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http://dx.doi.org/10.1016/j.jallcom.2015.02.127
0925-8388/Ó 2015 Elsevier B.V. All rights reserved.
138 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142
to phase transitions between the rhombohedral and other The SEM images of BF-BCTZS-1000x ceramics are shown in
ferroelectric phases. Accordingly, the addition of Sn into pseudocu- Fig. 2(a)–(e), and the variation of average grain size with their error
bic 0.725BF-0.275BCTZ may also induce a rhombohedral phase, bars is depicted in Fig. 2(f). The error bars indicate the 95% confi-
and the ferroelectric and piezoelectric properties may be dence interval for all compositions. The error bar for BF-BCTZS-0
enhanced. could not be seen since it is smaller than the size of the symbol.
In this work, 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3 It can be seen that Sn doping has significant influence on the mor-
ceramics were fabricated with a conventional solid-state reaction phology: compared with the observed pores and relatively small
method. Before sintering, 1 mol% MnO2 was added as a sintering grain size in the undoped sample, dense micrographs are observed
aid to facilitate densification, maintain charge neutrality, and sup- in Sn-modified samples; moreover, an obvious grain growth is
press impurity phases [11,25–27]. The structure of BF-BCTZS- manifested. According to the Ref. [28], some Sn ions serve as accep-
1000x ceramics was examined with XRD, and its dielectric, tors at the B sites of BaTiO3 in the form of Sn2+ and/or Sn3+.
ferroelectric, piezoelectric and magnetic properties were obtained. Therefore, when Sn ions substitute for Zr ions in BF-BCTZS-
1000x, oxygen vacancies would be created. Oxygen vacancies can
2. Experimental procedure promote grain growth due to an accelerated oxygen ion motion
[29,30], and this effect may explain the sharp increase of grain size
Lead-free 0.725BiFeO3-0.275Ba0.85Ca0.15Ti0.9Zr0.1xSnxO3 (BF-BCTZS-1000x, and the elimination of pores after Sn doping. These observed
x = 0, 0.025, 0.050, 0.075, 0.100) ceramics were prepared by a conventional solid-
results indicate that the addition of Sn is beneficial to the grain
state reaction method. AR-grade BaCO3, CaCO3, TiO2, ZrO2, SnO2, Bi2O3, Fe2O3
reagents were used as starting materials, and were grinded with ethanol in stain- growth and densification of the samples.
less-steel jars for 10 h. The powders were dried and calcined at 800 °C for 4 h. As shown in Fig. 3(a) and (b), obvious low-frequency dispersion
The calcined powders were mixed with 1 mol% MnO2 via ball milling, and then is revealed in BF-BCTZS-1000x ceramics. For all samples, dielectric
the resultant mixtures were dried and pressed into tablets with diameters of constant (er) decreases with increasing frequency, while dielectric
10 mm under 10 MPa. The tablets were sintered at 930 °C for 4 h in air. Mn is added
as a sintering aid before the sintering procedure. In our experiments, the same
loss (tan d) increases with increasing frequency. Both the dielectric
amount of Mn is added in all samples, so the effect of Mn addition is the same to constant and loss of BF-BCTZS-1000x ceramics are obviously
all samples. improved after Sn doping. The BF-BCTZS-75 shows the optimized
The structure of BF-BCTZS-1000x was examined by X-ray diffraction (XRD) (D- room-temperature dielectric performance (10 kHz): er = 407,
MAX 2200VPC, RIGAKU, Japan) via Cu-a radiation (1.541 Å). Surface morphology of
tan d = 0.030. The improvement of room-temperature dielectric
the BF-BCTZS-1000x ceramics was obtained with scanning electron microscopy
(SEM) (Quanta 400F, FEI/OXFORD/HKL, the Netherlands). Sintered tablets were properties may be due to both intrinsic and extrinsic factors. The
grinded into powders in an agate mortar for magnetic measurements. Magnetic pseudocubic–rhombohedral structural phase transition can induce
field dependence of magnetization was recorded at room temperature with a physi- a striking change in dielectric properties, while the enlarged grain
cal property measurement system (PPMS, Quantum Design, America). Silver elec- size and decreased porosity may also be related.
