微弧氧化法制备二氧化钛陶瓷膜及其性质研究
摘要
通过对不同能量参数及不同电解液组分条件下制备的钛合金微弧氧化膜层表面及截面形貌的分析,探讨了陶瓷层的生长过程及影响钛合金微弧氧化膜层表面形貌变化的因素。研究表明:微弧氧化膜层的表面形貌及生长过程受控于能量参数的模式选择,在恒定的电参数下随着氧化时间的延长,膜层表面的微孔直径增大,微孔间的孔径偏差增大,孔的数量减少;电流密度、电压和占空比对微弧氧化膜层形貌的影响规律与氧化时间对其的影响相似;随脉冲频率的增加,孔的数量增加,膜层表面的微孔直径减小,微孔间的孔径偏差减小,粗糙度值降低。与此同时,电解液的组分对也是至关重要的因素,由实验分析可知,在磷酸盐电解液中制得的二氧化钛薄膜的各项性能要好于比其他电解液中制备的陶瓷膜
The growth process of ceramic coatings formed by micro-arc oxidation on titanium were studied by the analysis of the surface and sectional pattern for ceramic coatings that treated by different electrical parameter and electrolyte.
The results indicate that the choice and control of electrical parameter play a key role in the surface morphology and growth of ceramic coatings.With the Prolonging oxidation time the micropores number on the surface of the coatings decreases obviously, while the size and the deviation of micropores increases under constant electrical parameters.The current density、voltage and duty cycle have a influencing rule to morphology of ceramic coatings were similar to oxidation time.As the frequency increased, the micropores number on the surface of the coatings increases, the Pores size and the deviation of mieropores decreased, so did the surface roughness. At the same time, the impact of the electrolyte is also essential. By the experimental analysis we concluded that the performance of the ceramic coatings which was treated in the phosphate electrolyte was better than the others.
The growth process of ceramic coatings formed by micro-arc oxidation on titanium were studied by the analysis of the surface and sectional pattern for ceramic coatings that treated by different electrical parameter and electrolyte.
The results indicate that the choice and control of electrical parameter play a key role in the surface morphology and growth of ceramic coatings.With the Prolonging oxidation time the micropores number on the surface of the coatings decreases obviously, while the size and the deviation of micropores increases under constant electrical parameters.The current density、voltage and duty cycle have a influencing rule to morphology of ceramic coatings were similar to oxidation time.As the frequency increased, the micropores number on the surface of the coatings increases, the Pores size and the deviation of mieropores decreased, so did the surface roughness. At the same time, the impact of the electrolyte is also essential. By the experimental analysis we concluded that the performance of the ceramic coatings which was treated in the phosphate electrolyte was better than the others.
引文
[1]薛文斌,邓志威,等.有色金属表面微弧氧化技术评述[J].金属热处理.2000:1-3
[2]高殿奎,姜桂英,等.铝合金微弧氧化陶瓷层石墨相的形成及作用[J].表面技术2001,30(4):28-29
[3]宋希剑,秦东,等.铸造高硅铝合金表面微弧氧化陶瓷层的耐磨性[J].材料保护.2000,33(4):51-52
