纳米SiO_2/Ni-P-Co复合镀层的研究
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摘要
本论文应用电化学镀的方法,研究了在钢的表面均匀沉积Ni-P-Co合金镀层和纳米SiO2/Ni-P-Co复合镀层。研究NaH2PO2含量、电流密度、CoSO4含量和温度对Ni-P-Co合金镀层的影响。在研究Ni-P-Co合金镀层的基础上,向镀液中添加纳米SiO2,研究了纳米SiO2含量对复合镀层的结构与性能的影响,并应用扫描电镜研究了复合镀层的形核、长大机理。研究结果表明纳米SiO2/Ni-P-Co复合镀层具有较高的硬度,其显微硬度可达502 HV,纳米SiO2/Ni-P-Co复合镀层的耐蚀性和耐磨性均高于Ni-P-Co镀层。最佳工艺配方定为:NaH2PO2浓度50~60g/L,CoSO4浓度70~80g/L,温度50~60℃,纳米SiO2浓度6g/L。当要求施镀速度较大时,电流密度可选为6A/dm2,当要求镀层具有较高光洁度时,选3A/dm2。
In this paper, the method of electrochemistry plates is applied to depositing Ni-P-Co alloy coatings and nano-SiO2/Ni-P-Co composite coatings on the surface of steel. The effects of NaH2PO2 content, the current density, CoSO4 content and temperature on the Ni-P-Co alloy coatings were investigated. Based research on Ni-P-Co alloy coatings, adding the nano-SiO2 to the electroless plating solution, the effects of nano-SiO2 content on the structure and properties of the composite coatings. The shape of the composite coatings and the grow up mechanism of plating layer were studied by SEM analysis. The results show that nano-SiO2/Ni-P-Co composite coatings has a high hardness, its micro-hardness is up to 502HV, the corrosion resistance and wear resistance of the nano-SiO2/Ni-P-Co composite coatings is higher than Ni-P-Co coatings. The study shows that the optimal components of the electroless plating solution were 50~60g/L NaH2PO2 and 70~80g/L CoSO4. Plating temperature is 50~60℃. The nano-SiO2 conformable content in plating layer is 6g/L. The current density chooses 6A/dm2 when the velocity of electroless plating is clipping. It is choosed to 3A/dm2 when glabrous degree of plating layer is well.
In this paper, the method of electrochemistry plates is applied to depositing Ni-P-Co alloy coatings and nano-SiO2/Ni-P-Co composite coatings on the surface of steel. The effects of NaH2PO2 content, the current density, CoSO4 content and temperature on the Ni-P-Co alloy coatings were investigated. Based research on Ni-P-Co alloy coatings, adding the nano-SiO2 to the electroless plating solution, the effects of nano-SiO2 content on the structure and properties of the composite coatings. The shape of the composite coatings and the grow up mechanism of plating layer were studied by SEM analysis. The results show that nano-SiO2/Ni-P-Co composite coatings has a high hardness, its micro-hardness is up to 502HV, the corrosion resistance and wear resistance of the nano-SiO2/Ni-P-Co composite coatings is higher than Ni-P-Co coatings. The study shows that the optimal components of the electroless plating solution were 50~60g/L NaH2PO2 and 70~80g/L CoSO4. Plating temperature is 50~60℃. The nano-SiO2 conformable content in plating layer is 6g/L. The current density chooses 6A/dm2 when the velocity of electroless plating is clipping. It is choosed to 3A/dm2 when glabrous degree of plating layer is well.
