钢铁表面微弧氧化技术的研究
|
摘要
微弧氧化是近年来在国内兴起的一种表面处理技术,它主要用于对铝、镁、钛等金属及其合金的表面改性处理,由于其工艺简单,处理的表面性能优越,其应用前景也被国内外业内人士十分看好。微弧氧化的概念提出于20世纪50年代,到70年代后期逐步引起国外学术界的研究兴趣,80年代开始成为国外学者的研究热点,目前国外在该技术上的实用化研究进展很快,并在某些领域开始尝试性应用。美、德、日、俄在这个方向的研究尚处于世界领先水平。我国直到90年代中期才开始关注这项技术的,技术水平相对比较落后。国内在钢铁表面进行微弧氧化研究主要是采用热浸镀铝的方法,其原理与铝合金表面微弧氧化相同,但这种方法存在一个致命的缺陷,就是其结合力不好,生成的陶瓷膜容易脱落。在钢铁表面进行微弧氧化,原位生成陶瓷膜,国内还没有人研究,国外研究的也很少。
本文首先对钢铁表面腐蚀、微弧氧化、钢铁表面热浸镀铝微弧氧化等机理进行了阐述,以此为基础,对钢铁表面微弧氧化原位生成陶瓷膜的机理进行了初步探索。然后以此原理为依据,对实验方案进行了设计,确定了在钢铁表面生成Al_2O_3陶瓷和在加工过程中采用以铝酸钠(NaAlO_2)、硅酸钠(Na_2SiO_3)和氢氧化钾(KOH)为主的混合工作液。并对工艺方法进行了探索,通过对钢铁表面直接微弧氧化、钢铁表面磷化处理后再进行微弧氧化、自然腐蚀后再进行微弧氧化等一系列工艺方法的研究,找到了在钢铁表面微弧氧化原位生成陶瓷膜的方法。最后采用扫描电镜(SEM)及X射线衍射相结构分析(XRD)对陶瓷氧化膜微观形貌及膜层结构进行分析,并对实验中的一些现象进行了解释。
Microarc oxidation is one of the surface treatment technology that recently arisen at home, it’s main used to surface modification on aluminous, magnesian, titanic and their alloy surface, because of the simpleness of its technical process and the predominant performance of treated surface, the applying prospect is very bullish by inside and outside insider. The conception of MAO came into being in 1950s. But not until 1970s the technology began to be studied. And it became the focus of research on abroad in 1980s. At present practical research progressed rapidly at abroad, and it tried to be applied in some fields. At this research direction, American, Germany, Japan, Russia are leading the way in the world. Not until 1990s our country began to research this technology, and compared to the foreign level, our technology far fall behind them. The research on micro-arc oxidation on steel at home is main use hot-dip aluminizing, its principle is similar to micro-arc oxidation on aluminum, but this method has a fatal defect, the adhesion of the ceramics coating is not well, easily to be scaled off. Using micro-arc oxidation on steel in-situ synthesis ceramics coating, nobody study this at home, also few people study abroad.
