Bi过量以及冷却方式对BiFeO3-BaTiO3陶瓷的相结构及电学性能的影响

doi:10.15541/jim20170005

摘要/Abstract

摘要：

采用传统固相烧结法制备了0.7BiFeO₃-0.3BaTiO₃-xBi₂O₃(0≤x≤0.05)无铅压电陶瓷, 研究了Bi补偿量x和冷却方式对其相结构、微观形貌和综合电学性能的影响。结果表明：所有样品均为菱方相(R)和伪立方相(PC)两相共存, 0≤x≤0.01样品为纯的钙钛矿结构, 且x=0.01样品的两相比例C_R/C_PC接近1; x>0.01样品中出现富Bi杂相Bi₂₅FeO₄₀。与冷却方式相比, 优化Bi补偿量更有利于提升BFBT-xBi₂O₃陶瓷的压电性能。随着x增大, d₃₃先增大后减小, 在x=0.01时获得最优值。由于较小的晶粒、较合适的C_R/C_PC以及较大的残余应变, 水冷BFBT-0.01Bi₂O₃陶瓷获得了最优的压电性能(d_33水冷=141 pC/N、k_p=27%)和高T_C=507℃。研究结果表明, BFBT基陶瓷有希望成为兼具高压电性能和高T_C的无铅压电材料体系之一。

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关键词: BiFeO₃-BaTiO₃, Bi补偿量, 冷却方式, 相结构, d₃₃

Abstract:

A series of 0.7BiFeO₃-0.3BaTiO₃-xBi₂O₃(0≤x≤0.05) ceramics were prepared with solid reaction method under furnace, air and water cooling. The effects of excess Bi and cooling methods on phase structure, morphology and comprehensive electrical properties were investigated. All the ceramics show coexisting R-PC phase whose ratio C_R/C_PC is close to 1 at x = 0.01, apart from the appearance of an impurity phase Bi₂₅FeO₄₀ when x>0.01. Compared with cooling way, optimizing excess Bi content is more beneficial to enhance the piezoelectric performance of BFBT-xBi₂O₃. The d₃₃ firstly increases and then decreases with x increment, and gets an optimal value at x = 0.01. Smaller grain size and suitable C_R/C_PC, larger residual strain all contribute to the enhanced piezoelectricity (d₃₃=141 pC/N, k_p=27%) and a high Curie temperature (T_C = 507℃) in water-cooled BFBT-0.01Bi₂O₃ ceramic. The present work indicates that BFBT based lead-free piezoelectric ceramics are promising candidates for high temperature applications with both high performance and high T_C.

Key words: BiFeO₃-BaTiO₃, Bi compensation, cooling method, phase structures, d₃₃

中图分类号:

TM282

马剑, 张波萍, 陈建银. Bi过量以及冷却方式对BiFeO₃-BaTiO₃陶瓷的相结构及电学性能的影响[J]. 无机材料学报, 2017, 32(10): 1035-1041.

MA Jian, ZHANG Bo-Ping, CHEN Jian-Yin. Excess Bi and Cooling Method on Phase Structure and Electrical Properties of BiFeO₃-BaTiO₃ Lead-free Ceramics[J]. Journal of Inorganic Materials, 2017, 32(10): 1035-1041.

图/表 11

图1 炉冷(a)、空冷(b)和水冷(c)BF-BT-xBi2O3陶瓷的XRD图谱

Fig. 1 XRD patterns of the BFBT-xBi2O3 ceramics

图2 炉冷、空冷、水冷BF-BT-xBi2O3陶瓷在2θ=27°~28.5°的XRD图谱(a~c), 2θ(110)角度(d)以及残余应变ε(e)随x的变化关系

Fig. 2 (a-c) Enlarged XRD patterns in the 2θ range of 27°-28.5°, and (d) the 2θ(110)value and (e) the residual strain ε as a function of x for BFBT-xBi2O3 ceramics by furnace cooling, air cooling and water cooling

图3 炉冷(a)、空冷(b)、水冷(c)BF-BT-0.01Bi2O3陶瓷的Rietveld精修图谱

Fig. 3 Rietveld fitted spectra of the BFBT-0.01Bi2O3 ceramics

表1 BF-BT-0.01Bi2O3陶瓷的精修晶格参数和相比例

Table 1 Rietveld refined lattice parameters and phase ratio of the BFBT-0.01Bi2O3 ceramics

