630 Journal of The American Ceramic Society-Ouchi
48, No, 12
generally accepted t h a t the departure from stoichiometry in
these systems, with the consequent occurrence of lattice
vacancics and imperfections, makes the movement of ions so
facile t h a t i t is impossible for either impurities or pores t o
build up on the grain boundaries, thus preventing discon-
tinuous grain growth.
Contrary t o t h e work of Iida,‘ b u t in agreement with the
work 01 N i ~ h o l s o n , ’the
~ increase in grain size with sintering
time appeared to follow the empirical law G3 = ht.
Acknowledgments
Thc author exprcsses his gratitude to the Steetley Organization
Rcsearcli Dcpartrncnt for generous financial support of this re-
searcii, anti tfianks A . J. B. Welch for initiating and supervising
thc work.
References
\.‘oshido Iida, ”Sintering of High-Purity Nickcl Oxide,”
.I. An?. Qvccm. SOC.,41 [lo1 397-406 (1958).
Yoshido Iida atid Shunro Ozaki, “Sintering of High-Purity
Nickel Oxidc, 11,” iDid., 42 151 219-28 (1959).
a I<. M . Spriggs, L. A. Brissette, and T . Vasilos, “Pressure-
Siiitercd Nickel Oxide,” Am. Ceram. SOC.Hull., 43 [ 8 ] 572-77
(1064).
Piezoelectric Properties of Pb(Mg, Nb, )O -
PbTiO -PbZrO Solid Solution Ceramics
3 3
b y H I R O M U OUCHI, KATSUO NAGANO, a n d SHIGERU HAYAKAWA
Rcsearch Laboratory, Wireless Division, Matsushita Electric Industrial Company, Limited, Kadoma, Osaka, Japan
Ceramic and electrical properties and crystal
structures of the system Pb(Mgl/,NbP/J03-
PbTi03-PbZrOa are described. The system is
composed of three crystal phases at room tem-
perature : pseudocubic, tetragonal, and rhombo-
hedral. A high dielectric constant and radial
coupling coefficient and low resonant resistance
were obtained for the compositions near the
morphotropic transformation. The composition
P b (Mgl/,Nb~/~)~.?37~Ti~
437aZr01 2 5 0 3 had the lowest
temperature coefficient of resonant frequency.
I. Introduction
r r I R t h e fundamental studies on lead titanate zirconate,
A1 ’b (Ti-Zr)Oa, were made by Shirane et u1.I and by
Sawaguchi,3 much attention was given to its piezoelectric
properties. Sincc Jaffe et al found t h a t thc system Pb(Ti-
Zr)Os h a d a high potential as a n electromechanical trans-
ducer, modifications of Pb(Ti-Zr)03 and t h e effects of addi-
tives were studied extensively t o improve the piezoelectric
properties. The modifications were made by partial replace-
ment of T i 4 +with Sn4+or Hf4+,5and a partial replacement of
P b 2 + with Ca2+, Sr2+,bor Ba2f.7 Effective additives for
improving the dielectric constant, insulating resistance, and
aging behavior were Laz03, NbzOs,* SbzO3, RizOa,Yand Cr,-
03.1O
Recently, Smolenskir and Agranovskayall and Krainik and
Agranovskaya12 developed a possible method of preparing
et a1 Vol.
Jacques Robin, “Metallic Oxalates as Starting Materials for
Preparation of Solid Solutions of Metal Oxides,” Bull. Soc. Chim.
