Materials Letters: Yongshang Tian, Yansheng Gong, Dawei Meng, Songquan Cao

Materials Letters 153 (2015) 44–46
Contents lists available at ScienceDirect
Materials Letters
journal homepage: www.elsevier.com/locate/matlet
Structure and electrical properties of Ir4 þ -doped 0.5Ba0.9Ca0.1

TiO3–0.5BaTi0.88Zr0.12O3–0.12%La ceramics via a modified Pechini
method
Yongshang Tian, Yansheng Gong n, Dawei Meng n, Songquan Cao
Faculty of Material Science and Chemistry, China University of Geosciences, Wuhan 430074, PR China
art ic l e i nf o a b s t r a c t
Article history: 0.5Ba0.9Ca0.1TiO3–0.5BaTi0.88Zr0.12O3–0.12%La–xIr4 þ (x ¼ 0–1.25%) (BCT–BZT–La–xIr4 þ ) ceramics were

Received 27 January 2015 synthesized using a modified Pechini method. The effects of iridium content (x) on the crystal structure
Accepted 4 April 2015 and electrical properties of the ceramics were studied. All samples showed a pure orthorhombic
Available online 13 April 2015
perovskite structure, and the lattice parameters decreased gradually with increasing x. The temperatures
Keywords: associated with the orthorhombic–tetragonal and tetragonal–cubic phase transitions were dependent on
Ir4 þ -doped the iridium content. Ceramics doped with 0.75% Ir4 þ exhibited the highest relative permittivity and the
Crystal structure lowest loss tangent ( o 1%), suggesting that iridium entered the matrix and enhanced the grain size. The
Diffused phase transition diffused phase transition initially weakened, then strengthened with increasing x, indicating that the
Electrical properties
ferroelectric properties were influenced by the iridium content. The optimal electrical properties, i.e.,
d33 ¼ 269 pC/N, kp ¼0.26, and Qm ¼ 77, were obtained at x ¼0.50%.
& 2015 Elsevier B.V. All rights reserved.
1. Introduction tionally, the effects of Ir4þ -doping on the crystal structure and electrical
properties of the ceramics were investigated.
Lead-free piezoelectric ceramics have attracted great attention from
the scientific community in recent decades. For instance, BaTiO3 (BT)-
based ceramics are considered as one of the promising materials for
the replacement of lead-based materials [1,2]. However, the prepara- 2. Experimental
tion of BT-based ceramics via a conventional solid-state method
typically requires high sintering temperatures of 1400–1500 1C [3], 0.5Ba0.9Ca0.1TiO3–0.5BaTi0.88Zr0.12O3–0.12%La–xIr4 þ (x¼0, 0.25,
leading to crystal distortion, high internal stress, hard domain wall 0.50, 0.75, 1.00, and 1.25%) (BCT–BZT–La–xIr4 þ ) ceramics were
rotation, and inferior electrical properties [4,5]. Thus, developing an synthesized by a modified Pechini method using Ba(CH3COO)2, Ca
alternative system that requires low sintering temperatures, while (NO3)3, Ti(OC4H9)4, Zr(NO3)3, La(NO3)3, Ir(NO3)4, citric acid, and
featuring excellent comprehensive electrical properties is of interest. ethylene glycol as the raw materials. In a typical synthesis, La
Recently, the improvement in the piezoelectric properties of BT- (NO3)3 and Ir(NO3)4 aqueous solutions were added to the BCT–BZT
based ceramics by doping or substituting was demonstrated [6,7]. complex. Subsequently, the resulting precursors were calcined at
Particularly, La-doped BT-based ceramics that displayed outstanding 850 1C to obtain the nanoparticles. The nanoparticles were then
dielectric and piezoelectric properties had attracted much attention ground and uniaxially pressed into disk-shaped discs of 20 mm in
[8,9]. However, there are few studies on BT-based ceramics doped with diameter using 2 wt% polyvinyl alcohol as a binder at 150 MPa.
platinum group metals. In this study, Ir4þ -doped 0.5Ba0.9Ca0.1TiO3– Subsequently, the green bodies were sintered at 1260 1C for 5 h in
0.5BaTi0.88Zr0.12O3–0.12%La ceramics were synthesized using a mod- air atmosphere to produce the ceramics.
ified Pechini method at a low sintering temperature of 1260 1C. Addi- The crystal structure of the ceramics was determined by X-ray
diffraction (XRD; X’Pert PRO) with Cu-Kα radiation. The relative
permittivity (εr) and loss tangent (tan δ) were determined using a
precision LCR meter (TH-2819) at 10 kHz. After the samples were
n
Corresponding authors. Tel.: þ 86 27 67883731; fax: þ 86 27 67883731.
