铝合金磷酸盐体系微弧氧化技术研究进展
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摘要
铝合金具有密度低、强度高、塑性好等优点,在航空航天、机械电子、车辆船舶等领域有着广泛的应用前景,但铝合金表面硬度低、耐蚀性较差,这限制了其更广泛的应用。采用磷酸盐电解液体系对铝合金表面进行微弧氧化处理生成氧化膜层,能够有效提高铝合金表面硬度、耐蚀性等性能,是近年来热门的表面处理技术。本文概述铝合金微弧氧化研究历程以及微弧氧化的机制,总结六偏磷酸钠、磷酸二氢钠等单一磷酸盐及其复合体系下铝合金微弧氧化在表面形貌、相组成、硬度厚度、耐蚀性方面的特点,指出目前磷酸盐体系下铝合金微弧氧化中存在一些问题,如因各牌号铝合金中Si、Zn、Mn等元素含量不同而导致的电解液作用机理不同、大型铝合金件局部区域微弧氧化处理困难从而导致处理后得到的微弧氧化膜层不均匀、铝合金微弧氧化膜层在一定厚度范围内会降低基体膜层的抗疲劳性等。今后的研究还需要在磷酸盐电解液体系中各组分的作用、电解液与基体铝合金作用的机理、基体铝合金各元素对微弧氧化过程的影响等方面继续探索。
Aluminum alloy has the advantages of low density,high strength and good plasticity. It has a wide application prospect in aerospace,mechanical electronics,vehicle ships and other fields. However,aluminum alloy surface has low hardness and poor corrosion resistance,which limit its wide application. Using micro-arc oxidation under phosphate electrolytic system to form oxide coating on aluminum alloy surface,it can effectively improve the surface hardness and corrosion resistance,and is a hot surface treatment technology in recent years. In this paper,the research process and the mechanism of micro-arc oxidation are introduced. Mainly summarizes the characteristics of micro-arc oxidation of aluminum alloy under single phosphates such as sodium hexametaphosphate,sodium dihydrogen phosphate,etc on surface topography,phase composition,the coating of hardness and thickness,corrosion resistance,as well as these characteristics in its composite system. It is indicated that micro-arc oxidation of aluminum alloy under the current phosphate system has some problems,such as the differences in the mechanism of electrolyte due to the different content of Si,Zn,Mn and other factors in various grades of aluminum alloy,the difficulty in the partial micro-arc oxidation treatment in the local region of large aluminum alloy parts,so as to result in the nonuniform micro-arc oxide coating after the treatment,which can decrease the fatigue resistance of the base coating in the thickness range,and the anti-fatigue property of the substrate coating will be reduced within a certain thickness range. Future research also needs to continue to explore the effects of various components in the phosphate electrolytic liquid system,the mechanism of interaction between electrolyte and matrix aluminum alloy,and the effects of matrix aluminum alloy elements on micro-arc oxidation process.
Aluminum alloy has the advantages of low density,high strength and good plasticity. It has a wide application prospect in aerospace,mechanical electronics,vehicle ships and other fields. However,aluminum alloy surface has low hardness and poor corrosion resistance,which limit its wide application. Using micro-arc oxidation under phosphate electrolytic system to form oxide coating on aluminum alloy surface,it can effectively improve the surface hardness and corrosion resistance,and is a hot surface treatment technology in recent years. In this paper,the research process and the mechanism of micro-arc oxidation are introduced. Mainly summarizes the characteristics of micro-arc oxidation of aluminum alloy under single phosphates such as sodium hexametaphosphate,sodium dihydrogen phosphate,etc on surface topography,phase composition,the coating of hardness and thickness,corrosion resistance,as well as these characteristics in its composite system. It is indicated that micro-arc oxidation of aluminum alloy under the current phosphate system has some problems,such as the differences in the mechanism of electrolyte due to the different content of Si,Zn,Mn and other factors in various grades of aluminum alloy,the difficulty in the partial micro-arc oxidation treatment in the local region of large aluminum alloy parts,so as to result in the nonuniform micro-arc oxide coating after the treatment,which can decrease the fatigue resistance of the base coating in the thickness range,and the anti-fatigue property of the substrate coating will be reduced within a certain thickness range. Future research also needs to continue to explore the effects of various components in the phosphate electrolytic liquid system,the mechanism of interaction between electrolyte and matrix aluminum alloy,and the effects of matrix aluminum alloy elements on micro-arc oxidation process.
引文
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[11]贾文攀.微弧氧化几何尺寸效应研究[D].哈尔滨:哈尔滨工业大学,2010.
