Journal of Non-Crystalline Solids 235237 (1998) 567569

Diuse phase transitions in ferroelectric ceramics

a,b,*
A. Fundora azquez a, J. Portelles a, F. Calder
, A. V on a, J.M. Siqueiros b

a
Facultad de Fsica-IMRE, Universidad de la Habana, San L azaro y L, Vedado, CP 10400, Cuba
b
Cntro de Ciencias de la Mat. Condens., Instituto de Fsica-UNAM, Laboratorio de Ensenada, Apartado Postal 2681, Ensenada,
Baja California, M exico 22800, Mexico

Abstract
The diuse phase transition (DPT) in ferroelectric ceramics of the type Pb(Fe1=2 Nb1=2 )O3 has been studied by the
SmolenskyIsupov's theory. A Gaussian-logarithmic distribution for the relaxation time was obtained from the as-
sumption that the activation energies have a Gaussian distribution. The dielectric permittivity is obtained by taking into
account these approximations. Experimental curves of the dielectric permittivity as a function of temperature at dier-
ent frequencies are reported. 1998 Elsevier Science B.V. All rights reserved.

1. Introduction oretical and experimental analysis of the permit-

tivity and the dielectric losses and assuming, in
Since the discovery of Pb(Mg1=3 Nb2=3 )O3 in the SmolenskyIsupov's theory, that the activation
1954 [1], it was found that the dielectric permit- energy has a Gaussian distribution. This assump-
tivity of this ferroelectric material has a depen- tion leads to a Gaussian-logarithmic functional be-
dence on temperature and frequency that cannot havior for the relaxation time.
be explained by the classical ferroelectric relax-
ation theory for phase transitions. Many theories
2. Experimental procedure
have been developed to study the diuse phase
transition (DPT) and most of them rely on cation
The samples used in this study were prepared by
disorder. Presently, the SmolenskyIsupov theory
the conventional ceramic method [5]. The calcina-
[2] is accepted and is based on the composition
tion temperature was 900C. The samples were sin-
uctuation [3] of dierent polar microregions
tered at 1200C in a 0.5 g PbZrO3 atmosphere for 1
where dierent ions B0 and B00 try to occupy the
h. The dielectric permittivity and dielectric loss re-
same crystallographic site B, in a simple perovskite
sponse as a function of frequency and temperature
structure (ABO3 ).
were measured using a PC controlled impedance
Our system is a PFN ceramic that Randall [4]
bridge (BM 507). Measurements were made with
has classied as a normal ferroelectric ceramic
a heating rate of 1C/min from 25C to 150C.
(without DPT). In this work, we studied the diuse
phase transition in the PFN system based on the-
3. Modication of the SmolenskyIsupov's theory

*
Corresponding author. Tel.: 52 617 44602; fax: 52 617 44603; Diuse phase transitions (DPT) take place in
e-mail: abefun@isicaen.unam.mx. materials where the composition uctuations lead
0022-3093/98/$19.00 1998 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 0 9 3 ( 9 8 ) 0 0 5 6 7 - 5
568 A. Fundora et al. / Journal of Non-Crystalline Solids 235237 (1998) 567569
 2 
to large uctuations in the Curie temperature. In 1 ln s=s0
general it is assumed [1,2] that the Curie tempera- f s ds p exp d lns; 5
2pa2 2a2
tures have a Gaussian distribution around some
average Tc with a mean square deviation, d, which where s0 (1/c) exp (U0 /kT) and a r/kT. r stands
is the parameter characterizing the degree of dif- for the activation energy uctuations. In order to
fusivity of the transition. solve this equation we approximate it by the fol-
According to the SmolenskyIsupov theory the lowing function:
8
e0 and e00 as functions of temperature and relax- >
> d lns s
ation time are given by < p
>
2pa2
for a 6 ln 6 a;
s0
f s ds   6
8pl2 V0 n 1 >
>  s
e0 e1 1 >
:  
0 for ln  > a:
7kT 1 x2 s2 s0