France, 1953, No. 233 [11-121 1078-84.
D. Dolliinore and D. Nicholson, “Thermal Deconiposition of
Oxalates: I,” J . Chem. Soc., 1962, 960-65.
R . A. Brown, “Sintering in Very Pure Magnesium Oxide and
Magncsium Oxide Containing Vanadium,” Am. Cevam. Soc. B d . ,
44 [6]483-87 (1965).
R A. Brown, “Sintering in Calcium Oxide and Calcium
Oxidc Containing Strontium,” Am. Ceram. Soc. Hull., 44 [9] 693-
95 (1965).
Andre Boulle and J. L. Dorernieux, “Effect of the Nature of
the Atmosphere on the Thermal Decomposition of the Oxalates
of Iron, Cobalt, and Nickel,” Comfit. Rend., 248, 2211-13 (1959).
J W. Mcllor, Comprehensive Treatise on Inorganic and
Theoretical Chemistry, Vol. XV; pp. 375-76. Longmans, Green
and Co., London, 1936.
N. V. Sidgwick, Chemical Elements and Their Compounds,
Vol. 11; pp. 1430, 1449. Clarendon Press, Oxford, 1950.
11 H. B. Charman, R. M. Dell, and S. S. Teale, “Cheinisorption
on M e t d Oxides: I,” Trans. Faraday Soc., 59 [482] 453-69
(1963).
l 2 M. T. Shim and W. J. Moore, “Diffusion of Kickel in Nickel
Crystals of Nickel Oxide,” J . Phys.
l4 G. C. Nicholson, “Grain Growth in Zinc’Oxide.” j . A h .
Ceram. Soc., 48 [4] 214-15 (1965).
/3 /3 3
perovskite structure compositions of various atoms and found
a complex compound, Pb(Mgl/,NbP/,)03, which had a dielec-
tric constant of 12,(i00 at a Curie temperature of - ld°C and
a spontaneous polarization of li X lo-” coulonibs/cm2 at
10°C. Since the Curie temperature of -15°C is too low
t o permit use as a piezoelectric above room temperature, the
Pb(Mgi/,Nb2/JO3 modification is interesting because it raises
the Curie temperature. T h e present study was carried o u t
with the system xPb(Mgl/,Nb2/,)03-yPbTiOa-zPbZrOa (x +
y + z = 1) t o obtain a higher Curie temperature and higher
piezoelectric properties at room temperature, The Curie
temperatures of PbTiOa and PbZr03 are 490” and 230”C,
respectively. It was also a purpose of the present study t o
show a morphotropic transformation in the ternary system,
which was expected from the difference in the crystal struc-
ture of each compound at room temperature.
11. Experimental Procedures
( 1 ) Sample Preparation
Raw materials were obtained from chemical reagent grade
PbO (99.5%), TiOB (98%), Zr02 (99.5%), NbZOs (98% and
0.9% Ta205),and MgO (93.4% and 6.5% water). A mixture
of t h e raw material of a given composition was wet-milled
Received January 12, 1965; revised copy received May 5, 1965.
The writers are, respectively, group leader, research ceramist,
and section head, Piezoelectric Ceramics Group, Dielectric and
Ferroelectric Material Research Section, Research Laboratory,
Wireless Division, Matsushita Electric Industrial Company, Ltd.
December 19Ii.5 Piezoelectric Properties of Pb (Mglp Nb2I3)03-Pb Ti03-PbZrOs Ceramics 63 1
Table I. Composition, Sintering Temperature, and Ceramic, Dielectric, and Piezoelectric Properties of Various
Solid Solutions
After poling
Composition* 7
_____*_-

