铝合金阳极氧化耐磨防腐涂层制备与性能研究
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摘要
介绍了铝合金阳极氧化的多种分类方法、阳极氧化机理、铝合金阳极氧化的新进展，重点介绍了铝合金阳极氧化中应用最广泛的两种：普通阳极氧化和硬质阳极氧化，这两种阳极氧化根据应用场合的不同，具备不同的性能要求，两种阳极氧化的工艺也有所差异。
针对国内在特殊场合对铝合金耐磨性、耐腐蚀性的高要求，结合铝合金阳极氧化工艺以及阳极氧化膜多孔的特点，本文分别在阳极氧化电解液中添加耐磨性物质n-SiC和减磨性物质PTFE，使之进入到铝合金阳极氧化膜中，达到提高耐磨性或耐腐蚀性的性能要求。
使用正交实验方法优化了复合阳极氧化工艺参数，得到了添加n-SiC复合阳极氧化最佳工艺方案为：温度20℃，n-SiC添加量20 mg／L，电流密度2A／dm~2，氧化总时间40 min；添加PTFE复合阳极氧化最佳工艺方案为：温度10℃、PTFE体积含量15％、电流密度2A／dm~2、氧化总时间40 min。
运用测厚仪、显微硬度仪、金相显微镜对普通氧化膜、硬质氧化膜、添加SiC复合氧化膜、添加PTFE复合氧化膜等四种氧化膜的表面、横截面作了分析和研究。运用扫描电镜和X射线能谱仪证实了n-SiC和PTFE已经进入了氧化膜中。运用磨损试验机、盐雾腐蚀试验箱对复合阳极氧化膜性能作了性能检测，通过耐磨性检测表明添加n-SiC可以提高耐磨性，使复合阳极氧化膜变得耐磨；添加PTFE可以起到减摩的功用，磨损量大大减少，在载荷10牛顿时摩擦系数降到0.13：对耐腐蚀性的检测表明添加n-SiC或添加PTFE都延长了耐腐蚀时间，添加n-SiC复合氧化膜的耐腐蚀时间为207小时，添加PTFE复合氧化膜的耐腐蚀时间为210小时。
Variety classification methods, anode oxidize mechanism, progress of anode oxidize aluminium alloy are introduced. Two kinds of aluminium alloy anodic oxidation, common anodic oxidation and hard anodic oxidation are introduced in this paper. The two kinds of anodic oxidation have different performances and different process according to applying occasion.
Especially for high anti-wear and anti-corrosion of aluminium alloy film in peculiar field of china ,we study on anode oxidize aluminium alloy technics and porous aluminium alloy,then add abrasion resistance matter n-SiC or PTFE to oxidize electrolyte ,let n-SiC or PTFE deposit in the aluminium alloy film.the film get good wearable and anti-corrosive.
The orthogonality experiment method has been used to optimize the technological parameters of the composite anode oxidize,addition n-SiC technological parameters show that: Temperature 20℃、n-SiC 20 mg/L、 current density 2 A/dm~2、oxide general time 40 minutes ; addition PTFE technological parameter show that: Temperature 10℃、PTFE 15% of the whole volume、current density 2 A/dm2、oxide general time 40 minutes.
These surfaces and interfaces of common anode oxide coating、hard anode oxide coating、addition n-SiC composite anode oxidize coating and addition PTFE composite anode oxidize coating were investigated by these instruments such as thickness measuring instrument 、 micro hardness instrument 、 metallographic microscope. SEM and EDS instrument have confirmed that SiC and PTFE had already entered into the oxidized film. After detecting those anode oxidize film performance by abrasion tester and salt fog corrosion ,the abrasion resistance detecting indicates that addition n-SiC can improve anti-wear,and addition PTFE can arriving at friction reducing,the friction coefficients can lowered to 0.13.And salt fog corrosion detecting indicates that addition n-SiC or addition PTFE can prolong corrosion resistance time: addition n-SiC composite anode oxidize can bear 207 hours , addition PTFE composite anode oxidize can bear 210 hours.
