REFERENSI TAYueming Li Wen Chen Jing Zhou Qing Xu Huajun Sun Renxin Xu - Dielectric and Piezoelecrtic Properties of Lead-Free

Materials Science & Engineering B 112 (2004) 59
www.elsevier.com/locate/mseb
Dielectric and piezoelecrtic properties of lead-free

(Na0.5Bi0.5)TiO3NaNbO3 ceramics
Yueming Lia,b, Wen Chena,*, Jing Zhoua, Qing Xua, Huajun Suna, Renxin Xua
a
Institute of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, PR China
b
Jingdezhen Ceramics Institute, Jingdezhen 333001, PR China
Received 25 February 2004; accepted 26 April 2004
Abstract
In this paper, lead-free [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 (x = 00.08) ceramics were fabricated by using conventional ceramic technique.
The phase structure of the solid solution has been determined by the X-ray diffraction. Dielectric study revealed that the dielectric relaxor
behavior becomes more obviously by doping of NaNbO3 into (Na0.5Bi0.5)TiO3. The samples in the composition range from x = 0.01 to 0.02
exhibited excellent electrical properties, piezoelectric constant d33 = 8088 pC/N; electromechanical planar coupling coefficients kp = 17.92%.
The results show that the [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 ceramics are one of the promising lead-free materials for ultrasonic transducer
applications.
# 2004 Elsevier B.V. All rights reserved.
Keywords: Dielectric properties; Piezoelectric properties; Na0.5Bi0.5TiO3; Perovskite; Relaxor
1. Introduction
Lead oxide based ferroelectrics, represented by lead
zirconate titanate (Pb(Zr, Ti)O3, PZT) are widely used for
piezoelectric actuators, sensors and transducers due to their
excellent piezoelectric properties [1,2]. However, volatilization of toxic PbO during high-temperature sintering not only
causes environmental pollution but also generate un-stability of composition and electrical properties of products.
Therefore, it is necessary to develop environment-friendly
lead-free piezoelectric ceramics to replace PZT based ceramics, which has become one of the main trends in present
development of piezoelectric materials.
Sodium bismuth titanate, Na0.5Bi0.5TiO3 (NBT), is a
kind of perovskite (ABO3-type) ferroelectric discovered
by Smolenskii et al. in 1960 [3]. NBT is considered to be
an excellent candidate of lead-free piezoelectric ceramics
and
because it is rhombohedral symmetry with a = 3.891 A
a = 898360 at room temperature. It is ferroelectric with a
relatively large remanent polarization, Pr = 38 mC/cm2, and
* Corresponding author. Tel.: +86 27 8786 4033; fax: +86 27 8764 2079.
E-mail address: [email protected] (W. Chen).
0921-5107/$ see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.mseb.2004.04.019
a relatively large coercive field, Ec = 7.3 kV/mm [3]. It

reveals a very interesting anomaly of dielectric properties as
a result of low temperature phase transition from ferroelectric to anti-ferroelectric phase at 200 8C. However,
NBT has a drawback of high conductivity and high coercive
field Ec to cause problems in poling process. To improve its
properties, solid solution of NBT with BaTiO3 [4], SrTiO3
[5], K0.5Bi0.5TiO3 [6,7], NaNbO3 [8] have been investigated.
Lanthanum (La2O3) was also introduced to modify NBTs
properties [9].
In this paper, the lead-free [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 [(1 x)NBTxNN, x = 00.08] solid solution was
fabricated by using conventional ceramic technique. The
dielectric and piezoelectric properties of (1 x)NBTxNN
were also characterized.
2. Experimental
The conventional solid state reaction method was used
to prepare [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 (x = 0, 0.01,
0.02, 0.03, 0.04, 0.05, 0.06, 0.08) ceramics. Reagent grade
oxide or carbonate powders of Bi2O3, Na2CO3, TiO2 and
Y. Li et al. / Materials Science & Engineering B 112 (2004) 59
Nb2O5 are used as starting raw materials. The oxides and

