不锈钢基Ni-HAP生物材料的复合电镀研究
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摘要
本文主要研究了HAP粒子与金属Ni颗粒在不锈钢基体上的共沉积。不锈钢含有Cr和较多的稳定奥氏体元素Ni，耐蚀性好，具有较高的塑性，易加工成型，亦无毒，在医疗上(外科)已有广泛应用。虽然在不锈钢电镀方面国内外已进行过大量的研究，但在不锈钢基体上进行复合电镀处理却报道较少。本文采用有效的预处理方法将Ni-HAP复合镀层与不锈钢牢固结合起来，以获得结合力强、与人体组织相容性好、具有临床医学应用前景的镀层。
本课题首先对羟基磷灰石粉末的制备作了研究，确定了最佳制备方法，并对制备过程中各工艺参数对HAP粉末的影响作了研究，从而确定出最佳的工艺参数。通过XRD检测，说明所得粉末为纯净的HAP；并对粉末的粒径进行了粗略计算，结果表明，晶体的平均结晶尺寸在35nm左右。
在复合镀过程中，研究了镀液的温度和阴极电流密度对镀液稳定性和沉积速度的影响；同时，研究了镀液中HAP的浓度、阴极电流密度、温度、搅拌速度等对镀层中HAP含量的影响，并确定了它们的最佳工艺参数。
运用XRD、SEM、EDS、显微硬度检测等手段分析了复合镀层的表面形貌、组织结构、镀层成分、显微硬度、耐磨性等；同时对镀层的结合力、耐蚀性等方面也进行了研究；结果表明，镀层是由Ni和HAP组成；硬度随着镀层中HAP含量的增加而增大；耐磨性比钝Ni镀层要好；耐腐蚀性随着镀层中HAP含量的增加而下降。
同时，对复合电沉积机理进行了分析，结果表明，微粒的ζ电位、有效电荷密度和电极与溶液界面间的场强对复合电沉积有很大的影响；两步吸附机理能够较好的解释复合电沉积的实质。
The deposition of Ni and HAP on the stainless steel substrate was studied in this paper. The stainless steel contains Cr and the more austenite element Ni, having better corrosion resistance, higher plasticity and easier processing, as well not poisonous, and it had already been applied on the medical treatment extensively. Although the investigations on plating on the stainless steel have widely been carried on both home and abroad, the research about deposition Ni-HAP composite coating on the stainless steel was less. Some valid processing treatments were used in order to make the binding strength of the layer and the stainless steel better, and make it possible to apply them to the medical fields.
Firstly, the influence of the technological parameters on the preparation of the HAP powder was investigated. The XRD examination indicated that the powder was the pure HAP. An approximately calculation for the particle diameter showed the average size of particle diameter of crystal is 35 nm or so.
The influence of the temperature and the cathode electric current density on the stability of plating solution and the deposition speed have been studied.Meanwhile, some processing parameters ,such as the concentration of HAP in plating solution, cathode electric current density, temperature of solution, mixing speed, the HAP content in layer etc.,have been studied and the optimum parameters were obtained.
The micro-structure, micro-hardness, wear resistance, etc., of the coatings were analysed by XRD, SEM, EDS and other instruments. Moreover, the binding strength and corrosion resistance of coatings were also studied. The results indicate that the layer is composed of the Ni and the HAP. The hardness increases with the increasing of the HAP content in the layer; Wear resistance is better than the coating of Ni; Corrosion resistance become badly with the increasing of the HAP content in layer.
In addition, the mechanism of composite deposition was preliminarily discussed.The results indicate that theζelectric potential of the particle, the valid charge density and the strength of electric field between the electrode and the interface have significant influence on the composite electricity depositions; The Two- Step adsorb mechanism can satisfactorily explain the nature of composite electricity deposition.
