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Journal of the European Ceramic Society 35 (2015) 533–540

Effect of Li2O addition on sintering and piezoelectric properties

of (Ba,Ca)(Ti,Sn)O3 lead-free piezoceramics
Lei Zhao a , Bo-Ping Zhang a,∗ , Peng-Fei Zhou a , Li-Feng Zhu a , Jing-Feng Li b
a School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China
b State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Received 27 June 2014; received in revised form 22 August 2014; accepted 28 August 2014
Available online 16 September 2014

Abstract
This work investigated the enhanced sintering and electrical properties of (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3 -xLi2 O (BCTSLix , x = 0, 1, 2, 3, 4, 5 and
6 mol%) lead-free piezoelectric ceramics benefiting from the Li2 O addition. Highly dense BCTS ceramics with good piezoelectric properties were
fabricated at reduced sintering temperatures by adding a small amount of Li2 O. It was found that the sintering densification is promoted mainly by
reaction liquid phase at the early sintering stage and the formation of oxygen vacancies should be considered as an additional factor. The coexistence
of R and T phases was confirmed by the Raman spectrum at a temperature range from−50 ◦ C to 40 ◦ C as x = 2 and at room temperature for all
other Li2 O added samples, while their specific ratio of R to T phase decreases with increasing Li2 O addition. Better properties with d33 = 457 pC/N,
kp = 25.18% and Qm = 491 were obtained when adding 4 mol% Li2 O, which are attributed dominantly to the appropriate specific ratio of R to T
phase because of the similar grain size and density for samples at 3 ≤ x ≤ 6.
© 2014 Elsevier Ltd. All rights reserved.

Keywords: Lead-free piezoceramics; Low sintering temperature; Li2 O; Raman spectra

1. Introduction
Pb(Zr1−x Tix )O3 (PZT) based ceramics have been widely
used for more than 50 years as piezoelectric actuators,
sensors and transducers due to their excellent piezoelectric
properties, but its use will be gradually replaced by lead-free
piezoelectric ceramics such as BaTiO3 (BT), (K,Na)NbO3 or
(Bi1/2 Na1/2 )TiO3 for environment protecting concerns. BT
was first discovered as a piezoelectric ceramic but is now
mostly used as a dielectric material rather than a piezoelectric
material mainly because of its low Curie temperature (Tc)
and inferior piezoelectric properties (d33 = 191 pC/N) to PZT.
Recently, high-performance BT based ceramics such as
(Ba,Ca)(Ti,Zr)O3 (BCTZ)1,2 and (Ba,Ca)(Ti,Sn)O3 (BCTS)3–7
have been developed by co-doping Ca2+ /Zr4+ or Ca2+ /Sn4+ . Li
et al. [3,4] have reported that (Ba0.98 Ca0.02 )(Ti0.96 Sn0.04 )O3
and (Ba0.97 Ca0.03 )(Ti0.94 Sn0.06 )O3 ceramics both sintered
∗ Corresponding author. Tel.: +86 10 62334195; fax: +86 10 62334195.
E-mail address: bpzhang@ustb.edu.cn (B.-P. Zhang).
at 1500 ◦ C have high d33 of 510 pC/N and 440 pC/N,
respectively. Higher d33 of 568 pC/N and 530 pC/N has
been achieved in (Ba0.95 Ca0.05 )(Ti0.92 Sn0.08 )O3 6 and
(Ba0.91 Ca0.09 )(Ti0.916 Sn0.084 )O3 7 systems, respectively.
