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Journal of the European Ceramic Society 35 (2015) 533–540
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.
1. Introduction 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
Pb(Zr1−x Tix )O3 (PZT) based ceramics have been widely been achieved in (Ba0.95 Ca0.05 )(Ti0.92 Sn0.08 )O3 6 and
used for more than 50 years as piezoelectric actuators, (Ba0.91 Ca0.09 )(Ti0.916 Sn0.084 )O3 7 systems, respectively.
sensors and transducers due to their excellent piezoelectric At present, the highest d33 in BaTiO3 –11BaSnO3 ceramic is
properties, but its use will be gradually replaced by lead-free 697 pC/N at 40 ◦ C in the vicinity of two converged triple points
piezoelectric ceramics such as BaTiO3 (BT), (K,Na)NbO3 or with coexisting multiphase.8 However, the sintering tempera-
(Bi1/2 Na1/2 )TiO3 for environment protecting concerns. BT tures of high-performance BCTS piezoelectric ceramics are all
was first discovered as a piezoelectric ceramic but is now over 1400 ◦ C,3–8 which impedes the practical applications of
mostly used as a dielectric material rather than a piezoelectric BT-based ceramics. Therefore, the densification temperature
material mainly because of its low Curie temperature (Tc) is need to be reduced for fabricating high-performance BT
and inferior piezoelectric properties (d33 = 191 pC/N) to PZT. based piezoelectric ceramics to realize large-scale applica-
Recently, high-performance BT based ceramics such as tions. Adding sintering aids is a simple, effective and mostly
(Ba,Ca)(Ti,Zr)O3 (BCTZ)1,2 and (Ba,Ca)(Ti,Sn)O3 (BCTS)3–7 used method to lower the sintering temperature. Li2 O as a
have been developed by co-doping Ca2+ /Zr4+ or Ca2+ /Sn4+ . Li sintering aid has been used to lower the sintering temperature
et al. [3,4] have reported that (Ba0.98 Ca0.02 )(Ti0.96 Sn0.04 )O3 of Ba(Ti0.95 Zr0.05 )O3 (from 1250 ◦ C to 900 ◦ C)9 and BT
and (Ba0.97 Ca0.03 )(Ti0.94 Sn0.06 )O3 ceramics both sintered (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
∗ Corresponding author. Tel.: +86 10 62334195; fax: +86 10 62334195. the added Li2 O can not only lower the sintering temperature but
E-mail address: bpzhang@ustb.edu.cn (B.-P. Zhang). 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- where x is mol% of Li2 O) were prepared by conventional solid-
erties of Li2 O-added (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3 ceramics state synthesis. The raw materials were BaCO3 , CaCO3 , SnO2
were investigated with a special emphasis on the influence of and TiO2 (>99%, all from ShanTouXilong Chemical Factory
Li2 O content (x). The low-temperature sintering mechanism of GuangDong, China). The weighed powders were mixed by using
Li2 O was also discussed. 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
2. Experimental procedure 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
A series of Li2 O-added (Ba0.95 Ca0.05 )(Ti0.90 Sn0.10 )O3 calcinated BCTS powders and then ball-milled again under the
ceramics (abbreviated as BCTSLix , x = 0, 1, 2, 3, 4, 5 and 6, 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) 533–540 535
compensation, which is favorable for the mass transport during the peak at about 2θ = 45◦ (abbreviated as peak-45) shifts to
sintering and greatly promotes grain growth and densification low angles as adding Li2 O as shown in Fig. 3b, indicating the
sintering.12 On the other hand, when all the liquid is consumed, enlargement of the lattice. The ionic radius of Li+ (0.74 Å) is
the mass transport through the liquid phase cannot be realized larger than the radii of Ti4+ (0.61 Å) and Sn4+ (0.71 Å) at B-sites,
anymore and the sintering is slowed down at 900–1020 ◦ C for but smaller than the radii of Ba2+ (1.34 Å) and Ca2+ (0.99 Å)
BCTSLi4 ceramic. Nevertheless, because of the presence of VO•• at A-sites. The substitution of Li+ for Ti4+ at B-sites would
in Li2 O doped BCTS matrix phase, the lattice-diffusion coeffi- enlarge the lattice.12,13 Besides, since cation with low valence
cient is higher than that of BCTS. This is reflected in the second has weaker binding force with O2− , the smaller binding force
sintering step, which starts at 1020 ◦ C for BCTSLi4 and is about with O2− of Li+ than that of Ti4+ and Sn4+ also results in the
30 ◦ C lower than that (1050 ◦ C) for BCTS. If the amount of expansion of lattice. So we speculate the enlarged lattice here
the liquid produced during the reaction is high enough, the sin- is due to the difference not only in the ionic size between Li+
tering would complete before all the liquid is consumed via and Ti4+ /Sn4+ but also in the binding force with O2− . Another
adding more Li2 O, which would result in the change from the characteristic in Fig. 3b is that all the peak-45 is asymmetric,
two-step sintering regime to one-step. Valant et al. [11] have ruling out the possibility of a single rhombohedral (R), pseudo-
found one-step sintering regime in 0.3 wt.% (about 2.3 mol%) cubic (PC) or cubic (C) phase where a symmetric singlet peak
Li2 O added BaTiO3 and 0.4 wt.% (about 2.9 mol%) Li2 O added existed. So BCTSLix ceramics may have a single tetragonal (T)
(Ba,Sr)TiO3 , in both cases the sintering temperature was signif- or orthorhombic (O) phase, or coexisting two or more phases
icantly reduced to 820 ◦ C and 880 ◦ C, respectively. At the same at room temperature. The full width at half maximum (FWHM)
time, the excess liquid and its subsequent evaporation would of peak-45 in Fig. 4a indicates an increased trend from 0.30◦ to
produce the formation of intergranular pores and their largen- 0.50◦ as x increases from 0 to 6. While the FWHM of peaks at
ing apart from the grown grains as x > 4 (Fig. 1e and f). Hence, about 2θ = 31.5◦ and 39◦ , abbreviated as peak-31.5 and peak-39,
the increased density and grain growth in Fig. 1 are attributed respectively, lies in 0.25–0.30◦ . The peak positions for (1 1 0)R ,
to both the reactive liquid-phase sintering and the generation of (1 1 0)R , (1 1 1)R , (1 1 1)R and (200)R in R phase (PDF#86–1569)
VO•• . 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
3.2. Phase structure 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
Fig. 3 shows XRD patterns of BCTSLix ceramics compared and peak-45 reveals a phase transition which will be discussed
with the standard cards of R-phase (PDF#75–2264) and T-phase later rather than grain sizes, which is also well in accordance
(PDF#86–1569) BaTiO3 . All samples in Fig. 3a have a pure with those provided by FESEM.