carbonates were mixed in ethanol with agate balls by ball
milling for 4 h. After being mixed, the dried powder was
calcined at 850900 8C for 2 h. The calcined powder was
reground by ball milling for 6 h. The dried powder was mixed
with polyyinyl alcohol and pressed at 150 MPa into pellets
20 mm in diameter and about 1.5 mm in thickness. The green
compacts were sintered at various temperatures (1150
1200 8C) for 2 h in air atmosphere. Silver paste was fired
on the surfaces of the disc as electrodes. The specimens for
measurement of piezoelectric properties were poled in silicon
oil at 80 8C under 34 kV/mm for 15 min.
X-ray powder diffraction (XRD) patterns were taken on a
D/MAX-III X-ray diffractometer with Cu Ka radiation (l =
) and graphite monochrometer. The relative dielec1.5418 A
tric constant er and dissipation factor (tan d) at room and
elevated temperature were measured at 1, 10 and 100 kHz
using TH2816 LRC meter. Piezoelectric constant d33 of the
samples were measured by means of quasistatic d33 meter
(ZJ-3A) based on Berlincourt method. Dielectric and piezoelectric properties were measured by means of the resonance-antiresonance method using a precision impedance
analyzer (HP4294A). The electromechanical coupling factor kp was calculated from the resonance and antiresonance
frequencies based on the Onoes formulas [10].
with a = 0.389 nm and a = 89.68. The result reveals that solid

solution samples without any secondary impurity phases can
be prepared in the NBTNN system. With increasing of
NaNbO3 content, the diffraction peaks shift toward a lower
, ionic diameter)
angle since it is expected the Ti4+ (0.61 A
5+
could substitute by Nb (0.64 A). The substitution seems to

have caused the enlargement of the NBT unit cell.
3.2. Dielectric properties of (1x)NBTxNN
The XRD analysis of the ceramics powder shows that

(1 x)NBTxNN is pure of single phase with a perovskite
structure and forms a solid solution (Fig. 1). At room
temperature, the NBT is rhombohedral ferroelectric,
whereas NaNbO3 is known to be an orthorhombic structure
anti-ferroelectric [11]. XRD pattern of NBT, all of the peaks
could be indexed on the basis of the rhombohedral unit cell
3.2.1. Temperature dependence of the dielectric constant

The temperature dependence of dielectric constant (er) at
10 kHz for (1 x)NBTxNN samples with 0 x 0.08 is
shown in Fig. 2. For undoped NBT, two sharp phase
transition are observed at 180 and 305 8C, corresponding
to the phase transitions of ferroelectric (rhombohedral)anti-ferroelectric (tetragonal) (at Tf) and anti-ferroelectric
(tetragonal)-paraelectric (tetragonal) (at Tc), respectively
[4,12]. For the samples with x = 0.01, 0.02 and 0.03, the two
phase transitions are also observed. However, their phase
transition temperatures shift to lower temperatures and the
peaks become much broader than that of pure NBT. When
the NaNbO3 content is higher than 0.04 (x 0.04), only
one rounder e peak is observed in the examined temperature range. At room temperature, the dielectric constant
er (x = 00.08) varies from 467 to 889, the dielectric loss
tangent, tan d is 4.116.26 % (Table 1), indicating that
(1 x)NBTxNN ceramics should be suitable for practical
application.
The temperature dependence of dielectric constant er and
dielectric loss tan d of (1 x)NBTxNN samples with x =
0.02, 0.04, 0.06, 0.08 under various frequencies is shown in
Fig. 3. A strong frequency dispersion of the dielectric
permittivity is clearly seen for all samples. The temperature
(Tm) of the dielectric constant maximum increases and the
em value decreases with increasing frequency. It is proved
that NBT is a relaxor ferroelectric and the Na+ and Nb5+ codoped NBT make the ceramics become more relaxor-like
ferroelectric.
Fig. 1. Powder XRD patterns of the (1 x)NBTxNN ceramics.
Fig. 2. Temperature dependence of the dielectric constant (er) of (1 x)NBT

