Pr/Mn改性BaTiO_3 陶瓷的PTC效应研究
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摘要
为得到高性能PTC材料,本文采用溶胶-凝胶法制备了Pr、Mn掺杂摩尔分数分别为0.001,0.002,0.003,0.004,0.005和0.006的BaTiO3粉体。所制粉体经TEM分析,粒径在30nm左右,分布均匀。将粉体烧结成瓷后对其进行了Pr扩渗,Mn扩渗,先Pr后Mn扩渗,先Mn后Pr扩渗以及Pr、Mn共同扩渗,并对改性后BaTiO3陶瓷的组成、结构、形貌及电性能的变化进行了研究。
对于掺Pr系列,室温电阻率均在105m数量级,比纯BaTiO3陶瓷的1012m有明显降低;掺Pr摩尔分数为0.004的BaTiO3陶瓷经Pr元素气相扩渗后室温电阻率最低,为0.35m,再对其进行Mn元素气相扩渗,出现了明显PTC效应。对于掺Mn系列,室温电阻率均在1013m数量级,比纯BaTiO3陶瓷的室温电阻率要高,但Mn元素的加入对提升陶瓷PTC效应是有利的;Pr、Mn气相扩渗后室温电阻率也明显降低,最低为2.01m。纯BaTiO3陶瓷经Pr、Mn两种元素共同扩渗后,在25℃~300℃范围内,电阻率可由104m数量级降至102m数量级,出现了NTC效应。
XRD测试表明,Pr、Mn气相扩渗后BaTiO3陶瓷的钙钛矿结构没有发生明显改变。XPS测试结果表明,Pr、Mn气相扩渗后BaTiO3陶瓷中均存在相应被扩渗元素,且有C元素存在。Ba、Ti和O的结合能比纯BaTiO3陶瓷中的Ba、Ti和O的结合能均增大2eV,而Pr、Mn掺杂BaTiO3陶瓷中的Ba、Ti和O的结合能均比纯BaTiO3陶瓷中的Ba、Ti和O的结合能高11eV左右,证明气相扩渗法能将化学元素引入到陶瓷体系中。SEM测试表明,Pr、Mn气相扩渗后,BaTiO3陶瓷晶粒生长完整,粒度分布均匀,气孔率下降。
In order to get high performance PTC material,different kinds of Pr/Mn modified BaTiO3 powders whose doping mole fraction was 0.001, 0.002, 0.003, 0.004, 0.005 and 0.006 separately were prepared by sol-gel method. The prepared powders were analyzed by TEM,the grain sizes were about 30nm and the grains distributed equalitily.Then the powders were sintered for preparing ceramics,the sintered ceramics were penetrated by Pr,Mn,Pr fistly and then Mn,Mn firstly and then Pr,Pr and Mn together.Then constitutes,structures.appearances and electric capability of the modified BaTiO3 ceramics were investigated.
For the BaTiO3 ceramics doped by Pr, resisitivity at room temperature are all about 105m,which is much lower than that of BaTiO3 ceramic,which is 1012m;The resisitivity of the BaTiO3 ceramics doped by 0.004 mole Pr and then penetrated by Pr is the lowest ,it is 0.35m;Then the ceramic was penetrated by Mn,and the effect of the positive temperature coefficient of resistivity appeared. For the BaTiO3 ceramics doped by Mn, resisitivity at room temperature are all about 1013m,which is higher than that of BaTiO3.But the doping of Mn can increase the peak value of PTC effect. And the lowest resisitivity is 2.01m after penetration.The BaTiO3 showed the effect of negative temperature coefficient of resistivity after it was penetrated by Pr and Mn together,and the resistivity could decrease from 104 mto 102 m.
The results of XRD test showed that ,the perovskite structure of BaTiO3 penetrated by Pr/Mn did not change obviously.The results of XPS test showed that ,the correspond element and the element carbon were found in the BaTiO3 after it was penetrated, and the binding energys of Ba,Ti and O were all increased 2eV than those in the pure BaTiO3 ceramic,but those in the BaTiO3 ceramic doped by Pr or Mn were all increased 11eV. All of these indicated that the method of gas penetration could make the elements into the cramics.The results of SEM test showed that,after pentration of Pr or Mn,the gowth of the BaTiO3’s grain was more integrity , the grains distributed equally and the porosity declined.