(mole 1%) Sintering Dielectric Dissipation Radial Resonant Mechanical

,. ..... ~~ ~. 7 temp. Density constant a t factor a t coupling resistance, quality factor,
I Y z ( O C ) (dcm3) 1 kc 1 kc (%) (!A) R (ohm) OM

87.5 12.5 1250 7.24 2847 1.23 4.6 139 2 404

75.0 25.0 1270 7.27 2689 3.66 14.4 95 0 109
75.0 12.5 12.5 1270 7.36 1521 2.97 20.4 58 0 151
75.0 25.0 1270 7.07 973 2.09 8.0 462 0 150
62.5 37.5 1270 7.49 2027 2.83 18.2 62 2 134
62.5 25.0 12.5 1270 7.57 1277 2.80 26.2 86 4 82
62. 5 12.5 25.0 1270 7.63 1046 3.10 16.4 56 1 306
59.0 41.0 1270 7.44 1296 1.13 24.4 40 0 193
56.0 44.0 1270 7.47 999 1.04 23.6 48 9 214
5 3 .0 47 0 1270 7.52 1002 0.94 22.0 55 2 219
50 . 0 50.0 1270 7.54 915 1.22 19.7 82 3 2 10
50.0 40.0 10.0 1270 7.55 1481 1.34 30.4 33 3 146
50.0 3- .-
., I) 12.5 1270 7.58 1848 1.35 34.6 21 0 113
50 0 37.0 13.0 1270 7.51 1433 1.85 30.1 38 4 132
50 . 0 34.0 16.0 1270 7.49 1193 2.24 25.0 55 6 152
50. 0 31 . 0 19.0 1270 7.52 1038 2.49 26.1 53 I 171
50.0 25 0 25.0 1280 7.55 1011 3.15 25.7 45 0 189
50.0 12.5 37. 5 1290 7.62 756 3.18 25.7 44 3 255
50.0 ;io.o 1300 7.23 330 1.89 7.5 814 0 568
43.75 43. 75 12.5 1260 7.40 1356 1.70 25.7 47 3 156
37.5 (i2 5 1240 7.41 397 1.09 9.8 373 0 410
37.5 50 0 12.5 1260 7.57 840 1.60 27.4 49 5 187
37.5 40.5 22.0 1260 7.66 1716 1.96 39.2 28 4 94
37.5 :17. 5 25.0 1280 7.60 1587 2.32 48.0 18 9 96
37.5 :+I. 5 28.0 1280 7.58 1247 2.07 30.2 55 4 114
l37.5 25.0 37.5 1290 7.54 806 3.02 30.2 44 3 178
z . 5 12.5 30. 0 1300 7.65 557 3.24 23.7 62 1 286
31.25 : < I 25
. 3i.5 1290 7.57 989 3.17 28.0 51.6 151
25.0 75.0 1230 7.33 263 1.60 5.9 1394.0 300
25.0 (2.5 12.5 1250 7.47 487 1.64 24.6 72.0 262
25.0 5 0 .0 25.0 1300 7.50 920 1.43 29.0 66.7 126
25,o 43 0 32.0 1300 7.50 1254 1.67 30.3 33.0 173
25.0 40.0 35.0 1300 7.55 1274 2.05 46.3 25.5 101
25.0 37 5 37.5 1300 7.61 976 2.52 49.8 27.0 103
25.0 37.0 38.0 1300 7.50 1061 2.49 47.5 26 2 103
25.0 :34.0 41.0 1300 7.51 1049 2.26 39.9 36 0 109
25.0 :(I . o 44.0 1300 7.42 675 3.19 30.1 70.2 147
25.0 28.0 47.0 1300 7.44 630 3.55 29.7 62.8 175
25.0 25.0 50.0 1300 7.54 566 3.32 29.5 64.1 221
25.0 12 5 62.5 1300 7.47 493 2.97 20.7 80.0 314
25.0 75,O 1300 7.45 533 3.27 7.3 384.0 383
18.75 18.75 62.5 1300 7.51 429 3.10 23.4 87.5 277
18.7 81.3 1220 7.08 224 1.26 7.0 1695.0 250
12.5 87.5
-- 1200 6.54 137 3.20 No piezoelectricity
12.5 0
i .I. 12.5 1250 7.46 302 2.22 19.4 142.7 360
12.5 62 5 25.0 1310 7.55 404 0.95 25.7 89.0 246
12.5 .iO.0 37.5 1310 7.53 825 1.02 42.1 34.8 133
12.5 If;. 5 41.0 1310 7.50 912 1.69 44.6 33.7 109
12.5 18 5 44.0 1310 7.49 1246 1.65 49.2 20.6 101
12.5 40 5 47.0 1310 7.53 1090 1.50 45.8 28.1 108
12.5 :37.5 50.0 1310 7.44 593 2.45 44.0 47.1 121
12.5 31.5 53.0 1310 7.43 554 3.25 26.0 83.6 219
12.5 25.0 62.5 1310 7.43 432 2.90 25.0 92.5 235
12.5 12.5 75.0 1310 7.41 288 2.56 19.9 129.3 391
f i . 25 6.25 87.5 1300 7.22 251 2.75 12.5 275.4 462
1. o 48.0 51.0 1230 7.08 688 1.09 34.5 77.9 107
1 0 45.0 54.0 1230 7.12 514 1.55 33.6 59.8 186
1. o 42 0 57.0 1230 7.14 412 1.67 28.6 99 3 193

