低电阻率BaTiO_3PTCR陶瓷材料的制备
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摘要
近年来,低电阻BaTiO_3PTCR陶瓷材料在汽车电路过流过载保护、片式元件等方面得到了广泛的应用, PTCR材料电阻率的降低能够扩展高性能PTCR材料的应用范围,低电阻BaTiO_3PTCR陶瓷材料仍然是值得研究的。
在综述低电阻率BaTiO_3PTCR陶瓷材料的制备和理论研究现状的基础上,提出了研究中存在的问题。通过实验,对低电阻率BaTiO_3PTCR材料的制备进行研究;研究烧结与低电阻率PTCR陶瓷材料性能的关系,同时研究烧结助熔剂Al2O3在BaTiO_3PTCR陶瓷材料中的作用。
主要内容包括低电阻率BaTiO_3PTCR材料配方的设计,工艺的设计以及制备样品的测试与分析。
在低电阻率BaTiO_3PTCR材料配方的设计中,阐述了BaTiO_3PTCR材料半导化的原理以及掺入的元素的作用,包括其对材料电阻率的影响,晶粒大小影响和PTC效应的影响等。
对烧结后陶瓷的测试主要包括电阻率,电阻温度特性曲线,样品的表面形貌等,并对测试结果进行了分析,得出施主掺杂量、受主掺杂量以及液相掺杂剂的掺入量与材料电阻率的关系。文中根据得到的关系做出了曲线图,并作为设计配方的依据。在工艺方面,通过调节烧结温度,得出烧结温度对低电阻率BaTiO_3PTCR材料的影响,同时找到一个合适的烧结温度。
最后,总结了以前所作的工作以及本项目的进展情况,同时对本项目还有待进一步解决的问题以及今后还需要做的工作做了相关展望。
Recent years, BaTiO_3PTCR ceramics with low resistivity is widely used in over-current overload protection circuit,chip components and spaceflights.Reducing the resistivity of PTCR material is important because it can expand the scope of application of PTCR material,the sudy of BaTiO_3PTCR ceramics with low resistivity is important.
In this paper,the existing questions on the studying of BaTiO_3PTCR ceramics with low resistivity were proposed,according to the reviewing of the conditions of preparation and the development of theory of it .Through a large amount of experiments,we studied the methods of preparation of low resistivity BaTiO_3PTCR ceramics.
This article mainly covers the the design of BaTiO_3PTCR ceramics with low resistivity, the design of preparation,the test of the material and the analysis of the test results. In the design of BaTiO_3PTCR material with low-resistivity, this paper expound the mechanism of BaTiO_3PTCR becaming semiconducting materials, as well as the role of the element doped into the material, including its influence on the material resistivity, grain size and PTC effect.
After sintering, the resistivity of the material ,the relation between resistance and temperature and the surface morphology of samples are tested .After analysing the testing results ,we find the relationgship between the resistivity of the material and the donor-doped ,the co-donor-doped and the sintering aids doped into the material .Based on the relationship,we get a curve used for designing the material .In the producing process,through regulation of sintering temperature ,we study the influence of the sintering temperature and find a fitting sintering temperature
Finally, by generalizing the work that before, the further question which also will wait for to solve has been taken out to analyze.