引文
1蔡珣.表面工程技术工艺方法400种.北京:机械工业出版社,2006
2徐滨士,朱绍华,刘世参.材料表面工程.哈尔滨:哈尔滨工业大学出版社,2005
3 Steinbach J, Ferkel H. Nano-structured Ni-Al2O3 films prepared by D.C. and pulsed D.C. electroplating J. Script Mater. 2001(44):1813～1816
4 Mandich N V, Dennis J K. Code position of nano-diamonds with chromium. Metal Finishing, 2001, 99 (6): 117～119
5严冬升,冯瑞,材料新星—纳米材料科学.长沙:湖南科学技术出版社,1997
6徐滨士.表面工程的应用与展望.中国科学技术前沿(1999/2000).中国工程院版.北京:高等教育出版社,2000:337~358
7徐滨士,马世宁,梁秀兵等.表面工程的进展.金属热处理,2002,27(7):1~3
8 Benea L, Bonora P L, Borello A, et al. Wear corrosion properties of nano-structured SiC-nickel composite coatings obtained by electroplating. Wear, 2001, 249(10-11): 995～1003
9 Deguchi T, Imai K, Matsui H, et al. Rapid electroplating of photo catalytically highly active TiO2-Zn nano-composite films on steel. J. Mater. Science, 2001(36): 4723
10梁志杰.现代表面镀覆技术.第1版.北京:国防工业出版社,2005
11 Moller A, Hahn H. Synthesis and characterization of nano-crystalline Ni/ZrO2 composite coating. Nano-structured Materials, 1999(12): 259～262
12 Stojak J L, Talbot J B. Effect of particles on polarization during electrode position using a rotating cylinder electrode. J. Applied. Electrode, 2001, (31): 559～564
13周小平,土鹏飞.纳米SiO2颗粒与镍基复合刷Ni-P合金镀层组织与磨损特性.湖北学院学报.2004,19 (1):27～30
14宋国君,舒文艺.聚合物基纳米复合材料.材料导报,1996(4):57～62
15胡圣飞,徐声钩,李纯清.超微刚性无机粒子及其填充塑料.现代塑料加工应用,1998(2):61～64
16曾戎,高分子纳米复合材料研究进展(I)—高分子纳米复合材料的制备、表征和应用前景.宇航材料工艺,1999(2):6～8
17周瑞发,韩雅芳,陈祥宝.纳米材料技术.北京:国防工业出版社,2003
18郭卫红,李盾,唐颂超等.纳米材料及其在塑料改性中的应用.工程塑料应用,1998,26(4):11～13
19杨剑,滕凤恩.纳米材料综述.材料导报,1997,11(2):6～10.17.张玉龙,李长德,纳米技术与纳米塑料,北京:中国轻工业出版社,2002
20 Brenner A. , Couch D. E. , Williams E. K. Electro deposition of alloys of phoshorus with nickel or cobalt . J. Res Natl BurStand , 1950 , 44 : 109～119
21何建波,吴肖安,黄辉等.电镀镍磷合金研究现状及前景.浙江工业大学学报,1999,27(1):62~70
22张春丽,周琦,赵平.电镀镍磷合金工艺初探.材料保护,2005,38(2):31~33
23 Lashmore D. S. , Ratzker M. , Pratt K. W. Electrodeposition and corrosion performance of Ni-P amorphous alloys. Plating and Surface Finishing , 1986 , 9 :74～82
24 Bundler M.. Electrochemical behavior of electrodeposition of Ni-P amorphous alloys. Z Anorg Allg Chem , 1965 ,340 :113～119
25 Raj Naryan , Mungole M. N. Electrodeposition of Ni-P alloy coatings. Surface Technology , 1985 , 24 :233～242
26于岗.电镀Ni-P合金机理及性能的研究.上海科研情报所资料,319298
27吴玉程,洪钟.化学(电)沉积镍磷合金的腐蚀防护特性.化工腐蚀与防护,1991(1):28～36
28黄清安.在电镀镍磷合金中亚磷酸阴极行为的研究.武汉大学学报.自然科学版.1982(4):55～60
29曾跃,姚士兵,周绍民.现场表面拉曼光谱研究Ni-P合金电沉积机理.物理化学学报,2000,16(2):154~158
30李吉学,国秀珍.化学镀Ni-P合金Ni-P合金镀层相结构与硬度的研究.表面技术,2001,30(1):6～7
31屠振密.电镀合金原理与工艺.北京:国防工业出版社,1993:11~14,333~337; 336~337
32程森,王昆林,赵高敏.镍基纳米SiC复合Ni-P合金镀层的摩擦学性能.清华大学学报(自然科学版),2002,42(4):516～519
33周绍民.金属电沉积原理与方法.上海:上海科学技术出版社,1987:10~14
34张博.Ni-Co-P/WC(nm)复合镀层研究及硅的表面金属化:[学位论文],广州:广东工业大学,2001
35张允诚,胡如南.电镀手册(第2版).北京:国防工业出版社,1997