针对国内在特殊场合对铝合金耐磨性、耐腐蚀性的高要求，结合铝合金阳极氧化工艺以及阳极氧化膜多孔的特点，本文分别在阳极氧化电解液中添加耐磨性物质n-SiC和减磨性物质PTFE，使之进入到铝合金阳极氧化膜中，达到提高耐磨性或耐腐蚀性的性能要求。
使用正交实验方法优化了复合阳极氧化工艺参数，得到了添加n-SiC复合阳极氧化最佳工艺方案为：温度20℃，n-SiC添加量20 mg／L，电流密度2A／dm~2，氧化总时间40 min；添加PTFE复合阳极氧化最佳工艺方案为：温度10℃、PTFE体积含量15％、电流密度2A／dm~2、氧化总时间40 min。
运用测厚仪、显微硬度仪、金相显微镜对普通氧化膜、硬质氧化膜、添加SiC复合氧化膜、添加PTFE复合氧化膜等四种氧化膜的表面、横截面作了分析和研究。运用扫描电镜和X射线能谱仪证实了n-SiC和PTFE已经进入了氧化膜中。运用磨损试验机、盐雾腐蚀试验箱对复合阳极氧化膜性能作了性能检测，通过耐磨性检测表明添加n-SiC可以提高耐磨性，使复合阳极氧化膜变得耐磨；添加PTFE可以起到减摩的功用，磨损量大大减少，在载荷10牛顿时摩擦系数降到0.13：对耐腐蚀性的检测表明添加n-SiC或添加PTFE都延长了耐腐蚀时间，添加n-SiC复合氧化膜的耐腐蚀时间为207小时，添加PTFE复合氧化膜的耐腐蚀时间为210小时。
Variety classification methods, anode oxidize mechanism, progress of anode oxidize aluminium alloy are introduced. Two kinds of aluminium alloy anodic oxidation, common anodic oxidation and hard anodic oxidation are introduced in this paper. The two kinds of anodic oxidation have different performances and different process according to applying occasion.
Especially for high anti-wear and anti-corrosion of aluminium alloy film in peculiar field of china ,we study on anode oxidize aluminium alloy technics and porous aluminium alloy,then add abrasion resistance matter n-SiC or PTFE to oxidize electrolyte ,let n-SiC or PTFE deposit in the aluminium alloy film.the film get good wearable and anti-corrosive.
The orthogonality experiment method has been used to optimize the technological parameters of the composite anode oxidize,addition n-SiC technological parameters show that: Temperature 20℃、n-SiC 20 mg/L、 current density 2 A/dm~2、oxide general time 40 minutes ; addition PTFE technological parameter show that: Temperature 10℃、PTFE 15% of the whole volume、current density 2 A/dm2、oxide general time 40 minutes.
These surfaces and interfaces of common anode oxide coating、hard anode oxide coating、addition n-SiC composite anode oxidize coating and addition PTFE composite anode oxidize coating were investigated by these instruments such as thickness measuring instrument 、 micro hardness instrument 、 metallographic microscope. SEM and EDS instrument have confirmed that SiC and PTFE had already entered into the oxidized film. After detecting those anode oxidize film performance by abrasion tester and salt fog corrosion ,the abrasion resistance detecting indicates that addition n-SiC can improve anti-wear,and addition PTFE can arriving at friction reducing,the friction coefficients can lowered to 0.13.And salt fog corrosion detecting indicates that addition n-SiC or addition PTFE can prolong corrosion resistance time: addition n-SiC composite anode oxidize can bear 207 hours , addition PTFE composite anode oxidize can bear 210 hours.
