煅烧工艺对钽粉微观结构和电性能的影响
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摘要
采用K_2TaF_7金属钠还原—高温高真空煅烧—镁还原脱氧工艺制备了电容器用高比容钽粉,系统研究了高真空和一定的升温速率下,煅烧温度、煅烧时间对钽粉微观结构和高压电性能的影响。用场发射式扫描电镜(FESEM)、BET分析仪和激光粒度分布仪(LDSA)对电容器用高比容钽粉的微观结构进行表征,对该钽粉制成的烧结阳极的湿式电性进行检测。结果表明:随着煅烧温度的升高或煅烧时间的延长,粉末团聚体的尺寸增大,烧结颈变粗,团聚体的大小趋于均匀一致,团聚体之间微细孔隙明显减少;钽粉烧结阳极的电性能在高压(大于55 V)形成时得到优化,表现为漏电流(LC)小,容量(CV)高,损耗(tgδ)小,但低压(小于40 V)形成时钽粉烧结阳极的容量(CV)低。研究认为,比表面积介于1.30~1.50 m~2·g~(-1)的还原粉在1300℃煅烧40 min,钽粉综合性能最优。
Tantalum powder with high capacitance employing capacitor was prepared by K_2TaF_7 sodium metal reduction,high temperature and high vacuum calcining and magnesium reductive deoxygenating technology. The effects of calcining temperature and residence time on the microstructure of tantalum powder and high voltage electrical property under high vacuum and certain heating rate were studied systematically. Microstructure of tantalum powder with high capacitance was characterized by field emission scanning electron microscopy( FESEM),BET and laser particle size analyzer( LDSA) and the wet electrical property of sintering anode mading of tantalum powder was tested. The results showed that with the increase of calcining temperature and residence time the size of aggregate increased,the sintering neck coarsened,the size of aggregate tended to be uniform and the fine pores between aggregate decreased significantly. The performance of tantalum powder sintering anode was optimized at high formation voltage( greater than 55 V) characterized by small leakage current( LC),high capacity( CV) and small loss( tgδ),but the tantalum powder sintering anode formed at low voltage( less than 40 V) had low capacity( CV). Research suggested that reductive tantalum powder with specific area of 1. 40 m~2·g~(-1) and calcined under 1300 ℃ for 40 min had the best comprehensive performance.
Tantalum powder with high capacitance employing capacitor was prepared by K_2TaF_7 sodium metal reduction,high temperature and high vacuum calcining and magnesium reductive deoxygenating technology. The effects of calcining temperature and residence time on the microstructure of tantalum powder and high voltage electrical property under high vacuum and certain heating rate were studied systematically. Microstructure of tantalum powder with high capacitance was characterized by field emission scanning electron microscopy( FESEM),BET and laser particle size analyzer( LDSA) and the wet electrical property of sintering anode mading of tantalum powder was tested. The results showed that with the increase of calcining temperature and residence time the size of aggregate increased,the sintering neck coarsened,the size of aggregate tended to be uniform and the fine pores between aggregate decreased significantly. The performance of tantalum powder sintering anode was optimized at high formation voltage( greater than 55 V) characterized by small leakage current( LC),high capacity( CV) and small loss( tgδ),but the tantalum powder sintering anode formed at low voltage( less than 40 V) had low capacity( CV). Research suggested that reductive tantalum powder with specific area of 1. 40 m~2·g~(-1) and calcined under 1300 ℃ for 40 min had the best comprehensive performance.
引文
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[13]Liu Y G,Yi J F.The influence of forming sintering process on the electrical properties of tantalum capacitors with solid electrolyte[J].Rare Metals and Cemented Carbides.2008,36(4):17.(刘勇刚,易金锋.成形烧结过程对固体电解质钽电容器电性能的影响[J].稀有金属与硬质合金,2008,36(4):17.)
[14]Wu Z Z,Yao W D,Yuan K Y.Influence of oxygen content on the formation of anode oxide film and leakage current of tantalum electrolytic capacitor[J].Rare Metals and Cemented Carbides,2006,34(2):32.(伍尊中,姚卫东,袁坤阳.氧含量对钽电解电容器阳极氧化膜形成及漏电流的影响[J].稀有金属与硬质合金,2006,34(2):32.)
[15]Hou B F,Zhan Y Z,Ma C Y.Research on application of 100 m F·V·g-1tantalum powder in tantalum chip capacitor[J].EIectronics Process Techno Iogy,2006,27(3):141.(侯宝峰,湛永中,马翠英.100 m F·V·g-1钽粉在片式钽电容器上的应用研究[J].电子工艺技术,2006,27(3):141.)