36吴玉程,邓宗钢.非晶态镍磷合金的组织结构与性能.中国有色金属学报,1998, 8(3):415～418
37邵光杰,秦秀娟,于学升.电镀Ni-P合金Ni-P合金镀层工艺研究.材料保护,2000,33(6): 3~5
38韩文政,遇元宏,时小军.化学镀Ni-P工艺对Ni-P合金镀层结构和性能的影响.材料保护,2002,35(6):51～52
39董允,张廷森,林晓娉.现代表面工程技术(第1版).北京:机械工业出版社,2000
40邵光杰.Ni-P、(Ni-P)- SiC镀层的电沉积及其组织性能:[学位论文],秦皇岛:燕山大学,2002
41王龙彪,黄清安,陈永言等.Ni-P-Co合金的电沉积及析氢反应电催化行为的研究.材料保护,2000,33(2):1~3
42渡边澈.非晶态Ni-P合金沉积特性的研究.金属表面技术,1981,32(12): 600~606
43卢燕平.镍磷合金镀层在盐酸中的耐蚀性.材料保护,1991,24 (1):17～20
44 Raj N. , Mungole M. N.. Electrodeposition of Ni-P alloy coatings. Surface Technology , 1985 , 24 :233～242
45陈静.电沉积镍基合金及其耐磨耐蚀性能研究.材料开发与应用,1999,14(2):14～16
46武刚,李宁,周德瑞等.电沉积Co-Ni-Al2O3复合镀层微观结构及高温性能.复合材料学报2004,21(2):8～13
47涂伟毅,徐滨士,董世运等.纳米陶瓷颗粒的电催化效应及其在复合刷镀层中的化学状态.无机化学学报,2005,21(8):1137～1142
48 Fleischmann M. , Thirsk H. R. .Advances in Electrochemistryand Electrochemical Engineering , Vol. 3 , Interscience , New York ,1963 , Chapter 3
49涂伟毅,徐滨士,董世运等.纳米二氧化硅对镍电沉积影响及在复合镀层中的化学键合状态.化学学报2004,62(20):2010~2014
50 Zhang Z. K., Cui Z. L. Nanometer Technology and Nanometer Materials , Beijing: National Defence Industry Press , 2000
51 Yin M. Z. , Yao X. , Wu X. Q. , Chin J. . Fabrication and characterization of nanoporous silica film.Mater. Res. 2003, 17(2):220~224
52 Tu W. Y. , Xu B. S. , Jiang B. , Chin. J. . Microstructure and co-deposition mechanism of n-SiO2/Ni composite coating prepared by electro-brush plating, Mater. Res.2003, 17(5):530~536
2徐滨士,朱绍华,刘世参.材料表面工程.哈尔滨:哈尔滨工业大学出版社,2005
3 Steinbach J, Ferkel H. Nano-structured Ni-Al2O3 films prepared by D.C. and pulsed D.C. electroplating J. Script Mater. 2001(44):1813～1816
4 Mandich N V, Dennis J K. Code position of nano-diamonds with chromium. Metal Finishing, 2001, 99 (6): 117～119
5严冬升,冯瑞,材料新星—纳米材料科学.长沙:湖南科学技术出版社,1997
6徐滨士.表面工程的应用与展望.中国科学技术前沿(1999/2000).中国工程院版.北京:高等教育出版社,2000:337~358
7徐滨士,马世宁,梁秀兵等.表面工程的进展.金属热处理,2002,27(7):1~3
8 Benea L, Bonora P L, Borello A, et al. Wear corrosion properties of nano-structured SiC-nickel composite coatings obtained by electroplating. Wear, 2001, 249(10-11): 995～1003
9 Deguchi T, Imai K, Matsui H, et al. Rapid electroplating of photo catalytically highly active TiO2-Zn nano-composite films on steel. J. Mater. Science, 2001(36): 4723
10梁志杰.现代表面镀覆技术.第1版.北京:国防工业出版社,2005
11 Moller A, Hahn H. Synthesis and characterization of nano-crystalline Ni/ZrO2 composite coating. Nano-structured Materials, 1999(12): 259～262
12 Stojak J L, Talbot J B. Effect of particles on polarization during electrode position using a rotating cylinder electrode. J. Applied. Electrode, 2001, (31): 559～564
13周小平,土鹏飞.纳米SiO2颗粒与镍基复合刷Ni-P合金镀层组织与磨损特性.湖北学院学报.2004,19 (1):27～30
14宋国君,舒文艺.聚合物基纳米复合材料.材料导报,1996(4):57～62
15胡圣飞,徐声钩,李纯清.超微刚性无机粒子及其填充塑料.现代塑料加工应用,1998(2):61～64
16曾戎,高分子纳米复合材料研究进展(I)—高分子纳米复合材料的制备、表征和应用前景.宇航材料工艺,1999(2):6～8