[12]HUSSEIN R O,NIE X,NORTHWOOD D O.An investigation of ceramic coating growth mechanisms in plasma electrolytic oxidation(PEO)processing[J].Electrochimica Acta,2013,112(12):111-119.
[13]赵东山,牛宗伟,刘洪福.基于人工神经网络的微弧氧化膜层厚度预测模型的建立[J].材料导报,2013,27(4):158-162.
[14]牛宗伟,李明哲.GA-BP神经网络的钛合金微弧氧化膜层厚度预测模型的建立[J].电镀与涂饰,2015,34(7):381-385.
[15]MI T,JIANG B,LIU Z,et al.Plasma formation mechanism of micro-arc oxidation[J].Electrochimica Acta,2014,123(4):369-377.
[16]潘明强,狄士春.微弧氧化火花放电等离子体源的形成机制研究[J].稀有金属材料与工程,2011,40(2):333-338.
[17]YAHALOM J,ZAHAVI J.Experimental evaluation of some electrolytic breakdown hypotheses[J].Electrochimica Acta,1971,16(5):603-607.
[18]BOSTA M M S A,MA K J,CHIEN H H.The effect of MAOprocessing time on surface properties and low temperature infrared emissivity of ceramic coating on aluminium 6061 alloy[J].Infrared Physics&Technology,2013,60(5):323-334.
[19]HWANG I J,SHIN K R,LEE J S,et al.Formation of black ceramic layer on aluminum alloy by plasma electrolytic oxidation in electrolyte containing Na2WO4[J].Materials Transactions,2012,53(53):559-564.
[20]陈喜娣,蔡启舟,尹荔松.铝合金表面微弧氧化技术的研究现状及展望[J].轻合金加工技术,2014,42(7):12-18.
[21]周海晖,旷亚非,侯朝辉,等.LF4合金在磷酸盐-氢氧化钠溶液中的微弧氧化[J].湖南大学学报(自然科学版),2001,28(5):67-71.
[22]MU W,HAN Y.Study on micro-arc oxidized coatings on magnesium in three different electrolytes[J].Rare metal materials&engineering,2010,39(7):1129-1134.
[23]王双,郭锋,白海瑞,等.不同电解液体系中锆合金微弧氧化陶瓷层组织结构和耐磨性能[J].稀有金属材料与工程,2010,39(4):739-742.
[24]刘雁玲.活塞铝合金微弧氧化热障涂层生长及组织性能[D].西安:西安工业大学,2012.
[25]WASEKAR N P,JYOTHIRMAYI A,KRISHNA L R,et al.Effect of micro arc oxidation coatings on corrosion resistance of 6061-Al alloy[J].Journal of Materials Engineering&Performance,2008,17(5):708-713.
[26]SHEN D J,CAI J R,GUO C H,et al.Evolution of residual stresses in micro-arc oxidation ceramic coatings on 6061 AI alloy[J].Chinese Journal of Mechanical Engineering,2013,26(6):1149-1153.
[27]牛犇,张晓燕,孙涛,等.电解液体系对铸造铝合金微弧氧化陶瓷层组织和性能的影响[J].热加工工艺,2012,41(4):130-132.
[28]张欣宇,方明,吕江川,等.电解液参数对铝合金微弧氧化的影响[J].材料保护,2002,35(8):39-41.
[29]张宇,宋仁国.磷酸盐对铸造铝合金微弧氧化陶瓷涂层的影响[J].陶瓷学报,2017,38(4):507-510.
[30]文陈,郝雪龙,崔庆新,等.Fe2+浓度对2Al2铝合金微弧氧化膜性能的影响[J].中国表面工程,2017,30(5):67-73.
[31]费航军,张军斌,孙长涛,等.磷酸盐体系电解液对铝合金微弧氧化层性能影响研究[J].热加工工艺,2014,43(12):139-14.
[32]刘荣明,郭锋,娅娅.铝合金微弧氧化磷酸盐体系电解液研究及陶瓷层分析.[J].表面技术,2007,36(2):29-31.
[33]沈钰,苗景国,吴润.7075铝合金磷酸盐体系微弧氧化电解液的研究[J].轻合金加工技术,2015,43(7):45-49.
[34]王红美,尹艳丽,杜军,等.磷酸盐浓度对5083铝合金微弧氧化膜组织与耐腐蚀性能的影响[J].中国表面工程,2016,29(5):109-115.
[35]张潆月,蒋永峰,包晔峰,等.磷酸盐溶液中纯铝微弧氧化陶瓷层磨损特性研究[J].热加工工艺,2013,42(4):141-148.