在综述低电阻率BaTiO_3PTCR陶瓷材料的制备和理论研究现状的基础上,提出了研究中存在的问题。通过实验,对低电阻率BaTiO_3PTCR材料的制备进行研究;研究烧结与低电阻率PTCR陶瓷材料性能的关系,同时研究烧结助熔剂Al2O3在BaTiO_3PTCR陶瓷材料中的作用。
主要内容包括低电阻率BaTiO_3PTCR材料配方的设计,工艺的设计以及制备样品的测试与分析。
在低电阻率BaTiO_3PTCR材料配方的设计中,阐述了BaTiO_3PTCR材料半导化的原理以及掺入的元素的作用,包括其对材料电阻率的影响,晶粒大小影响和PTC效应的影响等。
对烧结后陶瓷的测试主要包括电阻率,电阻温度特性曲线,样品的表面形貌等,并对测试结果进行了分析,得出施主掺杂量、受主掺杂量以及液相掺杂剂的掺入量与材料电阻率的关系。文中根据得到的关系做出了曲线图,并作为设计配方的依据。在工艺方面,通过调节烧结温度,得出烧结温度对低电阻率BaTiO_3PTCR材料的影响,同时找到一个合适的烧结温度。
最后,总结了以前所作的工作以及本项目的进展情况,同时对本项目还有待进一步解决的问题以及今后还需要做的工作做了相关展望。
Recent years, BaTiO_3PTCR ceramics with low resistivity is widely used in over-current overload protection circuit,chip components and spaceflights.Reducing the resistivity of PTCR material is important because it can expand the scope of application of PTCR material,the sudy of BaTiO_3PTCR ceramics with low resistivity is important.
In this paper,the existing questions on the studying of BaTiO_3PTCR ceramics with low resistivity were proposed,according to the reviewing of the conditions of preparation and the development of theory of it .Through a large amount of experiments,we studied the methods of preparation of low resistivity BaTiO_3PTCR ceramics.
This article mainly covers the the design of BaTiO_3PTCR ceramics with low resistivity, the design of preparation,the test of the material and the analysis of the test results. In the design of BaTiO_3PTCR material with low-resistivity, this paper expound the mechanism of BaTiO_3PTCR becaming semiconducting materials, as well as the role of the element doped into the material, including its influence on the material resistivity, grain size and PTC effect.
After sintering, the resistivity of the material ,the relation between resistance and temperature and the surface morphology of samples are tested .After analysing the testing results ,we find the relationgship between the resistivity of the material and the donor-doped ,the co-donor-doped and the sintering aids doped into the material .Based on the relationship,we get a curve used for designing the material .In the producing process,through regulation of sintering temperature ,we study the influence of the sintering temperature and find a fitting sintering temperature
Finally, by generalizing the work that before, the further question which also will wait for to solve has been taken out to analyze.
引文
[1]祝炳和,姚尧,赵梅瑜等. PTC陶瓷制造工艺与性质.第一版.上海:上海大学出版社,2001.1~2
[2]孙晓龙,曲远方,马卫兵.PTC材料发展概况.化学工业与工程,2002,19(4):320~323
[3]刘慕园,杨宾峰. PTC热敏电阻的特点及应用.河南职业技术师范学院学报, 2002,30(1):49~50