trodes were fired on both sides of the tablets for electrical measurements. The
frequency and temperature dependent dielectric response of the BF-BCTZS-1000x
The dielectric constant at 10 kHz of BF-BCTZS-1000x ceramics is
ceramics was obtained with a precision LCR meter (E4980A, Agilent Inc., shown as a function of temperature in Fig. 3(c). The dielectric
America). Ferroelectric properties were examined via a ferroelectric test system anomaly revealed in the vicinity of 410 °C corresponds to the
(Precision Premier II, Radiant Technologies Inc., America). Before d33 measurements, Curie temperature, at which the ferroelectric–paraelectric phase
the electrode tablets were polarized under 7.0 kV/mm at 90 °C for 40 min in silicon
transition occurs, and the present observation is consistent with
oil bath. The piezoelectric coefficient (d33) of the tablets was obtained with a d33
meter (ZJ-4AN, Institute of Acoustics, Academic Sinica, China). previous report [21]. The dielectric anomaly is rather broad in
the case of the undoped BF-BCTZ samples, indicating the diffuse
nature of such phase transition [31]. This anomaly becomes much
3. Results and discussion
more pronounced after the substitution of Sn. The diffuseness of
the phase transition can be quantitatively depicted with the
The XRD patterns of the BF-BCTZS-1000x ceramics are shown in
diffusivity c, which is defined in the modified Curie–Weiss law
Fig. 1. A pure perovskite structure is revealed in all BF-BCTZS-
[32]:
1000x samples, suggesting that the Sn ions have diffused into the
lattice of BF-BCTZ. Peaks of impurity phases were found existing
in calcined powders of BF-BCTZS-1000x but absent in sintered 1=er 1=emax ¼ ðT T C Þc =C ðT > T C Þ; ð1Þ
tablets, indicating that the addition of MnO2 into the solid solu-
tions has suppressed the impurity phases. The XRD patterns of
where c = 1 represents a normal ferroelectric material, and c = 2
undoped BF-BCTZ ceramics reveal a pseudocubic (referred to as
represents a complete relaxor ferroelectric material. The c
PC) structure, while the splitting of (1 1 1)PC into (0 0 6)R and
decreases monotonically from 1.958 to 1.361 with x = 0 to 0.100,
(2 0 2)R in the vicinity of 39° clearly shows that the Sn-doped sam-
revealing that the BF-BCTZS-1000x system undergoes a composi-
ples are rhombohedral (R).
tional relaxor-to-ferroelectric phase transition with the increasing
Sn content. In BF-based ceramics, the TC usually increases with
the increase of the tolerance factor [33]. Accordingly, in the case
of BF-BCTZ whose tolerance factor is 0.988 < 1, the increase of the
tolerance factor resulting from the substitution of a smaller B-site
dopant will lead to an increase of the TC. As a B-site dopant, Sn4+
ion has a radius of 0.69 Å, smaller than 0.73 Å for Zr4+ [34], thus
the TC of BF-BCTZS-1000x increases as the Sn content increases.
The TC as a function of composition (x) is shown in the inset of
Fig. 3(c), and an almost linear increase from 401.0 °C to 418.8 °C
is revealed with the increasing Sn content, which is consistent with
the above analysis.
