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Temperature stability, structural evolution and dielectric properties

of BaTiO3–Bi(Mg2/3Ta1/3)O3 perovskite ceramics
Dandan Ma, Xiuli Chenn, Guisheng Huang, Jie Chen, Huanfu Zhoun, Liang Fang
Ministry-province Jointly-constructed Cultivation Base for State Key Laboratory of Processing for Non-ferrous Metal and Featured Materials, Guangxi Zhuang
Autonomous Region, Key Laboratory of New Processing Technology for Nonferrous Metals and Materials, Ministry of Education, School of Materials Science and
Engineering, Guilin University of Technology, Guilin 541004, China
Received 8 January 2015; received in revised form 5 February 2015; accepted 5 February 2015

Abstract

Lead-free (1
x)BaTiO3
xBi(Mg2/3Ta1/3)O3 [(1
x)BT
xBMT, 0 r x r0.1] perovskite solid solutions were synthesized via the conven-
tional solid state reaction technique. Raman spectra and XRD analysis demonstrate that a systematically structural evolution from a tetragonal to
pseudo-cubic phase occurred near 0.01 ox o 0.03. A phenomenon from a normal ferroelectric behavior to diffusive and dispersive relaxor-like
characteristic was also observed. As BMT content further increases (0.06r x r 0.1), the temperature stability of permittivity was markedly
improved (Δε/ε30 1Cr 715%), high relative permittivity ( 1000–2000) and low loss ( r 2%) were obtained over a wide temperature range
from 30 1C to 150 1C at 1 kHz. Moreover, when x ¼ 0.08 and 0.1, Δε/ε30 1C was r 7 10%. These results indicate that (1
x)BT
xBMT
ceramics could be suitable for thermally stable dielectric applications.
& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: D. BaTiO3; Phase structure; Dielectric temperature stability

1. Introduction permittivity and good temperature-stability, especially for the

Multilayer ceramic capacitors (MLCC) are one of the most
important electronic components at the surface mounting of
electronic circuits, military equipments and automation industries
[1]. At room temperature (RT), dielectrics must possess high
permittivity (41000) for MLCC applications [2]. Barium titanate
(BaTiO3, BT) has been reported as a satisfactory perovskite
compound for MLCC applications because of its outstanding
dielectric properties [3]. Nevertheless, BT ceramics have three
phase transitions at about 125 1C, 0 1C, and
90 1C, leading to
three dielectric anomalies, which restricts the applications of BT
in the electronic information manufacturing industry [4]. To solve
the above mentioned problem, a number of BaTiO3–based solid
solutions [5–14] have been researched owing to their high relative
n
Corresponding author. Tel./fax: þ 86 773 5896436.
nn
Corresponding author.
E-mail addresses: cxlnwpu@163.com (X. Chen),
zhouhuanfu@163.com (H. Zhou).
addition of Bi-based [general formula-Bi(Me)O3] perovskite
materials to BaTiO3, such as BaTiO3–Bi(Mg0.5Zr0.5)O3 [6,7],
BaTiO3–Bi(Zn0.5Zr0.5)O3 [15], BaTiO3–Bi(Li1/3Tii2/3)O3 [16],
BaTiO3–BiScO3 [17,18], and BaTiO3–Bi(Mg0.5Ti0.5)O3 [19,20].
These ceramics show a common phenomenon that the curves of
dielectric constant as a function of temperature (ε–T) flatten
gradually with increasing the Bi(Me)O3 content, which is highly
attractive for MLCC applications.
Recently, Wang et al. [21] investigated that BaTiO3–Bi
(Mg2/3Nb1/3)O3 ceramics displayed a potential application in
MLCC. In our previous work [22], BaTiO3–Bi(Mg2/3Nb1/3)O3
solid solutions showed good dielectric temperature stability
over a wide temperature range from 20 to 240 1C for thermal
stability device applications. Based on the above analysis, the
substitution of A-site by Bi þ 3 and/or B-site by (Mg þ 2 and
Nb þ 5) can tailor the dielectric properties of BT. Considering
the identical valence and similar ionic radius of Nb5 þ and
Ta5 þ , we could anticipate that Bi(Mg2/3Ta1/3)O3 would
improve the temperature stability of the BaTiO3 ceramic. In

http://dx.doi.org/10.1016/j.ceramint.2015.02.036
0272-8842/& 2015 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: D. Ma, et al., Temperature stability, structural evolution and dielectric properties of BaTiO3–Bi(Mg2/3Ta1/3)O3 perovskite ceramics,
Ceramics International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.02.036
2 D. Ma et al. / Ceramics International ] (]]]]) ]]]–]]]

the present work, temperature stability, structural evolution

and dielectric properties of (1
x)BaTiO3–xBi(Mg2/3Ta1/3)O3
(0r x r 0.1) ceramics were investigated. Furthermore, the
structure-property relationship of ceramics was also discussed.

