铸态Ti-Ni-Sn合金组织和性能的研究
摘要
随着能源问题和环境问题的日益突出,为了寻找传统能源的替代产品,人们在热电材料方面做了不少有益的探索,热电材料的研制也成为了研究的热点。本文采用电弧炉真空氩气保护下熔炼与铸造的方法,制备了TiNiSn材料。重点对TiNiSn热电材料腐蚀性能、组织形貌及热电性能和热膨胀等性能进行了研究。
对铸态下获得的TiNiSn材料所做的相鉴别分析表明,在铸态TiNiSn材料中存在着TiNiSn、TiNi2Sn、Ni3Sn2、TiNi、Ti3Ni4、Ti6Sn5,同时材料中存在Sn相;能谱分析表明铸态TiNiSn材料中存在着Ti6Sn5、TiNi2Sn相,同时材料中存在微裂纹;利用透射电镜观察分析铸态TiNiSn材料中存在Ti6Sn5和Ti3Ni4相。
用3wt.% NaCl水溶液进行的浸泡腐蚀实验的结果表明,经过热处理后材料的耐蚀性有了明显的提高。铸态试样的点蚀和应力腐蚀同时进行,在浸泡进行到25天的时候试样表面已完全腐蚀;热处理96小时的试样表面没有发生明显的点蚀,腐蚀进行到55天时表面还没有达到完全的腐蚀。铸态和热处理态的试样中都存在铸造和加工缺陷,腐蚀总是首先从这些地方开始的,850℃下热处理96小时的试样的点缺陷基本消除,但应力缺陷的仍然存在于材料中,因此在腐蚀的过程中,还是出现了自试样的边缘部位开始的应力腐蚀。XPS结果表明,浸泡试样的表面反应产物是Sn的氧化物,Ti和Ni在浸泡的过程中脱离了试样表面。
电化学实验表明,热处理48小时和热处理96小时的试样都出现了明显的钝化区,热处理96小时试样的维钝电流密度低于热处理48小时试样的维钝电流密度,显示了TiNiSn材料随着热处理时间的增加,耐腐蚀性能不断提高的特性。
物理性能测试结果表明,随着测试温度的升高,铸态TiNiSn材料的电阻率下降,Seebeck系数、热导率和优值系数都升高。材料的抗压和硬度试验表明,该材料属脆性材料,热处理的进行能提高材料的硬度。
Thermoelectric materials are currently being investigated for their potential against the problems of energy and environment. They can be served as a substitution of traditional energy. TiNiSn materials were prepared in arc furnace under Ar atmosphere. Corrosion properties, morphology, physical properties, and some mechanical properties of TiNiSn material were investigated.
XRD analysis of as-cast TiNiSn material showed that it was difficult to get single-phase TiNiSn. TiNi2Sn, Ni3Sn2, TiNi, Ti3Ni4, Ti6Sn5, and Sn were tested in the sample. Results of energy spectrum analysis of the as-cast sample showed that there were Ti6Sn5 and TiNi2Sn phases, and also there were some micro-cracks in the material. TEM image of as-cast TiNiSn material and diffraction pattern on appointed site showed that there were Ti6Sn5 and Ti3Ni4 in the as-cast TiNiSn material.
Results showed that resistance ability of corrosion in 3wt.% NaCl solution can be improved by heat treatment. The as-cast sample corroded fast, there are pitting corrosion and surface tension corrosion. It was corroded thoroughly after 25 days. There are not pitting corrosion on the sample treated for 96 hour, and this sample was not corroded thoroughly until the 55th days. There were many casting flaws and processing stresses in the as-cast and heat treatment samples. And the corrosion started from those areas. Pitting flaws in the sample of 96 hours heat treatment in vacuum furnace were basically eliminated, but the processing stresses still existed. Corrosion of this sample was mainly surface tension corrosion. Results of XPS showed that Sn was oxidized on surface of the sample. Ti and Ni were corroded off the surface of the sample.
There are significant passivation areas in samples treated for 48h and 96h, current density of sample treated for 96h is higher than sample treated for 48h. With increase of heat treatment time, corrosion resistance increases.