[4]李加升. PTC热敏电阻及其应用分析.益阳职业技术学院学报,2006,6(2):56~57
[5]曹明贺.低电阻率BaTiO3PTCR陶瓷材料制备及理论研究. [博士学位论文].武汉:华中科技大学图书馆,2002,8
[6]祝炳和. BaTiO3半导瓷PTC现象的机理研究进展.电子元件与材料, 2003,22(11):21~24
[7]周东祥,龚树萍. PTC材料及应用.第一版.武汉:华中理工大学出版社, 1989.45~46
[8]陈勇,龚树萍,黎慧等.基于溶胶-凝胶法制备BaTiO3基PTCR纳米陶瓷粉体研究.功能材料,2002,38(增刊):617~620
[9]朱盈权.国内外高纯BaTiO3的生产现状[J].电子元件与材料,2005,24(12): 55~60
[10]莫以豪,李标荣,周国良.半导体陶瓷及其敏感元件.第一版.上海:上海科技出版社,1983.55~56
[11]周东祥,张绪礼,李标荣.半导体陶瓷及应用.第一版.武汉:华中理工大学出版社,1991.134~136
[12] E.Brzozowski, M.S.Castro. Influence of Nb5+ and Sb3+ dopants on the defect profile,PTCR effect and GBBL characteristics of BaTiO3 ceramics. Journal of the European Ceramic Society,2004,24,2499~2507
[13]郑锦清,赵蕊红. TiCN对钛酸钡基PTC热敏陶瓷性能的影响.电子元件与材料, 2008,27(1): 45~47
[14] Hilkat E, Berat Y, Osman O T. The effect of TiCl3 on the microstructure of donor-doped boron-added Ti-excess BaTiO3[J]. J Eur Ceram Soc,2006, 26(14): 2909~2913
[15]何福诚,朱正和.结构化学.第一版.北京:高等教育出版社,1990.120~136
[16] Yuh-Yi Lu, Chun-Hung and Tseung-Yuen.Effect of soaking on the temperature coefficient of resistivity of semiconducting barium titanate PTCR ceramics.J.Am.Ceram.Soc,1994, 77(9):2461~2464
[17] Brian C. LaCourse and Vasantha R.W.Amarakoon.Characterization of the firing schedule for positive temperature coefficient of resistance BaTiO3. Am.Ceram.Soc, 1995, 78(12):3352~3356
[18]周东祥,龚树萍,姜胜林等. AST液相添加剂对PTCR陶瓷电性能的影响.功能材料,1998,29(3): 290~292
[19] Dongxiang Zhou, Minghe Cao, Shuping Gong. A nove method of preparing Ba0.96Ca0.04Ti1.02O3 ceramics with low room temperature resistivity[J]. Materials Science and Engineering,2003,B(99) : 399~402
[20]郑占申,曲远方,李晓雷等. Ni、Mn加入量及工艺对PTCR复合材料的性能影响.复合材料学报, 2005,23(5): 39~43
[21] Pernice P, Esposito s, Aronne. A.Structure and non-isothermal crystallization of glasses in the BaO-B2O3-TiO2 system[J]. phys chem. Glasses,1998,39(4):722~729
[22] Takahashi Y, Saitoh K, Benino Y,et al. Formation of Ba2TiGe2O8 phase in BaO-TiO2-GeO2 glasses and their optical non-linearities[J]. Journal of Non-crys-talline Solids,2004,41(5):412~416
[23]曹明贺,袁俊,周东祥等.低电阻率Ba0.92Ca0.08Ti1.02O3PRCR陶瓷界面缺陷态研究[J].无机材料学报,2003,18(6):1235~1239
[24]吕文中,汪小红等.电子材料物理.第一版.北京,电子工业出版社,2002.97~98
[25]殷之文.电介质物理学.第二版.北京,科学出版社,2003. 38~39
[26]李小燕,曲远方,王晓凤. Zn-V-B玻璃料对(Ba,Sr)TiO3陶瓷微观结构和PTC效应的影响.天津大学学报,2008,41(7):828~832
[27]张庆军,莫文玲,沈毅等.烧成制度对BaTiO3介电性能的影响.中国陶瓷,2006,42(7):46~48
[28]曹明贺,周东祥,龚树萍. Ca对BaTiO3PTCR热敏电阻性能的影响.电子元件与材料,2000,25(8):828~832
[29]钟维烈.铁电物理学.第一版.北京,科学出版社,1996.54~56
[30]钟海波.钛酸钡系高温PTC材料的研究. [硕士学位论文].武汉:华中科技大学图书馆,2005,8
[31]黄庆,高廉,曲远方. BaTi03基PTC陶瓷低阻化新途径与显微分析[J].硅酸盐学报,2003,31(8): 54~56.
