无铅高居里温度PTC材料的研究
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摘要
PTC材料是一种温度敏感的铁电半导体材料,是近年来发展迅速的新型电子材料之一。PTC陶瓷材料因其独特的机-电-热物理性能,在电子信息、自动控制、生物技术、能源交通等领域得到了广泛应用,与陶瓷电容器和压电陶瓷并列成为铁电陶瓷的三大应用领域。但是,目前高居里温度PTC材料都是用含铅物质作为居里温度移动剂来制备的,而铅是对人体和环境有很大的危害。因此,需要研制一种新型环保无铅高居里温度PTC材料。
     本文采用固相合成法预先合成BNT,作为居里温度移动剂在二次合成时和其它物质一起加入,制备新型环保的无铅高居里温度PTC材料。借助X射线衍射仪(XRD)、扫描电子显微镜(SEM)、阻温特型测试仪(R-T)、伏安特性测试仪(V-A)等仪器对所制备的材料的微观组织及其制备的样品性能的进行了测试和表征。
     结果表明:在烧成温度850℃~950℃之间预先合成的BNT,可以作为制备无铅高居里温度PTC材料的高居里温度移动剂替代铅。如果BNT不预先合成而是以各自的化合物的形式加入,Bi和Na的化合物就会在制备的各个过程损失,而不能起到居里温度移动剂的效果。预先合成的BNT和主晶相BaTiO_3及其它添加剂进行二次合成,制备出无铅高居里温度PTC材料。添加剂为Ca,施主添加剂以Y_2O_3所制备的PTC材料在微观组织和电性能都较好。
     本实验采用预先合成的BNT,替代含铅物质作为居里温度移动剂制备出居里温度大于130℃的PTC材料,所制备的PTC元件室温电阻小于1kΩ,升阻比为10~2;为电子材料领域研制新型环保的无铅PTC材料起到了一定的作用。
PTC materials is a kind of temperature-sensitive ferroelectric semiconductor, which is one of new type electronic materials developed rapidly during the recent years. For particular mechanical-electronic-caloric physical property, PTC materials have been used broadly in the electronic information, autocontrol, biology technology, energy sources and traffic fields, is intituled paratacticly three applied areas of the ferroelectric ceramic with ceramic capacitor and piezoelectric ceramic. However, at present high-curie temperature PTC materials mostly used lead-substance to move the curie temperature. It is well known that lead is very harmful to person and environment. So it is necessary to develop a kind of new-type environmental lead-free high-curie temperature PTC materials.
     In this thesis, we firstly prepared BNT with solid composed method and prepared new-type environmental lead-free high-curie temperature PTC materials with the BNT and other additives. Also characterized the PTC materials' microstructure and tested its samples' property by X-ray diffraction (XRD), scanning electron microscopy (SEM), Resistance-Temperature apparatus, Volt-Ampere testing apparatus and so on.
     Experiment results show that: the BNT which is sintered at the temperature from 850℃to 950℃can be used the moving-curie temperature substance instead of lead. If the BNT is not composed beforehand, the elements Bi and Na will be lost during the course and result in not moving the curie temperature. Through the second compose of BNT, main crystal BaTiO_3 and other additives, the lead-free high-curie temperature PTC materials can be prepared. The PTC materials' microstructure and electrical property is better with additives Ca and donated additives Y_2O_3.
     The PTC materials that we prepare in this experiment is better. Its curie temperature go beyond 130℃, the sample's resistance at the room temperature is less than 1kΩ, the ratio between the maximum resistance and the minimum resistance is 10~2. This PTC materials make some action on the electrical materials for researching new-type environmental lead-free PTC materials.