poled in a silicone oil bath under a direct-current electric field of
E-mail addresses: gongysh@cug.edu.cn (Y. Gong), 25 kV/cm at 25 1C for 40 min, the piezoelectric constants (d33) were
dwmeng@cug.edu.cn (D. Meng). determined by a Piezo-d33 meter (ZJ-3A). The impedance analyzer
http://dx.doi.org/10.1016/j.matlet.2015.04.020
0167-577X/& 2015 Elsevier B.V. All rights reserved.
Y. Tian et al. / Materials Letters 153 (2015) 44–46 45
(Agilent-4292A) was used to determine the electromechanical cou- the tetragonal–cubic (TC) and orthorhombic–tetragonal (TO–T)
pling (kp) and mechanical quality (Qm) factors. phase transitions were observed were 110 1C and 50 1C,
respectively. As observed, TO–T decreased slightly, while TC initially
decreased and then remained unchanged with increasing x. These
3. Results and discussion findings suggested that iridium could modify the ferroelectric
phase transition temperature and influence the ferroelectric prop-
Fig. 1 shows the XRD patterns of the BCT–BZT–La–xIr4 þ erties [11]. The variations in TC at high iridium contents were
ceramics prepared with different iridium contents. All samples attributed to the presence of crystal defects and small grains
showed a pure perovskite structure (ABO3) without any secondary sediment. With increasing x, the dielectric peaks became narrower
phases, indicating that iridium was successfully impregnated into and then broadened with further increases in x. This finding
the ABO3 lattice. As observed from Fig. 1(b), the unique (0 2 2) and indicated that the diffused phase transition was influenced by
(2 0 0) diffraction peaks were consistent with the orthorhombic the iridium content. Variations in the diffusion, as measured by
(O) structure (JCPDS # 81–2200). The shift of the (0 2 2) and (2 0 0) the diffuseness exponent (γ), shown in Fig. 4, were consistent with
diffraction peaks to high 2θ angles with increasing x was attrib- the analysis discussed above [12]. Additionally, the low tan δ was
uted to the substitution of Zr4 þ (with an ionic radius of 0.087 nm) associated with subtle flaws in the crystals, indicating the success-
with smaller Ir4 þ (0.072 nm) [10]. ful incorporation of iridium into the matrix of the ceramics. The
Fig. 2 shows the lattice parameters of the BCT–BZT–La–xIr4 þ highest εr (7800) and lowest tan δ (o 1%) observed at x ¼0.75%
ceramics prepared with various iridium contents. The lattice were attributed to the large grain size and dense microstructure of
parameters (a, b, and c), as calculated by Jade 5.0, decreased with the ceramics [13].
increasing x, suggesting that the presence of iridium weakened the The electrical properties, i.e., d33, Qm, and kp, of the BCT–BZT–
O symmetry of the ceramics. The calculated lattice parameters La–xIr4 þ ceramics prepared with different iridium contents are
variations were consistent with the diffraction peaks shift shown in Fig. 4. As noted, d33 and kp first increased and then
observed in Fig. 1 owing to the decreased interplanar spacing decreased with increasing iridium contents—d33 reached a max-
upon substitution of iridium ions. In addition, the crystalline imum value of 269 pC/N at x ¼0.50%, kp reached a maximum value
schematic representation of the ceramic prepared with x¼ 0.75% of 0.28 at x¼ 0.75%, while Qm showed an opposite trend, reaching a
is shown in Fig. 2(a), which reveals the internal crystal structure of minimum value of 68 at x ¼0.75%. The results associated with the
the ceramic. BCT–BZT–La–xIr4 þ ceramics at x 0.50% were attributed to low
Fig. 3 shows the temperature dependence of εr and tan δ of the internal stress, few crystal defects, and weak pinching effect in the
BCT–BZT–La–xIr4 þ ceramics prepared with various iridium con- domain wall with large grain size [13,14]. Accordingly, it could be
tents assessed at a frequency of 10 kHz. The temperatures at which concluded that iridium could modify the structure and improve
Fig. 1. (a) XRD patterns and (b) corresponding selected regions of the BCT–BZT–La– Fig. 3. Temperature dependence of the relative permittivity (εr) and loss tangent
xIr4 þ ceramics. (tan δ) of the BCT–BZT–La–xIr4 þ ceramics assessed at a frequency of 10 kHz.
Fig. 4. Diffuseness exponent (γ), piezoelectric constant (d33), mechanical quality