2. Experimental

Polycrystalline ceramic samples of (1
x)BT–xBMT (0r

xr0.1) solid solutions were prepared via the conventional solid
state reaction technique. Carbonates and oxides were the main raw
powders, including BaCO3 (99%, Guo-Yao Co. Ltd., Shanghai,
China), TiO2 (99.99%, Guo-Yao Co. Ltd., Shanghai, China),
Bi2O3 (99%, Guo-Yao Co. Ltd., Shanghai, China), MgO (98.5%,
Guo-Yao Co. Ltd., Shanghai, China) and Ta2O5 (99.99%, Guo-
Yao Co. Ltd., Shanghai, China). Stoichiometric proportions of BT
and BMT were mixed in alcohol medium using zirconia balls
for 4 h. The slurries were dried and then calcined at 1100 and
800 1C for 4 h, respectively. Subsequently, (1
x)BT–xBMT (0r
xr0.1) powders were weighed and milled in alcohol medium
using zirconia balls for 4 h. The resultant powders were mixed
with 5 wt% of polyvinyl alcohol and pressed into pellets with
12 mm in diameter and 2 mm in thickness by uniaxial pressing at
200 MPa, at room temperature. The pellets were embedded with
calcined powders of the same composition to minimize alkaline
elements volatilization and sintered at different temperatures,
depending on the added content of BMT, ranging from 1290 to
1410 1C for 2 h in air. Fig. 1. (a) X-ray diffraction patterns of (1
x)BT–xBMT (0.00r xr0.10)
X-ray diffraction (XRD) patterns were recorded at room ceramics, the enlarged photograph is the XRD of Fig. 1(a) in the range of 2θ
temperature using an X-ray diffractometer (X'Pert PRO) with from 441 to 461. (b) Lattice parameters of (1
x)BT–xBMT ceramics as a
function of BMT content. Inset shows the c/a values of (1
x)BT–xBMT
CuKα radiation (λ¼ 0.15406 nm) operated at 40 kV and 40 mA
ceramics as a function of BMT content.
with a step size of 0.021. The phase analysis for the XRD data was
performed with PanAlytical software (X'Pert Highscore Plus).
Raman spectroscopy was carried out on a Thermo Fisher indicating a transformation from tetragonal phase (P4mm) to
Scientific DXR using a 10 mW laser with a wavelength of pseudo-cubic symmetry [23,24].
532 nm. The microstructural observation of the samples was The variation of lattice parameters of (1
x)BT–xBMT
performed using a scanning electron microscopy (Model ceramics as a function of x is demonstrated in Fig. 1(b). As
JSM6380-LV SEM, JEOL, Tokyo, Japan). Silver electrodes were xr 0.01, the parameter a increased and c decreased with
coated on both sides of the pellets, and then fired at 650 1C for increasing x. The parameter a became identical to c with x
30 min. Dielectric properties were measured with an applied Z 0.03, and the parameters c and a increased with further
voltage of 500 mV over 100 Hz–1 MHz from room temperature increasing x. This variation is consistent with the shift of the
to 500 1C using a precision impedance analyzer (Model 4294A, (200) reflection toward lower 2θ angles, as shown in Fig. 1(a).
Hewlett-Packard Co., Palo Alto, CA) at a heating rate of 3 1C/min. The c/a ratio decreased from 1.0096 for x ¼ 0 to 1.0083 for
x¼ 0.01, and became equal to 1 at x Z 0.03, as shown in the
3. Results and discussion inset of Fig. 1(b). The unit cell volume of (1
x)BT–xBMT
(0r x r 0.1) specimens was calculated from the XRD data. It
Fig. 1(a) shows the room temperature X-ray diffraction was evidently viewed that the unit cell volume increased
(XRD) patterns of (1
x)BT–xBMT samples. All samples almost linearly with the increase of x. The coordination of
display the symmetry related to a single perovskite phase A-sites in a typical cubic perovskite ABO3 structure is 12
(JCPDS: #75-0460) and no additional diffraction peaks of [25,26]. It is anticipated that the radius of Bi3 þ
impurity or secondary phases were observed in the XRD (1.03 Å o r3Biþ o 1.61 Å) should substitute for Ba2 þ (1.61 Å)
patterns, which indicates that Bi(Mg2/3Ta1/3)O3 has fully at A site, while Ti4 þ (0.604 Å) should be replaced by Mg2 þ
diffused into the lattice of BaTiO3 and formed a solid solution. (0.72 Å) and Ta5 þ (0.64 Å) at B-site. The substitution of B-
The enlarged XRD patterns of the samples in the range of 2θ site may be the main influence factor on the BT lattice. The
from 441 to 461 clearly demonstrate that a pseudo-cubic phase BO6 octahedra possess the unit cell volume and lead to the
appeared and increased gradually with increasing BMT con- dilatation of the crystal unit cell, which is consistent with the
tent. The merging of (002)/(200) diffraction peaks into a single XRD analysis that the merged peak of (002) and (200) shifted
(200) peak occurred near the compositions of 0.01 o xo 0.03, markedly to lower angles.