xNN ceramics at 10 kHz.
3. Results and discussions

3.1. The X-ray diffraction patterns of (1 x)NBTxNN
ceramics
Table 1
The dielectric and piezoelectric properties of (1 x)NBTxNN ceramics
NaNbO3 content (x)
eT33 =e0 (10 kHz)
Tan d (%) (10 kHz)
d33 (pC/N)
kp (%)
Qm
0
0.01
0.02
0.03
0.04
0.05
0.06
0.08
467
637
624
754
753
801
811
889
4.11
5.60
5.90
5.96
6.26
5.40
6.01
4.53
61
80
88
60
50
32
31
17.95
17.48
17.92
14.90
12.50
12.38
12.50
140
90
87
85
92
69
52
3143
3178
3173
3188
3187
3197
3220
This relaxor phenomenon has been found in many

compounds such as Pb(Mg1/3Nb2/3)O3, Pb(Zn1/3Nb2/3)O3,
(Pb, La)(Zr, Ti)O3 and doped BaTiO3 with perovskite
structure [1316]. The relaxor behavior can be induced
by many reasons such as the merging of micropolar regions
into macropolar regions [16], local compositional fluctuation [17], superparaelectric[18] and dipolar glass model
[19]. In the solid solution of (1 x)NBTxNN, Na+ and
Bi3+ ions co-occupy the A-site of ABO3 perovskite structure, Ti4+ and Nb5+ ions co-occupy the B-site, therefore
the cations disorder in perovskite unit cell should be
one of the reason for the appearance of relaxor state.
On the other hand, it is known that the NaNbO3 shows
anti-ferroelectric at room temperature. In this case, the

macrodomain in pure NBT should be divided into microdomains with increasing Na+ and Nb5+ ion doping, which
also may result in the appearance of the more relaxor-like
behavior.
3.2.2. Diffusion phase transition
For a normal ferroelectric, the dielectric constant above
the Curie temperature follows the CurieWeiss law
described by:
e
C
T T0
(1)
Fig. 3. Temperature dependence of dielectric constant (er) and dielectric loss (tan d) for (1 x)NBTxNN ceramics at 1, 10, 100 kHz with (a) x = 0.02, (b) x = 0.04,
(c) x = 0.06, and (d) x = 0.08.

Table 2
The CurieWeiss temperature (T0), the CurieWeiss constant (C), the
temperature above the dielectric constant follows the CurieWeiss law
(Tcw), and the diffuseness coefficient (g) for (1 x)NBTxNN ceramics at
10 kHz
Fig. 4. The inverse dielectric constant (1/er) as a function of temperature at

10 kHz for (1 x)NBTxNN ceramics with x = 0.02, 0.04, 0.06, and 0.08
(the symbols: experimental data, the solid line: fitting to CurieWeiss law).
where C is the CurieWeiss constant, and T0 is the Curie

Weiss temperature. Fig. 4 shows the inverse e as a function of
temperature at 10 kHz, the fitting results obtained by Eq. (1)
are listed in Table 2. Deviation from the CurieWeiss law
can be defined by DTm as the following:
DTm Tcw Tem
(2)
where Tcw is the temperature at which e starts to follow the

CurieWeiss law, and Tem is the temperature at which e value
reaches the maximum.
It is found that the dielectric constant of (1 x)NBT
xNN ceramics obeys the CurieWeiss law at temperature
Composition
x = 0.02
x = 0.04
x = 0.06
x = 0.08
T0 (8C)
C 107 (8C)
Tcw (8C)
DTm = Tcw Tm (8C)
g
300
2.579
340
40
1.295
285
1.325
340
55
1.42
275
0.711
340
65
1.525
305
0.612
360
55
1.56
increasing with the increase x (Table 2), implying that the

diffusion phase transition behavior have been enhanced with
increasing doping content.
A modified empirical expression was proposed by
Uchino et al. to describe the diffusion of the ferroelectric
phase transition [20]:
1 1

