摘要
本文以制备低压ZnO压敏陶瓷材料为目的,论述了低压ZnO压敏陶瓷的性能、用途、分类、实现低压化的方法、国内外的研究动态及发展趋势;研究了制备低压ZnO压敏陶瓷的基本工艺和方法,包括压制成型时的压强和粘结剂用量的选择;研究了烧结工艺中烧结温度、保温时间及升温速率对低压ZnO压敏陶瓷电性能和致密度的影响规律,优化了低压ZnO压敏陶瓷的烧结工艺。研究结果表明:坯体的成型极限压强为20Mpa、粘结剂加入量为12wt%时低压ZnO压敏陶瓷的各项性能最优;低压ZnO压敏陶瓷的最佳的烧成工艺条件为:烧成温度1200℃,保温时间2h,升温速率7℃/min。
本文首次采用正交试验法,利用制备ZnO压敏陶瓷的常规工艺,系统研究了Bi、Ti、Co、Mn、Sn、Sb等6种元素氧化物对ZnO压敏陶瓷性能的影响,得出低压ZnO压敏陶瓷的最佳配方为:1.25%Bi_2O_3+0.4%TiO_2+0.4%Co_2O_3+1%MnO_2+1%SnO_2+1%Sb_2O_3 +94.95%ZnO。在最佳烧结工艺条件下烧结,压敏电压为10.15V,漏电流为2.05μA,非线性系数为22.2。
在低压配方的基础上,通过添加稀土元素氧化物Y_2O_3做了改性试验,研究了Y_2O_3掺杂对低压ZnO压敏陶瓷电性能的影响规律及作用机制。研究发现:Y_2O_3的加入能使低压ZnO压敏陶瓷的非线性系数增大,漏电流相应的减小,但同时会使压敏电压大幅度提高,同时,Y_2O_3的掺杂会使低压ZnO压敏陶瓷的晶粒尺寸明显减小,并且大小和分布更为均匀。
In this paper, low-voltage ZnO varistor ceramics were comprehensively analyzed. Properties, application,classification,method of low-voltage,studying situation and developing trend of low-voltage ZnO varistor ceramics were also discussed. The techniques and methods of low-voltage ZnO varistor ceramics were studied;The influence of forming pressure and agglomerant dosage in the forming process on properties of low-voltage ZnO varistor ceramics were researched too; The influence of sintering temperature,holding time and heating rate on the electrical properties and density of low-voltage ZnO varistor ceramics were also investigated. The sintering process of low-voltage ZnO varistors were optimized.The results show that forming limited pressure is 20Mpa and agglomerant dosages is 12wt%,the properties of low-voltage ZnO varistors is optimum; It can obtain the best conditions for sintering process when sintering temperature is 1200℃,holding time is 2 hours and heating rate is 7℃/min.
Unlike conventional test method,this paper is first studied through the orthogonal test.According to the kinds of additives in low-voltage ZnO varistor ceramics,the effects of elements oxide Bi,Ti,Co,Mn,Sn,Sb on the characteristics of low-voltage ZnO varistor ceramics were studied respectively with the conventional processing of ZnO varistor ceramics. Finally, the optimum composition of low-voltage ZnO varistor is: 1.25%Bi_2O_3+0.4%TiO_2+ 0.4%Co_2O_3+1%MnO_2+1%SnO_2+1%Sb_2O_3+94.95%ZnO.The good characteristic with V1mA= 10.15V, IL= 2.05μA, =22.5 could be got at the proper sintering process.
The influence of Y_2O_3 is used as additives on the electrical properties and mechanism of low-voltage ZnO varistor ceramics were studied.The results show that the addition of Y_2O_3 can increase the nonlinear coefficient of low-voltage ZnO varistors and decrease the leakage current,and at the same time improve the varistor voltage greatly.In addition,doping Y_2O_3 can reduce the size of ZnO grain evidently and make the grain size and distribution more uniform.