At present, the highest d33 in BaTiO3 –11BaSnO3 ceramic is
697 pC/N at 40 ◦ C in the vicinity of two converged triple points
with coexisting multiphase.8 However, the sintering tempera-
tures of high-performance BCTS piezoelectric ceramics are all
over 1400 ◦ C,3–8 which impedes the practical applications of
BT-based ceramics. Therefore, the densification temperature
is need to be reduced for fabricating high-performance BT
based piezoelectric ceramics to realize large-scale applica-
tions. Adding sintering aids is a simple, effective and mostly
used method to lower the sintering temperature. Li2 O as a
sintering aid has been used to lower the sintering temperature
of Ba(Ti0.95 Zr0.05 )O3 (from 1250 ◦ C to 900 ◦ C)9 and BT
(from 1300 ◦ C to 1000 ◦ C).10 Furthermore, the introduced
Li2 O can slightly increase Tc from 103 ◦ C to 107 ◦ C for
Ba(Ti0.95 Zr0.05 )O3 and from 120 ◦ C to 125 ◦ C for BT. Whether
the added Li2 O can not only lower the sintering temperature but
also enhance Tc in BCTS ceramics is still unclear. In the present

http://dx.doi.org/10.1016/j.jeurceramsoc.2014.08.042
0955-2219/© 2014 Elsevier Ltd. All rights reserved.
534 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540

Fig. 1. SEM images of thermally etched fracture surface for BCTSLix ceramics: (a) x = 0; (b) x = 1; (c) x = 2; (d) x = 3; (e) x = 4; (f) x = 5; (h) x = 6, and density (h).

study, the microstructure, crystal structure and electrical prop-
erties of Li2 O-added (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3 ceramics
were investigated with a special emphasis on the influence of
Li2 O content (x). The low-temperature sintering mechanism of
Li2 O was also discussed.
2. Experimental procedure
A series of Li2 O-added (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3
ceramics (abbreviated as BCTSLix , x = 0, 1, 2, 3, 4, 5 and 6,
where x is mol% of Li2 O) were prepared by conventional solid-
state synthesis. The raw materials were BaCO3 , CaCO3 , SnO2
and TiO2 (>99%, all from ShanTouXilong Chemical Factory
GuangDong, China). The weighed powders were mixed by using
a planetary ball mill with anhydrous ethanol with 300 rpm for
4 h in a nylon jar with zirconia balls and then dried at 80 ◦ C for
8 h in an oven. After calcinating dried powders at 1250 ◦ C for
4 h, Li2 O (99%) in the range from 0 to 6 mol% was mixed with
calcinated BCTS powders and then ball-milled again under the
same condition. Re-milled powders were dried at 80 ◦ C for 8 h in
 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
oven and pressed into disks of 10 mm in diameter and 1.5 mm in
thickness under 80 MPa using 2 wt.% polyvinyl alcohol (PVA)
as the binder. After burning out PVA at 650 ◦ C for 1 h in air,
samples were cooled to room temperature and then reheated to
1300 ◦ C with a rate of 5 ◦ C/min from room temperature and hold
for 4 h in air, and then cooled to room temperature with the same
rate. Silver electrodes were pasted on the top and bottom sur-
faces of the sintered samples and fired at 600 ◦ C for 30 min. A
poling was performed under an electric field of 3–4 kV/mm in
silicone oil bath for 30 min.
The phase structure was examined by X-ray diffraction
(XRD: D/max-RB, Rigaku Inc., Japan) with a Cu K␣ radiation
(λ = 1.5416 Å) filtered through a Ni foil. The apparent density
ρm was determined by Archimedes method. The relative density
ρr of BCTSLix ceramics was given by ρr = ρm /ρt × 100, where
ρt is the theoretical density which is calculated from the struc-
tural parameters determined from X-ray diffraction patterns by
assuming they have pure T or R phase. The microstructure of
sintered samples was observed by field emission scanning elec-
tron microscopy (FE-SEM: SUPRATM55, Carl Zeiss, Nakano,
Japan). Dielectric constant and dielectric loss were measured
using a LCR meter (TH2828S; Changzhou Tonghui Electronics
Co., Ltd. Changzhou, China) at 1 kHz. The Raman spectrum was
measured by the LabRAM HR800 (Horiba JobinYvon, Paris,
France). The piezoelectric property was measured using a quasi-
static piezoelectric coefficient d33 testing meter (ZJ-3A, Institute
of Acoustics, Chinese Academy of Sciences, Beijing, China).