Results of the physical property showed that with the increase of the temperature, electrical resisitivity of the as-cast TiNiSn material decreased. Seebeck coefficient, heat conductivity, and ZT value increased. The mechanical experiment indicated that TiNiSn material was brittle material. Heat treatment could improve hardness of the material.
对铸态下获得的TiNiSn材料所做的相鉴别分析表明,在铸态TiNiSn材料中存在着TiNiSn、TiNi2Sn、Ni3Sn2、TiNi、Ti3Ni4、Ti6Sn5,同时材料中存在Sn相;能谱分析表明铸态TiNiSn材料中存在着Ti6Sn5、TiNi2Sn相,同时材料中存在微裂纹;利用透射电镜观察分析铸态TiNiSn材料中存在Ti6Sn5和Ti3Ni4相。
用3wt.% NaCl水溶液进行的浸泡腐蚀实验的结果表明,经过热处理后材料的耐蚀性有了明显的提高。铸态试样的点蚀和应力腐蚀同时进行,在浸泡进行到25天的时候试样表面已完全腐蚀;热处理96小时的试样表面没有发生明显的点蚀,腐蚀进行到55天时表面还没有达到完全的腐蚀。铸态和热处理态的试样中都存在铸造和加工缺陷,腐蚀总是首先从这些地方开始的,850℃下热处理96小时的试样的点缺陷基本消除,但应力缺陷的仍然存在于材料中,因此在腐蚀的过程中,还是出现了自试样的边缘部位开始的应力腐蚀。XPS结果表明,浸泡试样的表面反应产物是Sn的氧化物,Ti和Ni在浸泡的过程中脱离了试样表面。
电化学实验表明,热处理48小时和热处理96小时的试样都出现了明显的钝化区,热处理96小时试样的维钝电流密度低于热处理48小时试样的维钝电流密度,显示了TiNiSn材料随着热处理时间的增加,耐腐蚀性能不断提高的特性。
物理性能测试结果表明,随着测试温度的升高,铸态TiNiSn材料的电阻率下降,Seebeck系数、热导率和优值系数都升高。材料的抗压和硬度试验表明,该材料属脆性材料,热处理的进行能提高材料的硬度。
Thermoelectric materials are currently being investigated for their potential against the problems of energy and environment. They can be served as a substitution of traditional energy. TiNiSn materials were prepared in arc furnace under Ar atmosphere. Corrosion properties, morphology, physical properties, and some mechanical properties of TiNiSn material were investigated.
XRD analysis of as-cast TiNiSn material showed that it was difficult to get single-phase TiNiSn. TiNi2Sn, Ni3Sn2, TiNi, Ti3Ni4, Ti6Sn5, and Sn were tested in the sample. Results of energy spectrum analysis of the as-cast sample showed that there were Ti6Sn5 and TiNi2Sn phases, and also there were some micro-cracks in the material. TEM image of as-cast TiNiSn material and diffraction pattern on appointed site showed that there were Ti6Sn5 and Ti3Ni4 in the as-cast TiNiSn material.
Results showed that resistance ability of corrosion in 3wt.% NaCl solution can be improved by heat treatment. The as-cast sample corroded fast, there are pitting corrosion and surface tension corrosion. It was corroded thoroughly after 25 days. There are not pitting corrosion on the sample treated for 96 hour, and this sample was not corroded thoroughly until the 55th days. There were many casting flaws and processing stresses in the as-cast and heat treatment samples. And the corrosion started from those areas. Pitting flaws in the sample of 96 hours heat treatment in vacuum furnace were basically eliminated, but the processing stresses still existed. Corrosion of this sample was mainly surface tension corrosion. Results of XPS showed that Sn was oxidized on surface of the sample. Ti and Ni were corroded off the surface of the sample.
There are significant passivation areas in samples treated for 48h and 96h, current density of sample treated for 96h is higher than sample treated for 48h. With increase of heat treatment time, corrosion resistance increases.