This paper firstly expatiate the principle of steel surface erode, micro-arc oxidation, steel surface hot-dip aluminizing microarc oxidation, and so on, on the basis of these principles, the principle of microarc oxidation on steel in-situ synthesis ceramics coating has been primarily explored. According to this principle, the thought of the experimentation has been designed, decided to make Al_2O_3 ceramics on steel and use which mixed liquid of NaAlO_2, Na_2SiO_3and KOH in the process. Then the technological process has been explored. The method of how to in-situ synthesize ceramics coating by microarc oxidation has been found after explored a series of technological process, such as directly microarc oxidation on steel, microarc oxidation on steel after phosphating, microarc oxidation on steel after natural erode, and so on. Finally using SEM and XRD, the micro-shape and fabric of the ceramic coating have been analyzed, and explained some phenomena of the experiment
本文首先对钢铁表面腐蚀、微弧氧化、钢铁表面热浸镀铝微弧氧化等机理进行了阐述,以此为基础,对钢铁表面微弧氧化原位生成陶瓷膜的机理进行了初步探索。然后以此原理为依据,对实验方案进行了设计,确定了在钢铁表面生成Al_2O_3陶瓷和在加工过程中采用以铝酸钠(NaAlO_2)、硅酸钠(Na_2SiO_3)和氢氧化钾(KOH)为主的混合工作液。并对工艺方法进行了探索,通过对钢铁表面直接微弧氧化、钢铁表面磷化处理后再进行微弧氧化、自然腐蚀后再进行微弧氧化等一系列工艺方法的研究,找到了在钢铁表面微弧氧化原位生成陶瓷膜的方法。最后采用扫描电镜(SEM)及X射线衍射相结构分析(XRD)对陶瓷氧化膜微观形貌及膜层结构进行分析,并对实验中的一些现象进行了解释。
Microarc oxidation is one of the surface treatment technology that recently arisen at home, it’s main used to surface modification on aluminous, magnesian, titanic and their alloy surface, because of the simpleness of its technical process and the predominant performance of treated surface, the applying prospect is very bullish by inside and outside insider. The conception of MAO came into being in 1950s. But not until 1970s the technology began to be studied. And it became the focus of research on abroad in 1980s. At present practical research progressed rapidly at abroad, and it tried to be applied in some fields. At this research direction, American, Germany, Japan, Russia are leading the way in the world. Not until 1990s our country began to research this technology, and compared to the foreign level, our technology far fall behind them. The research on micro-arc oxidation on steel at home is main use hot-dip aluminizing, its principle is similar to micro-arc oxidation on aluminum, but this method has a fatal defect, the adhesion of the ceramics coating is not well, easily to be scaled off. Using micro-arc oxidation on steel in-situ synthesis ceramics coating, nobody study this at home, also few people study abroad.
