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Ceramics International 38 (2012) 3591–3594

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Microstructure and electrical properties of

(Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics with a low
dielectric loss and a low sintering temperature
Tao Chen *, Ting Zhang, Jifang Zhou, Jianwei Zhang, Yuhong Liu, Guangchang Wang
Teaching and Research Section of Physics, Chengdu Medical College, Chengdu 610083, PR China
Received 19 December 2011; received in revised form 29 December 2011; accepted 29 December 2011
Available online 4 January 2012

Abstract
A low sintering temperature is demonstrated for (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 (BCLTZN-x) piezoelectric ceramics, where
BCLTZN-x lead-free piezoelectric ceramics were prepared by the normal sintering. Effects of Li and Nb on the microstructure and electrical
properties of these ceramics were investigated. The sintering temperature of BCLTZN-x ceramics was decreased greatly by introducing Li and Nb,
and the grain size of these ceramics decreases with increasing x. These ceramics with a small amount of Li and Nb maintain good piezoelectric
properties, together with a low sintering temperature and a lower dielectric loss. These ceramics with x = 0.01 demonstrate optimum electrical
properties: d33  353 pC/N, kp  41.1%, Tc  86 8C, er  4236, and tan d  0.75%.
# 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Electrical properties; Ceramics; Low sintering temperature; Ion substitution

1. Introduction have reported that the addition of LN improved the piezoelectric

properties of K0.50Na0.50NbO3 ceramics by forming the
BaTiO3 as the first ferroelectric oxide is often considered as polymorphic phase transition, and a higher Tc value is
a dielectric not a piezoelectric material because of a high simultaneously demonstrated. However, Chen et al. [14] found
dielectric constant and a relatively lower piezoelectricity [1–3]. that the piezoelectric properties of (1 x)BiScO3–xPbTiO3
A poor piezoelectric constant of 190 pC/N has been ceramics were enhanced greatly by the addition of LN, but its Tc
demonstrated for the BaTiO3 ceramic [3]. Although some value decreases. As a result, LN may play a different role on the
attempts have been conducted to improve its piezoelectric Tc value of piezoelectric materials, depending on their
properties, a relatively low d33 value has been obtained for these compositions [13,14]. Moreover, the addition of LN can also
BaTiO3-based ceramics [4–9]. In 2009, Ren et al. have found improve the piezoelectric properties of these materials [13,14].
that an outstanding d33 value has been observed for the Ca and In the present work, (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 x
Zr-modified BaTiO3 ceramics by constructing the phase NbxO3 (BCLTZN-x) lead-free piezoelectric ceramics were
boundary, but a high sintering temperature of >1500 8C is prepared by the conventional solid-state reaction. Effects of Li
necessary [10]. and Nb content on the microstructure and piezoelectric
It is well known that the LiNbO3 (LN) has a highest Tc value of properties of BCLTZN-x ceramics were investigated, and the
1150 8C among all known piezoelectric materials [11]. LN underlying physical mechanism was also addressed. A low
belongs to be a lithium niobate structure, and is often prepared in sintering temperature is obtained for the BCLTZN-x ceramics
the form of single crystals because it is very difficult to prepare together with a low dielectric loss.
the LN material in the polycrystalline form [12]. Guo et al. [13]
2. Experimental details
* Corresponding author. Tel.: +86 28 68289169; fax: +86 28 68289169.
E-mail addresses: chentaocmc@163.com, myfriendsroom@163.com (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 (x = 0, 0.01,
(T. Chen). 0.02, 0.04, 0.06, 0.08, and 0.10) piezoelectric ceramics were
0272-8842/$36.00 # 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
doi:10.1016/j.ceramint.2011.12.075
3592 T. Chen et al. / Ceramics International 38 (2012) 3591–3594