Please cite this article as: D. Ma, et al., Temperature stability, structural evolution and dielectric properties of BaTiO3–Bi(Mg2/3Ta1/3)O3 perovskite ceramics,
Ceramics International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.02.036
 D. Ma et al. / Ceramics International ] (]]]]) ]]]–]]]
Room temperature Raman spectra of (1
x)BT–xBMT
(0r x r 0.1) ceramics are shown in Fig. 2. The vibrational
modes are indexed in the diagram. Based on the Pokorny work
[27], the modes for x ¼ 0 were assigned as a single crystal
BaTiO3. In the regions from low to mid-wavenumber, the
Raman spectrum of pure tetragonal BaTiO3 was characterized
by a sharp band at  170 cm
1, a “silent” mode at  305
cm
1, asymmetric broader bands at  270 cm
1, 515 cm
1
and the high-frequency LO modes at around 715 cm
1 [28].
A1(TO) mode at  270 cm
1 is associated with the polar BO6
Fig. 2. Room temperature Raman spectra of (1
x)BT–xBMT (0.00rx
r0.10) ceramics.
Fig. 3. The SEM images of (1
x)BT–xBMT ceramics sintered at their optimized temperatures: (a) x¼ 0.01, 1370 1C, (b) x ¼0.03, 1370 1C, (c) x ¼0.08, 1330 1C,
and (d) x¼0.10, 1330 1C.
Please cite this article as: D. Ma, et al., Temperature stability, structural evolution and dielectric properties of BaTiO3–Bi(Mg2/3Ta1/3)O3 perovskite ceramics,
Ceramics International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.02.036
3
octahedra vibrations, which emerges just in the presence of a
ferroelectric phase [29,30]. The bands in the high-wavenumber
region (4 500 cm
1) are attributed to the vibrations of oxygen
octahedra. With the increase of B-site substituent content (x),
there are significant changes of the spectral signature, i.e. the
one at  180 cm
1 vanishes, and a new mode 1 can be viewed
in its place. Mode 1 is assigned with A–O vibrations and its
emergence indicates that there have Bi3 þ or Ba2 þ cations-
enriched nano-sized zones (clusters) [31]. The above men-
tioned changes are particularly conspicuous for xZ 0.03. The
resonance dip at  180 cm
1 emerges just for x ¼ 0 and
x¼ 0.01, but vanishes for x Z 0.03, demonstrating that the
long-range ferroelectric order is destroyed.
Fig. 3 illustrates the surface microstructures of (1-x)BT-
xBMT ceramics sintered at their optimized temperatures. It is
obviously observed that all samples contain few pores. The
grain size was affected extraordinarily by the content of BMT
addition. The grain size of samples becomes smaller and
uniform as x increases from 0.01 to 0.03, which indicates that
the addition of BMT results in the inhibition of the grain
growth. With further increasing the BMT content (x¼ 0.1), the
grain size of samples varies rarely, as shown in Fig. 3(d).
The relative permittivity and dielectric loss of (1
x)BT–
xBMT ceramics as a function of temperature at various frequen-
cies (1 kHz–1 MHz) are plotted in Fig. 4. Pure BT ceramic
exhibits a reasonably sharp Curie peak with tetragonal-cubic
phase transition and is typical of a normal ferroelectric with Curie
point, Tc  130 1C, which is consistent with the previous report
[6]. In this study, Bi3 þ has a slightly smaller radius than that of
Ba2 þ on the A-site, Mg2 þ (0.72 Å) and Ta5 þ (0.64 Å) have
4 D. Ma et al. / Ceramics International ] (]]]]) ]]]–]]]

Fig. 4. Relative permittivity and dielectric loss of (1
x)BT–xBMT (0.00rxr 0.10) as a function of temperature measured at frequencies from 1 kHz to 1 MHz.
Inserts illustrates the ln(1/ε
1/εm) as a function of ln(T
Tm) at 10 kHz for (1
x)BT–xBMT ceramics with x ¼0.01 and 0.03. [The symbols: experimental data; the
solid line: fitting to Eq. (1).]

Table 1
Comparison of dielectric properties of 0.94BT–0.06BMT, 0.92BT–0.08BMT
and 0.9BT–0.1BMT at 1 kHz with other works.

System Sintering εr Temperature- T-range/1C Δε/ Refs.

