镍磷合金及其纳米复合镀层的研究
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摘要
本文采用电沉积方法和化学沉积方法,对亚磷酸体系Ni-P合金及Ni-P-CNTs纳米复合镀层的工艺进行了研究,探讨了脉冲电沉积工艺参数和化学沉积工艺对镀层表面形貌、组织结构与性能的影响,研究和分析了Ni-P合金及其纳米复合镀层的耐磨性能及耐磨机理。
脉冲电沉积Ni-P合金的工艺研究表明,合理的脉冲参数能够提高镀层的外观质量和沉积速度.用SEM分析合金镀层发现,平均电流越大脉宽越小沉积速率越大,而占空比越大镀层表面晶粒细化效果越差。进行耐腐蚀性能测试,发现高频条件使得镀层的耐腐蚀性能更加优异。占空比对于镀层的耐腐蚀性能的影响明显,镀层耐腐蚀性能随着占空比的增大有逐渐减小的变化趋势,在占空比最小时表现出优异的耐腐蚀性能。
研究了有机小分子阳离子表面活性剂十六烷基三甲基溴化胺和阴离子表面活性剂柠檬酸修饰碳纳米管,并对其在水中的分散性能进行了研究。实验结果表明,通过有机小分子表面活性剂的修饰提高了碳纳米管在水中的分散。另外,还通过Zeta电位仪和粘度仪的测量探论了碳纳米管在水中的分散机理。
利用碳纳米管作为增强相制备镍磷基复合镀层，并对其表面形貌和耐摩擦磨损性能进行了测试分析。发现碳纳米管能均匀地嵌镶于基体中,并且端头露出,覆盖于基体表面；镀层具有优良的耐磨性和自润滑性。这是因为碳纳米管具有较高的强度和一定的自润滑性,加之以网络和缠绕形态分布于基体中,增大了复合相的粘结力,使碳纳米管在磨损时不易拨出而脱落。
In this paper, the techniques of electrodepositing Ni-P alloy coating and Ni-P-CNTs nano-composite coating from phosphorous acid system are investigated. Effects of technical conditions and heat treatment temperature on the surface morphology,structure and properties of electrodeposit are discussed. Wear resistance properties of Ni-P alloy coatings and Ni-P-CNTs nano-composite coatings are compared,and on th ebasis of that the wear resistance mechanism is analyzed.
Ni-P alloy coating was prepared by pulsed electrodeposition. It has been found that a reasonnable pulse parameters can improve appearance quality and deposition rate of the coating. By the method of SEM to analyze the structure of alloy coating, it has been noticed that if the average current is big and the pulse width is small then the deposition rate will be more fast, and the grain refinement effect of the coating will become worse if duty ratio increases. Corrosion resistance test on Ni-P alloy coating reveals that under high-frequency conditions the coating exhibits excellent performance in corrosion resistance. Duty ratio has significant impact oncorrosion-resistant of the coating.and it will show excellent resistance to corrosion when duty ratio is the smallest.
In order to improve the dispersion of CNTs in aqueous solution, the CNTs are modified by the cetyl trimethyl ammonium bromide (CTAB) and citric acid (CA), respectively, and the dispersion properties in aqueous solution are studied. The experimental results illuminate that the dispersion of CNTs in aqueous solution is improved by modification. Furthermore, the dispersed mechanism of MWNTs in de-ionized water was discussed through the study of Zeta potential analyzer and viscosity meter.
Carbon nanotube was used as a reinforcement agent to prepare Ni-P matrix composite coating. The tribological behaviour of the composite coating was examined on a reciprocating wear test machine. The surface morphology before and after wear test were analyzed with scanning electron microscopy. The results show that the carbon nanotubes were uniformly embedded in the matrix and one end protruded from the surface. It is found the Ni-P-carbon nanotube composite coating have high wear resistance and self-lubrication. CNTs layer on the matrix protect the surface of the matrix from wearing. Meanwhile the incorporation of the CNTs suppresses the plastic deformation and enhances the mechanical properties of the coating.