引文
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[3] 董允，张廷森，林晓娉．现代表面工程技术[M]．北京：机械工业出版社，2000．
[4] 王祝堂主编．铝材及其表面处理手册[M]．江苏：江苏科学技术出版社，1992．
[5] 林春华、葛祥荣等编．简明表面处理手册[M]．北京：机械工业出版社，1995．
[6] 马骏，赵占西，苏冬云．铸铝合金硬质阳极氧化工艺分析及改进[J]．表面技术，2006，35(6)：30-31．
[7] 王祝堂，田荣璋．铝合金及其加工手册[M]．长沙：中南大学出版社，2000．
[8] 刘静安，谢水生．铝合金材料的应用与技术开发[M]．北京：冶金工业出版社，2004．
[9] 谭昌瑶，王钧石．实用表面工程技术[M]．北京：新时代出版社，1998．
[10] 刘磊．铝合金常温脉冲硬质阳极氧化工艺及其组织性能研究[D]．上海：上海交通大学硕士学位论文，2000．
[11] K. Habib. Measurement of the a. c. Impedance of Aluminium Samples by Holographic Interferometry [J]. Optics and Lasers in Engineering, 1997, 28: 37-46.
[12] 徐滨士，刘世参．表面工程新技术[M]．北京：国防工业出版社，2002．
[13] K. R. Brown, M. S. Venie, R. A. Woods. The increasing use of aluminum in automotive applications [J]. JOM, July 1995: 20-23.
[14] 顾建成．6061铝合金的脉冲阳极氧化工艺及氧化膜微观组织和性能的研究[D]．上海：上海交通大学博士后论文，2002．
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[16] 曾晓雁、吴懿平．表面工程学[M]．北京：机械工业出版社，2000．
[17] 姚寿山等．表面科学与技术[M]．北京：机械工业出版社，2004．
[18] 《表面处理工艺手册》编审委员会．表面处理工艺手册[M]．上海：上海科学技术出版社，1988．
[19] 董允等．现代表面工程技术[M]．北京：机械工业出版社，1999．
[20] 蔡千华编译．铝的表面处理[J]．国外金属热处理，2005，26(1)．
[21] M Textor, M Amstutz. Surface analysis of thin films and interfaces in commercial aluminium products[J]. Analytica Chimiea Acta, 1994, 297: 15-26.
[22] I Vrublevsky. Study of chemical dissolution of the barrier oxide layer of porous alumina films formed in oxalic acid using a re-anodizing technique[J]. Applied Surface Science 2004, 236: 270-277.
[23] Ewa Wa ckelgard. A comparative study of the optical properties of nickel pigmented alumina films of different thicknesses exposed to elevated temperature and humidity [J]. Solar Energy Materials and Solar Cells, 1998, 54: 171-179.
[24] 董首山．化学转化膜[J]．腐蚀科学与防护技术，1990，56：44．
[25] Per Nostell, Ame Roos, Bjom Karlsson. Ageing of solar booster reflector materials [J]. Solar Energy Materials and Solar Cells, 1998, 54: 235-246.
[26] H. Habazaki. Formation of amorphous anodic oxide films of controlled composition on aluminium alloys[J]. Thin Solid Films, 1997, 300: 131-137.
[27] 钱苗根，姚寿山，张少宗．现代表面技术[M]．北京：机械工业出版社，1999．60-67．
[28] 王平．多孔型阳极氧化膜的形成机理[J]．材料保护，2005(6)：28-29．
[29] Yunxin Wu. A study of the optimization mechanism of solid lubricant concentration in Ni/MoS_2 self-lubricating composite[J]. Wear, 1997, 205: 64-70.
[30] A. Johansson~*, T. Tomdahl, L. M. Ottosson, M. Boman. Copper nanoparticles deposited inside the pores of anodized aluminium oxide using atomic layer deposition[J]. Materials Science and Engineering, 2003, 23: 823-826.
[31] 刘复兴，夏正才．铝合金阳极氧化膜膜孔微观结构研究[J]．MATERIALS PROTECTION，1994，27(1)．
[32] 刘爱民，李荣强，吴厚昌．铝合金硬质阳极氧化技术的现代进展[J]．材料保护，1997，30(11)：12-15．
[33] GB10125—88 人造气氛中的腐蚀试验 盐雾试验(SS试验)．
[34] Yasuo Kudoh. Covering anodized aluminum with electropolymerized polypyrrole via manganese oxide layer and application to solid electrolytic capacitor[J]. Journal of Power Sources, 1996, 60: 157-163.
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