The dielectric loss vs. temperature curves at 10 kHz are shown
in Fig. 3(d). Concave segments can be recognized at temperatures
slightly lower than the Curie temperatures. The concave segment
Fig. 1. XRD patterns of BF-BCTZS-1000x ceramics. of the undoped BF-BCTZ ceramic is much broader than those of
D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142 139
Fig. 2. SEM images of BF-BCTZS-1000x ceramics: (a) BF-BCTZS-0, (b) BF-BCTZS-25, (c) BF-BCTZS-50, (d) BF-BCTZS-75 and (e) BF-BCTZS-100; (f) average grain size as a function
of composition (x).
the Sn-doped samples. The evolution can be regarded as another external electric field (segment AB in Fig. 4(a) and (b)), the polar-
sign of the decrease of the diffusivity. ization of undoped BF-BCTZ declines apparently faster when the
The ferroelectric properties of BCTZS ceramics are illustrated in maximum applied field (Em) increases, while the slope of the P–E
Fig. 4. Apparent improvements after Sn doping can be seen by com- curves of BF-BCTZS-25 is almost independent of Em. This phe-
paring the P–E loops of undoped BF-BCTZ (Fig. 4(a)) with that of nomenon can be attributed to the knowledge that the polar
BF-BCTZS-25 (Fig. 4(b)). The slim relaxor-like hysteresis loop of nanoregions in relaxor ferroelectrics usually exhibit field-depen-
the undoped BF-BCTZ sample is quite different from those of the dent magnitude and are inhomogeneously poled, while normal fer-
Sn-doped ceramics, which are closer to the square-like hysteresis roelectrics possess uniform and homogeneously poled domains
loops of normal ferroelectrics. The remnant polarization (Pr) [36,37]. The prominent difference suggests that a compositional
increases obviously after the substitution of Sn for Zr, and the relaxor-to-ferroelectric phase transition is undergoing with the
squareness of the hysteresis is also improved, indicating an Sn modification, which agrees with the dielectric results in this
enhanced ferroelectricity. The Rsq = Pr/Ps can be utilized as a mea- work. The P–E loops for BF-BCTZS-1000x samples with different
surement of the squareness of the P–E loops, where Ps is the satu- Sn contents under an Em of 5.5 kV/mm are displayed in Fig. 4(c),
rated polarization [35]. The Rsq value of undoped BF-BCTZ ceramics and the evolutions of Pr and coercive field (Ec) are illustrated in
is only 0.24, while those of the Sn-doped ceramics are all around or Fig. 4(d). The Pr and Ec behave alike with the increasing Sn content.
above 0.50. To be noticed, during the removal of the positive When a maximum electric field of 5.5 kV/mm is applied, a
140 D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142
Fig. 3. Dielectric properties of BF-BCTZS-1000x ceramics: room-temperature frequency dependences of (a) dielectric constant and (b) dielectric loss, temperature
dependences of (c) dielectric constant and (d) dielectric loss at 10 kHz. Inset of (c): TC as a function of composition (x).
Fig. 4. Ferroelectric properties of BF-BCTZS-1000x ceramics: P–E hysteresis loops of with (a) x = 0 and (b) x = 0.025; (c) P–E loops with different Sn contents at an maximum
applied voltage of 5.5 kV/mm; (d) Pr and Ec as functions of composition (x).
maximum remnant polarization Pr (5.15 lC/cm2) is obtained in at The composition dependence of piezoelectric coefficient (d33) of
x = 0.050 with Ec = 3.50 kV/mm. For BF-BCTZS-75 (not shown), the BF-BCTZS-1000x ceramics is shown in Fig. 5. The substitution of Sn
breakdown field is so low that the regular P–E loop is not leads to obvious enhancement of piezoelectricity, which can be
accessible. attributed to the pseudocubic–rhombohedral phase transition,
D. Zhang et al. / Journal of Alloys and Compounds 637 (2015) 137–142 141
Acknowledgements
Fig. 5. Piezoelectric coefficient (d33) of BF-BCTZS-1000x ceramics as a function of
composition (x). This work was supported by the National Natural Science
Foundation of China under Grant Nos. 61176010 and 61172027,
Guangdong Natural Science Foundation under Grant No.
1414050000317, the Research Foundation of IARC-SYSU under
Grant No. IARC 2014-09.
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