脉冲电沉积Ni-P合金的工艺研究表明,合理的脉冲参数能够提高镀层的外观质量和沉积速度.用SEM分析合金镀层发现,平均电流越大脉宽越小沉积速率越大,而占空比越大镀层表面晶粒细化效果越差。进行耐腐蚀性能测试,发现高频条件使得镀层的耐腐蚀性能更加优异。占空比对于镀层的耐腐蚀性能的影响明显,镀层耐腐蚀性能随着占空比的增大有逐渐减小的变化趋势,在占空比最小时表现出优异的耐腐蚀性能。
研究了有机小分子阳离子表面活性剂十六烷基三甲基溴化胺和阴离子表面活性剂柠檬酸修饰碳纳米管,并对其在水中的分散性能进行了研究。实验结果表明,通过有机小分子表面活性剂的修饰提高了碳纳米管在水中的分散。另外,还通过Zeta电位仪和粘度仪的测量探论了碳纳米管在水中的分散机理。
利用碳纳米管作为增强相制备镍磷基复合镀层，并对其表面形貌和耐摩擦磨损性能进行了测试分析。发现碳纳米管能均匀地嵌镶于基体中,并且端头露出,覆盖于基体表面；镀层具有优良的耐磨性和自润滑性。这是因为碳纳米管具有较高的强度和一定的自润滑性,加之以网络和缠绕形态分布于基体中,增大了复合相的粘结力,使碳纳米管在磨损时不易拨出而脱落。
In this paper, the techniques of electrodepositing Ni-P alloy coating and Ni-P-CNTs nano-composite coating from phosphorous acid system are investigated. Effects of technical conditions and heat treatment temperature on the surface morphology,structure and properties of electrodeposit are discussed. Wear resistance properties of Ni-P alloy coatings and Ni-P-CNTs nano-composite coatings are compared,and on th ebasis of that the wear resistance mechanism is analyzed.
Ni-P alloy coating was prepared by pulsed electrodeposition. It has been found that a reasonnable pulse parameters can improve appearance quality and deposition rate of the coating. By the method of SEM to analyze the structure of alloy coating, it has been noticed that if the average current is big and the pulse width is small then the deposition rate will be more fast, and the grain refinement effect of the coating will become worse if duty ratio increases. Corrosion resistance test on Ni-P alloy coating reveals that under high-frequency conditions the coating exhibits excellent performance in corrosion resistance. Duty ratio has significant impact oncorrosion-resistant of the coating.and it will show excellent resistance to corrosion when duty ratio is the smallest.
In order to improve the dispersion of CNTs in aqueous solution, the CNTs are modified by the cetyl trimethyl ammonium bromide (CTAB) and citric acid (CA), respectively, and the dispersion properties in aqueous solution are studied. The experimental results illuminate that the dispersion of CNTs in aqueous solution is improved by modification. Furthermore, the dispersed mechanism of MWNTs in de-ionized water was discussed through the study of Zeta potential analyzer and viscosity meter.
Carbon nanotube was used as a reinforcement agent to prepare Ni-P matrix composite coating. The tribological behaviour of the composite coating was examined on a reciprocating wear test machine. The surface morphology before and after wear test were analyzed with scanning electron microscopy. The results show that the carbon nanotubes were uniformly embedded in the matrix and one end protruded from the surface. It is found the Ni-P-carbon nanotube composite coating have high wear resistance and self-lubrication. CNTs layer on the matrix protect the surface of the matrix from wearing. Meanwhile the incorporation of the CNTs suppresses the plastic deformation and enhances the mechanical properties of the coating.
引文
[1]邵光杰.秦秀娟.于升学.李慧等. 电沉积Ni-P合金镀层在酸性介质中耐蚀性能的研究.表面技术,2001,5
[2]周荣廷.化学镀镍的原理与工艺[M].北京：国防工业出版社,1975：34-41
[3]姜晓霞,沈伟.化学镀理论与实践[M].北京：国防工业出版社,2000：4-7
[4]孙克宁.化学镀Ni-P工艺研究[J].电镀与环保,1998,8(4)：18-20
[5]沃尔夫冈·里德尔.化学镀镍[M].上海：上海交通大学出版社,2004
[6]程秀云,张振华.电镀技术[M].北京：化学工业出版社,2003：1-2
[7]李宁,袁国伟,黎德育.化学镀镍基合金理论与技术[M].哈尔滨：哈尔滨工业大学出版社,2004
[8]李宁.化学镀实用技术[M].北京：化学工业出版社,2004
[9]陈亚.现代实用电镀技术[M].北京：国防工业出版社,2003：287-295
[10]屠振密,韩书梅,杨哲龙等.防护装饰性镀层[M].北京：化学工业出版社,1993.
[11]渡边澈.非晶态电镀及应用[M].北京：北京航空航天出版社，1993.
[12]唐睿.电镀Ni-W-P合金的组织纵横结构与性能研究.洛阳工学院学位论文,2001.