This paper firstly expatiate the principle of steel surface erode, micro-arc oxidation, steel surface hot-dip aluminizing microarc oxidation, and so on, on the basis of these principles, the principle of microarc oxidation on steel in-situ synthesis ceramics coating has been primarily explored. According to this principle, the thought of the experimentation has been designed, decided to make Al_2O_3 ceramics on steel and use which mixed liquid of NaAlO_2, Na_2SiO_3and KOH in the process. Then the technological process has been explored. The method of how to in-situ synthesize ceramics coating by microarc oxidation has been found after explored a series of technological process, such as directly microarc oxidation on steel, microarc oxidation on steel after phosphating, microarc oxidation on steel after natural erode, and so on. Finally using SEM and XRD, the micro-shape and fabric of the ceramic coating have been analyzed, and explained some phenomena of the experiment
引文
1 刘耀辉, 李颂. 微弧氧化技术国内外研究进展. 发展论坛. 2005,(1): 1~6 128~158
2 左洪波, 孔庆山,尚文琦. 等离子体增强电化学表面陶瓷化技术. 材料保护. 1995,28(7):21~22
3 X.Nie. Low Temperature Deposition of Cr(N)/TiO2 Coatings Using a Duplex of Process Unbalanced Magentron Sputtering and Microarc Oxidation. Surface and Coatings Technology. 2000:133~134
4 张耀辉. LY12 铝合金微弧氧化工艺及应用研究. 哈尔滨工业大学硕士论文. 2003:9~18
5 刘建平, 旷亚非. 微弧氧化技术及其发展. 材料导报. 1998,12(5):27~30
6 刘凤玲 , 骆更新 , 毛立信 . 微弧氧化与材料表面陶瓷化材料保护 . 1998,31(3):23~24
7 Sluginov N P. Electric Discharges in Water. J Russ Phys Chem. 1980,12(12):193
8 Mahyshev V. Microarc Oxidation, A New Method for Strenghening Aluminum Surfaces. Matelloberfkarche, 1995, 49(8): 65~69
9 侯亚丽, 刘忠德. 微弧氧化技术的研究现状. 电镀与精饰, 2005,(5): 1~9 61~83 232~249
10 蒋永锋, 李均名, 蒋百灵等. 镁合金微弧氧化陶瓷层形成因素的分析. 表面技术. 2001,4:32~33
11 Florian Patcas, Waldemar Krysmann. Preparation of Structured Egg-shell Cataly- sts for Selective Oxidations by The ANOF Technique. Catalysis Today. 2001(69):20~23
12 李淑华, 尹玉军, 程金生等. 微弧氧化技术与材料表面陶瓷化. 特种铸造及 有色合金. 2001,1:35~36
13 潘明强. 铝合金表面微弧氧化机理及工艺研究. 哈尔滨工业大学硕士论文. 2005:25~28
14 张文化, 胡正前, 马晋. 俄罗斯微弧氧化技术的研究进展. 世界有色金属. 2004(1): 20~23
15 Tongbo Wei, Fengyuan Yan, Jun Tian. Characterization and Wear and Corrosion Resistance of Microarc Oxidation Ceramic Coatings on Aluminum Alloy. Journ-al of Alloys and Compounds. 2004(5):20~30
16 Yaming Wang, Bailing Jiang, Lixin Guo. Dependence of Growth Features of Mi- croarc Oxidation Coatings of Titanium Alloy on Control Modes of Alternate Pulse. Materials Letters. 2003(026):30~35
17 Xuetong Sun, Zhaohua Jiang, Shigang Xin. Composition and Mechanical Properties of Hard Ceramic Coating Containing α-Al2O3 Produced by Microarc Oxidation on Ti–6Al–4V Alloy. Thin Solid Films. 2005,471:194~199
18 刘文亮. 铝合金在不同溶液中的微弧氧化膜层性能研究. 电镀与装饰. 1999, (4):21~23
19 张新平, 熊守美, 许庆彦等. 微弧氧化工艺参数对覆盖层厚度的影响规律模型. 材料保护. 2004,37(8):45~50
20 姜兆华, 吴晓宏, 王福平等. 磷酸盐-重铬酸钾体系中钛合金微等离子体表面陶瓷化. 材料工程. 2002(6):50~53
21 高殿奎, 沈德久, 王玉林. 低碳钢热浸镀铝微弧氧化陶瓷层厚度研究. 材料保护. 2001,34(5):8~11
22 于凤来. 铝合金微弧氧化陶瓷膜的制备和特性研究. 吉林大学硕士论文. 2001:7~9 16~22