[4]姜兆华,辛世刚,等.铝合金在水玻璃KOH-NaAIO_2体系中的微等离子体氧化[J],中国有色金属学报2000,10(4):519-524
[5]贺子凯,蒋玉思,等.铝合金微弧氧化生成陶瓷膜的研究[J].昆明理工大学学报.2001,26(1):17-20
[6]刘兆晶,左洪波,等.铝合金表面陶瓷膜层形成机理[J].中国有色金属学报.2000,10(6):859-863
[7]李淑华,程金生,等.微弧氧化过程中电流和电压变化规律的探讨[J].特种铸造及有色合金.2001:4-5
[8]N.P.Sluginov.J.Russ.Phys.Chem.Soc.1880,12(1-2 Phys):193-194
[9]薛文斌,邓志威,来永春,陈如意,张通和.有色金属表面微弧氧化技术评述.金属热处理,2000,(1):1-3
[10]T.H.Teh,A.Berkani,S.Mato,P.Skeldon,G.E.Thompson,H.Habazaki,K.Shimizu.Initial stages of plasma electrolytic oxidation of titanium.2003,45(12):2757-2768
[11]辛世刚.LY12铝合金微等离子体氧化陶瓷膜的制备工艺与性能研究.[博士学位论文].哈尔滨工业大学,2003
[12]张欣宇,方明,石玉龙.处理液参数对铝合金微弧氧化的影响.材料保护.2002,35(8):39-41
[13]王宗仁,孔庆山,巩桂芬.铝合金表面陶瓷化对前处理的依赖性.电镀与精饰2002,24(3):15-18
[14]G.Sundararajan and L.Rama Krishna.Mechanisms underlying the formation of thick alumina coatings through the MAO coating technology.Surf.Coat.Technol.2003,167(2-3):269-277
[15]高殿魁,姜桂荣,沈德久,王玉林.微弧氧化减摩陶瓷层的生成及其影响因素.中国有色金属学报.2001,11(2):199-202
[16]袁洋,罗状子.铝合金表面微弧氧化耐磨润滑涂层.材料保护.2002,35(5):4-6
[17]Gu Wei-chao,Shen De-jiu,Wang Yu-lin,Chen Guang-liang,Feng Wen-ran,Zhang Gu-ling and Yang Si-ze.Deposition of duplex Al2O3/aluminum coatings on steel using a combined technique of arc spraying and plasma electrolytic oxidation.Appl.Sur.Sci.2006,252(8):2927-2932
[18]沈德久,廖波,王玉林.影响铝微弧氧化陶瓷层电绝缘性的工艺因素探讨.材料开发与应用.2002,12(4):22-24
[19]李尚义,赵克定,常同立,龚建军.铝合金微弧氧化技术在仿真转台用连续回转电液伺服马达中的应用研究.液压与气动.2004,(12):43-45
[20]王强,姜继海,吴盛林,李奎峰.微弧氧化技术在水压齿轮泵中的应用探讨.液压与气动.2005,(8):72-74
[21]Yang Guangliang,L(u|¨)Xianyi,Bai Yizhen,Cui Haifeng and Jin Zengsun.The effects of current density on the phase composition and microstructure properties of micro-arc oxidation coating.J.Alloys Compd.2002,345(1-2):196-200
[22]Tongbo Wei,Fengyuan Yan and Jun Tian.Characterization and wear-and corrosion-resistance of microarc oxidation ceramic coatings on aluminum alloy.J.Alloys Compd.2005,389(1-2):169-176
[23]D.L.Boguta,V.S.Rudnev,P.S.G.ordienko.Current mode effect on the composition and characteristics of anodic-spark coatings.Protect.Met.2004,40(3):275-279
[24]G.Sundararajan,L.Rama Krishna.Mechanisms underlying the formation of thick alumina coatings through the MAO coating technology.Surf.Coat.Technol.,2003,167(2-3):269-277
[25]王德云,冬青,陈传忠.微弧氧化技术的研究进展[J].硅酸盐学报.2005,33(9):1133-1138
[26]幸泽宽,唐恩军.TC4钛合金微弧阳极氧化膜层结构与性能的研究[J].材料保护.2005,38(12):54-57
[27]郝建民,陈宏,张荣军.镁合金微弧氧化陶瓷层的耐蚀性[J].中国有色金属学报.2003,13(4):988-991
[28]马威,刘宝林,魏建华.纯钛表面微弧氧化处理后的细胞毒性研究[J].中国新医药.2003,2(12):12-14
[29]李建中,邵忠财.微弧氧化技术在AlMgTi及其合金中的应用[J].腐蚀科学与防护技术.2004,16(4):218-221
[30]Eisenbarth E,Velten D,Schenk M K.Interactions between cells and titanium surfaces[J].Biomol Eng.2002,19(2-6):243-249
[31]Liu F,Song Y,Wang F.Formation characterization of hydroxyl apatite titanium by micro arc oxidation and hydrothermal treatment[J].JBiosci Bioeng.2005,100(1):100-104