The planar electromechanical coupling coefficient kp was deter-
mined by resonance–antiresonance method using an Agilent
4294A (Hewlett-Packard, Palo Alto, CA) precision impedance
analyzer. Ferroelectric hysteresis loops were measured using a
ferroelectric tester (RT6000HVA; Radiant Technologies, Inc.,
Albuquerque, NM). The shrinkage curves from 50 ◦ C to 1250 ◦ C
for BCTS and BCTSLi8 ceramics were measured by a horizon-
tal pushrod dilatometer (Netzsch DIL402PC, Selb, Germany) at
a heating rate of 5 ◦ C/min.
3. Results and discussion
3.1. Microstructure and density
Fig. 1 shows SEM images of thermally etched surface and
density of BCTSLix ceramics sintered at 1300 ◦ C for 4 h. The
pristine BCTS ceramic in Fig. 1a has a porous microstruc-
ture with small grains of 2–4 ␮m, confirming that dense BCTS
ceramic is difficult to obtain below 1300 ◦ C since its densifica-
tion temperature has so far been reported to be 1400–1540 ◦ C.3–8
The similar porous microstructure is formed in Fig. 1b with
smaller grains of 1–2 ␮m after adding 1 mol% Li2 O. As fur-
ther increase in Li2 O content (x), a highly dense microstructure
along with grown grains is observed in Fig. 1c–g. Besides, intra-
granular porosity remains and intergranular pores are trapped at
grain boundaries as x ≥ 3, along with an increased pore size as
x ≥ 4. In accordance with the morphologies, the apparent den-
sity and relative density of BCTSLix specimens show a similar
varying trend as shown in Fig. 1h. The apparent density for the
pristine BCTS is 5.26 g/cm3 along with the relative density of
535
Fig. 2. Dynamic sintering curves of BT,11 BCTS and BCTSLi4 ceramics.
87%, which decrease to 4.95 g/cm3 and 81% at x = 1. Both appar-
ent density and relative density increase and then decrease as x
increases from 2 to 6, and achieve peak values of 6.02 g/cm3 and
98.5% at x = 4. All samples at 2 ≤ x ≤ 6 have a relative density
over 90%, showing a reduced sintering temperature by 150 ◦ C
at least to obtain dense BCTS ceramics.
It is commonly considered that liquid phase contributes to
grain growth and densification sintering in low temperature sin-
tering since the liquid phase facilitates both the dissolution and
migration of the species. However, the high melting point (above
1500 ◦ C) of Li2 O makes it impossible to form directly liquid
phase in the sintering process. The sintering mechanism of the
pristine BCTS and 4 mol% Li2 O doped counterpart were further
investigated by the dynamic sintering curves as shown in Fig. 2.
BCTS starts to shrink at 1050 ◦ C compared to that at 950 ◦ C
for BT,11 indicating that BCTS ceramic has a higher sintering
temperature than BT ceramics. While an obvious two-step sin-
tering regime is observed in BCTSLi4 ceramic. During the first
step at low temperatures (750–900 ◦ C) a reactive liquid-phase
sintering takes place in which an eutectic liquid may be formed
by BaCO3 , Li2 O and TiO2 and leads to about 3% contraction.
Then, the liquid would be consumed during subsequent sinter-
ing. At x = 1, a small quantity of liquid is formed which is too
little to promote the grain growth, whereas the evaporation of
the liquid restrains grain growth by robbing heat which inhibits
both grain growth and densification sintering. As a result, sam-
ple x = 1 shows the finest grains (Fig. 1b) and the lowest relative
density of 81% (Fig. 1h). As further increase in x, the content
of the liquid is enough to promote the grain growth besides the
evaporated part. So the grain growth and densification sintering
at 2 ≤ x ≤ 6 are ascribed to the reactive liquid-phase sintering.