对于掺Pr系列,室温电阻率均在105m数量级,比纯BaTiO3陶瓷的1012m有明显降低;掺Pr摩尔分数为0.004的BaTiO3陶瓷经Pr元素气相扩渗后室温电阻率最低,为0.35m,再对其进行Mn元素气相扩渗,出现了明显PTC效应。对于掺Mn系列,室温电阻率均在1013m数量级,比纯BaTiO3陶瓷的室温电阻率要高,但Mn元素的加入对提升陶瓷PTC效应是有利的;Pr、Mn气相扩渗后室温电阻率也明显降低,最低为2.01m。纯BaTiO3陶瓷经Pr、Mn两种元素共同扩渗后,在25℃~300℃范围内,电阻率可由104m数量级降至102m数量级,出现了NTC效应。
XRD测试表明,Pr、Mn气相扩渗后BaTiO3陶瓷的钙钛矿结构没有发生明显改变。XPS测试结果表明,Pr、Mn气相扩渗后BaTiO3陶瓷中均存在相应被扩渗元素,且有C元素存在。Ba、Ti和O的结合能比纯BaTiO3陶瓷中的Ba、Ti和O的结合能均增大2eV,而Pr、Mn掺杂BaTiO3陶瓷中的Ba、Ti和O的结合能均比纯BaTiO3陶瓷中的Ba、Ti和O的结合能高11eV左右,证明气相扩渗法能将化学元素引入到陶瓷体系中。SEM测试表明,Pr、Mn气相扩渗后,BaTiO3陶瓷晶粒生长完整,粒度分布均匀,气孔率下降。
In order to get high performance PTC material,different kinds of Pr/Mn modified BaTiO3 powders whose doping mole fraction was 0.001, 0.002, 0.003, 0.004, 0.005 and 0.006 separately were prepared by sol-gel method. The prepared powders were analyzed by TEM,the grain sizes were about 30nm and the grains distributed equalitily.Then the powders were sintered for preparing ceramics,the sintered ceramics were penetrated by Pr,Mn,Pr fistly and then Mn,Mn firstly and then Pr,Pr and Mn together.Then constitutes,structures.appearances and electric capability of the modified BaTiO3 ceramics were investigated.
For the BaTiO3 ceramics doped by Pr, resisitivity at room temperature are all about 105m,which is much lower than that of BaTiO3 ceramic,which is 1012m;The resisitivity of the BaTiO3 ceramics doped by 0.004 mole Pr and then penetrated by Pr is the lowest ,it is 0.35m;Then the ceramic was penetrated by Mn,and the effect of the positive temperature coefficient of resistivity appeared. For the BaTiO3 ceramics doped by Mn, resisitivity at room temperature are all about 1013m,which is higher than that of BaTiO3.But the doping of Mn can increase the peak value of PTC effect. And the lowest resisitivity is 2.01m after penetration.The BaTiO3 showed the effect of negative temperature coefficient of resistivity after it was penetrated by Pr and Mn together,and the resistivity could decrease from 104 mto 102 m.
The results of XRD test showed that ,the perovskite structure of BaTiO3 penetrated by Pr/Mn did not change obviously.The results of XPS test showed that ,the correspond element and the element carbon were found in the BaTiO3 after it was penetrated, and the binding energys of Ba,Ti and O were all increased 2eV than those in the pure BaTiO3 ceramic,but those in the BaTiO3 ceramic doped by Pr or Mn were all increased 11eV. All of these indicated that the method of gas penetration could make the elements into the cramics.The results of SEM test showed that,after pentration of Pr or Mn,the gowth of the BaTiO3’s grain was more integrity , the grains distributed equally and the porosity declined.