Results of the physical property showed that with the increase of the temperature, electrical resisitivity of the as-cast TiNiSn material decreased. Seebeck coefficient, heat conductivity, and ZT value increased. The mechanical experiment indicated that TiNiSn material was brittle material. Heat treatment could improve hardness of the material.
引文
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3马乔矢.半导体技术的应用和发展.沈阳建筑工程学院学报. 1999, (3): 37~41
4李喜贵,王运志,王海英等.热电材料的研究进展.河南师范大学学报(自然科学版). 2005, 33(3): 47~51
5刘宏,王继扬.半导体热电材料研究进展.功能材料. 2002, (2): 76~79
6许斌,王为.微型温差电器件及相关材料的研究现状.电源技术. 2006, (03): 24~27
7周芸,沈容,史庆南等.热电材料的最新进展.昆明理工大学学报(理工版). 2003, (3): 14~17
8张艳华,赵新兵,吉晓华.含镧的Bi2Te3基化合物的溶剂热合成及微观结构.中国稀土学报. 1997, (4): 7~9
9彭江英,杨君友,陈跃华等.机械球磨和烧结制备CoSb3的工艺研究.材料科学与工艺. 2005, 4(2): 112~116
10 G. S. Nolas, G. A. Slack, and S. B. Schujan. Semiconductor Calthrates: a Phonon Glass Electron Crystal Material with Potential for Thermoelectric Applications. Semicond. Semimet. 2001, (69): 255~300
11 T. Caillat, J. P. Fleurial and A. Borshchevsky. Preparation and Thermo-electric Properties of Semiconducting Zn4Sb3. J. Phys. Chem. Solids. 1997, 7(58): 1119~1125
12李红星,赵新兵,李伟文.新型热电材料的研究进展.材料导报. 2002, 6(16): 20
13 M. G. Kanatzidis. The Role of Solid-state Chemistry in the Discovery of New Thermoelectric Materials. Semicond. Semimet. 2001, (62): 51~100
14毛顺杰,栾伟玲,黄琥等.氧化物热电材料的研究现状与应用.硅酸盐通报. 2005, (3): 59~62
15 I. Terasaki, Y. Sasago, and K. Uchinokura. Large Thermoelectric Power in NaCo2O4 Single Crystals. Phys. Rev. B.. 1997, (56): 685~687
16 A. Balandin, K. L. Wang. Significant Decrease of the Lattice Thermal Conductivity due to Phonon Confinement in a Freestanding Semiconductor Quantum Well. Phys. Rev. B.. 1998, (58): 1544~1549
17 G. Chen. Phonon Engineering in Nanostructures for Solid-state Energy Conversion. Mater. Sci. Eng.. 2000, (292): 155~161
18 G. J. Snyder, J. R. Lim, C. K. Huan, et al. Thermoelectric Micro-device Fabricated by a Mems-like Electro- chemical Process. Nature Materials. 2003, (2): 28~53
19崔红梅,刘虹,李霞等.水热共还原法合成一维Sb2Se3纳米单晶带和单晶棒.机械工程材料. 2005, (7): 61~64
20李玲玲,张丽鹏,于先进.热电材料的研究进展.山东陶瓷. 2007, (2): 19~22
21马秋花,路朋献. N型热电材料的研究现状.电工材料. 2005, (4): 34
22胡淑红. BiTe基材料的制备及其热电性能研究.浙江大学博士学位论文. 2001
23钟广学.半导体致冷器件及其应用.北京:科学出版社, 1989. 17
24顾永明,郭燕明.生长速度对N型和P型Bi-Te热电材料性能的影响.上海大学学报(自然科学版). 1999, (4): 315
25裴勇,钱兴华,蒋文涛.半导体制冷优化设计方法的理论分析.制冷与空调. 2005, (6): 36~38
26宋春梅,刘华军,黄荣进.高压合成纳米晶Bi(0.85)Sb(0.15)的低温热电性能.材料研究学报. 2007, (2): 126~129
27王丹,徐桂英,张春燕等.热压法制备P型Si0.8Ge0.2合金及其热电性能.装备制造技术. 2007, (4): 50~55
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