[2]He J L,Zhang X Q,Yang G Q,Zheng A G.The key technique and R&D of capacitor grade tantalum powder[J].Materials China,2014,33(9-10):545.(何季麟,张学清,杨国启,郑爱国.电容器级钽粉关键技术与开发研究[J].中国材料进展,2014,33(9-10):545.)
[3]Guo S J.Powder Sintering Theory[M].Beijing:Metallurgical Industry Press,2002.165.(果世驹.粉末烧结理论[M].北京:冶金工业出版社,2002.165.)
[4]Chen L,Mao H H,Dong X C,Cheng Y W,Ren P,Luo G Q,Lin F K,Wang Z D,Zhang X Q,Liang H Y,Wang Z Q,Wang Q Y.The method of tantalum powder heat treatment[P].China Patent:CN 102120258 A,2011.(陈林,冒海红,董学成,程越伟,任凭,雒国清,林辅坤,王治道,张学清,梁宏原,王志清,王秋迎.钽粉的热处理方法[P].中国专利:CN102120258 A,2011.)
[5]Pan L T.A method and equipment of tantalum surface passivation[P].China Patent:CN102181818 A,2011.(潘伦桃.钽金属表面钝化方法及装置[P].中国专利:CN102181818 A,2011.)
[6]Pan L T.An equipment of tantalum surface passivation with the refrigerating apparatus[P].China Patent:CN202063985 U.2011.(潘伦桃.具有制冷装置的钽金属表面钝化装置[P].中国专利:CN 202063985 U.2011.)
[7]Li J Y,Sun B S,Wang D X,Ren X,He J L.Effects of oxygen content on morphology and capacity of tantalum powder by FFC process[J].Rare Metal Materials and Engineering,2013,42(4):849.(李军义,孙本双,王东新,任晓,何季麟.氧含量对FFC法制备钽粉形貌和电容的影响[J].稀有金属材料与工程,2013,42(4):849.)
[8]Pan L T,Zheng A G,Ma Y Z,Wang Z D.The method of valve metal powder doped with nitrogen to obtain the nitrogen-containing tantalum powder and nitrogencontaining niobium powder[P].China Patent:CN10113510A,2008.(潘伦桃,郑爱国,马跃忠,王治道.阀金属粉末的掺氮方法及由此获得的含氮钽粉和含氮铌粉[P].中国专利:CN 10113510A,2008.)
[9]Huang P Y.Principle of the Powder Metallurgy[M].Beijing:Metallurgical Industry Press,1997.265.(黄培云.粉末冶金原理[M].北京:冶金工业出版社,1997.265.)
[10]He J L,Pan L T,Lu Z D,Shi W F,Shu Y C,Zeng F P.Observation on morphology of sodium reduced tantalum powders and modifications to their physical properties[J].Ningxia Engineering Technology,2002,1(1):23.(何季麟,潘伦桃,卢振达,施文锋,舒永春,曾芳屏.钠还原钽粉围观形态的观察及物理性能的调控[J].宁夏工程技术,2002,1(1):23.)
[11]Wang W D,Chen W Q.The research of solid tantalum electrolytic capacitor leakage current[J].Advanced Measurement and Laboratory Management,2010,5:13.(王卫栋,陈伟强.固体钽电解电容器漏电流的研究[J].现代测量与实验室管理,2010,5:13.)
[12]Liu J X,Xiao D C,Wang B R.Failure analysis of tantalum capacitors[J].Electronic Components&Materials,2014,23(3):3.(刘家欣,肖大雏,王宾如.片状钽电容器失效分析[J].电子元件与材料.2014,23(3):3.)
[13]Liu Y G,Yi J F.The influence of forming sintering process on the electrical properties of tantalum capacitors with solid electrolyte[J].Rare Metals and Cemented Carbides.2008,36(4):17.(刘勇刚,易金锋.成形烧结过程对固体电解质钽电容器电性能的影响[J].稀有金属与硬质合金,2008,36(4):17.)
[14]Wu Z Z,Yao W D,Yuan K Y.Influence of oxygen content on the formation of anode oxide film and leakage current of tantalum electrolytic capacitor[J].Rare Metals and Cemented Carbides,2006,34(2):32.(伍尊中,姚卫东,袁坤阳.氧含量对钽电解电容器阳极氧化膜形成及漏电流的影响[J].稀有金属与硬质合金,2006,34(2):32.)
[15]Hou B F,Zhan Y Z,Ma C Y.Research on application of 100 m F·V·g-1tantalum powder in tantalum chip capacitor[J].EIectronics Process Techno Iogy,2006,27(3):141.(侯宝峰,湛永中,马翠英.100 m F·V·g-1钽粉在片式钽电容器上的应用研究[J].电子工艺技术,2006,27(3):141.)