23 马丽萍. LY12 铝合金微弧氧化工艺及应用研究. 哈尔滨工业大学硕士论文. 2001:50~56
24 Y. M. Wang, D. C. Jia, L. X. Guo. Effect of Discharge Pulsating on Microarc Oxidation Coatings Formed on Ti6Al4V Alloy. Materials Chemistry and Physics. 2005(90):11~18
25 李建中, 邵忠财, 康凤娣等. 微弧氧化技术在 Al、Mg、Ti 及其合金中的应用. 腐蚀科学与防护技术. 2004,16(4):32~50
26 钟涛生, 蒋百灵, 李均明. 微弧氧化技术的特点、应用前景及研究方向. 电镀与涂饰. 2005,24(6):30~60 13~19
27 侯朝辉. 铝及其合金的电化学表面强化处理. 湖南大学硕士论文. 2001:8~9
28 李凌. 钢铁表面热浸镀铝新工艺及镀层厚度控制模型研究. 武汉理工大学硕士论文. 2005:1 17
29 张玉梅. 关于钢铁氧化处理和磷化处理的实验研究及应用. 辽宁师专学报. 2003,5(1):5~29 40~43 60~65
30 曹楚南. 腐蚀电化学原理. 化学工业出版社, 1985:102~127
31 A. A. Voevodin, A. L. Yerokhin, V. V. Lyubimov. M. S. Donley and J. S. Zabinski.Characterization of Wear Protective Al-Si-O Coatings Formed on Al-based Alloys by Microarc Discharge Treatment. Surf, Coat. Technol. 1996, 86-87 516-521
32 Wood G .C., Pearson C . Corros.Sci. 1967,7( 2):119-125
33 Ikonopisov. S. Electrochim Acta. 1977,22(10):10 77-1082
34 Albella J. M, Montero I., Martinez J.M. Electrochim Acta.1987,32(2):255~258
35 Dittrich K H, Kurze P, Krysmann W. Structure and Properties of ANOF Layers. Crystal Res&Technol. 1984,19(1):93-99
36 Rudnev V. S, Vasileva M. S, Lukiyanchuk I. V. On the Surface Structure of Coatings Formed by Anodic Spark Method. Protection of Metal. 2004,40(4):352~357
37 F. Mecuson, T. Czerwiec, T. Bwlmonte. Diagnostics of an Electrolytic Microarc Process for Aluminium Alloy Oxidation. Surface & Coatings Technology. 2005,200:804~808
38 刘全心, 蔡启舟, 王立世等. 微弧氧化中火花形态的变化规律. 轻合金加工技术. 2005,33(5):40~45
39 Xuetong Sun, Zhaohua Jiang, Zhongping Yao. The Effects of Anodic and Cathodic Processes on the Characteristics of Ceramic Coatings Formed on Titanium Alloy Through the MAO Coating Technology. Applied Surface Science. 2005,252:441~447
40 Van T B, Brown S D, Wirtz G P. Mechanism of anode spark deposition. Am Ceram Soc Bull. 1977,56(6):563~566
41 李淑华, 程金生, 尹玉军等. 铝合金微弧氧化过程的特性研究及机理分析. 机械工程材料. 2001,25(11):27~33
42 Wenbin Xue, Zhiwei Deng, Ruyi Chen. Growth regularity of ceramic coatings formed by microarc oxidation on Al–Cu–Mg alloy. Thin Solid Films. 2001,372:114~117
43 V. Anita, N. Saito, O. Takai. Microarc Plasma Treatment of Titanium and Aluminum Surfaces in Electrolytes. Thin Solid Films. 2005,083:364~368
44 Yaming Wang, TIngquan Lei, Bailing Jiang. Growth, Microstructure and Mechanical Properties of Microarc Oxidation Coatings on Titanium Alloy in Phosphate-containing Solution. Applied Surface Science. 2004,233:258~267
45 李淑华, 程金生, 尹玉军等. 微弧氧化过程中电流和电压变化规律的探讨.特种铸造及有色合金. 2001,3:120~128
46 解世岳, 王从曾, 马捷等. 碳钢热浸镀铝及微弧氧化研究. 轻合金加工技术. 2003,31(9):263~275
47 张安富. 钢铁表面处理技术的一些进展. 腐蚀与防护. 1993,03:130~170
48 苏加国, 徐瑞东, 薛方勤等. 国内磷化工艺最新研究状况和进展. 云南冶金. 2002,30(1):52~70
49 邹正光, 尹传强, 李晓敏. 金属间化合物Al2O3,TiC陶瓷基复合材料的研究进展. 桂林工学院学报. 2005,25(2):36~40
50 蔡作乾, 王琏, 杨根. 陶瓷材料辞典. 化学工业出版社, 2002:119~124