Apart from the reactive liquid-phase sintering mechanism
during the first step at low temperatures, the emergence of
oxygen vacancies (VO•• ), generated in the matrix phase by
2BCTS
the defect equation: Li2 O −→ 2Li ••
Ti/Sn + 3VO + TiO2 /SnO2 ,
may be another reason for the accelerated grain growth and den-
sification sintering. The substitution of Li+ for high valence Ti4+
or Sn4+ leads to the creation of VO•• due to the ionic charge
536 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
Fig. 3. X-ray diffraction patterns of BCTSLix ceramics.
compensation, which is favorable for the mass transport during
sintering and greatly promotes grain growth and densification
sintering.12 On the other hand, when all the liquid is consumed,
the mass transport through the liquid phase cannot be realized
anymore and the sintering is slowed down at 900–1020 ◦ C for
BCTSLi4 ceramic. Nevertheless, because of the presence of VO••
in Li2 O doped BCTS matrix phase, the lattice-diffusion coeffi-
cient is higher than that of BCTS. This is reflected in the second
sintering step, which starts at 1020 ◦ C for BCTSLi4 and is about
30 ◦ C lower than that (1050 ◦ C) for BCTS. If the amount of
the liquid produced during the reaction is high enough, the sin-
tering would complete before all the liquid is consumed via
adding more Li2 O, which would result in the change from the
two-step sintering regime to one-step. Valant et al. [11] have
found one-step sintering regime in 0.3 wt.% (about 2.3 mol%)
Li2 O added BaTiO3 and 0.4 wt.% (about 2.9 mol%) Li2 O added
(Ba,Sr)TiO3 , in both cases the sintering temperature was signif-
icantly reduced to 820 ◦ C and 880 ◦ C, respectively. At the same
time, the excess liquid and its subsequent evaporation would
produce the formation of intergranular pores and their largen-
ing apart from the grown grains as x > 4 (Fig. 1e and f). Hence,
the increased density and grain growth in Fig. 1 are attributed
to both the reactive liquid-phase sintering and the generation of
VO•• .
3.2. Phase structure
Fig. 3 shows XRD patterns of BCTSLix ceramics compared
with the standard cards of R-phase (PDF#75–2264) and T-phase
(PDF#86–1569) BaTiO3 . All samples in Fig. 3a have a pure
perovskite structure without any trace of impurity within the
detectable limit of the XRD, indicating that added Li+ has diff-
used into BCTS lattices to form a solid solution. All the XRD
patterns are similar to each other, suggesting the similar phase
symmetry at room temperature. Compared to the case of BCTS,
the peak at about 2θ = 45◦ (abbreviated as peak-45) shifts to
low angles as adding Li2 O as shown in Fig. 3b, indicating the
enlargement of the lattice. The ionic radius of Li+ (0.74 Å) is
larger than the radii of Ti4+ (0.61 Å) and Sn4+ (0.71 Å) at B-sites,
but smaller than the radii of Ba2+ (1.34 Å) and Ca2+ (0.99 Å)
at A-sites. The substitution of Li+ for Ti4+ at B-sites would
enlarge the lattice.12,13 Besides, since cation with low valence
has weaker binding force with O2− , the smaller binding force
with O2− of Li+ than that of Ti4+ and Sn4+ also results in the
expansion of lattice. So we speculate the enlarged lattice here
is due to the difference not only in the ionic size between Li+
and Ti4+ /Sn4+ but also in the binding force with O2− . Another
characteristic in Fig. 3b is that all the peak-45 is asymmetric,
ruling out the possibility of a single rhombohedral (R), pseudo-
cubic (PC) or cubic (C) phase where a symmetric singlet peak
existed. So BCTSLix ceramics may have a single tetragonal (T)
or orthorhombic (O) phase, or coexisting two or more phases
at room temperature. The full width at half maximum (FWHM)
of peak-45 in Fig. 4a indicates an increased trend from 0.30◦ to
0.50◦ as x increases from 0 to 6. While the FWHM of peaks at
about 2θ = 31.5◦ and 39◦ , abbreviated as peak-31.5 and peak-39,
respectively, lies in 0.25–0.30◦ . The peak positions for (1 1 0)R ,
(1 1 0)R , (1 1 1)R , (1 1 1)R and (200)R in R phase (PDF#86–1569)
and (1 0 1)T , (1 1 0)T , (1 1 1)T , (0 0 2)T and (2 0 0)T in T phase
(PDF#75–2264) are shown in Fig. 4b–d. The biggest difference
between 2θ around 31.5◦ , 39◦ and 45◦ is 0.076◦ , 0.122◦ and
0.216◦ , respectively. The varied FWHM for peak-31.5, peak-39
and peak-45 reveals a phase transition which will be discussed
later rather than grain sizes, which is also well in accordance
with those provided by FESEM.