Temperature max range/1C εrmid r15%
(1C) tan δ r0.02

0.9BT– 1290 1440 30–350 1C – [6]

0.1BMZ
0.9BT– 1310 6800 – 30–240 1C [22]
0.1BMN
0.94BT– 1370 2000 30–195 1C 30–150 1C This
0.06BMT work
0.92BT– 1330 1534 30–190 1C 30–150 1C This
0.08BMT work
0.9BT– 1330 1278 30–198 1C 30–150 1C This
0.1BMT work

nBT–BMZ: (1
x)BaTiO3–xBi(Mg0.5Zr0.5)O3; BT–BMN: (1
x)BaTiO3–xBi

(Mg2/3Nb1/3)O3; BT–BMT: (1
x)BaTiO3
xBi(Mg2/3Ta1/3)O3.

Fig. 5. (a) Δε/ε30 1C, (b) relative permittivity (εr) and dielectric loss (Tan δ) as
a function of temperature from 30 to 200 1C at 1 kHz for (1
x)BT–xBMT
ceramics (x ¼0.06, 0.08 and 0.10), where Δε¼ ε(30 1C–200 1C)–ε30 1C.
larger radii than that of Ti4 þ (0.604 Å) on the B-site. Hence, the
cations disorder on the A-site and B-site may arouse relaxor-like
behavior in the BT-BMT ceramics.
The relaxor properties of BT–BMT ceramics can be
described effectively via a modified Curie–Weiss law [32,33]:
1 1 ðT
T m Þγ

¼
ε εm C
where εm is the maximum value of the relative permittivity, and C
is the Curie constant. γ is a diffusion coefficient, whose value can
range from 1 (a normal ferroelectric) to 2 (an ideal relaxor). The
values of γ for 0.99BT-0.01BMT and 0.97BT–0.03BMTceramics
at 10 kHz were gained from the slopes of ln(1/ε–1/εm) versus ln
(T–Tm) plots in Fig. 4(a) (see the insets). The γ value varies from
1.21 to 1.40, indicating a relaxor-like behavior.
Fig. 5 demonstrates the temperature stability of permittivity (Δε/
ε30 1C), relative permittivity (εr) and dielectric loss (tan δ) as a
function of temperature from 30 1C to 200 1C at 1 kHz for (1
x)
BT–xBMT ceramics (x¼ 0.06, 0.08 and 0.1). It is obviously seen
that the addition of BMT has a great effect on the dielectric
properties of ceramics. With the increase of x, the temperature
stability of permittivity (Δε/ε30 1C) was improved, but the relative
permittivity (εr) was depressed. All compositions possess the
optimum dielectric performance with small Δε/ε30 1C values (r 7
ð1Þ 15%), high relative permittivity ( 1000–2000) and low dielectric
loss (tan δr0.02) over a broad temperature range from 30 to
150 1C. Especially for the samples of x¼ 0.08 and x¼ 0.1, the
values of Δε/ε30 1C are within 710%. Table 1 lists the maximum
relative permittivity, dielectric loss, and the temperature stability of
permittivity in the operational temperature range with several
dielectric materials. It can be seen that (1
x)BT–xBMT (0.01r
xr0.1) ceramics show small Δε/ε30 1C values and high relative
permittivity ( 1000–2000), especially a significantly lower

Please cite this article as: D. Ma, et al., Temperature stability, structural evolution and dielectric properties of BaTiO3–Bi(Mg2/3Ta1/3)O3 perovskite ceramics,
Ceramics International (2015), http://dx.doi.org/10.1016/j.ceramint.2015.02.036
 D. Ma et al. / Ceramics International ] (]]]]) ]]]–]]]
dielectric loss (r0.02) over a wide temperature range from 30 to
190 1C, which could be a candidate for devices with the advantages
of lower insertion loss.
4. Conclusions
Lead-free (1
x)BT–xBMT (0.01rxr0.1) ceramics have
been prepared by the solid state processing technique. A system-
atically structural transition from tetragonal to pseudo-cubic phase
was observed near 0.01oxo0.03. With the further increase of
BMT content (0.06rxr0.1), good temperature stability of
permittivity (Δε/ε301C r 715%), high relative permittivity
( 1000–2000) and low dielectric loss (r2%) were acquired
over a broad temperature range of 30 1C–150 1C at 1 kHz. These
results indicate that (1
x)BT–xBMT (x¼ 0.06–0.1) ceramics
could have a potential application for X8R-type [X and 8 are
the minimum and maximum working temperatures (
55 to
150 1C), respectively. R is maximum temperature coefficient of
capacitance] capacitors.
Acknowledgments
This work was supported by National Natural Science
Foundation of China (Nos. 11364012 and 11464009), Natural
Science Foundation of Guangxi (No. 2013GXNSFAA019291,
2014GXNSFAA118326, and 2014GXNSFAA118312), Project
of Guangxi Scientific Research and Technical Development
(No. 1348020-11), and Project of Outstanding Young Teachers'
Training in Higher Education Institutions of Guangxi.
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