51 G. Sundararajan, L. Rama Krishna. Mechanisms Underlying the Formation of Thick Alumina Coatings Through the MAO Coating Technology. Surface and Coatings Technology. 2003:20-23
52 Jun Liang, Baogang Guo, Jun Tian. Effects of NaAlO2 on Structure and Corrosion Resistance of Microarc Oxidation Coatings Formed on AM60B Magnesium Alloy in Phosphate-KOH Electrolyte. Surface & Coatings Technology. 2005,199:121~126
2 左洪波, 孔庆山,尚文琦. 等离子体增强电化学表面陶瓷化技术. 材料保护. 1995,28(7):21~22
3 X.Nie. Low Temperature Deposition of Cr(N)/TiO2 Coatings Using a Duplex of Process Unbalanced Magentron Sputtering and Microarc Oxidation. Surface and Coatings Technology. 2000:133~134
4 张耀辉. LY12 铝合金微弧氧化工艺及应用研究. 哈尔滨工业大学硕士论文. 2003:9~18
5 刘建平, 旷亚非. 微弧氧化技术及其发展. 材料导报. 1998,12(5):27~30
6 刘凤玲 , 骆更新 , 毛立信 . 微弧氧化与材料表面陶瓷化材料保护 . 1998,31(3):23~24
7 Sluginov N P. Electric Discharges in Water. J Russ Phys Chem. 1980,12(12):193
8 Mahyshev V. Microarc Oxidation, A New Method for Strenghening Aluminum Surfaces. Matelloberfkarche, 1995, 49(8): 65~69
9 侯亚丽, 刘忠德. 微弧氧化技术的研究现状. 电镀与精饰, 2005,(5): 1~9 61~83 232~249
10 蒋永锋, 李均名, 蒋百灵等. 镁合金微弧氧化陶瓷层形成因素的分析. 表面技术. 2001,4:32~33
11 Florian Patcas, Waldemar Krysmann. Preparation of Structured Egg-shell Cataly- sts for Selective Oxidations by The ANOF Technique. Catalysis Today. 2001(69):20~23
12 李淑华, 尹玉军, 程金生等. 微弧氧化技术与材料表面陶瓷化. 特种铸造及 有色合金. 2001,1:35~36
13 潘明强. 铝合金表面微弧氧化机理及工艺研究. 哈尔滨工业大学硕士论文. 2005:25~28
14 张文化, 胡正前, 马晋. 俄罗斯微弧氧化技术的研究进展. 世界有色金属. 2004(1): 20~23
15 Tongbo Wei, Fengyuan Yan, Jun Tian. Characterization and Wear and Corrosion Resistance of Microarc Oxidation Ceramic Coatings on Aluminum Alloy. Journ-al of Alloys and Compounds. 2004(5):20~30
16 Yaming Wang, Bailing Jiang, Lixin Guo. Dependence of Growth Features of Mi- croarc Oxidation Coatings of Titanium Alloy on Control Modes of Alternate Pulse. Materials Letters. 2003(026):30~35
17 Xuetong Sun, Zhaohua Jiang, Shigang Xin. Composition and Mechanical Properties of Hard Ceramic Coating Containing α-Al2O3 Produced by Microarc Oxidation on Ti–6Al–4V Alloy. Thin Solid Films. 2005,471:194~199
18 刘文亮. 铝合金在不同溶液中的微弧氧化膜层性能研究. 电镀与装饰. 1999, (4):21~23
19 张新平, 熊守美, 许庆彦等. 微弧氧化工艺参数对覆盖层厚度的影响规律模型. 材料保护. 2004,37(8):45~50
20 姜兆华, 吴晓宏, 王福平等. 磷酸盐-重铬酸钾体系中钛合金微等离子体表面陶瓷化. 材料工程. 2002(6):50~53
21 高殿奎, 沈德久, 王玉林. 低碳钢热浸镀铝微弧氧化陶瓷层厚度研究. 材料保护. 2001,34(5):8~11
22 于凤来. 铝合金微弧氧化陶瓷膜的制备和特性研究. 吉林大学硕士论文. 2001:7~9 16~22
23 马丽萍. LY12 铝合金微弧氧化工艺及应用研究. 哈尔滨工业大学硕士论文. 2001:50~56
24 Y. M. Wang, D. C. Jia, L. X. Guo. Effect of Discharge Pulsating on Microarc Oxidation Coatings Formed on Ti6Al4V Alloy. Materials Chemistry and Physics. 2005(90):11~18
25 李建中, 邵忠财, 康凤娣等. 微弧氧化技术在 Al、Mg、Ti 及其合金中的应用. 腐蚀科学与防护技术. 2004,16(4):32~50
26 钟涛生, 蒋百灵, 李均明. 微弧氧化技术的特点、应用前景及研究方向. 电镀与涂饰. 2005,24(6):30~60 13~19
27 侯朝辉. 铝及其合金的电化学表面强化处理. 湖南大学硕士论文. 2001:8~9