Cooling method	Space group	Lattice parameters/nm			α=β=γ/(°)	R_wp/%	C_R/C_PC	d₃₃/(pC·N^-1)
Cooling method	Space group	a	b	c	α=β=γ/(°)	R_wp/%	C_R/C_PC	d₃₃/(pC·N^-1)
C-PDF#31-0174	PM-3M	0.4031	0.4031	0.4031	90.00	-	-
R-PDF#72-2112	R-3M	0.3952	0.3952	0.3952	90.00	-	-
Furnace cooling	PM-3M	0.3999	0.3999	0.3999	90.00	13.2	51/49	122
Furnace cooling	R-3M	0.3999	0.3999	0.3999	89.80	13.2	51/49	122
Air cooling	PM-3M	0.4029	0.4029	0.4029	90.00	9.8	54/46	130
Air cooling	R-3M	0.4027	0.4027	0.4027	90.00	9.8	54/46	130
Water cooling	PM-3M	0.4040	0.4040	0.4040	90.00	10.7	60/40	141
Water cooling	R-3M	0.4030	0.4030	0.4030	90.01	10.7	60/40	141

图4 炉冷(a1)~(a4)、空冷(b1~b4)、水冷(c1)~(c4)BF-BT-xBi2O3陶瓷的SEM照片

Fig. 4 SEM images of the BFBT-xBi2O3 ceramics sintered at 1020℃ for 4 h then by furnace cooling (a1)-(a4), air cooling (b1)-(b4) and water cooling (c1)-(c4)

图5 炉冷、空冷、水冷BF-BT-xBi2O3陶瓷的平均晶粒尺寸(a)和相对密度(b)

Fig. 5 Average grain size (a) and relative density (b) for the BFBT-xBi2O3 ceramics by furnace cooling, air cooling and water cooling

图6 炉冷、空冷、水冷BF-BT-0.01Bi2O3陶瓷的电滞回线

Fig. 6 Ferroelectric hysteresis loops (a-g) and Pr (h) as a function of x for the BFBT-xBi2O3 ceramics by furnace cooling, air cooling and water cooling

图7 炉冷、空冷、水冷BF-BT-0.01Bi2O3陶瓷的介电常数 εr(a)与介电损耗tanδ(b)

Fig. 7 Temperature dependences of dielectric constant εr (a) and dielectric loss tanδ (b) for the BFBT-0.01Bi2O3 ceramics by furnace cooling, air cooling and water coolingThe inset is TC and CR/CPC under different cooling modes

图8 炉冷、空冷、水冷BF-BT-xBi2O3陶瓷的漏电流密度J、压电系数d33、平面机电耦合系数kp和机械品质因数Qm随x变化关系

Fig. 8 Leakage current density J(a), piezoelectric coefficient d33(b), planar electromechanical coupling coefficient kp(c) and mechanical quality factor Qm(d) as a function of x for the BFBT- xBi2O3 ceramics by furnace cooling, air cooling and water cooling

图9 炉冷、空冷、水冷BF-BT-0.01Bi2O3陶瓷的平均晶粒尺寸、CR/CPC、Pr以及残余应变ε

Fig. 9 Average grain size, CR/CPC, Pr, and residual strain ε of the BFBT-0.01Bi2O3 ceramics sintered at 1020℃ for 4 h then by furnace cooling, air cooling and water cooling

表2 BFBT基陶瓷的电学性能

Table 2 Electrical properties of the BF-BT based ceramics

Compositions	P_r/(μC·cm^-2)	E_C/(kV·cm^-1)	d₃₃/(pC·N^-1)	T_C/℃	Ref.
0.7BiFeO₃-0.3BaTiO₃-0.01Bi₂O₃	10.7	16.1	141	507	This work
0.65BiFeO₃-0.35BaTiO₃	30.6	27.9	104	414	[25]
0.7BiFeO₃-0.3BaTiO₃	26.0	33.0	134	510	[21]
0.75BiFeO₃-0.25BaTiO₃-Mn	22.9	39.3	116	619	[10]
0.8BiFeO₃-0.2BaTiO₃-0.15wt% SiO₂	-	-	86	628	[26]
0.705BiFeO₃-0.275BaTiO₃-0.02Bi_0.5Na_0.5TiO₃-1mol%MnO₂	27.4	-	140	-	[18]
0.715BiFeO₃-0.275BaTiO₃-0.01Bi(Mg_0.5Zr_0.5)O₃- MnO₂	9.0	27.0	130	575	[23]

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Bi过量以及冷却方式对BiFeO₃-BaTiO₃陶瓷的相结构及电学性能的影响

Excess Bi and Cooling Method on Phase Structure and Electrical Properties of BiFeO₃-BaTiO₃ Lead-free Ceramics

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