引文
[1]傅静,徐政.ZnO压敏陶瓷的性能及发展.现代技术陶瓷,2004,1(99):31
[2] V.C.de Sousa,M.R.Morelli,M.S.Castro,et al. Electrical properties of ZnO-based varistors prepared by combustion synthesis. Journal of Materials Science Materials in Electronics, 2002,13(6):319-325
[3]张力,马存云.电路保护元件的发展与与应用.电子片件应用,2002,4(7):1-4
[4]王兰义.多层片式ZnO压敏陶瓷的现状与发展方向.电子元件与材料,2003,(77):42-43
[5]张大卫,施利毅,徐东,等.ZnO压敏陶瓷烧结工艺优化.材料导报,2009,23(1):91-94
[6]王兰义.日本氧化锌避雷器的发展动向.电磁避雷器,1999,(3):27
[7]刘东雨,徐鸿,杨昆,等.ZnO压敏陶瓷的发展现状.中国科技论文在线学报,2003
[8]张丛春,周东祥,龚树萍.低压ZnO压敏电阻材料研究及发展概况.功能材料,2001,32(4): 343-347
[9]王振林,李盛涛.氧化锌压敏陶瓷制造及应用.北京:科学出版社,2009
[10] K.Eda,A.Lga,M.Matsuoka.Curren Creep In Nonohmic ZnO Ceramics.Appl.Phys.,1979, 18(5):997-998
[11] K.Eda,A.Lga,M.Matsuoka.Degradation Mechanism of non-Ohmic Zinc Oxide Ceramies. Appl.Phys.,1980,51(5):2678-2684
[12] G.P.Mohanty,L.V.Azaroff.Electron Density Distribution in ZnO Crystals.Chem.Phys., 1961,35(4):1268-1270
[13]王立惠.低压ZnO压敏陶瓷的制备及性能研究:[学位论文].昆明:昆明理工大学,2006
[14]周东祥,张绪礼,李标荣.半导体陶瓷及应用.武汉:华中理工大学出版社,1989
[15]刘文斌,徐光亮,刘桂香.添加剂在ZnO压敏陶瓷中作用机理的综述.南方金属,2004(2):1-4
[16] J.A.Varela,D.Poleti.Structural and electrical properties of ZnO varistors containing different spinel phases. Ceramics International,2001,27(1):115-122
[17] J.M.Driear.Effect of dopant valence state on the microstructure of ZnO varistors.Grain Boundary Phenomena in Electronic Ceramics.Ohio,Am Ceram Soc,Inc,1981
[18]许业文,何忠伟,徐政,等.Co2O3和MnCO3掺杂对低压ZnO压敏电阻电性能的影响.材料科学与工程学报, 2005,23(4):525-528
[19]范积伟,刘向洋,李小朋.压敏材料的发展及趋势.2010第十七届电压敏学术年会论文集.半导体器件应用,2010,86-88
[20] M.N.Rahaman.Ceramic Processing and Sintering.Msrcel Dekker,Inc.,1995
[21]肖胜根,甘国友,严继康.浅谈ZnO压敏电阻器低压化.佛山陶瓷,2006,5:27-30
[22]朱俊鑫.SrTiO3陶瓷变阻器.压电与声光,1992,14(2):22-27
[23]许毓春,李慧峰,王士良.SiO2对TiO2系压敏陶瓷电性能的影响.压电与声光,1994, 16(5): 41-43
[24]张丛春.低压ZnO压敏材料及可靠性研究: [学位论文].武汉:华中科技大学,2002
[25]周亚栋,杨燕玫.低压ZnO变阻器的研究.北京工业大学学报,1994,20(1)
[26] S.A.Pianaro,P.R.Bueno,E.Longo,et al.A new SnO2-based Varistor system.Mater. Sci. Lett., 1995,14(10):692-694
[27]何忠伟,徐政,孙丹峰.TiO2掺杂对ZnO压敏电阻低压化过程的影响.硅酸盐学报,2004, 32(9):1161-1164
[28]郭会明,朱凤英,梅来宝.掺杂TiO2制备低压ZnO压敏陶瓷.南京工业大学学报,2003, 25(1):59-62
[29]肖明.TiO2掺杂对ZnO压敏陶瓷的晶粒生长研究.湖北大学学报, 2001, 23(2):134-138
[30] V.Makarov,M.Trontelj.Novel varistor material based on tungsten oxide.Mater. Sci. Lett., 1994,13(13):937-939
[31]石汝军,王成礼,李岩,等.Co2O3的理化性能对ZnO压敏陶瓷电性能的影响.山东陶瓷, 2000,23(3):7-9
[32]张丛春,周东样.Co,Mn的掺杂形式对低压氧化锌压敏陶瓷电性能的影响.电子元件与材料, 2000,(6):7-9
[33]徐国跃,谢国治.Mn离子的价态变化与ZnO压敏陶瓷的V-I非线性.材料研究学报, 2000,14(2):198-201
[34]袁方利,凌远兵,李晋林.化学共沉淀粉体制备ZnO压敏陶瓷.无机材料学报,1998, 13(2):171-175