28 李凌. 钢铁表面热浸镀铝新工艺及镀层厚度控制模型研究. 武汉理工大学硕士论文. 2005:1 17
29 张玉梅. 关于钢铁氧化处理和磷化处理的实验研究及应用. 辽宁师专学报. 2003,5(1):5~29 40~43 60~65
30 曹楚南. 腐蚀电化学原理. 化学工业出版社, 1985:102~127
31 A. A. Voevodin, A. L. Yerokhin, V. V. Lyubimov. M. S. Donley and J. S. Zabinski.Characterization of Wear Protective Al-Si-O Coatings Formed on Al-based Alloys by Microarc Discharge Treatment. Surf, Coat. Technol. 1996, 86-87 516-521
32 Wood G .C., Pearson C . Corros.Sci. 1967,7( 2):119-125
33 Ikonopisov. S. Electrochim Acta. 1977,22(10):10 77-1082
34 Albella J. M, Montero I., Martinez J.M. Electrochim Acta.1987,32(2):255~258
35 Dittrich K H, Kurze P, Krysmann W. Structure and Properties of ANOF Layers. Crystal Res&Technol. 1984,19(1):93-99
36 Rudnev V. S, Vasileva M. S, Lukiyanchuk I. V. On the Surface Structure of Coatings Formed by Anodic Spark Method. Protection of Metal. 2004,40(4):352~357
37 F. Mecuson, T. Czerwiec, T. Bwlmonte. Diagnostics of an Electrolytic Microarc Process for Aluminium Alloy Oxidation. Surface & Coatings Technology. 2005,200:804~808
38 刘全心, 蔡启舟, 王立世等. 微弧氧化中火花形态的变化规律. 轻合金加工技术. 2005,33(5):40~45
39 Xuetong Sun, Zhaohua Jiang, Zhongping Yao. The Effects of Anodic and Cathodic Processes on the Characteristics of Ceramic Coatings Formed on Titanium Alloy Through the MAO Coating Technology. Applied Surface Science. 2005,252:441~447
40 Van T B, Brown S D, Wirtz G P. Mechanism of anode spark deposition. Am Ceram Soc Bull. 1977,56(6):563~566
41 李淑华, 程金生, 尹玉军等. 铝合金微弧氧化过程的特性研究及机理分析. 机械工程材料. 2001,25(11):27~33
42 Wenbin Xue, Zhiwei Deng, Ruyi Chen. Growth regularity of ceramic coatings formed by microarc oxidation on Al–Cu–Mg alloy. Thin Solid Films. 2001,372:114~117
43 V. Anita, N. Saito, O. Takai. Microarc Plasma Treatment of Titanium and Aluminum Surfaces in Electrolytes. Thin Solid Films. 2005,083:364~368
44 Yaming Wang, TIngquan Lei, Bailing Jiang. Growth, Microstructure and Mechanical Properties of Microarc Oxidation Coatings on Titanium Alloy in Phosphate-containing Solution. Applied Surface Science. 2004,233:258~267
45 李淑华, 程金生, 尹玉军等. 微弧氧化过程中电流和电压变化规律的探讨.特种铸造及有色合金. 2001,3:120~128
46 解世岳, 王从曾, 马捷等. 碳钢热浸镀铝及微弧氧化研究. 轻合金加工技术. 2003,31(9):263~275
47 张安富. 钢铁表面处理技术的一些进展. 腐蚀与防护. 1993,03:130~170
48 苏加国, 徐瑞东, 薛方勤等. 国内磷化工艺最新研究状况和进展. 云南冶金. 2002,30(1):52~70
49 邹正光, 尹传强, 李晓敏. 金属间化合物Al2O3,TiC陶瓷基复合材料的研究进展. 桂林工学院学报. 2005,25(2):36~40
50 蔡作乾, 王琏, 杨根. 陶瓷材料辞典. 化学工业出版社, 2002:119~124
51 G. Sundararajan, L. Rama Krishna. Mechanisms Underlying the Formation of Thick Alumina Coatings Through the MAO Coating Technology. Surface and Coatings Technology. 2003:20-23
52 Jun Liang, Baogang Guo, Jun Tian. Effects of NaAlO2 on Structure and Corrosion Resistance of Microarc Oxidation Coatings Formed on AM60B Magnesium Alloy in Phosphate-KOH Electrolyte. Surface & Coatings Technology. 2005,199:121~126