本课题首先对羟基磷灰石粉末的制备作了研究，确定了最佳制备方法，并对制备过程中各工艺参数对HAP粉末的影响作了研究，从而确定出最佳的工艺参数。通过XRD检测，说明所得粉末为纯净的HAP；并对粉末的粒径进行了粗略计算，结果表明，晶体的平均结晶尺寸在35nm左右。
在复合镀过程中，研究了镀液的温度和阴极电流密度对镀液稳定性和沉积速度的影响；同时，研究了镀液中HAP的浓度、阴极电流密度、温度、搅拌速度等对镀层中HAP含量的影响，并确定了它们的最佳工艺参数。
运用XRD、SEM、EDS、显微硬度检测等手段分析了复合镀层的表面形貌、组织结构、镀层成分、显微硬度、耐磨性等；同时对镀层的结合力、耐蚀性等方面也进行了研究；结果表明，镀层是由Ni和HAP组成；硬度随着镀层中HAP含量的增加而增大；耐磨性比钝Ni镀层要好；耐腐蚀性随着镀层中HAP含量的增加而下降。
同时，对复合电沉积机理进行了分析，结果表明，微粒的ζ电位、有效电荷密度和电极与溶液界面间的场强对复合电沉积有很大的影响；两步吸附机理能够较好的解释复合电沉积的实质。
The deposition of Ni and HAP on the stainless steel substrate was studied in this paper. The stainless steel contains Cr and the more austenite element Ni, having better corrosion resistance, higher plasticity and easier processing, as well not poisonous, and it had already been applied on the medical treatment extensively. Although the investigations on plating on the stainless steel have widely been carried on both home and abroad, the research about deposition Ni-HAP composite coating on the stainless steel was less. Some valid processing treatments were used in order to make the binding strength of the layer and the stainless steel better, and make it possible to apply them to the medical fields.
Firstly, the influence of the technological parameters on the preparation of the HAP powder was investigated. The XRD examination indicated that the powder was the pure HAP. An approximately calculation for the particle diameter showed the average size of particle diameter of crystal is 35 nm or so.
The influence of the temperature and the cathode electric current density on the stability of plating solution and the deposition speed have been studied.Meanwhile, some processing parameters ,such as the concentration of HAP in plating solution, cathode electric current density, temperature of solution, mixing speed, the HAP content in layer etc.,have been studied and the optimum parameters were obtained.
The micro-structure, micro-hardness, wear resistance, etc., of the coatings were analysed by XRD, SEM, EDS and other instruments. Moreover, the binding strength and corrosion resistance of coatings were also studied. The results indicate that the layer is composed of the Ni and the HAP. The hardness increases with the increasing of the HAP content in the layer; Wear resistance is better than the coating of Ni; Corrosion resistance become badly with the increasing of the HAP content in layer.
