ZrO_2掺杂ZnO压敏瓷的性能及晶粒生长研究
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摘要
以球磨法制备Zr O2掺杂Zn O压敏瓷,通过扫描电镜对其显微组织进行了分析,探讨了Zr O2掺杂对Zn O压敏瓷电性能的影响并且研究了晶粒的生长。研究结果表明,随着保温时间的延长,致密度和非线性系数均呈现先增加后减小的趋势;而对Zn O压敏瓷的漏电流和电位梯度的影响则呈现先减小后增加的波浪型变化。Zr O2掺杂Zn O压敏瓷的晶粒尺寸要比基础配方Zn O压敏瓷的晶粒尺寸要小,可能是因为Zr原子半径与Zn原子半径接近,Zr O2固溶在氧化锌晶粒中,抑制了氧化锌晶粒尺寸的增长。由计算可得Zr O2掺杂氧化锌压敏瓷的晶粒生长动力指数(n=5.0)比基础配方氧化锌压敏瓷的晶粒生长动力指数(n=3.9)大。球磨基础配方的Zn O-Bi2O3系压敏瓷的晶粒生长激活能(Q)较大,Q=(231±27)k J/mol。这可能是Zr O2协同尖晶石钉扎在Zn O压敏瓷的晶粒边界,通过颗粒阻滞机理使Zn O压敏瓷的晶粒生长速度降低,从而使Zn O压敏瓷的晶粒生长激活能增大。
Zn O-Bi2O3 based varistor ceramics and Zr O2 doped Zn O varistor ceramics are sintered by using different sintering time, and the electrical properties and microstructure of the varistor ceramics are studied in this paper. The results indicate that with increasing sintering time, the density and the nonlinear coefficients of Zr O2 doped Zn O varistor ceramics first increase and then decrease, however, the leakage current and the threshold voltage first decrease and then increase. The grain size of Zr O2 doped Zn O varistor ceramics is smaller than the grain size of Zn O-Bi2O3 based varistor ceramics. The most probable reason is that Zr atomic radius is close to Zn atomic radius. So Zr is dissolved in solid solution with Zn O grains and inhibits the growth of Zn O grain. The grain growth exponent(n) of Zr O2 doped Zn O varistor ceramics is larger than Zn O-Bi2O3 based varistor ceramics. The growth activation energy(Q) of Zn O-Bi2O3 based varistor ceramics prepared by ball milling is large, Q=231±27 k J/mol. Maybe this is because Zr O2 and spinel particle pin the Zn O grain-boundaries creating a drag mechanism that reduces the grain boundary mobility and increases the apparent activation energy.
Zn O-Bi2O3 based varistor ceramics and Zr O2 doped Zn O varistor ceramics are sintered by using different sintering time, and the electrical properties and microstructure of the varistor ceramics are studied in this paper. The results indicate that with increasing sintering time, the density and the nonlinear coefficients of Zr O2 doped Zn O varistor ceramics first increase and then decrease, however, the leakage current and the threshold voltage first decrease and then increase. The grain size of Zr O2 doped Zn O varistor ceramics is smaller than the grain size of Zn O-Bi2O3 based varistor ceramics. The most probable reason is that Zr atomic radius is close to Zn atomic radius. So Zr is dissolved in solid solution with Zn O grains and inhibits the growth of Zn O grain. The grain growth exponent(n) of Zr O2 doped Zn O varistor ceramics is larger than Zn O-Bi2O3 based varistor ceramics. The growth activation energy(Q) of Zn O-Bi2O3 based varistor ceramics prepared by ball milling is large, Q=231±27 k J/mol. Maybe this is because Zr O2 and spinel particle pin the Zn O grain-boundaries creating a drag mechanism that reduces the grain boundary mobility and increases the apparent activation energy.
引文
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[17]章天金,周东祥,姜胜林.Al2O3掺杂Zn O压敏陶瓷的晶粒生长研究[J].功能材料,2000,31(5):519-521.ZHANG Tianjin,ZHOU Dongxiang,JIANG Shenglin.Grain growth of sintered Zn O with Al2O3addition[J].Journal of Functional Materials,2000,31(5):0519-0521
[18]SENDA T,BRADT R C.Grain growth in sintered Zn O and Zn O-Bi2O3ceramics[J].Journal of the American Ceramic Society,1990,73(1):106-114.