The phase transition of BCTSLix ceramics was further
defined from the curves of dielectric permittivity versus tem-
perature (εr -T) as shown in Fig. 5. BCTSLi1 has a bad
dielectric property due to its low density. All other sam-
ples have two phase-transition points and the higher one
 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
Fig. 4. (a) The full width at half maximum (FWHM) of X-ray diffraction peaks in
Fig. 3 abbreviated as peak-31.5, peak-39 and peak-45 as a function of x; (b–d) X-
ray diffraction peaks in R (PDF#75–2264) and T phase (PDF#86–1569) around
a selected 2θ range of about 31.5◦ , 39◦ and 45◦ .
corresponds to paraelectric–ferroelectric (named TC ) phase
transition. TC of BCTS is 52 ◦ C and lower than 75 ◦ C of
(Ba0.91 Ca0.09 )(Ti0.916 Sn0.084 )O3 7 sintered at 1450 ◦ C, which is
attributed to increased Sn4+ at B-sites.8 TC of BCTSLix ceram-
ics further decreases to 46–48 ◦ C as x increases from 2 to 6,
owing to the substitution of Li+ for the ions at B-sites, similar
to the case for Li2 CO3 -doped PZN-PZT ceramics,14 but inverse
to slightly increased TC in Li2 O-doped Ba(Ti0.95 Zr0.05 )O3 9 and
BaTiO3 .10 Apart from TC , another phase-transition maximum is
observed at 8 ◦ C for BCTS and 32 ◦ C for BCTSLix (2 ≤ x ≤ 6).
Fig. 5. Dielectric constant (εr ) and loss (tanδ): (a) temperature dependence at 1 kHz for BCTSLix ceramics, (b) x dependence at room temperature at 1 kHz for
BCTSLix ceramics, (c) temperature dependence at 1, 10 and 100 kHz for BCTSLi4 ceramic.
537
It is still difficult to determine the exact phase structure by εr -T
curve, even taking the XRD into consideration. The dielectric
loss (tanδ) is as high as 25% at room temperature as x = 0 and
is maintained at 0–2.5% as 1 ≤ x ≤ 6 in the whole measured
temperature. The variations of εr and tanδ with x at room tem-
perature in Fig. 5b show an increased εr and a decreased tanδ
as 2 ≤ x ≤ 6, which is attributed to the increased density. Fig. 5c
shows the frequency dependence of εr and tanδ for BCTSLi4 .
Compared to εr , tanδ is more sensitive to frequency.