In addition, the mechanism of composite deposition was preliminarily discussed.The results indicate that theζelectric potential of the particle, the valid charge density and the strength of electric field between the electrode and the interface have significant influence on the composite electricity depositions; The Two- Step adsorb mechanism can satisfactorily explain the nature of composite electricity deposition.
引文
[1] 崔福斋，冯庆玲．生物材料学[M]．北京：北京科学出版社，1996，30-45
[2] Hench L. L. , J. Am. Ceram[J]. Soc. , 1991, 74(7): 1487-1510
[3] Jones J. R. , Hench L. L. , J. Mater[J]. Sci. , 2001, 17 (8): 891-899
[4] 陈治清．关于无机生物材料的发展战略[J]．材料学报．1993，3(5)：49-50
[5] 贡长生，张克林．新型功能材料[M]．北京：化学工业出版社，2001，535-546
[6] 沈卫，顾燕芳，刘昌盛．羟基磷灰石生物陶瓷的研究[J]．硅酸盐通报，1996，20(3)：45-51
[7] 曲海波，程奎，沈鸽等．羟基磷灰石生物陶瓷在医学方面的应用[J]．硅酸盐通报，2000，5(6)：52-56
[8] 王迎军，朱建业，郑月华．羟基磷灰石生物陶瓷力学性能的研究[J]．中国陶瓷，1994，4：12-17
[9] Kawasaki T. Chromatography, 1990, 6(1): 125-128
[10] 沈卫等．羟基磷灰石的表面特性[J]．硅酸盐通报，1996，5(1)：45-51
[11] 朱晏军，沈春华，戴红莲等．生物医用纳米羟基磷灰石(HA)的制备及性能测试[J]．佛山陶瓷，2004，84(1)：13-16
[12] Jarch M, Kay JF, Gunner KI, et al. Biomaterial, 1977, 1(12): 79-83
[13] Petaka P, Hofilands W, et al. Society Biomat. 15th Annual Meeting, 1989, 103-110
[14] Orly I. J. Biomed. Mater. Res. , 1989, 23 (5): 14-33
[15] Ducheyne P. J. Biomed. Mater. Res. , 1987, 17(10): 219-230
[16] Jarcho J, Bolen CH, Thomas MB, et al. J. Mater. Res. 1976, 11(9): 20-27
[17] 张士成，李世普，袁润章．磷灰石超微粉对骨癌Os-732细胞形态的影响[J]．武汉工业人学学报，1996，18(1)：12—15
[18] 任卫，曹献英，冯凌云等．纳米羟基磷灰石合成及表面改性的途径和方法[J]．硅酸盐通报，2002，21(1)：38-43
[19] 资文华，陈庆华等．羟基磷灰石生物的研究状况及发展趋势[J]．中国陶瓷工业，2003，10(1)：38-43
[20] 储成林等．致密羟基磷灰石生物陶瓷烧结行为和力学性能[J]．功能材料，1999，5(6)：606—609
[21] 姚秀敏等．多孔羟基磷灰石的制备[J]．无机材料学报，2003，4(3)：467—472
[22] 张建民．电化学方法制备磷酸钙生物陶瓷镀层[J]．中国陶瓷，1998，34(5)：38-40
[23] 曾爱香．金属基陶瓷涂层的制备、应用及发展[J]．陶瓷研究，1998，13(4)：7-10
[24] 廖其龙，徐光亮，尹光福等．羟基磷灰石生物陶瓷的医学研究[J]．功能材料，1999，33(3)：338-340
[25] P. L. Tranquilli, A. Merolli. et al. . J. Mater. Sci. , 1994, 5: 345-350
[26] Liu Changsheng, Huang Yue, Shen Wei, et al. , Biomaterials, 2001, 22 (10): 301-306
[27] 郑昌琼，冉均国，尹光福等．成都科技大学学报[J] ，1996，93(5)：67-71
[28] 徐光亮，聂轶霞，赖振宇等．生物陶瓷材料研究[J]．无机材料学报，2002，17(3)：600-604
[29] Kazuyaki Hosoi, Toshiyuki Hashida, Hideaki Talahashi, et al. . J. Am. Ceram. Soc. , 1996, 79(10): 14-25
[30] Weng Wenjian. Baptista J L. J. Am. Ceram. Soc. , 1998, 82 (1): 27-32
[31] 宋云京，温树林，李木森等．溶胶．凝胶法制备HAP的研究[J]．无机材料学报，2002，17(5)：985-991
[32] RamachandraRao R, et al. . J. Mater. Sci. Mater Med. , 1997, 8: 511-518
[33] 刘昌盛，沈卫，崔锦华等．羟基磷灰石生物陶瓷制备的动力学研究[J]．华东理工大学学报，1996，22(10)：530-535
[34] 李新化．羟基磷灰石生物陶瓷糖化粉体制备及其在钛基体上的涂覆[J]．合肥工业大学，2003，12(5)11-28
[35] Knowles J. C. , Callcut S. , Georgiou G. Biomaterials[M] , 2000, 89-100
[36] 戴安邦．元素周期表[M]．南京：南京大学出版社，1980，40-60
[37] 陈天玉．不锈钢表面处理技术[M]．北京：化学工业出版社，2004，77-85