[2]GHENO S M,KIMINAMI R H G A,MORELLI M R,et al.Electric force microscopy investigations of barrier formations in Zn O-based varistors[J].Journal of the European Ceramic Society,Electroceramics XI Special Issue,2010,30(2):549-554.
[3]HUAN C,GANG F.Influence of ionic bismuth on intrinsic defects in Zn O varistors[J].Solid-State Electronics,2012,67(1):27-29.
[4]CHENG L H,LI G R,YUAN K Y,et al.Improvement in nonlinear properties and electrical stability of Zn O varistors with B2O3 additives by nano-coating method[J].Journal of the American Ceramic Society,2012,95(3):1004-1010.
[5]王矜奉,陈洪存,王文新,等.Zr掺杂的Sn O2瓷的压敏和介电性质[J].电子元件与材料,2003,22(4):8-10.WANG Jinfeng,CHEN Hongcun,WANG Wenxin,et al.Voltage-sensitive and dielectric properties of Zr-doped Sn O2 ceramics[J].Electronic Components&Materials,2003,22(4):8-10.
[6]XU D,CHENG X N,YUAN H M,et al.Microstructure and electrical properties of Y(NO3)3·6H2O-doped Zn O-Bi2O3-based varistor ceramics[J].Journal of Alloys and Compounds,2011,509(38):9312-9317.
[7]XU D,WANG B,LIN Y H,et al.Influence of Lu2O3on electrical and microstructural properties of Ca Cu3Ti4O12ceramics[J].Physica B:Condensed Matter,2012,407(13):2385-2389.
[8]XU D,ZHANG C,CHENG X N,et al.Dielectric properties of Zn-doped CCTO ceramics by sol-gel method[J].Advanced Materials Research,2011,197-198:302-305.
[9]XU D,ZHANG C,LIN Y H,et al.Influence of zinc on electrical and microstructural properties of Ca Cu3Ti4O12ceramics prepared by Sol-Gel process[J].Journal of Alloys and Compounds,2012,522(0):157-161.
[10]XU D,CHENG X N,ZHAO G P,et al.Microstructure and electrical properties of Sc2O3-doped Zn O-Bi2O3-based varistor ceramics[J].Ceramics International,2011,37(3):701-706.
[11]XU D,SHI X F,CHENG X N,et al.Microstructure and electrical properties of Lu2O3-doped Zn O-Bi2O3-based varistor ceramics[J].Transactions of Nonferrous Metals Society of China,2010,20(12):2303-2308.
[12]徐东,程晓农,徐红星,等.烧结温度对氧化锌压敏瓷显微组织和电性能的影响[J].河南科技大学学报:自然科学版,2009,30(6):8-11.XU Dong,CHENG Xiaonong,XU Hongxing,et al.Effect of sintering temperature on microstructure and electrical properties of Zn O-Bi2O3-based varistor ceramics[J].Journal of Henan University of Science and Technology:Natural Science,2009,30(6):8-11.
[13]SANTOS P A,MARUCHIN S,MENEGOTO G F,et al.The sintering time influence on the electrical and microstructural characteristics of Sn O2varistor[J].Materials Letters,2006,60(12):1554-1557.
[14]HOUABES M,BERNIK S,TALHI C,et al.The effect of aluminium oxide on the residual voltage of Zn O varistors[J].Ceramics International,2005,31(6):783-789.
[15]NAHM C W.Influence of sintering time on electrical and dielectric behavior,and DC accelerated aging characteristics of Dy3+-doped Zn O-Pr6O11-based varistors[J].Materials Chemistry and Physics,2005,94(2-3):275-282.
[16]HNG H H,CHAN P L.Microstructure and current-voltage characteristics of Zn O-V2O5-Mn O2varistor system[J].Ceramics International,2004,30(7):1647-1653.
[17]章天金,周东祥,姜胜林.Al2O3掺杂Zn O压敏陶瓷的晶粒生长研究[J].功能材料,2000,31(5):519-521.ZHANG Tianjin,ZHOU Dongxiang,JIANG Shenglin.Grain growth of sintered Zn O with Al2O3addition[J].Journal of Functional Materials,2000,31(5):0519-0521
[18]SENDA T,BRADT R C.Grain growth in sintered Zn O and Zn O-Bi2O3ceramics[J].Journal of the American Ceramic Society,1990,73(1):106-114.