CT Tem g
e em
(3)
where g and C are assumed to be constant, the g value is

between 1 and 2. The limiting values g = 1 and g = 2 obey the
equation to CurieWeiss law which are the character for the
case of normal ferroelectric and for an ideal relaxor ferroelectric, respectively [21,22].
The value (1/e 1/em) was plotted against the (T Tm)
and the curves are shown in Fig. 5. A linear relationship is
observed for all samples. The slope of the fitting curves is
used to determine the g value. The g value varies from 1.295
to 1.56 (Table 2), indicating that the (1 x)NBTxNN solid
Fig. 5. The value (1/e 1/em) as a function of (T Tm) at 10 kHz for (1 x)NBTxNN ceramics with x = 0.02, 0.04, 0.06, and 0.08 [the symbols: experimental
data; the solid line: fitting to Eq. (3)].
solutions are more relaxor ferroelectric characteristic with

the increase doping of Na+ and Nb5+ ions.
3.3. Piezoelectric properties (1 x)NBTxNN ceramics
The piezoelectric properties of (1 x)NBTxNN ceramics are also listed in Table 1. The pure NBT sample shows
good piezoelectric properties: d33 = 61 pC/N, kp = 17.95%.
The relative large piezoelectric constants d33 = 3188 pC/N
and electromechanical planar coefficients kp = 12.517.92%
were also observed for the doped NBT ceramics in the
composition range of x = 0.010.08. This should attribute
co-effect of the soft additive Nb5+ ion doping at B-site and
hard additive Na+ ion doping at A-site. When x = 0.010.02,
relative good piezoelectric properties such as the piezoelectric constant d33 = 8088 pC/N, kp = 17.92% were
obtained, which should be attribute the dominant of doping
Nb5+ ion. However, with further increasing the doping
content of NaNbO3 (x = 0.030.08), the piezoelectric properties decreased, which may be the reason for the dominant
of doping Na+ ion. Although NaNbO3 is anti-ferroelectric,
the morphotropic phase boundary does not appear between
NBT and NaNbO3 in this composition range. Therefore, it is
presumed that the piezoelectricity of NBT loses gradually by
adding NaNbO3 more than threshold content. Similar phenomenon was also found in KNbO3LaFeO3 system [23].
4. Conclusions
The [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 solid solution
has been successfully synthesized by using conventional
ceramics technique. Dielectric study revealed that (1 x)NBTxNN solid solutions become more relaxor ferroelectric characteristic with the increase the content NaNbO3.
Excellent electrical properties, piezoelectric constant
d33 = 8088 pC/N, electromechanical planar coupling coefficients kp = 17.92% can be observed in the composition
range of x = 0.010.02. It is obvious that the [Na0.5(1+x)Bi0.5(1x)](Ti(1x)Nbx)O3 solid solution ceramics are one
of the promising lead-free ceramics for high frequency
ultrasonic transducer applications.
Acknowledgements
This work is supported by the National Natural Science
Foundation of China (Grant no. 50272044), Natural Science
Foundation of Hubei, China (Grant no. 2002AB076), and
Nippon Sheet Glass Foundation for Materials Science and
Engineering (Japan).
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Materials Science & Engineering B 112 (2004) 59

Dielectric and piezoelecrtic properties of lead-free

a relatively large coercive field, Ec = 7.3 kV/mm [3]. It

Y. Li et al. / Materials Science & Engineering B 112 (2004) 59

Nb2O5 are used as starting raw materials. The oxides and

with a = 0.389 nm and a = 89.68. The result reveals that solid

could substitute by Nb (0.64 A). The substitution seems to

The XRD analysis of the ceramics powder shows that

3.2.1. Temperature dependence of the dielectric constant

Fig. 1. Powder XRD patterns of the (1 x)NBTxNN ceramics.

Fig. 2. Temperature dependence of the dielectric constant (er) of (1 x)NBT

3. Results and discussions

Y. Li et al. / Materials Science & Engineering B 112 (2004) 59

eT33 =e0 (10 kHz)

Tan d (%) (10 kHz)

This relaxor phenomenon has been found in many

anti-ferroelectric at room temperature. In this case, the

Y. Li et al. / Materials Science & Engineering B 112 (2004) 59

Fig. 4. The inverse dielectric constant (1/er) as a function of temperature at

where C is the CurieWeiss constant, and T0 is the Curie

where Tcw is the temperature at which e starts to follow the

increasing with the increase x (Table 2), implying that the

where g and C are assumed to be constant, the g value is

Y. Li et al. / Materials Science & Engineering B 112 (2004) 59

solutions are more relaxor ferroelectric characteristic with

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