8pl2 V0 n xs Finally, the expressions for the real and the imag-
e00 ; 2 inary parts of the dielectric constant will be
7kT 1 x2 s2   
0 8pl2 V0 n 1 1 x2 s20 e2a
where l is the dipolar moment in a polarized re- e e1 1 ln ; 7
7kT 4a 1 x2 s20 e2a
gion, V0 is the average volume in this region, s is
the relaxation time and n is the number of relaxors 8pl2 V0 n  
per unit volume e00 tan1 xs0 ea tan1 xs0 ea : 8
7kT
N DT T Tc 2
n p e 2d2 ; 3
2pd2
4. Results
where N 1/V0 is the maximum number of relax-
ors and T DT/2 with DTT is the range of Cu- In Fig. 1 the theoretical and the experimental
rie temperatures of the polar regions that curves of e0 vs. T are shown for dierent fre-
contribute to the polarization.
In this theory only one relaxation time, s, is as-
sumed:
1
s eU =kT ; 4
c
where U is the activation energy, k is Boltzmann's
constant and c is the Debye frequency. In the
SmolenskyIsupov theory only the aect of the
composition uctuations in the distribution of Cu-
rie temperature across the crystal is taken into ac-
count. We additionally assume that this
uctuation also aects the dipolar moment magni-
tude of polar microregions (PMR) and, conse-
quently, not all the PMR in the crystal have the
same activation energy.
We assume that, just as for the Curie tempera-
ture, the activation energy has also a Gaussian dis-
tribution around an average value, U0 , with a
mean square deviation, r. Therefore, according
to Eq. (4), the relaxation time will have a Gauss- Fig. 1. Theoretical and experimental curves of e0 vs. T at dier-
ian-logarithmic distribution: ent frequencies.
 A. Fundora et al. / Journal of Non-Crystalline Solids 235237 (1998) 567569
Fig. 2. Theoretical and experimental curves of e0 vs. f at 131C
and 186C.
quencies. Here we can observe that, as the fre-
quency changes, the temperature corresponding
to the maximum of the dielectric permittivity
is displaced towards higher temperatures. There-
fore we can state that the phase transition is
diusive. The continuous line in Fig. 1 repre-
sents the experimental data and the discrete
points were obtained through Eq. (7). The
agreement between both suggests that the distri-
bution function proposed for the relaxation time
is correct.
In Fig. 2 the dependence of e0 with the frequen-
cy at 131C and 186C is shown. For both temper-
atures and using the proposed distribution
function for the relaxation time, agreement be-
tween the theoretical and experimental results
was obtained. Using only one relaxation time,
such agreement would have been impossible to
obtain. In Fig. 3 we observe the dependence of
ln(s) vs. 1/T. Since this is obviously not a linear
dependence, it is not possible to ignore the depen-
dence of the activation energy with the tempera-
ture.
569
Fig. 3. ln(s) vs. 1/T curves in the PFN system.
5. Conclusion
We proposed a modication to the Smolensky
Isupov theory where we assume a temperature de-
pendence of the activation energy. The close agree-
ment with the experimental results is a strong
argument in favor of our model. Furthermore
the relaxation time is a Gaussian-logarithmic dis-
tribution function which leads to the conclusion
that, in disagreement with other reports [6], the
PFN system has a diuse phase transition in the
analyzed frequency range.
References
[1] G.A. Smolesnky, V.A. Isupov, Soviet J. Techn. Phys 24
(1954) 1375.
[2] V.V. Kirillov, V.A. Isupov, Ferroelectrics 5 (1971) 3.
[3] V.A. Isupov, Soviet J. Techn. Phys. 26 (1956) 1912.
[4] C.A. Randall, A.S. Bhalla, J. Appl. Phys 29 (1990) 2.
[5] J. Portelles, PhD dissertation, Fac. Fsica. Havana Univer-
sity, 1994.
[6] C.A. Randall, A.S. Bhalla, J. Mater. Sci. 29 (1990) 5.