[32]Gong D W,Craig A G,Varghese.Titanium oxide nanotube arrays prepared by anodic ox idation[J].J.Mater.Res.2001,16(12):3331-3334
[33]R.A.法西罗夫斯基,VN.凯斯特尔曼等.聚合物的胶粘作用[M].北京:化学工业出版社,2004:106-112
[34]毕冬梅,龙北玉.钛合金微弧氧化膜形成过程中的特性研究[J].云南大学学报.2005,27(5):548-551
[35]E.V.Parfenov,R.R.Nevyantseva and S.A.Oorbatkov.Process control for plasma electrolytic removal of TiN coatings.Surf.Coat.Technol.2005,199(2-3):198-204
[36]X.Nie,C.Tsotsos,A.Wilson,A.L.Yerokhin,A.Leyland and A.Matthews.Characteristics of a plasma electrolytic nitrocarburising treatment for stainless steels.Surf.Coat.Technol.2001,139(2-3):135-142
[37]C.Tsotsos,A.L.Yerokhin,A.D.Wilson,A.Leyland and A.Matthews.Tribological evaluation of AISI 304stainless steel duplex treated by plasma electrolytic nitrocarburising and diamond-like carbon coating.Wear.2002,253(9-10):986-993
[38]M.Tarakci,K.Korkmaz,Y.Gencer and M.Usta.Plasma electrolytic surfacecarburizing and hardening of pure iron.Surf.Coat.Technol.2005,199(2-3 ):205-212
[39]S.V.lvanov,N.S.Salmanov and M.N.Salmanov.Borosulfocabonitriding of cutting tools in electrolyte plasma.Met.Sci.Heat Treat.2002,44(9-10):405-406
[40]Xin-Mei Li and Yong Han.Porous nanocrystalline Ti(CxNl?x)thick films by plasma electrolytic carbonitriding.Electrochem.Commu.2006,8(2):267-272
[2]高殿奎,姜桂英,等.铝合金微弧氧化陶瓷层石墨相的形成及作用[J].表面技术2001,30(4):28-29
[3]宋希剑,秦东,等.铸造高硅铝合金表面微弧氧化陶瓷层的耐磨性[J].材料保护.2000,33(4):51-52
[4]姜兆华,辛世刚,等.铝合金在水玻璃KOH-NaAIO_2体系中的微等离子体氧化[J],中国有色金属学报2000,10(4):519-524
[5]贺子凯,蒋玉思,等.铝合金微弧氧化生成陶瓷膜的研究[J].昆明理工大学学报.2001,26(1):17-20
[6]刘兆晶,左洪波,等.铝合金表面陶瓷膜层形成机理[J].中国有色金属学报.2000,10(6):859-863
[7]李淑华,程金生,等.微弧氧化过程中电流和电压变化规律的探讨[J].特种铸造及有色合金.2001:4-5
[8]N.P.Sluginov.J.Russ.Phys.Chem.Soc.1880,12(1-2 Phys):193-194
[9]薛文斌,邓志威,来永春,陈如意,张通和.有色金属表面微弧氧化技术评述.金属热处理,2000,(1):1-3
[10]T.H.Teh,A.Berkani,S.Mato,P.Skeldon,G.E.Thompson,H.Habazaki,K.Shimizu.Initial stages of plasma electrolytic oxidation of titanium.2003,45(12):2757-2768
[11]辛世刚.LY12铝合金微等离子体氧化陶瓷膜的制备工艺与性能研究.[博士学位论文].哈尔滨工业大学,2003
[12]张欣宇,方明,石玉龙.处理液参数对铝合金微弧氧化的影响.材料保护.2002,35(8):39-41
[13]王宗仁,孔庆山,巩桂芬.铝合金表面陶瓷化对前处理的依赖性.电镀与精饰2002,24(3):15-18
[14]G.Sundararajan and L.Rama Krishna.Mechanisms underlying the formation of thick alumina coatings through the MAO coating technology.Surf.Coat.Technol.2003,167(2-3):269-277
[15]高殿魁,姜桂荣,沈德久,王玉林.微弧氧化减摩陶瓷层的生成及其影响因素.中国有色金属学报.2001,11(2):199-202
[16]袁洋,罗状子.铝合金表面微弧氧化耐磨润滑涂层.材料保护.2002,35(5):4-6
[17]Gu Wei-chao,Shen De-jiu,Wang Yu-lin,Chen Guang-liang,Feng Wen-ran,Zhang Gu-ling and Yang Si-ze.Deposition of duplex Al2O3/aluminum coatings on steel using a combined technique of arc spraying and plasma electrolytic oxidation.Appl.Sur.Sci.2006,252(8):2927-2932
[18]沈德久,廖波,王玉林.影响铝微弧氧化陶瓷层电绝缘性的工艺因素探讨.材料开发与应用.2002,12(4):22-24