[35] N.Raghu,T.R.N.Kutty.Relationship between nonlinear resistivity and varistor forming mechanisn in ZnO ceramics. Appl. Phys Lett.,1992,60(1):100-102
[36]周亚栋,杨燕玫.低压ZnO变阻器的研究.北京工业大学学报,1994,20(1)
[37]章天金,周东祥,龚树萍,等.籽晶法制备低压ZnO压敏电阻器.电子元件与材料,1998, 17(4):10-11
[38]石康源,张绪礼,王筱珍.ZnO导电陶瓷的微观结构与导电机理.功能材料,1996,27(1): 6163-6168
[39] Wong,Joe.Barrier voltage measurement in metal oxide Varistors.Appl.Phys., 1976, 47(11): 4971-4974
[40] M.Tao,B.Ai,O.Dorlanne.Different“single-grain junctions”within a ZnO Varistors, Appl. Phys.,1987,6l(4):1562-1568
[41] A.Peigney,H.Andrianjatovo,R.Legros,et al.Influence of chemical composition on sintering of bismuth-titanium-doped zinc oxide,Mater. Sci.,1992,27:2397-2405
[42] H.Suzuki,R.C.Bradt.Grain growth of ZnO in ZnO-Bi2O3 ceramics with TiO2 additions, Am.Ceram. Soc.,1995,78(5):1354-1360
[43]张丛春,周东祥,龚树萍.TiO2掺杂对低压ZnO压敏陶瓷性能的影响.压电与声光,2001, 23(3):195-197
[44]王兰义,徐政魁,唐国翌.ZnO压敏陶瓷粉体的研究进展.功能材料,2008,39(8): 1237-1241
[45] T.K.Gupta,W.D.Straub.Effect of annealing on the ac leakage components of the ZnO Varistor.Ⅱ.Resistive current.Appl. Phys.,1990,68(2):845-850.
[46]肖胜根,甘国友,严继康.浅谈ZnO压敏电阻器低压化.佛山陶瓷, 2006,16(5):27-30
[47] D.C.Look.Recent advances in ZnO material and devices.Mater. Sci. Eng.,2001,80(1-3): 383-387
[48] A.Anastasiou,M.H.J.Lee,C.Leach.Ceramic varistors based on ZnO–SnO2.Journal of the European Ceramic Society,2004,24:1171-1175
[49]李世普.特种陶瓷工艺学.武汉:武汉工业大学出版社,1990
[50] Charles B.Boss,Kenneth J.Fredeen.Concepts,Instrumentation,and Techniques in Inductively Coupled Plasma Optical Emission Spectrometry. Second Edition,Perkin-Elmer Corporation, Printed in USA,1997;14-15
[51]王计军.ZnO压敏陶瓷制备工艺优化及TiO2和LiOH掺杂研究:[学位论文].西安:西安科技大学,2007
[52]李标荣,张绪礼.电子陶瓷物理.武汉:华中理工大学出版社,1992
[53]张丛春,周东祥,龚树萍. Sb2O3掺杂对ZnO压敏陶瓷晶界特性和电性能的影响.硅酸盐学报,2001, 29(6):602-605
[54] Ian Gilbert,Robert Freer.Donor and acceptor doping of zinc oxide varistors.Journal of Physics:Condensed Matter,2002,14(4):945-954
[55]刘宏玉,孔慧,马学鸣.掺杂Y2O3氧化锌压敏陶瓷的显微组织及电性能.压电与声光,2007,29(6):686-688
[56]龙香楷,费自豪,庞驰.Y2O3掺杂对ZnO压敏陶瓷电性能的影响.陶瓷,2010(4):25-27
[57] Slvako Bernik,Sreco Macek,Ai Bui. Microstructural and electrical characteristics of Y2O3-doped ZnO-Bi2O3-based varistor ceramics.Journal of European Ceramic Society,2001,21:1875-1878
[58]郭占英.掺杂对ZnO系压敏陶瓷显微结构和电性能影响的研究:[学位论文].沈阳:沈阳工业大学,2007
[59]陈志清,谢恒.氧化锌压敏陶瓷及其在电力系统中的应用.水力水电出版社,1993
[60]刘宏玉.高电位梯度氧化锌压敏陶瓷的制备、显微组织结构及电性能研究:[学位论文].上海:华东师范大学,2006
[61]王茂华,胡克鳌,赵斌元,等.Y2O3掺杂对低压氧化锌压敏电阻材料结构和电学性能的影响.材料科学与工程学报,2005,23(6):789-791