引文
[1] 曲远方.功能陶瓷及应用[M].北京:化学工业出版社.2003.01
    [2] 席军,刘廷华.PTC热敏电阻的开发应用现状[J].塑料.2005,34(4):79-84
    [3] 刘慕园,杨宾峰.PTC热敏电阻的特点及应用[J].河南职业技术师范学院学报.2002.3:49-51
    [4] 周海亮,杜懋陆,倪超等.PTC热敏电阻及其发展趋势[J].内江师范学院学报.2004.19 (6):17-21
    [5] Willardson R. What's Ahead in Semiconductor Military Electronics. 1957. 10: 16-22
    [6] 周东祥,龚树萍.PTC材料及应用[M].武汉:华中理工大学出版社,1989
    [7] 陆轶,龚斌,陆神龙.PTC热敏电阻器的电阻温度特性及应用[J].大学物理实验.:1998.9:16-20
    [8] 钟海波.钛酸钡系高温PTC材料的研究:[D].武汉:华中科技大学电子科学与技术系.2005.05
    [9] 薛泉林.PTC热敏电阻器发展与应用动态[J].山东陶瓷.1997.12:9-13
    [10] 胡林彦.钛酸钡基PTC陶瓷的微观结构及PTC机理研究:[D].唐山:河北理工大学材料学.2005.03
    [11] 周秀娟,刘心宇.PTC陶瓷材料的发展及应用[J].电工材料.2005.3:38-41
    [12] 明华.PTC陶瓷发展潜力大趋势预测[J].市场观察.1997.11:11
    [13] 陈新奇,叶勐,何宇等.PTC热敏电阻材料的低阻化研究[J].北京工业大学学报.1994.9:66-69
    [14] Qi Jianquan, Gui Zhilun, Wu Yajing, Li Longtu, Influence of Manganese on PTCR Effect in BaTiO_3-based Ceramics doped with Bi_2O_3 Vapour. Materials chemistry and physics [J]. 73(2002): 97-100
    [15] 王恩信,恽正中,杨传仁等.日本热敏电阻的开发与研制[J].通用元器件.世界电子元器件.ECN1997.7:53-57
    [16] 潘宇,陈旭,任萍等.高温PTC陶瓷研究进展[J].压电与声光.1998,20(5):326-329
    [17] 王厚坤.高居里点无铅化热敏电阻材料的研究:[D].成都:成都理工大学材料系.2006
    [18] 朱盈权.PTC热敏电阻的现状与发展趋势[J].电子元件与材料.2002.06:26-27
    [19] 祝炳和等.PTC陶瓷制造工艺与性质[M].上海:上海大学出版社.2001
    [20] 关振铎等编著.无机材料物理性能[M].北京:清华大学出版社.2000
    [21] 天津大学,华南理工学院合编.电子陶瓷[M].北京:国防工业出版社.1979
    [22] 钟吉品.半导体陶瓷及晶界电容器半导化和晶界势垒的研究:[D].上海:上海硅酸盐 研究所.1988
    [23] 徐廷献,沈继跃,薄占满等.电子陶瓷材料[M].天津:天津大学出版社.1993
    [24] 朱云松,徐天华.高温PTC陶瓷中铅对Tc移动效果的实验[J].电子元件与材料.1997(3):20-22
    [25] 史慧.溶胶-凝胶法制备(NaBi)_(1/2)TiO_3压电陶瓷及性能分析[D].清华大学材料系 2004.06:7-10
    [26] Heywang W. Resistivity anomaly in doped borium titanate[J], J Am Ceram Soc, 1964, 47(10): 484
    [27] Heywang W. Bariumtitanat als sperrschichthalbleiter [J], Solid-state Electron, 1961, 3(1): 51
    [28] Daniels J, Wernicke R. New aspects of in improved PTC model [J], Philips Res Rep, 1976, 31: 544
    [29] Daniels J, Hardtl K H. The PTC effect of barium titanate[J], Philips Tech Rev, 1978/1979, 38: 73
    [30] S B Desu, D A Payne.. J Am Ceram Soc[J], 1990, 73(11): 3391-3421
    [31] V M Fridkin, Ferroelectic semiconductors, Nauka, Noscow, USSR, 1976
    [32] Roseman R D, Kim J. Ferroelectrics, 1996, 177: 273-282
    [33] Roseman R D, Ferroelectrics[J], 1998, 215: 31-45
    [34] Kim J, Roseman R D. Ferroelectrics, [J] 1996, 177: 255-271
    [35] Roseman R, Liu Gaosheng. Ferroelectrics[J], 1999, 221: 181-185
    [36] A. M. Seuter, Defect chemistry and electrical transport properties of barium titanate, PhilipsRes[J]. Rep., Suppl., 1973, 3: 1-84
    [37] G. V. Lewis, C. R. A. Catlow, R. E. W. Casselton, PTCR effect in BaTiO_3[J],, JAm CeramSoc, 1985, 68(10): 55-58