in a rubber-lined ball mill with sardonyx balls, dried, and
prcsscd into a tablet at a compacting pressure of 400 kg/cm2.
Each tablet was placed in a porcelain crucible with a cover
and was calcined at 85OOC for 2 hr. The calcined material
was wet-milled for 17 hr using the previously mentioned
ball mill and was then dried. The ground material, with a
small amount oE water, was pressed into a tablet 20 mm in
diameter by 2 nim thick a t a pressure of 700 kg/cm2. The
compact was sintered on a platinum sheet covered with an
Alj03 crucible to prevent the evaporation of PbO. The ter-
nary system has less evaporated PbO than the binary system
PbTiOs-PbZrOs and is easily sintered. The sintering tem-
pcratures required for producing a high-density sintered
body were determined by measuring the density (Table I).
The sintering time was 45 min. The sintered body was
lapped to a thickness of 1 mm. Electrodes were formed
by painting the body with silver paste and firing at 8OOoC.
( 2 ) Electrical Properties
Electrical capacitance and loss tangent were measured with
a capacitance bridge* at 20°C, 50y0rh, and at a frequency of
1kc. Curie temperature was determined by the usual method
and electrical volume resistivity was measured by an elec-
trometer? with a dc voltage of 10 v/mm.
* General Radio Type 716-C.
f Takeda liiken Type B-84.
A32 Journal of ?'he American Ceramic Society-Ouchi
A
4 / * \
.' . . ... ,*
h
4
" "
. I(
4
"
PbTi03 2- PbZr03
MOLE BASIS
Fig. 1. Compositions studied in the system Pb (Mgi/,Nb2/,)O3-
PbTiOs-PbZrOa and phase boundaries at room temperature,
where T = ferroelectric tetragonal; R = ferroelectric rhombo-
hedral; PC = ferroelectric pseudocubic.
( 3 ) Poling
Poling was done in silicon oil a t 100°C by applying a field
of 4 ltv/mm €or 1 hr. The sample in silicon oil was cooled
to room temperature in 30 min. with the field maintained.
( 4 ) Piezoelectric Properties
Twenty four hours altcr poling, the radial coupling coeffi-
cient was mcasured by a method similar to that of the In-
stitute oi Radio Engineers Standards 13 Thc resonant fre-
quency, or the radial fundamental mode, and the resonant
teiistancc were measured a t 20OC and 50% rh. The mechan-
ical quality factor, QV, was calculated from the following
cq~iatiori:
1 located at 0.2'iPb(Mgi/,Nba/,)O,, 0.38PbTi03, and 0.35Pb-
Vdf =
47r(fa - J'r)RC
fa =antiresotiant frequency (cycles/sec).
f r = resonant frcqucncy (cycles/sec).
/Z = resonant rcsistance (ohms).
C = clectrical capacitance (farads).
'The resonant rcsistance was obtained by matching thc highest
voltage at thc resonant I'requcncy with that obtained by
substitution of a selected known resistance.
( 5 ) X - R a y Analyses
X-ray powder diflraction examinations were made with a
recording diflractometer* using Cu Kol radiation through a
nickel filter a t room temperature or occasionally a t high
temperature.
111. Results and Discussion
(I) Phase Relations
A morphotropic transfornmation between a tetragonal
