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Frontiers of Materials Science

ISSN 2095-025X

ISSN 2095-0268(Online)

CN 11-5985/TB

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Front. Mater. Sci.    2016, Vol. 10 Issue (2) : 203-210    https://doi.org/10.1007/s11706-016-0342-z
RESEARCH ARTICLE
Effects of Cr2O3 doping on the microstructure and electrical properties of (Ba,Ca)(Zr,Ti)O3 lead-free ceramics
Xiang XIA(),Xiangping JIANG(),Chao CHEN,Xingan JIANG,Na TU,Yunjing CHEN
Jiangxi Key Laboratory of Advanced Ceramic Materials, School of Materials Science and Engineering, Jingdezhen Ceramic Institute, Jingdezhen 333001, China
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Abstract

Lead-free ceramics (Ba0.85Ca0.15)(Zr0.9Ti0.1)O3–x wt.%Cr2O3 (BCZT–xCr) were prepared via the conventional solid-state reaction method. The microstructure and electrical properties of BCZT–xCr samples were systematically studied. XRD and Raman results showed that all samples possessed a single phased perovskite structure and were close to the morphotropic phase boundary (MPB). With the increase of the Cr content, the rhombohedral–tetragonal phase transition temperature (TR–T) increases slightly, and the Curie temperature (TC) shifts towards the low temperature side. XPS analysis reveals that Cr3+ and Cr5+ ions co-existed in Cr-doped BCZT ceramics, indicating the different impact on the electrical properties from Cr ions as “acceptor” or “donor”. For the x = 0.1 sample, relative high piezoelectric constants d33 (~316 pC/N) as well as high Qm (~554) and low tanδ (~0.8%) were obtained. In addition, the AC conductivity was also investigated. Hopping charge was considered as the main conduction mechanism at low temperature. As the temperature increases, small polarons and oxygen vacancies conduction played important roles.
Keywords lead-free ceramics      electrical properties      BCZT      XPS analysis     
Corresponding Author(s): Xiang XIA,Xiangping JIANG   
Online First Date: 29 April 2016    Issue Date: 11 May 2016
 Cite this article:   
Xiang XIA,Xiangping JIANG,Chao CHEN, et al. Effects of Cr2O3 doping on the microstructure and electrical properties of (Ba,Ca)(Zr,Ti)O3 lead-free ceramics[J]. Front. Mater. Sci., 2016, 10(2): 203-210.
 URL:  
https://academic.hep.com.cn/foms/EN/10.1007/s11706-016-0342-z
https://academic.hep.com.cn/foms/EN/Y2016/V10/I2/203
Fig.1  XRD patterns of BCZT–xCr ceramics in the 2θ range of (a) 20°–70° and (b) 45.0°–45.8°.
Fig.2  Room-temperature Raman spectra of BCZT–xCr ceramics with different Cr2O3 contents.
Fig.3  SEM images of BCZT–xCr ceramics with different Cr2O3 contents: (a)x = 0; (b)x = 0.025; (c)x = 0.05; (d)x = 0.075; (e)x = 0.1.
Fig.4  The temperature dependence of (a) relative dielectric constant, where the inset is the region of TR–C peak, and (b) dielectric loss measured at 100 kHz, where the inset is room temperature tanδ of BCZT–xCr ceramics.
x /wt.% TC /°C tanδ /% Ec /(kV·cm-1) Pr /(μC·cm-2) Qm d33 /(pC·N-1) kp /%
0 98 2.8 3.4 17.6 144 385 44.9
0.025 93 2.2 2.5 13.8 251 350 33.2
0.05 89 1.5 2.7 15.1 265 331 34.6
0.075 89 1.2 2.8 16.1 391 314 31.6
0.1 88 0.8 3.2 13.9 554 316 31.8
Tab.1  The electrical properties of BCZT–xCr ceramics
Fig.5  XPS spectra of Cr 2p3/2 of BCZT–xCr ceramics for x = 0.1.
Fig.6  P–E hysteresis loops of BCZT–xCr ceramics: (a)x = 0; (b)x = 0.025; (c)x = 0.05; (d)x = 0.075; (e)x = 0.1. (f) Coercive field Ec and remnant polarization Pr of the samples as a function of the amount of the Cr2O3 content.
Fig.7  Effect of Cr2O3 contents on the piezoelectric constants d33, planar mode electromechanical coupling coefficient kp and mechanical quality factor Qm of BCZT–xCr ceramics.
Fig.8  The behaviors of the AC conductivity with temperature at different frequencies for two representative BCZT–xCr ceramics: (a)x = 0; (b)x = 0.05.
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