Fig. 2. Lattice parameters of the BCT–BZT–La–xIr4 þ ceramics. The inset (a) shows factor (Qm), and electromechanical coupling factor (kp) of the BCT–BZT–La–xIr4 þ
the crystalline schematic of the ceramic prepared with x¼ 0.75%. ceramics.
46 Y. Tian et al. / Materials Letters 153 (2015) 44–46
the electrical properties of BCT–BZT–La ceramics upon reasonable Teaching Laboratory of China University of Geosciences
iridium doping. (SKJ2014037) for their financial support.
4. Conclusions
Ir4 þ -doped 0.5Ba0.9Ca0.1TiO3–0.5BaTi0.88Zr0.12O3–0.12%La (BCT– References

BZT–La–xIr4 þ ) ceramics were synthesized via a modified Pechini
method using a sintering temperature of 1260 1C. XRD results [1] Rödel J, Jo W, Seifert KTP, Anton EM, Granzow T, Damjanovic D. J Am Ceram
Soc 2009;92:1153–77.
indicated no secondary phases formed. Additionally, iridium could [2] Takenaka T, Nagata H. J Eur Ceram Soc 2005;25:2693–700.
modify the orthorhombic structure of the ceramics. Variations in [3] Sun H, Zhang Y, Liu X, Liu Y, Chen W. Ceram Int 2015;41:555–65.
TC and TO–T with increasing iridium contents suggested that [4] Wang P, Li Y, Lu Y. J Eur Ceram Soc 2011;31:2005–12.
[5] Zheng P, Zhang JL, Shao SF, Tan YQ, Wang CL. Appl Phys Lett 2009;94:032902.
iridium influenced the diffused phase transition of the ferro-
[6] Liu WF, Ren XB. Phys Rev Lett 2009;103:257602.
electric properties. The dielectric properties of the ceramics were [7] Zhang SW, Zhang H, Zhang BP, Zhao G. J Eur Ceram Soc 2009;29:3235–42.
improved by the addition of a small amount of iridium dopant. The [8] Sun ZX, Pu YP, Dong ZJ, Hu Y, Liu XY, Wang PK, et al. Mater Lett 2014;118:1–4.
[9] Huang X, Zhang J, Ji L, Qi H, Wang J J. Alloys Compd 2014;592:105–8.
optimal electrical properties, i.e., d33 ¼ 269 pC/N, kp ¼ 0.26, and
[10] Wu JG, Xiao DQ, Wu WJ, Chen Q, Zhu JG, Yang ZC, et al. J Eur Ceram Soc
Qm ¼77, were detected at x¼ 0.50%. 2012;32:891–8.
[11] Zheng P, Song K, Qin H, Zheng L, Zheng L. Curr Appl Phys 2013;13:1064–8.
[12] Thakur OP, Prakash C, James AR J. Alloys Compd 2009;470:548–51.
Acknowledgements [13] Wu J, Xiao D, Wu W, Chen Q, Zhu J, Yang Z, et al. Scr Mater 2011;65:771–4.
[14] Ehmke MC, Daniels J, Glaum J, Hoffman M, Blendell JE, Bowman KJ. J Am
Ceram Soc 2013;96:2913–20.
The authors thank the Fundamental Research Funds for the
National University (CUG120118) and the Open Foundation of

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Materials Letters 153 (2015) 44–46

Contents lists available at ScienceDirect

Structure and electrical properties of Ir4 þ -doped 0.5Ba0.9Ca0.1

Article history: 0.5Ba0.9Ca0.1TiO3–0.5BaTi0.88Zr0.12O3–0.12%La–xIr4 þ (x ¼ 0–1.25%) (BCT–BZT–La–xIr4 þ ) ceramics were

Fig. 4. Diffuseness exponent (γ), piezoelectric constant (d33), mechanical quality

Ir4 þ -doped 0.5Ba0.9Ca0.1TiO3–0.5BaTi0.88Zr0.12O3–0.12%La (BCT– References

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