[36]魏刚,韩新罡,雷其林,等.ZL114A微弧氧化膜层的耐蚀性能研究[J].热加工工艺,2017(14):180-182.
[37]张玉波,苗景国,沈钰,等.镁合金微弧氧化电解液配方研究进展[J].轻合金加工技术,2015,43(9):13-17.
[38]WANG P,WU T,XIAO Y T,et al.Effect of Al2O3micropowder additives on the properties of micro-arc oxidation coatings formed on 6061 aluminum alloy[J].Journal of Materials Engineering&Performance,2016,25(9):1-5.
[39]崔丽华,郝建民.压铸铝合金微弧氧化膜微观形貌和结构表征[J].2013,42(12):134-137.
[40]但敏,童洪辉,沈丽如,等.六偏磷酸钠对LD7铝合金微弧氧化陶瓷膜结构及耐腐蚀性能的改善应用[J].材料保护,2011,44(5):11-13.
[41]刘亚娟,徐晋勇,高成,等.铝合金微弧氧化技术的研究进展[J].材料导报,2010,24(16):217-220.
[42]帅刚,马世宁,邱骥,等.大型铝合金件焊接区微弧氧化技术研究进展[J].特种铸造及有色合金,2015,35(7):709-713.
[43]蒋百灵,刘东杰.制约微弧氧化技术应用开发的几个科学问题[J].中国有色金属学报,2011,21(10):2402-2407.
[2]伍婷,龚成龙,王平.中国微弧氧化技术研究进展[J].热加工工艺,2015,44(24):16-19.
[3]张文华,胡正前,马晋.俄罗斯微弧氧化技术研究进展[J].轻合金加工技术,2004,32(1):25-29.
[4]王彩丽,赵立新,邵忠财.铝合金、镁合金微弧氧化功能陶瓷膜的研究进展[J].电镀与环保,2008,28(6):4-7.
[5]王晓波,田修波,巩春志,等.一种低能耗微弧氧化电解液的设计方法[J].表面技术,2012,41(5):85-88.
[6]白照高,闵雪涛.微弧氧化技术的应用与发展[J].热加工工艺,2015,44(6):12-14.
[7]薛文彬,邓志威,来永春.铝合金微弧氧化陶瓷膜的形成过程及其特性[J].电镀与精饰,1996,18(5):3-6.
[8]邓志威,来永春,薛文彬,等.微弧氧化材料表面陶瓷化机理的探讨[J].原子核物理评论,1997,14(3):193-195.
[9]蒋百灵,白力静,蒋永峰,等.铝合金微弧氧化技术[J].西安理工大学学报,2000,16(2):138-142.
[10]WANG Z X,LV W G,CHEN J,et al.Characterization of ceramic coating on ZK60 magnesium alloy prepared in a dual electrolyte system by micro-arc oxidation[J].Rare Metals,2013,32(5):459-464.
[11]贾文攀.微弧氧化几何尺寸效应研究[D].哈尔滨:哈尔滨工业大学,2010.
[12]HUSSEIN R O,NIE X,NORTHWOOD D O.An investigation of ceramic coating growth mechanisms in plasma electrolytic oxidation(PEO)processing[J].Electrochimica Acta,2013,112(12):111-119.
[13]赵东山,牛宗伟,刘洪福.基于人工神经网络的微弧氧化膜层厚度预测模型的建立[J].材料导报,2013,27(4):158-162.
[14]牛宗伟,李明哲.GA-BP神经网络的钛合金微弧氧化膜层厚度预测模型的建立[J].电镀与涂饰,2015,34(7):381-385.
[15]MI T,JIANG B,LIU Z,et al.Plasma formation mechanism of micro-arc oxidation[J].Electrochimica Acta,2014,123(4):369-377.
[16]潘明强,狄士春.微弧氧化火花放电等离子体源的形成机制研究[J].稀有金属材料与工程,2011,40(2):333-338.
[17]YAHALOM J,ZAHAVI J.Experimental evaluation of some electrolytic breakdown hypotheses[J].Electrochimica Acta,1971,16(5):603-607.
[18]BOSTA M M S A,MA K J,CHIEN H H.The effect of MAOprocessing time on surface properties and low temperature infrared emissivity of ceramic coating on aluminium 6061 alloy[J].Infrared Physics&Technology,2013,60(5):323-334.
[19]HWANG I J,SHIN K R,LEE J S,et al.Formation of black ceramic layer on aluminum alloy by plasma electrolytic oxidation in electrolyte containing Na2WO4[J].Materials Transactions,2012,53(53):559-564.