[13]Lanhmore D S, Ratzker M. Pratt K W. Electrodeposition and corrotion performance of Ni-P atmosphous alloys. Plating and Surface Finishing.1986,9: 74-82.
[14]Bundler M. electrochemical behavior of electrodeposition of Ni-P amorphous alloys. Z Anorg Allg Chem.1965,340:113-119.
[15]Raj Naryan, Mungole M N. Electrodeposition of Ni-P alloy coatings. Surface Techcology,1985.24:233-242.
[16]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
[17]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.
[18]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.
[19]候进,侯庆军.脉冲电镀的含义及常用形式[J].中国电镀材料信息2002,2(7)：68-73
[20]向国朴.脉冲电镀发展概况[J]电镀与涂饰.2000,19(4)：43-47
[21]向国朴编著.脉冲电镀的理论与应用[M].天津：科学技术出版社,1989：94-95.
[22]杨哲龙,安茂忠,李国强等.脉冲参数对光亮银镀层性能的影响[J].材料保护,1998,31(6)：17.
[23]侯丛福,王菊,于桂云等.脉冲参数对镀层微观结构及性能的影响[J].材料保护,2001,34(1)：10-11.
[24]张允诚编著.电镀手册[M].北京：国防工业出版社,1997：622-635
[25]曾华梁编著.电镀工艺手册[M].北京：机械工业出版社,1997：645-647.
[26]李国英主编表面工程手册[M].北京：机械工业出版社，1997：6-153-6-155
[27]屠振密,韩书梅,杨哲龙等.防护装饰性镀层[M].北京：化学工业出版社,1993
[28]张景双,石金声,石磊等.电镀溶液与镀层性能测试[M].北京：化学工业出版社,2003.
[29]刘燕萍,李林峰.脉冲电沉积Ni-P合金机理的研究[J].电镀与环保,1997,17(5)：12-14.
[30]Metzger and Th. Florian. The deposi Cion of dispersion hardened coatings by means of electroless nickel, Trans. IMF,1976,54:174 - 177
[31]李宁,袁国伟,黎德育等.化学镀镍基合金理论与技术[M].哈尔滨：哈尔滨工业大学出版,2000
[32]Treacy M M J, Ebbesen T W, Gibson J M, et al. Exceptionally high Young's modulus observed for individual Carbon nanotubes[J]. Nature,1996, 381:678-680
[33]Bower C, Rosen B and Jin L. deformation of carbon nanotubes in nanotube-polymer composites. Appl. Phys. Lett,1999,74:3317-3319
[34]董树荣,涂江平,张孝彬.碳纳米管增强铜基复的力学性能和物理性能[J].材料研究学报,2001,14：132-136
[35]贾志杰,徐才录,梁吉,等.关于尼龙-6/碳纳米管复合材料的研究[J].新型炭材料,1999,14：32-35
[36]董树荣,张孝彬.碳纳米管增强铜基复合材料的滑动磨损特性研究[J].摩擦学学报,1999,19：1-6
[37]李玲.表面活性剂与纳米技术[M].北京：化学工业出版社,2004
[38]谢亚杰,王伟,刘深等.表面活性剂制备技术与分析测试[M].北京：化学工业出版社,2006
[39]Joseph Z, Hava K. Properties of Electrodeposited Composite Coating[J]. Plating and Surface Finishing,1982,69:76-82
[40]黄新民,吴玉程,郑玉春,等. 分散方法对纳米颗粒化学复合镀层组织与性能的影响. 电镀与精饰,1999,21(5)：12
[41]刘贵昌,杨哲龙.复合镀层的沉积规律和憎液性[J].材料保护,1997,30(9)：1-4
[42]常利民,徐宏,周晓光,等.表面活性剂在N-P-PTFE复合镀液的影响.松辽学刊(自然科学版),1998,3:45
[43]蒋斌,徐滨士,董世运等.纳米复合镀层的研究现状[J].材料保护,2002,35(6)：1-3
[2]周荣廷.化学镀镍的原理与工艺[M].北京：国防工业出版社,1975：34-41
[3]姜晓霞,沈伟.化学镀理论与实践[M].北京：国防工业出版社,2000：4-7
[4]孙克宁.化学镀Ni-P工艺研究[J].电镀与环保,1998,8(4)：18-20
[5]沃尔夫冈·里德尔.化学镀镍[M].上海：上海交通大学出版社,2004
[6]程秀云,张振华.电镀技术[M].北京：化学工业出版社,2003：1-2
[7]李宁,袁国伟,黎德育.化学镀镍基合金理论与技术[M].哈尔滨：哈尔滨工业大学出版社,2004
[8]李宁.化学镀实用技术[M].北京：化学工业出版社,2004
[9]陈亚.现代实用电镀技术[M].北京：国防工业出版社,2003：287-295
[10]屠振密,韩书梅,杨哲龙等.防护装饰性镀层[M].北京：化学工业出版社,1993.