    [38] B. Hoffman, A model of grain boundary barriers in doped BaTiO_3 ceramics[J], Solid-stateelectron, 1973, 16(5): 623-628
    [39] P. Gerthsen, B. Hoffman, Current-Voltage characteristics and capacitance of single grainboundaries in semiconducting BaTiO_3 ceramics[J], ibid., 1973, 16: 617
    [40] Weirong Huo, Yuanfang Qu. Effect of (Bi_(1/2)Na_(1/2))TiO_3 on the Cuire Temperature and PTC effects of BaTiO_3-based positive temperature coefficient ceramics[J]. Sensors and Actuatous A 128(1996): 265-69
    [41] Jingchang Zhao, Longtu Li, Zhilun Gui. Influence of Lithum modification on the properties of Y-doped Sr_(0.5)Pb_(0.5)TiO_3 thermistors[J]. Sensors and Actuatous A 95(2001): 46-50
    [42] Peter Supancic. Mechenical Stability of BaTiO_3-based PTC thermitor components: experimental investigation and theoretical modeling. Journal of the European Ceramic society. 20(2000): 2009-2024
    [43] Anatolii Belous, Oleg V'yunov, Leonid Kovalenko. Formation and electrophysical properties of Y-containing positive temperature coefficient of resistance ceramics doped by calcium, strontium and manganese[J], Materials Research Bulletin. 39(2004): 297-308
    [44] 张爱菊,沈毅,张晨.草酸盐共沉淀法制备高性能无铅PTC粉体[J].中国陶瓷工业.2005.10:21-24
    [45] 谢志勇,马卫兵,曲远方,卢艳.双施主掺杂对BaTiO_3基PTC陶瓷性能的影响[J].电子元件与材料.2003.01:11-13
    [46] 薛泉林.新型的高可靠PTC热敏电阻器[J].江苏陶瓷.1995.03:2-5
    [47] 王评初.驰豫铁电体相变研究的最新进展[J].哈尔滨理工大学学报.2002.12:64-65
    [48] 王佩军,李德修,张树波.BaSrTiO_3热敏陶瓷材料的研制和应用[J].云南大学报.1994.03:29-34
    [49] 许早峤.(Bi_(0.5)Na_(0.5))TiO_3-BaTiO_3无铅压电陶瓷体系研究[D].南京:南京工业大学硕士学位论文.2004
    [50] 鄢洪建.(Bi_(0.5)Na_(0.5))TiO_3-BaTiO_3无铅压电陶瓷体系的设计、制备、及性能研究:[D].成都:四川大学材料系博士学位论文.2004
    [51] 李月明.(Bi_(0.5)Na_(0.5))TiO_3-BaTiO_3无铅压电陶瓷的制备、结构与电性能研究:[D].武汉:武汉理工大学博士学位论文.2004
    [52] 王燕.(Bi_(1/2)Na_(1/2))TiO_3基无铅压电陶瓷的水热合成、结构与性能研究:[D].武汉:武汉理工大学硕士学位论文.2005
    [53] 王晓颖.钛酸铋钠基压电陶瓷的制备及性质研究:[D].济南:山东大学凝聚态物理硕士学位论文.2005
    [54] 张庆军,张晨等.BaTiO3基PTC陶瓷材料粉体制备和烧成制度的电子显微研究[J]:电子显微学报.J.Chin.Electr.Microsc.Soc.2003.22(6):524~525
    [55] 刘欢.多层片式PTCR热敏元件制备技术研究:[D].武汉:华中科技大学硕士学位论文.2004
    [56] 四川大学.钛酸铋钠钾锂系无铅压电陶瓷.CN.1511800A.2004.07
    [57] Hagiyev, M. S., Ismailzade, I. H., Abiyev, A. K. Pyroelectric Properties of(Bi_(0.5)Na_(0.5))TiO_3 Ceramics[J]. Ferroelectric. 1984, 56: 215-217
    [58] Xiaoxing, W., Helen, L-W. C., Chung-loong, C. Piezoelectric and Dielectric Properties of CeO_2-added (Bi_(0.5)Na_(0.5))_(0.94)Ba_(0.06)TiO_3 Lead-free Ceramics[J]. SolStat Comm. 2003 (125): 359-399
    [59] Pronin, I. P., Syrnikov, P. P., Egorov, V. A., et al. Peculiarities of Phase-Transitions in Sodium-Bismuth Titanate[J]. Ferroelectrics. 1980, 25: 395-397