phase (PbTiOa) and a pseudocubic phase (Pb(Mgl/,Nb2/,)03)
was found a t 0.41 mole fraction PbTiO3, and that between
a tetragonal and rhombohedral phase (PbZr03),was found at
0.45 mole fraction PbTiOs, as shown in Fig. 1. The tetrag-
onal phase area is bounded by a convex curve to PbTiOs
in the present ternary compositions whereas the area of
tetragonal phase in PbTi03-PbZr0s-Pb0 : SnOz compositions5
is bounded by a concave curve to PbTi03. A difference in
these phase boundary shifts is related to ionic radii of the B site
ion in a perovskite-type A1303 c0mpound1~but it cannot be
fully explained at present. A morphotropic transformation
betwcen the rhombohedra1 and the pseudocubic phase is still
ilncertain but may be drawn as shown in Fig. 1 within the
* Rigaku Denki D3F.
et al. Vol. 48, No. 12
4.74
selI'
---
"k
PbTIO.
.25
.75
.SO
.50
.75
.25
PbZrO,
0
C O M P O S I T I O N (MOLE 1
Fig. 2. Lattice constant of Pb(Mgl/,Nb2/,)03-PbTiOa-PbZrO~
at room temperature. Values for the binary system when
Pb(Mgi/,Nby,)03 = 0 are taken from Jaffe et al. (Ref. 5 ) .
accuracy of the present experiment. A triple point may be
Zr03.
The lattice parameter of tetragonal PbTi03 is a = 3.905
A and c/a = 1.06316and the axial ratio decreases with an in-
crease in Pb(Mgl/,Nbz/,)03 and PbZr03 as shown in Fig. 2.
(2) Curie Temperature
Curie temperatures of Pb(Mgr/,Nbs/,)03 and PbTiOa
are - 1 5 O and 49OoC, respectively. When these materials
form a solid solution, the Curie temperature is expected to
vary with the composition. Figure 3 shows the variation
in Curie temperature for the system Ph(Mg~/,Nbi/,)O3-
PbTiO3. Curie temperatures of the binary system vary al-
most linearly with the amount of each component but show a
kink at the composition of the morphotropic transformation.
Curie temperatures for the systems 0.25Pb (Mgl/,Nbz/,)O,-
yPbTi03-zPbZrOs and 0.50Pb(Mgl/,Nb~/,)Os~yPhTiOs--zPb-
Zr03 also decrease with an increase in PbZrO:<as shown in
Figs. 4 and 5. The Curie temperature curves of ihc ternary
system also show kinks at the composition of the inorpho-
tropic transformation. The kinks are in good agreement with
the results of the phase determinations.
( 3 ) Sintered Density
It is difficult to obtain a well sintered body of PbTi0316-18
and PbZr03 because PbTiO3 has an abnormal anisotropic
crystallographic transformation a t the Curie temperature of
49OoC (i.e. transformation from a cubic to a tetragonal
phase) and PbZrOs shows violent evaporation of Pb0.19
I n Pb(Mgl/,Nbg/,)Os, it is difficult to obtain a good ceramic
because of a narrow range of sintering temperature. Since,
however, the Pb(Mgl/,Nb2/,)03-PbTi03-PbZr03 compositions
are free from these difficulties, sintering becomes much easier.
Table I shows the sintered density for each composition a t
various firing temperatures with a constant heating time of
December 1965 Piezoelectric Properties oJ’ I’O(Mg113 Nb213)03-PbI’iO3-PbZrOs Ceramics 633
5004 x103 X=075
X=0:625
3
2 E%?S
,.
. x=o.
0
~ ~ 0 . 2
x=aiX5
I-
Z
CUBIC
$g 2
V