Fig. 6a-1 and -2 shows the evolution of Raman spec-
tra with temperature for the pristine BCTS ceramic. Modes
at 170, 190, 250, 302, 490, 525 and 720 cm−1 observed at
−80 ◦ C in Fig. 6a-1 are all the feature of R phase especially
at about 170 and 190 cm−1 .15,16 Since most modes also can be
observed in O phase (including modes at 250, 302, 490, 525 and
720 cm−1 )15,16 and T phase (including modes at 250, 302, 525
and 720 cm−1 ),15–18 it is difficult to either exclude the exist-
ence of T or T and O phase(s) or determine their appearing
temperature. This Raman spectrum at −80 ◦ C is similar to the
case of Ba(Ti0.90 Sn0.10 )O3 16 at −100 ◦ C which has existing R,
O and T phases. We speculate that the pristine BCTS ceramic
may also have coexisting R, O and T phases at −80 ◦ C. With
increasing temperature to −40 ◦ C, mode at 490 cm−1 disappears
or merges with the neighboring 525 cm−1 mode, indicating the
absence of O phase, which is also attributed to higher relative
intensity for mode at 190 cm−1 than that for mode at 250 cm−1
above −40 ◦ C as marked by solid lines in Fig. 6a-2. No other
mode disappears in the temperature range of −40–20 ◦ C, indi-
cating coexisting R and T phases, which is different from the
single T-symmetry Ba(Sn0.10 Ti0.90 )O3 at 20 ◦ C.16 Meanwhile,
the intensity of modes at 170 and 190 cm−1 gets weak and
their intensity gap narrowed obviously with raising tempera-
ture to 20 ◦ C as marked by dotted lines in Fig. 6a-2, which is
attributed to the decreased specific ratio of R to T phase. As fur-
ther increasing temperature, modes at 170 and 190 cm−1 vanish
gradually, indicating the disappearance of R phase. At 60 ◦ C,
538 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
Fig. 6. Raman spectra of the investigated BCTSLix ceramics: (a, b) the evolution
with temperature of the Raman spectra for BCTS and BCTSLi4 ; (c) room-
temperature Raman spectra of BCTSLix specimens.
weak modes at 302 and 720 cm−1 , and broad modes at 250 and
525 cm−1 which are the feature of high-temperature C phase17
are observed, showing the coexistence of T and C phases. And
T phase decreases gradually at higher temperature resulting in
further weakened modes at 302 and 720 cm−1 . In εr -T curves
(Fig. 5), a phase-transition maximum appears at 8 ◦ C for BCTS
which locates at R and T phases coexisted temperature range. So
the phase-transition maximum at 8 ◦ C for BCTS corresponds to
partial R to T transition. In another words, R to T transition may
happen at a temperature range rather than a temperature point.
Similar phenomenon also happens for T to C transition.
Fig. 7. Variations of d33 , kp and Qm of BCTSLix ceramics as a function of x.
As shown in Fig. 6b-1 and 6b-2, BCTSLi4 indicates similar
Raman spectra with temperature to the case of BCTS, in which
R, O and T phases coexisted at −80 ◦ C, the O phase disappears at
about −50 ◦ C, R and T phases coexisted in −50–40 ◦ C accompa-
nying the decreased specific ratio of R to T phase with increasing
temperature and the coexisting T and C phases are observed over
60 ◦ C. So the phase-transition maximum appeared at 32 ◦ C in
εr -T curve as 2 ≤ x ≤ 6 are also corresponding to R-T transition.
Fig. 6c shows similar Raman spectra at room-temperature
for BCTSLix samples to each other because of the coexisting R
and T phases. With increasing x, both the intensities of modes
at 162 and 198 cm−1 get weak and the discrepancy of the rela-
tive intensity between modes at 190 and 250 cm−1 in Fig. 6c-2
decreases gradually. All that reveals the specific ratio of R to
T phase decreases with increasing x although the quantitative
analysis is hard to do, similarly to the case for the pristine BCTS
ceramic leaded by raising temperature. This result also matches
the variation of the FWHM of X-ray diffraction peaks around
31.5◦ , 39◦ and 45◦ as shown in Fig. 4a. Compared to the constant
FWHM of peak-31.5 and peak-39, the increased lift asymmetry
of peak-45 (Fig. 3b) with x along with a widened FWHM value
(Fig. 4a) attributes to the decreased ratio of R to T phase since
the later has the lowest 2␪ = 45.091◦ around 45◦ .