perovskite structure without any trace of impurity within the The phase transition of BCTSLix ceramics was further
detectable limit of the XRD, indicating that added Li+ has diff- defined from the curves of dielectric permittivity versus tem-
used into BCTS lattices to form a solid solution. All the XRD perature (εr -T) as shown in Fig. 5. BCTSLi1 has a bad
patterns are similar to each other, suggesting the similar phase dielectric property due to its low density. All other sam-
symmetry at room temperature. Compared to the case of BCTS, ples have two phase-transition points and the higher one
L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540 537
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.
538 L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540
weak modes at 302 and 720 cm−1 , and broad modes at 250 and Fig. 7 shows piezoelectric constant d33 , planar mode
525 cm−1 which are the feature of high-temperature C phase17 eletromechanical coupling coefficient kp and mechanical qual-
are observed, showing the coexistence of T and C phases. And ity factor Qm for BCTSLix (0 ≤ x ≤ 6) ceramics as a function
T phase decreases gradually at higher temperature resulting in of x. d33 , kp and Qm of the pristine BCTS ceramic are 30 pC/N,
further weakened modes at 302 and 720 cm−1 . In εr -T curves 10% and 124, respectively. Due to the low density, the piezoelec-
(Fig. 5), a phase-transition maximum appears at 8 ◦ C for BCTS tric properties of BCTSLi1 ceramic cannot be measured. Except
which locates at R and T phases coexisted temperature range. So for BCTSLi1 , d33 of BCTSLix increases as x increases from 2
the phase-transition maximum at 8 ◦ C for BCTS corresponds to to 4 and achieves a maximum value of 457 pC/N at x = 4, and
partial R to T transition. In another words, R to T transition may decreases as x further increases to 6. kp and Qm have the same
happen at a temperature range rather than a temperature point. variation tendency with d33 , achieving the peak values 25.18%
Similar phenomenon also happens for T to C transition. and 491 at x = 4. In the modified BaTiO3 -based ceramics, both
L. Zhao et al. / Journal of the European Ceramic Society 35 (2015) 533–540 539
Fig. 8. Ferroelectric hysteresis loops and remnant polarization and coercive field of BCTSLix ceramics.
the increased grain size and density are helpful for enhancing coexisting R and T phases at the temperature range of −80 ◦ C to
piezoelectric property.1,19 Furthermore, the coexisting two or 40 ◦ C for BCTS sample, all BCTSLix ceramics have coexisting
more phases also contribute greatly high d33 .1–8 In the present R and T phases at room temperature, and the specific ratio of
study, both the grain size and density are similar to each other R to T phase decreases with increasing temperature or x. Bet-
for samples at 3 ≤ x ≤ 6, while all samples are of the coexistence ter piezoelectric properties of d33 = 457 pC/N, kp = 25.18% and
of R and T phases along with a decrease trend on the specific Qm = 491 were obtained at x = 4, which is attributed to the appro-
ratio of R to T with increasing x. So the better d33 of 457 pC/N priate specific ratio of R to T phase considering both the similar
at x = 4 is attributed to the appropriate specific ratio of R to T grain size and density for samples at 3 ≤ x ≤ 6.
phase.
Fig. 8 indicates the ferroelectric hysteresis (P–E) loops and
remnant polarization (Pr) and coercive field (Ec) as a function Acknowledgments
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 This work was supported by Specialized Research Fund
other hand, P–E loops at 2 ≤ x ≤ 6 show “pinched” shapes as for the Doctoral Program of Higher Education (grant no.
shown in the inset of Fig. 8a, which is similar to the case of 20130006110006) and National Natural Science Foundation of
Li2 O-doped BaTiO3 ceramic.10 This may be attributed to the China (grant no. 51472026 and 51332002).
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 References
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