2
a
l-
0
-I
W
!!I
a

.25 50 2 (a, PbZrO,

COMPOSITION (MOLE)
Fig. 6. Dielectric constant at 20°C and 1 kc for the system
xPb(Mgi/3Nbz/,)0s-yPbTi03-zPbZr03 with Pb(Mgl/,Nbz/,)O,
as a parameter. Values for the binary system when x = 0
I I are taken from Jaffe et al. (Ref. 5 ) .
Pb(MggNw0, .75 50 .25 0
COMPOSITION ( MOLE)
Fig. 3. Curie temperature, T c , of Pb(Mgl/,-
Nbya)Os-PbTiO3 solid solution ceramics. W

I . I
X 0 01 125 25 375 50 59
.470 95 435 40 375 375 41
0 ,026 54 44 35 25 I25 0
MOLE
Fig. 7. Dielectric constant and radial coupling coefficient of
xPb (Mgi/,Nb~/3)0~-yPbTiO~-zPbZr03 at a composition of
morphotropic transformatlon. Values for the binary system
when x = 0 are taken from Jaffe e t a l . (Ref. 5 ) .

, PbZrOs
PbTiOa .75 .50 .25 0
COMPOSITION (MOLE) 45 min. It is seen that a fairly high density is ohtained for
Fig. 4. Curie temperature of 0.25 Pb- the ternary compositions. The density ol 0.176PbTi03-
-
Mg1/,Nbz/,)O3 yPbTiOs - zPbZrOs solid 0.525PbZr03, however, unexpectedly decreases with the
solution ceramics. addition of a small amount of Pb(Mgi/,Nbl/,)O3 and then
increases with further additions. A similar decrease is also
reported by Sinyakov and Stafrichuk20 but is not at present
understood. Chemical analyses of PbO in a sintered tmdy
300 also indicated that compositions near a triple point showed the
least evaporation of PbO. There was no water absorption
- CUBIC in the compositions having a high density although their
2 observed densities were “7.5 g/cm3 which is below the average
X-ray density of 8. This indicates the existence of closed
pores in the sintered body.
( 4 ) Dielectric Constants
Dielectric constants af-ler poling are shown in Table I and
TETRJ PSEUDO Fig. 6. Figure 6 shows the dielectric constants of yPbTi03-
I
I
CUBIC zPbZrOs with xPb(Mg:/,Nbn/,)03 as a parameter. Since
I Pb(Mg:/,Nbz/,)Os has a high dielectric constant of 9000 a t
I
room temperature, the dielectric constant of yPbTi03-
0 .25 .JoPbZrO., zPbZr03 increases with the addition of Pb(Mgi/,Nb2/,)03.
P b T i Q s .50 25 0
I n each series (Fig. 6 ) the composition with maximum dielec-
COMPOSITION (MOLE)
tric constant coincides with the morphotropic transformation.
Fig. 5 . Curie temperature of 0.50
P b (Mgy,N by3)O,-yP bTiO3 zPbZr03 - This is in agreement with the behavior observed by JaEe
et aL5 Figure 7 shows the dielectric constant of the system
solid solution ceramics.
 Journal of l'he American Ceramic Society-Ouchi et al. Vol. 48, No. 12
XIO'
( I-X-3 1PbTi 0,

12[
II

10.

9.
c
8.
2
s
0
7.
V
6.
u
E
I- 5-
w
V
4.
w-0
-I

3.

I
2.
0 25 .50 .75 PKMghNqOs
L
(XI I.
COMPOSITION (MOLE) I I
Fig. 8. Radial coupling coefficient at 20°C for system xPb- 0 50 100 150 200 250 300
(Mg~/,Nb~/,)O~-yPbTiO,l-zPbZrO.~ with PbZrOs as a param- TEMPERATURE ('C)
eter. Fig. 10. Temperature dependence of radial coupling coeffi-
cient and dielectric constant for the composition ( A ) Pb-
and ( B ) Pb(Mg1/3Nb2/3)~.1~j-
(Mgl/3Nbz/r)o.zsTi~.3182r0.31803
Tio.37Zro.~O3.

