperature (°C)

Figure 12. Relative change in length (A1Bo)versus temperature behavior of PZT-4, PZT-5A, PZT-5H, and PLZT-
9/65/35 ceramics.

Mechanical Testing

Each test specimen fractured at a point between the inner two positions through which the mechanical
load was applied. As shown in Table 3, the PZT-4 ceramics possessed the highest average MOR value,
followed by the PZT-5A, PLZT-9/65/35, and PZT-5H compositions, respectively. All of the specimens
tested in this work exhibited a MOR value that was within 10% of the average value for that composition.

21
 _ : i_ _;:_: / i¸¸ : _(i

Table 3. Modulus of Rupture (MOR) data for PZT-based ceramics.

Composition Average MOR (MPa)

PZT-4 95.2
PZT-5A 81.8
PZT-5H 61.5
PLZT-9/65/35 69.3

Discussion

All of the materials evaluated in this investigation were found to possess properties that are suitable
for use in aircraft and spacecraft systems. The selection of candidate materials for use in these systems is,
however, strongly dependent upon the operational conditions under which the device will be employed.
This is particularly important when selecting materials for low temperature (i.e., < -50°C) or high ....
temperature (i.e., >150°C) applications.

Of the materials evaluated in this work, the PZT-5H ceramics were found to possess the highest 10311
and d33coefficients at 25°C, followed by the PZT-5A and PZT-4 compositions, respectively. Although
the PZT-5H ceramics exhibit the highest room temperature piezoelectric properties, this composition has
a T c value of 170°C which can be a limiting factor in applying this material in systems such as jet engines
that could expose the actuator to temperatures above its Curie point.

Alternatively, both the PZT-4 and PZT-5A ceramics possess To values in excess of 300°C. The higher
Curie temperatures of these materials make them more appropriate selections for higher-temperature
applications. Although both of these compositions possess relatively high T c values, the resistivity of
PZT-4 decreases significantly above 120°C and it may, therefore, not be an attractive alternative for use
above 100°C under high electric-field conditions. Near room temperature, however, PZT-4 has many
useful characteristics, the most important of which is the retention of its polarization state over time when
activated continuously using a large electric field [1].

The selection of actuator materials for low-temperature applications also requires careful
consideration. In this work, the [c1311and d33values of PZT-4 decreased less than 10% when cooled from
room temperature to -150°C. Conversely, the d constants of both PZT-5A and PZT-5H decreased by
approximately 50% when cooled over the same temperature interval. The relative stability of the
properties of the PZT-4 ceramics between -150 and 25°C suggests that this material is a good candidate
for some cryogenic applications. However, additional testing should be performed before this material is
selected for use at temperatures below -150°C.

In addition to the temperature dependency of the piezoelectric properties, the dielectric constants of
these materials must also be considered when evaluating candidate materials. In many aerospace
systems, the power required to operate a device is a critical design issue. As shown below, the power
consumed during the sinusoidal operation of a piezoelectric actuator is directly proportional to the
capacitance of the device by the relation [25]:

P=_.C.f.U 2
(13)

where P is the power consumed (Watts), C is the capacitance of the actuator (Farads), f is the operational
frequency (Hertz), and U is the peak-to-peak operational voltage (V._p). Thus, the selection of a material

22
 with goodpiezoelectric
propertiesmustbeweighedagainstthepowerconsumed
by the deviceto ensure
thatthepowerbudgetfor thecompletesystemis maintained.

Thedesignofanopticalpositioningdevicefor a space-based spectrometer

systemis atypicalexample
of sucha designtrade-off.In a reportby Wiseet al. [26],thepowerconsumed by similarly-sizedPZT-
5A andPZT-5Hhigh-displacement RAINBOWactuatorstackswascompared.In thatstudy,PZT-5A
stackswerefoundto meetthe system'sperformance specifications
whileconsuming 0.7Wattsof power
whereasthePZT-5Hstacksrequired1.8Wattsof continuous powerwhenoperated at 1Hz. As shownin
Equation13,theinfluenceof thepiezoelectriccompositionselectedwouldbecomemorepronounced if
theactuatorwererequiredto operateathigherfrequencies thanthoseusedin thesystemdescribed in that
study.

Overthe courseof this investigation,the propertiesof four PZT-based ceramicswereevaluated

between-150to 250°C,andthe temperature-dependent propertiesof thesematerialswererelatedto
existingaerospace
applicationsof thesematerials.In additionto thefour compositions
evaluated
herein,
severalotherpiezoelectric
andelectrostrictive
compositions alsoexistwhichmaypossess properties
that
aremoreappropriate for a givensetof designparameters.As such,the initial selectionof candidate
materialsshouldnotbelimitedonlyto thoseevaluated herein.