17周瑞发,韩雅芳,陈祥宝.纳米材料技术.北京:国防工业出版社,2003
18郭卫红,李盾,唐颂超等.纳米材料及其在塑料改性中的应用.工程塑料应用,1998,26(4):11～13
19杨剑,滕凤恩.纳米材料综述.材料导报,1997,11(2):6～10.17.张玉龙,李长德,纳米技术与纳米塑料,北京:中国轻工业出版社,2002
20 Brenner A. , Couch D. E. , Williams E. K. Electro deposition of alloys of phoshorus with nickel or cobalt . J. Res Natl BurStand , 1950 , 44 : 109～119
21何建波,吴肖安,黄辉等.电镀镍磷合金研究现状及前景.浙江工业大学学报,1999,27(1):62~70
22张春丽,周琦,赵平.电镀镍磷合金工艺初探.材料保护,2005,38(2):31~33
23 Lashmore D. S. , Ratzker M. , Pratt K. W. Electrodeposition and corrosion performance of Ni-P amorphous alloys. Plating and Surface Finishing , 1986 , 9 :74～82
24 Bundler M.. Electrochemical behavior of electrodeposition of Ni-P amorphous alloys. Z Anorg Allg Chem , 1965 ,340 :113～119
25 Raj Naryan , Mungole M. N. Electrodeposition of Ni-P alloy coatings. Surface Technology , 1985 , 24 :233～242
26于岗.电镀Ni-P合金机理及性能的研究.上海科研情报所资料,319298
27吴玉程,洪钟.化学(电)沉积镍磷合金的腐蚀防护特性.化工腐蚀与防护,1991(1):28～36
28黄清安.在电镀镍磷合金中亚磷酸阴极行为的研究.武汉大学学报.自然科学版.1982(4):55～60
29曾跃,姚士兵,周绍民.现场表面拉曼光谱研究Ni-P合金电沉积机理.物理化学学报,2000,16(2):154~158
30李吉学,国秀珍.化学镀Ni-P合金Ni-P合金镀层相结构与硬度的研究.表面技术,2001,30(1):6～7
31屠振密.电镀合金原理与工艺.北京:国防工业出版社,1993:11~14,333~337; 336~337
32程森,王昆林,赵高敏.镍基纳米SiC复合Ni-P合金镀层的摩擦学性能.清华大学学报(自然科学版),2002,42(4):516～519
33周绍民.金属电沉积原理与方法.上海:上海科学技术出版社,1987:10~14
34张博.Ni-Co-P/WC(nm)复合镀层研究及硅的表面金属化:[学位论文],广州:广东工业大学,2001
35张允诚,胡如南.电镀手册(第2版).北京:国防工业出版社,1997
36吴玉程,邓宗钢.非晶态镍磷合金的组织结构与性能.中国有色金属学报,1998, 8(3):415～418
37邵光杰,秦秀娟,于学升.电镀Ni-P合金Ni-P合金镀层工艺研究.材料保护,2000,33(6): 3~5
38韩文政,遇元宏,时小军.化学镀Ni-P工艺对Ni-P合金镀层结构和性能的影响.材料保护,2002,35(6):51～52
39董允,张廷森,林晓娉.现代表面工程技术(第1版).北京:机械工业出版社,2000
40邵光杰.Ni-P、(Ni-P)- SiC镀层的电沉积及其组织性能:[学位论文],秦皇岛:燕山大学,2002
41王龙彪,黄清安,陈永言等.Ni-P-Co合金的电沉积及析氢反应电催化行为的研究.材料保护,2000,33(2):1~3
42渡边澈.非晶态Ni-P合金沉积特性的研究.金属表面技术,1981,32(12): 600~606
43卢燕平.镍磷合金镀层在盐酸中的耐蚀性.材料保护,1991,24 (1):17～20
44 Raj N. , Mungole M. N.. Electrodeposition of Ni-P alloy coatings. Surface Technology , 1985 , 24 :233～242
45陈静.电沉积镍基合金及其耐磨耐蚀性能研究.材料开发与应用,1999,14(2):14～16
46武刚,李宁,周德瑞等.电沉积Co-Ni-Al2O3复合镀层微观结构及高温性能.复合材料学报2004,21(2):8～13
47涂伟毅,徐滨士,董世运等.纳米陶瓷颗粒的电催化效应及其在复合刷镀层中的化学状态.无机化学学报,2005,21(8):1137～1142
48 Fleischmann M. , Thirsk H. R. .Advances in Electrochemistryand Electrochemical Engineering , Vol. 3 , Interscience , New York ,1963 , Chapter 3
49涂伟毅,徐滨士,董世运等.纳米二氧化硅对镍电沉积影响及在复合镀层中的化学键合状态.化学学报2004,62(20):2010~2014
50 Zhang Z. K., Cui Z. L. Nanometer Technology and Nanometer Materials , Beijing: National Defence Industry Press , 2000
51 Yin M. Z. , Yao X. , Wu X. Q. , Chin J. . Fabrication and characterization of nanoporous silica film.Mater. Res. 2003, 17(2):220~224
52 Tu W. Y. , Xu B. S. , Jiang B. , Chin. J. . Microstructure and co-deposition mechanism of n-SiO2/Ni composite coating prepared by electro-brush plating, Mater. Res.2003, 17(5):530~536