    [60] Vakhrushev, S. B., Isupov, V. A., Kvyatkovsky, B. E. Phase-Transitions and Soft Modes in Sodium Bismuth Titanate[J]. Ferroelectrics. 1985, 63: 153-160
    [61] Suchanicz, J., Poprawski, R., Matyjasik, S. Some Properties of Na_(0.5)Bi_(0.5)TiO_3[J]. Ferroelectrics. 1997, 192: 329-333
    [62] Suchanicz, J. Time Evolution of the Phase Transformation in Na_(0.5)Bi_(0.5)TiO_3 [J]. Ferroelectrics. 1997, 200: 319-325
    [63] Suchanicz, J. Peculiarities of Phase Transitions in Na_(0.5)Bi_(0.5)TiO_3 [J]. Ferroelectrics 1997, 190: 77-81
    [64] S. G. Lushnikova, S. N.. vasaliya. Temperature dependence of the generalized vibrational density of states of sodium bismuth titanate in the ferroelectric phase[J]. Solid State Communications 116(2000): 41-45
    [65] I. G.. Siny, E. Husson. A central peak in light scattering from the relaxor-type ferroelectric Na_(1/2)Bi_(1/2)TiO_3 [J]. Physica B 293(2001): 382-389
    [65] Bao-Jin Chu, Da-Ren Chen. Electrical properties of Na_(1/2)Bi_(1/2)TiO_3-BaTiO_3 ceramics[J]. Journal of the European Ceramic Society 22(2002): 2115-2121
    [66] Qi Jianquan, Gui Zhilun. Difference of Bi_2O_3 doping effect between vapor process and solid process on Ba_(1-x)Sr_xTiO_3 semiconducting ceramics[J]. Materials Science and Engineering B95 (2002): 283-286
    [67] 株式会社村田制作所.用于PTC热敏电阻的复合材料和陶瓷及其制造方法.CN 247842A 2003.03
    [68] 谈家琪,沈记耀.PTC热敏电阻发热体瓷料[J].天津大学.2002:27-28
    [69] 冯士明,吴晓东.半导体BaTiO_3陶瓷PTC效应的研究[J].硅酸盐学报.1989 17(1):53-57
    [70] 周东祥,姜胜林等.氧化气氛热处理对BaTiO_3热敏电阻电性能的影响[J].功能材料.1999,30(2):172-174
    [71] 刘欢,龚树萍等.片式PTCR瓷片的制备及烧结工艺的研究[J].压电与声光.2005,27(3):267-269
    [72] 王守仁,王继勋等.浅述PTC正温度系数热敏电阻器原理及应用[J].传感器技术.1993.增刊:52~58
    [73] 杨华斌,刘心宇.烧结工艺对BaTiO_3基PTCR电阻-温度系数的影响[J].电工材料,2005,04:17-20
    [74] 唐珍兰,胡君遂.厚膜PTC热敏电阻烧结峰值温度的研究[J].材料与表面处理技术.2006,01:113-115
    [75] 朱盈权,何海清.BaTiO_3系PTCR热敏电阻器用烧结助剂的研究[J].电子元件与材料.1998,6:4-6
    [76] 朱盈权,侍 刚,何海清,祝炳和.碳酸钙对BaTiO_3系PTC热敏电阻电性能的影响[J].电子元件与材料.1999.10:17-19
    [77] Anatolii Belous, Oleg V'yunov, Leonid Kovalenko. Formation and electrophysical properties of Y-containing positive temperature coefficient of resistance ceramics doped by calcium, strontium, and manganese. Materials Research Bulletin 39(2004): 297-308
    [78] 卓克祥.BaTiO_3热敏电阻陶瓷添加物效应机理的探讨[J].福州大学学报(自然科学版).1990,18(1):83-87
    [79] 朱盈权.BaTiO3系PTC热敏电阻施主加入物的研究[J].电子元件与料.1996.10:33-38
    [80] 谢志勇,马卫兵等.双施主掺杂对BaTiO_3基PTC陶瓷性能的影响[J].电子元件与材料.2003.22(1):11-12
    [81] Jingchang Zhao, Longtu Li, Zhilun Gui. Influence of lithium modification on the properties of Y-dopped Sr0.5Pb0.5YiO3 thermistors[J]. Sensors and Actuations A 95(2001): 46-50

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