Conclusions

The dielectric, ferroelectric, and piezoelectric properties of three piezoelectric ceramics (PZT-4, PZT-
5A, and PZT-5H) and one electrostrictive ceramic (PLZT-9/65/35) were measured over a temperature
range of-150 to 250°C. Additionally, the thermal expansion characteristics of each composition were
measured from 25 to 600°C, and the moduli of rupture were measured at 25°C. As the materials were
heated above room temperature, PLZT-9/65/35 and PZT-5H were found to possess T c values of 71 and
170°C, respectively. Neither the PZT-4 nor the PZT-5A ceramics exhibited a dielectric constant maxima
below 250°C. Thermal expansion data indicate that these materials undergo phase transformations at 310
and 350°C, respectively.

All of the ceramic materials evaluated exhibited their maximum PR values between 0 and 50°C. When
cooled to -150°C, however, the polarization properties decreased to approximately 10% of the room
temperature value for each composition. When heated above room temperature, the PLZT-9/65/35 and
PZT-5H ceramics exhibited paraelectric P-E behaviors above their respective Curie points. The P-E
behavior of the PZT-4 ceramics was influenced by the conductive nature of this composition above
120°C, whereas the PZT-5A ceramics exhibited square ferroelectric hysteresis loops, albeit with
decreased Ec values, up to 250°C.

The PZT-5H ceramics exhibited the largest piezoelectric coefficients at room temperature, followed
by the PZT-5A and PZT-4 compositions, respectively. When cooled to -150°C, the piezoelectric
properties of the PZT-4 ceramics were found to remain relatively stable whereas the performance of the
PZT-5A and PZT-5H materials decreased by approximately 50%. Conversely, when heated to 250°C, the
PZT-5A ceramics possessed the largest piezoelectric properties. The PZT-4 specimens also exhibited
strong piezoelectric resonances above room temperature. PZT-5H exhibited the largest piezoelectric
properties up to its Curie point (170°C). Above this temperature, however, no resonances were observed,
thus indicating that the specimens had been thermally de-poled.

All four of the materials evaluated in this study possess properties that are suitable for use in some

23
 aerospace applications. These findings indicate, however, that careful consideration must be made in
order to select optimum materials for a given set of operational conditions. This is particularly evident
when choosing materials for either low-temperature (i.e., < -50°C) or high-temperature (i.e., >150°C)
applications where the properties of the various materials deviate significantly from their room
temperature behaviors.

References

1. B. Jaffe, W.R. Cook, and H. Jaffe, Piezoelectric Ceramics, New York: Academic Press, Inc., 1971.

2. G.H. Haertling, "Piezoelectric and Electrooptic Ceramics," pp. 139-225 in Ceramic Materials for Electronics,
edited by R.C. Buchanan, New York: Marcel Dekker, Inc., 1986.

3. E.F. Crawley, "Intelligent Structures for Aerospace: A Technology Overview and A ssessment, " AIAA Journal,
32 [8] 1689-99, 1994.

4. S.S. Rao and M. Sunar, "Piezoelectricity and Its Use in Disturbance Sensing and Control of Flexible Structures:
A Survey," Applied Mechanics Reviews, 47 [4] 113-123, 1994.

5. R.G. Loewy, "Recent Developments in Smart Structures with Aeronautical Applications," Smart Materials and
Structures, 6 R11-R42, 1997.

6. R.E. Newnham and G.R. Ruschau," Smart Electroceranucs, " " Journal of the American Ceramic Society, 74 [3]
463-80, 1991.

7. K.B. Lazarus, E.F. Crawley, and J.D. Bohlmann, "Static Aeroelastic Control Using Strain Actuated Adaptive
S ,, . .
tructures, Journal of lntelhgent Matertal Systems and Structures, 2 [3] 386-410, 1991.

8. D.L. Palumbo, S.L. Padula, K.H. Lyle, J.H. Cline and R.H. Cabell, "Performance of Optimized Actuator and
Sensor Arrays in an Active Noise Control System," NASA TM 110281, 1996.

9. J. Heeg, "Analytical and Experimental Investigation of Flutter Suppression by Piezoelectric Actuation", NASA
TP 3241, 1993.

10. R.W. Moses, "Vertical Tail Buffeting Alleviation Using Piezoelectric Actuators - Some Results of the Actively
Controlled Response of Buffet-Affected Tails (ACROBAT) Program," NASA TM 110336, 1997.

11. P.P Friedman and T.A. Millott, "Vibration Reduction in Rotorcraft Using Active Control: A Comparison of
Various Approaches," Journal of Guidance, Control, and Dynamics, 18 664-73, 1994.

12. S.R. Hall and E.F. Prechtl, "Development of a Piezoelectric Servoflap for Helicopter Rotor Control," Smart
Materials and Structures, 5 26-34, 1996.

13. J. Shaw and N. Albion, "Active Control of the Helicopter Rotor for Vibration R eduction,
. ,, Journal of the
American Helicopter Society, 30 3-20, 1981.