引文
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2 干福熹. 信息材料. (天津): 天津大学出版社. 2000: 200~231
3 熊兆贤. 陶瓷材料的分形研究. (天津): 科学出版社. 2000: 1~5
4 W. Heywang. Resistivity Anomaly in Doped Borium Titanate. J Am Ceram Soc, 1964, 47(10): 484~485
5 刘岗, 严岩, 王峰等. 电子陶瓷用钛酸钡粉体制备方法研究进展. 绝缘材料. 2006(1): 56~59
6 张道范, 王天相. Bi:BaTiO3,(Bi,K):BaTiO3 晶体的生长及介电性质的研究. 人工晶体学报. 2001, 23(4): 274~276
7 王铁军, 胡林彦, 郑占申等. 钛酸钡 PTC 陶瓷的制备及显微分析. 中国陶瓷. 2005, 41(5): 17~20
8 王春风, 代军, 刘康强. 稀土掺杂的纳米钛酸钡的制备及其性能研究. 矿冶工程. 2006, 26(2): 74~77
9 胡芳仁. 溶胶凝胶自燃合成 BaTiO3,TiO2,ZrO2 和 A12O3 纳米粉体的研究. 北京科技大学博士论文. 2001: 24~35
10 关自斌, 高仁喜, 毛天舒等. 电子陶瓷用钛酸钡粉体制备技术进展及市场供需述评. 湿法冶金. 1997, (4): 1~10
11 李汉军, 施尔畏. 水热法制备 BaTiO3 粉体. 硅酸盐学报. 1999, 27(6): 714~720
12 李龙土. 功能陶瓷材料及其研究进展. 硅酸盐通报. 2005(5): 107~110
13 徐华蕊, 高嫌, 郭景坤. 水热合成高纯四方相认酸钡纳米粉末研究. 功能材料. 2001, 32(5): 558~560
14 施尔畏, 夏长泰. 水热法制备的 BaTiO3 微晶粒的特性. 无机材料学报. 1995, 10(4): 385~390
15 B. L. Newalkar, S. Komarneni, H. Katsuki. Microwave hydrothermal Synthesis and Characterization of Barium Titanate Powders. Materials Research Bulletin. 2001, 36(5): 2347~2355
16 E. R. Leite, M. A. Nobre. Particle Growth during Calcination of Polycation Oxides Synthesized by the Polymeric Precursors Method. J. Am. Ceram.Soc.1997, 80(11): 2649~2657
17 P. P. Phule, S. H. Risbud. Review-Low-temperature Synthesis and Processing of Electronic Materials in the BaO-TiO2 System. Journal of Materials Science. 1990, 25: 1169~1183
18 N. Chakrabarti. Maitipreparation of Ba(Zr,Ti)O3 by a Auto- com Bustion Method. J.Mater.Chem.1996, 6(7): 1169~1171
19 黄元龙, 赵光明. 溶剂/催化剂对 TiO2 溶胶-凝胶过程的影响. 功能材料. 1997, 28(1): 37~41
20 张天金, 彭芳明. 溶剂-凝胶工艺合成 TiO2 超微粉末的研究. 无机材料学报. 1996, 11(3): 433~439
21 D. Charles, E. Lakeman and A. David. Payne. Processing Effects in the Sol-Gel Preparation of PZT Dried Gels. Powders and Ferroelectric Thin Layers. 1992, 75(11): 3091~3096
22 Y. Park, M. Miyayama and T. Kudo. Fabrication of PbBi4Ti4O15 and Pb2Bi4Ti5O18 Thin Films by Sol-Gel Methed. J.Cram.Soc. 1999, 107(5): 413~418
23 P. Blanchart, J. F .Bauamrd. Effects of Yttrium Doping on the Grain and Grainboundary Resistivities of BaTiO3 for Positive Temperature Coefficient Thermistors. J. Am. Ceram. Soc, 1992, 75(5): 1068~1072
24 徐荣云. Al3+,Si4+ 对施主受主掺杂高居里点 BaTiO3 基 PTCR 材料性能的影响. 中国陶瓷. 2002, 38(4): 7~9
25 K.Yuki,K.Gawa.Synthesis of (Ba,Pb)(Zr,Ti)O3 Solid Solution Having No Composition Fluctuations. J. Am. Ceram. Soc. 2000, 25(15): 145~150
26 S. X. Zhao, H. X. Liu. Grain-Boundary Structure,Segregationan Properties of BariumTitanate Ceramics. Functional Materials. 2000, 31(3): 233~236
27 Z. Zhang, P. J. Pigram and R. N. Lamb. Intern Symp on Grain Boundary in Ceramics.Kosuge N. Ed. Am. Ceram. Soc.2001, 13(2): 15~17
28 J . Charles, Kraisinger. Engineering and Characterization of Dopant Scale Effects in Advanced Multiphase Electroceramics. The Pennsylvania State University. The Graduate School College of Earth and Mineral Sciences For the Degree of Philosophy. December 2001: 15~20
29 K. Park. Characteristics of Porous BaTiO3-based PTC Thermistors Fabricated by Adding Grahphite Powders. Materials Science and Engineering.B107(2004): 19~26
30 易回阳, 肖建中, 甘章华等.高分子基 PTC 复合材料的研究及其应用. 化学研究与应用. 2003, 15(6): 26~30
31 张绪礼. V2O3 基 PTC 热敏电阻陶瓷的研制.电子元件与材料.1988, 7(20): 13~16
32 黄仲臧, 沈嘉棋. 低电阻率高性能 PTCR 陶瓷材料.无机材料学报. 1999, 14(6): 939~944
33 N. Zaki, K. Kawaguchi. BaTiO3-based Positive Temperature Coefficient of Resistivity Ceramics with Low Resistivities Prepared by the Oxalate Method. J. Mater. Sci, 1995, 30(13): 3395~3400
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