I (I -X- X)PbTIO,

fraction and y = 0.37 to 0.435 mole fraction. The highest

radial coupling coefficients of each series (Fig. 9) are for the
compositions y = 0.37 to 0.375 mole fraction for x = 0.5
mole fraction; y = 0.375 to 0.405 mole fraction for x =
0.375 and 0.2.5 mole fraction; and y = 0.406 to 0.435 mole
fraction for x = 0.125 mole fraction. The foregoing com-
positions are in good agreement with those exhibiting maxi-
mums in dielectric constants (Fig. 6). It is concluded that
the high radial coupling coefficient is near the morphotropic
transformation for each compositional series. Figure 7 shows
the radial coupling coefficient of compositions a t the morpho-
tropic transformation. The minimum radial coupling co-
efficient is at the small addition of Pb(Mgi/,Nbz/,)O3 similar
to variations of the dielectric constant.
.25 50 -75 PbZrO,
Figure 10 shows temperature dependence of radial coupling
0
(2) coefficients and dielectric constants for two compositions.
COMPOSITION (MOLE) The ternary compositions are expected to have a high po-
Fig. 9 . Radial coupling coefficient at 20°C for system xPb- tential as electromechanical transducers up to 200OC.
(Mgl/,Nbz/,)Oi - yPbTiO:, - zPbZrOJ with Pb(Mgi/,Nb2/,)OS Resonant frequency of the ternary system of compositions
as a parameter. Values for the binary system when x = 0 in the range x = y = 0.375 to 0.625 mole fraction varies
are taken from Jaffe et al. (Ref. 5 ) .
slightly with temperature between 20" and 85OC as shown
in Fig. 11. This variation in the resonant frequency is very
small; the value a t the compositions x = 0.5, y = 0.375, and
x = y = 0.4375 was about 0.20%.
ad%( Mg~/,Nb~/,)O~-yPbTiO~-zPbZr0~ a t the composition of Mechanical quality factor and resonant resistance were
morphotropic translormation as a function of Pb(Mgl/,- also low a t the compositions where the high radial coupling
Nbz/,)Oj The dielectric constant of 0 475PbTi03-0 525- coefficient and dielectric constant were found (Table I).
PMrOa decreases considerably with a small addition of
I'b(Mgi/,Nbz/,)Oj This decrease may have resulted from the ( 6 ) Electrical Resistivity
low sintered density of compositions containing a small Figure 12 shows the temperature dependence of electrical
amount of Pb(Mgi/,Nbi/J03 The dielectric constant in- resistivity of xPb(Mgi/,Nb~/,)O~-yPbTiO3-zPbZr03. The
c r e a m and shows a maximum a t an addition of 0 5 0 mole electrical resistivity of the ternary compositions is higher
fraction of Pb (Mgl/3Nbl/a)0 I than that of the 0.5Pb(Mg1/,Nb2/,)03-0.5PbTiO3 solid solu-
tion and does not vary with the amount of PbZr03. Since
( 5 ) Piezoelectricity the activation energy of electrical conductivity does not vary
Figures 8 and 9 show the piezoelectric properties of the with the addition of PbZr03, the high resistivity of the ternary
5ystem xPb(Mgi/,Nbz/,)Ol yPbTi03-zPbZr03 a t various system may result from the replacement of Ti ions with Zr
values of x and z A composition of pseudocubic structure ions which interrupt the electrical conduction of the Ti
having a high Pb(Mgl/,Nbz/,)03 content exhibited a slight ions. The temperature-resistivity curves show a change in
piczoelectricity , similarly pure Pb(Mgi/,Nbz/,)03 had a piezo- slope at their Curie temperatures. The activation energy
electricity above its Curie temperature as reported by Smolen- below the Curie temperature is lower (19.7 kcal/mole) than
ski? and Agranovskaya A high radial coupling coefficient that (32.0 kcal/mole) above it. The reason for this is not
of over 45y0 was found a t a region of x = 0 125 to 0 375 mole known.
December 1905 Piezoelectric Properties oj” Ph (MgliaNb2ie)03-PbTi03-PbZrOa Ceramics
IV. Conclusions
( I ) ‘The solid solutions of the system nPb(Mgi/,Nbz/,)O3-
yl’bTi03-zPbZr03 are coniposcd of pseudocubic, tetragonal,
and rhombohedra1 crystal phases.
(2) Dielectric constant atid radial coupling cocfficient of thc
tcrnary systeni are high at the compositions near the morpho-
tropic transformation between the tetragonal and pseudocubic
or rhoinbohcdral phases. T h e low resonant resistance is
xicar the morphotropic transforination.
(3) Curie temperature varies with a change in t h e composi-
tion of the system and is reduced by addition OC Pb(Mgl/,-
Nh Z / J 03.
(4) T h e lowest temperature changc of resonant frequency
among t h e present spcciiiiens is found at the compositions
n = 0.375 t o 0.625 and y = 0.3‘75 t o 0.625 mole Iraction.
(5) T h e activation energy lor t h e electrical conductivity
above t h e Curie tcmperature is higher than t h a t below i t .
Acknowledgments
‘The authors exprcss their sincere thanks t o S. Kisaka, manager
of this laboratory, €or his encouragement during this study, to
Y.Iida, assistant manager, for his guidance, to S. Mori €or thc
X-ray pattcrns, and t o K . Iwamoto for his cooperation in the cx-
pcriniciital work.
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