14. A.J. Butterfield and S.E. Woodard, "Measured Spacecraft Instrument and Structural Interactions," Journal of
Spacecraft and Rockets, 33 [4] 556-62, 1996.

24
 15. W.L. Grantham, "NASA Future Mission"
" Needs and Benefits of Controls-Structures Interaction Technology,"
NASA TM 104034, 1991.

16.
S. Zhou, C. Liang, and C.A. Rogers, "Dynamic Design and Stress Characteristics of Integrated Piezoelectric
Patch Actuators," pp. 1360-74 in Proceedings of the Second lnternational Conference on Intelligent Materials
(ICIM '94), edited by C.A. Rogers and G.G. Wallace, 1994.

17. S. Zhou, C. Liang, and C.A. Rogers, "Integration and Design of Piezoelectric Patch Actuators," Journal of
Intelligent Material Systems and Structures, 6 [1] 125-33, 1995.

18. D. Shalev and J. Aboudi, "Coupled Micro to Macro Analysis of a Composite That Hosts Embedded
Piezoelectric Actuators," Journal oflntelligentMaterial Systems and Structures, 7 [1] 15-25, 1996.

19. D.B. Koconis, L.P. Kollar, and G.S. Springer, "Shape Control of Composite Plates and Shells with Embedded
Actuators, I. Voltages Specified," Journal of Composite Materials, 28 [5] 415-58, 1994.

20. D.B. Koconis, L.P. Kollar, and G.S. Springer, "Shape Control of Composite Plates and Shells with Embedded
Actuators, II. Desired Shape peclfied,
S
Journal of Composite
. ,,
Materials, 28 [3] 262-85, 1994.

21. J.L Fanson, E.H. Anderson, and D. Rapp, "Active Structures for Use in Precision Control of Large Optical
Systems," Optical Engineering, 29 [11] 1320-27, 1990.

22. "IRE Standards on Piezoelectric Crystals: Measurements of Piezoelectric Ceramics, 1961," Proceedings of the
IRE, 49, 1161-69, 1961.

23. "IEEE Standard on Piezoelectricity," ANSI/IEEE Standard 176-1987, 1987.

24. J.T. Jones and M.F. Berard, Ceramics: Industrial Processing and Testing, Ames, Iowa: Iowa State University
Press, 1972.

25. Anon., "Piezo Guide: Piezo Positioning Technology Part 1," Catalogue PZ 36E. Products for
Micropositioning, Physik Instrumente Catalogue 108-12/90.14.

26.
S.A. Wise, R.C. Hardy, and D.E. Dausch, "Design and Development of an Optical Path Difference Scan
Mechanism for Fourier Transform Spectrometers Using High-Displacement RAINBOW Actuators," in
Industrial and Commercial Applications of Smart Structures Technologies, edited by J.M. Sater, Proceedings of
SPIE, 3044 342-349, 1997.

25
 REPORT DOCUMENTATION PAGE I Fo,reApproved
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1.AGENCYUSEONLY(LeavebIank) I 2"REPORTDATEseptember
1998 I 3"REPORT
COVEREDCOntractOr
TYPEANDDATES
Report
4. TITLE AND SUBTITLE 5. FUNDING NUMBERS
Properties of PZT-Based Piezoelectric Ceramics Between -150 and 250C
C NAS1-96014
WU 522-32-11-02
6. AUTHOR(S)
Matthew W. Hooker

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) 8. PERFORMING ORGANIZATION

Lockheed-Martin Engineering & Sciences Co. REPORT NUMBER

Mail Stop 371

NASA-Langley Research Center
Hampton, VA 23681

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AGENCY REPORT NUMBER

National Aeronautics and Space Administration

Langley Research Center NASA/CR- 1998-208708
Hampton, VA 23681-2199

11. SUPPLEMENTARY NOTES

Langley Technical Monitor: Stephanie A. Wise

Final Report

12a. Dk_¥HiBUTION/AVAILABILITY STATEMENT

12b. DISTRIBUTION CODE
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Availability: NASA CASI (301) 621-0390
13. ABSTRACT (Maximum 200 words)

The properties of three PZT-based piezoelectric ceramics and one PLZT electrostrictive ceramic were measured
as a function of temperature. In this work, the dielectric, ferroelectric polarization versus electric field, and
piezoelectric properties of PZT-4, PZT-5A, PZT-5H, and PLZT-9/65/35 were measured over a temperature
range of-150 to 250C. In addition to these measurements, the relative thermal expansion of each composition
was measured from 25 to 600C and the modulus of rupture of each material was measured at room temperature.
This report describes the experimental results and compares and contrasts the properties of these materials with
respect to their applicability to intelligent aerospace systems.

14. SUBJECT TERMS

15. NUMBER OF PAGES
piezoelectric, PZT, PLZT, temperature 3O
16. PRICE CODE
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