[32] Matsuda H,Kuwabara M. Optical absorption in sol-gel-derived crystalline barium titanium fine particles[J].J Am ceram soc,1998,81(11):3010~3012
[33] Liu M L, Zhou H L,Chen Y R,et al. Room temperature solid-solid reactionpreparation of iron boron alloy nanoparticles and M ossbauer spectr[J].Mater Chem phys,2005,89(12) : 289~294
[34] Kowalski K,Ijjaali M,Bak T,et al. Electrical properties of Nb-doped BaTiO3[J]. J phy chem solids,2001,12(62):543~551
[35] Kowalski K,Ijjaali M,Bak T,et al. Electrical properties of Nb-doped BaTiO3[J]. J phy chem solids,2001,12(62):543~551
[36] Kolodiazhnyi,T. and Petric,A., Analysis of point defects in polycrystalline BaTiO3 by electron paramagnetic resonance.J. Phys.Chem.solids,2003,23(64), 953~966
[37] Morrison, F.D., Sinclair, D.C. and west,A.R., An alternative explanation for the origin of the resistivity anomaly in La-doped BaTiO3.J.Am.Ceram.Soc., 2001,14(84),474~476
[38] Rmmajo,M.,Brzozowski,E. and Castro,M.S.,Estudio del perfil de defectors y de la propiedades electricas de BaTiO3 dopado con Nb y La. Bol.Soc.Esp.cer.vidrio, 2002,23(41),31~35
[39] Nowotny,J.and Rekas. M., Positive temperature coefficient of resistivity for BaTiO3 based materials.Ceram.Int.,1991,17,227~241
[40]杨高洁. Al2O3基低温共烧陶瓷材料的研究. [硕士学位论文].武汉:华中科技大学图书馆,2008,6
[2]孙晓龙,曲远方,马卫兵.PTC材料发展概况.化学工业与工程,2002,19(4):320~323
[3]刘慕园,杨宾峰. PTC热敏电阻的特点及应用.河南职业技术师范学院学报, 2002,30(1):49~50
[4]李加升. PTC热敏电阻及其应用分析.益阳职业技术学院学报,2006,6(2):56~57
[5]曹明贺.低电阻率BaTiO3PTCR陶瓷材料制备及理论研究. [博士学位论文].武汉:华中科技大学图书馆,2002,8
[6]祝炳和. BaTiO3半导瓷PTC现象的机理研究进展.电子元件与材料, 2003,22(11):21~24
[7]周东祥,龚树萍. PTC材料及应用.第一版.武汉:华中理工大学出版社, 1989.45~46
[8]陈勇,龚树萍,黎慧等.基于溶胶-凝胶法制备BaTiO3基PTCR纳米陶瓷粉体研究.功能材料,2002,38(增刊):617~620
[9]朱盈权.国内外高纯BaTiO3的生产现状[J].电子元件与材料,2005,24(12): 55~60
[10]莫以豪,李标荣,周国良.半导体陶瓷及其敏感元件.第一版.上海:上海科技出版社,1983.55~56
[11]周东祥,张绪礼,李标荣.半导体陶瓷及应用.第一版.武汉:华中理工大学出版社,1991.134~136
[12] E.Brzozowski, M.S.Castro. Influence of Nb5+ and Sb3+ dopants on the defect profile,PTCR effect and GBBL characteristics of BaTiO3 ceramics. Journal of the European Ceramic Society,2004,24,2499~2507
[13]郑锦清,赵蕊红. TiCN对钛酸钡基PTC热敏陶瓷性能的影响.电子元件与材料, 2008,27(1): 45~47
[14] Hilkat E, Berat Y, Osman O T. The effect of TiCl3 on the microstructure of donor-doped boron-added Ti-excess BaTiO3[J]. J Eur Ceram Soc,2006, 26(14): 2909~2913
[15]何福诚,朱正和.结构化学.第一版.北京:高等教育出版社,1990.120~136
[16] Yuh-Yi Lu, Chun-Hung and Tseung-Yuen.Effect of soaking on the temperature coefficient of resistivity of semiconducting barium titanate PTCR ceramics.J.Am.Ceram.Soc,1994, 77(9):2461~2464
[17] Brian C. LaCourse and Vasantha R.W.Amarakoon.Characterization of the firing schedule for positive temperature coefficient of resistance BaTiO3. Am.Ceram.Soc, 1995, 78(12):3352~3356