[20]陈喜娣,蔡启舟,尹荔松.铝合金表面微弧氧化技术的研究现状及展望[J].轻合金加工技术,2014,42(7):12-18.
[21]周海晖,旷亚非,侯朝辉,等.LF4合金在磷酸盐-氢氧化钠溶液中的微弧氧化[J].湖南大学学报(自然科学版),2001,28(5):67-71.
[22]MU W,HAN Y.Study on micro-arc oxidized coatings on magnesium in three different electrolytes[J].Rare metal materials&engineering,2010,39(7):1129-1134.
[23]王双,郭锋,白海瑞,等.不同电解液体系中锆合金微弧氧化陶瓷层组织结构和耐磨性能[J].稀有金属材料与工程,2010,39(4):739-742.
[24]刘雁玲.活塞铝合金微弧氧化热障涂层生长及组织性能[D].西安:西安工业大学,2012.
[25]WASEKAR N P,JYOTHIRMAYI A,KRISHNA L R,et al.Effect of micro arc oxidation coatings on corrosion resistance of 6061-Al alloy[J].Journal of Materials Engineering&Performance,2008,17(5):708-713.
[26]SHEN D J,CAI J R,GUO C H,et al.Evolution of residual stresses in micro-arc oxidation ceramic coatings on 6061 AI alloy[J].Chinese Journal of Mechanical Engineering,2013,26(6):1149-1153.
[27]牛犇,张晓燕,孙涛,等.电解液体系对铸造铝合金微弧氧化陶瓷层组织和性能的影响[J].热加工工艺,2012,41(4):130-132.
[28]张欣宇,方明,吕江川,等.电解液参数对铝合金微弧氧化的影响[J].材料保护,2002,35(8):39-41.
[29]张宇,宋仁国.磷酸盐对铸造铝合金微弧氧化陶瓷涂层的影响[J].陶瓷学报,2017,38(4):507-510.
[30]文陈,郝雪龙,崔庆新,等.Fe2+浓度对2Al2铝合金微弧氧化膜性能的影响[J].中国表面工程,2017,30(5):67-73.
[31]费航军,张军斌,孙长涛,等.磷酸盐体系电解液对铝合金微弧氧化层性能影响研究[J].热加工工艺,2014,43(12):139-14.
[32]刘荣明,郭锋,娅娅.铝合金微弧氧化磷酸盐体系电解液研究及陶瓷层分析.[J].表面技术,2007,36(2):29-31.
[33]沈钰,苗景国,吴润.7075铝合金磷酸盐体系微弧氧化电解液的研究[J].轻合金加工技术,2015,43(7):45-49.
[34]王红美,尹艳丽,杜军,等.磷酸盐浓度对5083铝合金微弧氧化膜组织与耐腐蚀性能的影响[J].中国表面工程,2016,29(5):109-115.
[35]张潆月,蒋永峰,包晔峰,等.磷酸盐溶液中纯铝微弧氧化陶瓷层磨损特性研究[J].热加工工艺,2013,42(4):141-148.
[36]魏刚,韩新罡,雷其林,等.ZL114A微弧氧化膜层的耐蚀性能研究[J].热加工工艺,2017(14):180-182.
[37]张玉波,苗景国,沈钰,等.镁合金微弧氧化电解液配方研究进展[J].轻合金加工技术,2015,43(9):13-17.
[38]WANG P,WU T,XIAO Y T,et al.Effect of Al2O3micropowder additives on the properties of micro-arc oxidation coatings formed on 6061 aluminum alloy[J].Journal of Materials Engineering&Performance,2016,25(9):1-5.
[39]崔丽华,郝建民.压铸铝合金微弧氧化膜微观形貌和结构表征[J].2013,42(12):134-137.
[40]但敏,童洪辉,沈丽如,等.六偏磷酸钠对LD7铝合金微弧氧化陶瓷膜结构及耐腐蚀性能的改善应用[J].材料保护,2011,44(5):11-13.
[41]刘亚娟,徐晋勇,高成,等.铝合金微弧氧化技术的研究进展[J].材料导报,2010,24(16):217-220.
[42]帅刚,马世宁,邱骥,等.大型铝合金件焊接区微弧氧化技术研究进展[J].特种铸造及有色合金,2015,35(7):709-713.
[43]蒋百灵,刘东杰.制约微弧氧化技术应用开发的几个科学问题[J].中国有色金属学报,2011,21(10):2402-2407.