prepared by using the conventional solid-state reaction. Raw tetragonal phase, to a cubic phase with increasing Li and Nb
materials were BaCO3 (99%), CaCO3 (99%), TiO2 (99%), ZrO2 content. In this work, the BCLTZN-x ceramic with x = 0 has a
(99%), Li2CO3 (99%), and Nb2O5 (99.5%). These powders coexistence of two phases [9,15–18], a tetragonal phase
were milled in alcohol with agate balls for 24 h, and then dried gradually disappears for these ceramics with 0 < x < 0.06, and
and subsequently calcined at 1200 8C in air for 3 h. These then a cubic phase forms for these ceramics with x  0.06.
calcined powders were milled for 24 h again. The poly(- Moreover, the temperature-dependent dielectric constant in
vinylalcohol) (PVA) binder was used to improve the green Fig. 3 also confirms the existence of the phase transition of
strength of compacts, and mixed with these powders. These BCLTZN-x ceramics in this work.
mixed powders were pressed into the cylindrical pellets of Fig. 2(a)–(f) shows the surface morphologies of BCLTZN-x
1.0 cm in diameter and 1.0 mm in thickness under 10 MPa ceramics as a function of Li and Nb content. The average grain
pressure. The PVA binder was removed by sintering at 550 8C size of BCLTZN-x ceramics gradually decreases with increas-
for 6 h, and these pellets were finally sintered at a temperature ing Li and Nb content, which could be attributed to that Li and
of 1300–1400 8C for 2 h. Silver electrodes were fired on the top Nb acting as a grain growth inhibitor. As shown in Fig. 2(b),
and bottom surfaces of these ceramics, and then these ceramics small grain surrounds these larger ones, which helps to improve
were poled under a dc field of 3 kV/mm at 30 8C in a silicone the density of BCLTZN-x ceramics. Moreover, it was found that
oil bath for 30 min. some grains with a cubic shape begin to form for the BCLTZN-
The phase structure of these ceramics was analyzed by using x ceramics with x = 0.06, and gradually increase with further
X-ray diffraction (Bruker D8 Advanced XRD). Field emission increasing Li and Nb content, as shown Fig. 2(e) and (f). This
scanning electron microscopy (FE-SEM, Hitachi S-4800) was result is in agreement with the temperature dependence of the
employed to study the surface morphologies of these ceramics. dielectric constant in Fig. 3, confirming that the phase transition
The temperature dependence of the dielectric properties of is involved into these BCLTZN-x ceramics in this work.
these ceramics was measured by using a programmable furnace Fig. 3 plots the temperature dependence of the dielectric
with an LCR analyzer (TH2816). An impedance analyzer was constant (er) of BCLTZN-x ceramics with different Li and Nb
employed to characterize their dielectric properties, and their content, measured at 1 kHz. The er values located at Tm and the
ferroelectric properties were studied by using the Radiant Curie temperature (Tc) simultaneously decrease with increasing
precise workstation (Radiant Technologies, Medina, NY). The Li and Nb content, which is in agreement with the result
piezoelectric constant d33 of these ceramics was measured by reported by Chen et al. [14]. The classical Vegard behavior has
using a piezo-d33 meter (ZJ-3A, China). confirmed that Li+ and Nb5+ ions are incorporated into the A
site and B sites of the ABO3 perovskite structure, respectively
3. Experimental procedure [19]. In the present work, the introduction of Li and Nb cannot
induce a higher Tc value in the BCLTZN-x system as expected.
Fig. 1(a) shows the XRD patterns of BCLTZN-x ceramics as Although the present work is obviously different from that of
a function of Li and Nb content, measured at room temperature. the K0.5Na0.5NbO3–LiNbO3 system [13], it is very similar to
All ceramics have a pure phase, and no secondary phases are the reported result of the BiScO3–PbTiO3–LiNbO3 system [14].
detected. Therefore, a stable solid solution of BCLTZN-x is The decrease of Tc values could be attributed to the structural
formed in this work. Fig. 1(b) shows the expanded XRD evolution with increasing LN content. The insert of Fig. 3 plots
patterns of BCLTZN-x ceramics as a function of Li and Nb the er value of BCLTZN-x ceramics as a function of Li and Nb
content. These BCLTZN-x ceramics endure a phase transition content, measured at 1 kHz and room temperature. The er value
from the coexistence of rhombohedral and tetragonal phases, a of BCLTZN-x ceramics increases with increasing Li and Nb

Fig. 1. (a) XRD patterns and (b) expanded XRD patterns of (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics.
 T. Chen et al. / Ceramics International 38 (2012) 3591–3594 3593

Fig. 2. Surface morphologies of (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics: (a) x = 0, (b) x = 0.01, (c) x = 0.02, (d) x = 0.04, (e) x = 0.06, and (f) x = 0.10.

content, reaches a maximum at x = 0.02, and then decreases Fig. 5(a) shows the P–E loops of BCLTZN-x ceramics with
with further increasing Li and Nb content. The actual reason for different Li and Nb content, measured at 1 kHz and room
such a phenomenon is clearly demonstrated in Fig. 3. In this temperature. Ferroelectric properties of BCLTZN-x ceramics
work, a relatively high Tc value of 86 8C is observed for the gradually degrade with increasing x content, and a slim P–E
BCLTZN-x ceramic with x = 0.01. loop is observed for the ceramics with x > 0.04, as shown in
Fig. 4 shows the temperature dependence of the dielectric loss Fig. 5(a). These slim P–E loops also confirm the involvement of
(tan d) of BCLTZN-x ceramics with different Li and Nb content, a cubic phase in these ceramics with x > 0.04, which is in
measured at 1 kHz. The tan d value of BCLTZN-x ceramics agreement with the temperature dependence of dielectric
gradually decreases with increasing Li and Nb content, properties in Fig. 3. Fig. 5(b) plots the piezoelectric properties
confirming that the addition of Li and Nb helps to decrease of BCLTZN-x ceramics as a function of Li and Nb content,
the tan d value of BCTZ ceramics. The insert of Fig. 4 plots the measured at room temperature. The d33 value of BCLTZN-x
tan d value of BCLTZN-x ceramics as a function of Li and Nb ceramics slightly decreases at x  0.01, and quickly decreases
content, measured at 1 kHz and room temperature. The tan d with further increasing Li and Nb content. Similarity to the
value of BCLTZN-x ceramics decreases from 5.22% to 0.75% change of d33 values, the kp value of BCLTZN-x ceramics also
with increasing Li and Nb content with x = 0.01, and almost decreases with increasing Li and Nb content because of the
keeps unchanged for x  0.01. The actual reason for such a increase of a cubic phase. In this work, the BCLTZN-x ceramic
phenomenon is also shown in Fig. 4. Therefore, the addition of Li has optimum piezoelectric properties: d33  353 pC/N and
and Nb greatly decreases the tan d value of BCLTZN-x ceramics, kp  41.1%.
which is also much lower than the reported result [20].

Fig. 3. Temperature dependence of the dielectric constant of Fig. 4. Temperature dependence of the dielectric loss of
(Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics, where the insert is er (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics, where the insert is tan d
values as a function of x. values as a function of x.
3594 T. Chen et al. / Ceramics International 38 (2012) 3591–3594

Fig. 5. (a) P–E loops and (b) piezoelectric properties of (Ba0.85Ca0.15)1 xLix(Ti0.90Zr0.10)1 xNbxO3 ceramics as a function of x.

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