[19]李尚义,赵克定,常同立,龚建军.铝合金微弧氧化技术在仿真转台用连续回转电液伺服马达中的应用研究.液压与气动.2004,(12):43-45
[20]王强,姜继海,吴盛林,李奎峰.微弧氧化技术在水压齿轮泵中的应用探讨.液压与气动.2005,(8):72-74
[21]Yang Guangliang,L(u|¨)Xianyi,Bai Yizhen,Cui Haifeng and Jin Zengsun.The effects of current density on the phase composition and microstructure properties of micro-arc oxidation coating.J.Alloys Compd.2002,345(1-2):196-200
[22]Tongbo Wei,Fengyuan Yan and Jun Tian.Characterization and wear-and corrosion-resistance of microarc oxidation ceramic coatings on aluminum alloy.J.Alloys Compd.2005,389(1-2):169-176
[23]D.L.Boguta,V.S.Rudnev,P.S.G.ordienko.Current mode effect on the composition and characteristics of anodic-spark coatings.Protect.Met.2004,40(3):275-279
[24]G.Sundararajan,L.Rama Krishna.Mechanisms underlying the formation of thick alumina coatings through the MAO coating technology.Surf.Coat.Technol.,2003,167(2-3):269-277
[25]王德云,冬青,陈传忠.微弧氧化技术的研究进展[J].硅酸盐学报.2005,33(9):1133-1138
[26]幸泽宽,唐恩军.TC4钛合金微弧阳极氧化膜层结构与性能的研究[J].材料保护.2005,38(12):54-57
[27]郝建民,陈宏,张荣军.镁合金微弧氧化陶瓷层的耐蚀性[J].中国有色金属学报.2003,13(4):988-991
[28]马威,刘宝林,魏建华.纯钛表面微弧氧化处理后的细胞毒性研究[J].中国新医药.2003,2(12):12-14
[29]李建中,邵忠财.微弧氧化技术在AlMgTi及其合金中的应用[J].腐蚀科学与防护技术.2004,16(4):218-221
[30]Eisenbarth E,Velten D,Schenk M K.Interactions between cells and titanium surfaces[J].Biomol Eng.2002,19(2-6):243-249
[31]Liu F,Song Y,Wang F.Formation characterization of hydroxyl apatite titanium by micro arc oxidation and hydrothermal treatment[J].JBiosci Bioeng.2005,100(1):100-104
[32]Gong D W,Craig A G,Varghese.Titanium oxide nanotube arrays prepared by anodic ox idation[J].J.Mater.Res.2001,16(12):3331-3334
[33]R.A.法西罗夫斯基,VN.凯斯特尔曼等.聚合物的胶粘作用[M].北京:化学工业出版社,2004:106-112
[34]毕冬梅,龙北玉.钛合金微弧氧化膜形成过程中的特性研究[J].云南大学学报.2005,27(5):548-551
[35]E.V.Parfenov,R.R.Nevyantseva and S.A.Oorbatkov.Process control for plasma electrolytic removal of TiN coatings.Surf.Coat.Technol.2005,199(2-3):198-204
[36]X.Nie,C.Tsotsos,A.Wilson,A.L.Yerokhin,A.Leyland and A.Matthews.Characteristics of a plasma electrolytic nitrocarburising treatment for stainless steels.Surf.Coat.Technol.2001,139(2-3):135-142
[37]C.Tsotsos,A.L.Yerokhin,A.D.Wilson,A.Leyland and A.Matthews.Tribological evaluation of AISI 304stainless steel duplex treated by plasma electrolytic nitrocarburising and diamond-like carbon coating.Wear.2002,253(9-10):986-993
[38]M.Tarakci,K.Korkmaz,Y.Gencer and M.Usta.Plasma electrolytic surfacecarburizing and hardening of pure iron.Surf.Coat.Technol.2005,199(2-3 ):205-212
[39]S.V.lvanov,N.S.Salmanov and M.N.Salmanov.Borosulfocabonitriding of cutting tools in electrolyte plasma.Met.Sci.Heat Treat.2002,44(9-10):405-406
[40]Xin-Mei Li and Yong Han.Porous nanocrystalline Ti(CxNl?x)thick films by plasma electrolytic carbonitriding.Electrochem.Commu.2006,8(2):267-272