[11]渡边澈.非晶态电镀及应用[M].北京：北京航空航天出版社，1993.
[12]唐睿.电镀Ni-W-P合金的组织纵横结构与性能研究.洛阳工学院学位论文,2001.
[13]Lanhmore D S, Ratzker M. Pratt K W. Electrodeposition and corrotion performance of Ni-P atmosphous alloys. Plating and Surface Finishing.1986,9: 74-82.
[14]Bundler M. electrochemical behavior of electrodeposition of Ni-P amorphous alloys. Z Anorg Allg Chem.1965,340:113-119.
[15]Raj Naryan, Mungole M N. Electrodeposition of Ni-P alloy coatings. Surface Techcology,1985.24:233-242.
[16]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
[17]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.
[18]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.
[19]候进,侯庆军.脉冲电镀的含义及常用形式[J].中国电镀材料信息2002,2(7)：68-73
[20]向国朴.脉冲电镀发展概况[J]电镀与涂饰.2000,19(4)：43-47
[21]向国朴编著.脉冲电镀的理论与应用[M].天津：科学技术出版社,1989：94-95.
[22]杨哲龙,安茂忠,李国强等.脉冲参数对光亮银镀层性能的影响[J].材料保护,1998,31(6)：17.
[23]侯丛福,王菊,于桂云等.脉冲参数对镀层微观结构及性能的影响[J].材料保护,2001,34(1)：10-11.
[24]张允诚编著.电镀手册[M].北京：国防工业出版社,1997：622-635
[25]曾华梁编著.电镀工艺手册[M].北京：机械工业出版社,1997：645-647.
[26]李国英主编表面工程手册[M].北京：机械工业出版社，1997：6-153-6-155
[27]屠振密,韩书梅,杨哲龙等.防护装饰性镀层[M].北京：化学工业出版社,1993
[28]张景双,石金声,石磊等.电镀溶液与镀层性能测试[M].北京：化学工业出版社,2003.
[29]刘燕萍,李林峰.脉冲电沉积Ni-P合金机理的研究[J].电镀与环保,1997,17(5)：12-14.
[30]Metzger and Th. Florian. The deposi Cion of dispersion hardened coatings by means of electroless nickel, Trans. IMF,1976,54:174 - 177
[31]李宁,袁国伟,黎德育等.化学镀镍基合金理论与技术[M].哈尔滨：哈尔滨工业大学出版,2000
[32]Treacy M M J, Ebbesen T W, Gibson J M, et al. Exceptionally high Young's modulus observed for individual Carbon nanotubes[J]. Nature,1996, 381:678-680
[33]Bower C, Rosen B and Jin L. deformation of carbon nanotubes in nanotube-polymer composites. Appl. Phys. Lett,1999,74:3317-3319
[34]董树荣,涂江平,张孝彬.碳纳米管增强铜基复的力学性能和物理性能[J].材料研究学报,2001,14：132-136
[35]贾志杰,徐才录,梁吉,等.关于尼龙-6/碳纳米管复合材料的研究[J].新型炭材料,1999,14：32-35
[36]董树荣,张孝彬.碳纳米管增强铜基复合材料的滑动磨损特性研究[J].摩擦学学报,1999,19：1-6
[37]李玲.表面活性剂与纳米技术[M].北京：化学工业出版社,2004
[38]谢亚杰,王伟,刘深等.表面活性剂制备技术与分析测试[M].北京：化学工业出版社,2006
[39]Joseph Z, Hava K. Properties of Electrodeposited Composite Coating[J]. Plating and Surface Finishing,1982,69:76-82
[40]黄新民,吴玉程,郑玉春,等. 分散方法对纳米颗粒化学复合镀层组织与性能的影响. 电镀与精饰,1999,21(5)：12
[41]刘贵昌,杨哲龙.复合镀层的沉积规律和憎液性[J].材料保护,1997,30(9)：1-4
[42]常利民,徐宏,周晓光,等.表面活性剂在N-P-PTFE复合镀液的影响.松辽学刊(自然科学版),1998,3:45
[43]蒋斌,徐滨士,董世运等.纳米复合镀层的研究现状[J].材料保护,2002,35(6)：1-3