3.3. Piezoelectric and ferroelectric properties
Fig. 7 shows piezoelectric constant d33 , planar mode
eletromechanical coupling coefficient kp and mechanical qual-
ity factor Qm for BCTSLix (0 ≤ x ≤ 6) ceramics as a function
of x. d33 , kp and Qm of the pristine BCTS ceramic are 30 pC/N,
10% and 124, respectively. Due to the low density, the piezoelec-
tric properties of BCTSLi1 ceramic cannot be measured. Except
for BCTSLi1 , d33 of BCTSLix increases as x increases from 2
to 4 and achieves a maximum value of 457 pC/N at x = 4, and
decreases as x further increases to 6. kp and Qm have the same
variation tendency with d33 , achieving the peak values 25.18%
and 491 at x = 4. In the modified BaTiO3 -based ceramics, both
 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
Fig. 8. Ferroelectric hysteresis loops and remnant polarization and coercive field of BCTSLix ceramics.
the increased grain size and density are helpful for enhancing
piezoelectric property.1,19 Furthermore, the coexisting two or
more phases also contribute greatly high d33 .1–8 In the present
study, both the grain size and density are similar to each other
for samples at 3 ≤ x ≤ 6, while all samples are of the coexistence
of R and T phases along with a decrease trend on the specific
ratio of R to T with increasing x. So the better d33 of 457 pC/N
at x = 4 is attributed to the appropriate specific ratio of R to T
phase.
Fig. 8 indicates the ferroelectric hysteresis (P–E) loops and
remnant polarization (Pr) and coercive field (Ec) as a function
of x. A typical P-E loop is observed at x = 0. The ferroelec-
tric property is enhanced as x increases from 2 to 6. On the
other hand, P–E loops at 2 ≤ x ≤ 6 show “pinched” shapes as
shown in the inset of Fig. 8a, which is similar to the case of
Li2 O-doped BaTiO3 ceramic.10 This may be attributed to the
substitution of Li+ for Ti4+ or Sn4+ at B-sites, the acceptor doping
Li+ can form defect dipoles with oxygen vacancy as mentioned
above, which disrupt the ferroelectric order and decrease the
polarization states for the BCTS ceramics. With increasing x,
Pr increased and Ec decreased as shown in the inset Fig. 8b.
4. Conclusions
The adding effect of Li2 O content (x) on sintering and
electrical properties of (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3 lead-free
piezoceramics was investigated. Both the microstructure and
density of BCTS ceramic were improved by adding Li2 O,
emerging a reduced dense sintering temperature by more
than 150 ◦ C for BCTS ceramic as x > 2 mol%. Two-step sin-
tering mechanism leaded by reactive liquid phase and V•• O in (Ba0.9 Ca0.1 )(Ti1−x Snx )O3
was observed in Li2 O-added BCTS ceramics. Similar to the
539
coexisting R and T phases at the temperature range of −80 ◦ C to
40 ◦ C for BCTS sample, all BCTSLix ceramics have coexisting
R and T phases at room temperature, and the specific ratio of
R to T phase decreases with increasing temperature or x. Bet-
ter piezoelectric properties of d33 = 457 pC/N, kp = 25.18% and
Qm = 491 were obtained at x = 4, which is attributed to the appro-
priate specific ratio of R to T phase considering both the similar
grain size and density for samples at 3 ≤ x ≤ 6.
Acknowledgments
This work was supported by Specialized Research Fund
for the Doctoral Program of Higher Education (grant no.
20130006110006) and National Natural Science Foundation of
China (grant no. 51472026 and 51332002).
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