[18]周东祥,龚树萍,姜胜林等. AST液相添加剂对PTCR陶瓷电性能的影响.功能材料,1998,29(3): 290~292
[19] Dongxiang Zhou, Minghe Cao, Shuping Gong. A nove method of preparing Ba0.96Ca0.04Ti1.02O3 ceramics with low room temperature resistivity[J]. Materials Science and Engineering,2003,B(99) : 399~402
[20]郑占申,曲远方,李晓雷等. Ni、Mn加入量及工艺对PTCR复合材料的性能影响.复合材料学报, 2005,23(5): 39~43
[21] Pernice P, Esposito s, Aronne. A.Structure and non-isothermal crystallization of glasses in the BaO-B2O3-TiO2 system[J]. phys chem. Glasses,1998,39(4):722~729
[22] Takahashi Y, Saitoh K, Benino Y,et al. Formation of Ba2TiGe2O8 phase in BaO-TiO2-GeO2 glasses and their optical non-linearities[J]. Journal of Non-crys-talline Solids,2004,41(5):412~416
[23]曹明贺,袁俊,周东祥等.低电阻率Ba0.92Ca0.08Ti1.02O3PRCR陶瓷界面缺陷态研究[J].无机材料学报,2003,18(6):1235~1239
[24]吕文中,汪小红等.电子材料物理.第一版.北京,电子工业出版社,2002.97~98
[25]殷之文.电介质物理学.第二版.北京,科学出版社,2003. 38~39
[26]李小燕,曲远方,王晓凤. Zn-V-B玻璃料对(Ba,Sr)TiO3陶瓷微观结构和PTC效应的影响.天津大学学报,2008,41(7):828~832
[27]张庆军,莫文玲,沈毅等.烧成制度对BaTiO3介电性能的影响.中国陶瓷,2006,42(7):46~48
[28]曹明贺,周东祥,龚树萍. Ca对BaTiO3PTCR热敏电阻性能的影响.电子元件与材料,2000,25(8):828~832
[29]钟维烈.铁电物理学.第一版.北京,科学出版社,1996.54~56
[30]钟海波.钛酸钡系高温PTC材料的研究. [硕士学位论文].武汉:华中科技大学图书馆,2005,8
[31]黄庆,高廉,曲远方. BaTi03基PTC陶瓷低阻化新途径与显微分析[J].硅酸盐学报,2003,31(8): 54~56.
[32] Matsuda H,Kuwabara M. Optical absorption in sol-gel-derived crystalline barium titanium fine particles[J].J Am ceram soc,1998,81(11):3010~3012
[33] Liu M L, Zhou H L,Chen Y R,et al. Room temperature solid-solid reactionpreparation of iron boron alloy nanoparticles and M ossbauer spectr[J].Mater Chem phys,2005,89(12) : 289~294
[34] Kowalski K,Ijjaali M,Bak T,et al. Electrical properties of Nb-doped BaTiO3[J]. J phy chem solids,2001,12(62):543~551
[35] Kowalski K,Ijjaali M,Bak T,et al. Electrical properties of Nb-doped BaTiO3[J]. J phy chem solids,2001,12(62):543~551
[36] Kolodiazhnyi,T. and Petric,A., Analysis of point defects in polycrystalline BaTiO3 by electron paramagnetic resonance.J. Phys.Chem.solids,2003,23(64), 953~966
[37] Morrison, F.D., Sinclair, D.C. and west,A.R., An alternative explanation for the origin of the resistivity anomaly in La-doped BaTiO3.J.Am.Ceram.Soc., 2001,14(84),474~476
[38] Rmmajo,M.,Brzozowski,E. and Castro,M.S.,Estudio del perfil de defectors y de la propiedades electricas de BaTiO3 dopado con Nb y La. Bol.Soc.Esp.cer.vidrio, 2002,23(41),31~35
[39] Nowotny,J.and Rekas. M., Positive temperature coefficient of resistivity for BaTiO3 based materials.Ceram.Int.,1991,17,227~241
[40]杨高洁. Al2O3基低温共烧陶瓷材料的研究. [硕士学位论文].武汉:华中科技大学图书馆,2008,6
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