[38] 卜金纬，黄根良．化学复合镀几个关键工艺因素研究[J]．表面技术，2006，35(4)：48-52
[39] N. Guglielmi. J. Elechochem[M]. Soc. , 1972, 119-130
[40] 唐致远，郭鹤桐等．中国电子学会第二届电子电镀年会论文选编(下)，1982
[41] J. Zahavi, J. Hazac. Platingand Surface Finish. , 1983, 70 (2): 57-62
[42] J. Foster, A. M. J. Kadapper. Trans. Inst. [J]. Metal Finish, 1973, 51(1): 27-36
[43] 唐致远，郭鹤桐．复合电镀沉积机理研究[J]．电镀与精饰，1982，10(4)：1-10
[44] 郭鹤桐，刘淑兰．理论电化学[M]．北京：宇航出版社，1984，155-163
[45] N. Guglielmi. J. Elechochem. Soc. , 1972, 119-125
[46] I. Langmuir, J. Amer. Chem. Soe. , 1916, 124-131
[47] R. Narayan, B. H. Narayan. Reviews on Coating and Corrosion, 1981, 5(2): 145-150
[48] J. P. Celis, J. R. Roos. J. Elechochem. Soc. [M] , 1977, 124-142
[49] 内藤邦子．金属表面技术，1979，6(4)：185-190
[50] 郭鹤桐等．Ni-金钢石复合电镀的研究[J]．电镀与精饰．1982，6(1)：1-10
[51] 郭鹤桐，王兆勇．电镀技术[J]．天津大学学报，1985，15(1)：20-30
[52] C. White, J. Foster. Trans. Inst. Metal Finish, 1981, 12 (1): 8-20
[53] 郭鹤桐，覃奇贤，陈一新．复合电镀沉积机理研究[J]．天津大学学报，1986，5(4)：20-36
[54] 陈一新．天津大学应用化学系研究生硕士论文，1985
[55] H. C. Hamaker. Physica, 1937, 21 (4): 10-58
[56] S. G. Ash, D. H. Everett, C. L. Rader, J. Chem. Soc. . Faraday Trans. Ⅱ, 1973, 69-85
[2] Hench L. L. , J. Am. Ceram[J]. Soc. , 1991, 74(7): 1487-1510
[3] Jones J. R. , Hench L. L. , J. Mater[J]. Sci. , 2001, 17 (8): 891-899
[4] 陈治清．关于无机生物材料的发展战略[J]．材料学报．1993，3(5)：49-50
[5] 贡长生，张克林．新型功能材料[M]．北京：化学工业出版社，2001，535-546
[6] 沈卫，顾燕芳，刘昌盛．羟基磷灰石生物陶瓷的研究[J]．硅酸盐通报，1996，20(3)：45-51
[7] 曲海波，程奎，沈鸽等．羟基磷灰石生物陶瓷在医学方面的应用[J]．硅酸盐通报，2000，5(6)：52-56
[8] 王迎军，朱建业，郑月华．羟基磷灰石生物陶瓷力学性能的研究[J]．中国陶瓷，1994，4：12-17
[9] Kawasaki T. Chromatography, 1990, 6(1): 125-128
[10] 沈卫等．羟基磷灰石的表面特性[J]．硅酸盐通报，1996，5(1)：45-51
[11] 朱晏军，沈春华，戴红莲等．生物医用纳米羟基磷灰石(HA)的制备及性能测试[J]．佛山陶瓷，2004，84(1)：13-16
[12] Jarch M, Kay JF, Gunner KI, et al. Biomaterial, 1977, 1(12): 79-83
[13] Petaka P, Hofilands W, et al. Society Biomat. 15th Annual Meeting, 1989, 103-110
[14] Orly I. J. Biomed. Mater. Res. , 1989, 23 (5): 14-33
[15] Ducheyne P. J. Biomed. Mater. Res. , 1987, 17(10): 219-230
[16] Jarcho J, Bolen CH, Thomas MB, et al. J. Mater. Res. 1976, 11(9): 20-27
[17] 张士成，李世普，袁润章．磷灰石超微粉对骨癌Os-732细胞形态的影响[J]．武汉工业人学学报，1996，18(1)：12—15
[18] 任卫，曹献英，冯凌云等．纳米羟基磷灰石合成及表面改性的途径和方法[J]．硅酸盐通报，2002，21(1)：38-43
[19] 资文华，陈庆华等．羟基磷灰石生物的研究状况及发展趋势[J]．中国陶瓷工业，2003，10(1)：38-43
[20] 储成林等．致密羟基磷灰石生物陶瓷烧结行为和力学性能[J]．功能材料，1999，5(6)：606—609
[21] 姚秀敏等．多孔羟基磷灰石的制备[J]．无机材料学报，2003，4(3)：467—472
[22] 张建民．电化学方法制备磷酸钙生物陶瓷镀层[J]．中国陶瓷，1998，34(5)：38-40
[23] 曾爱香．金属基陶瓷涂层的制备、应用及发展[J]．陶瓷研究，1998，13(4)：7-10
[24] 廖其龙，徐光亮，尹光福等．羟基磷灰石生物陶瓷的医学研究[J]．功能材料，1999，33(3)：338-340
[25] P. L. Tranquilli, A. Merolli. et al. . J. Mater. Sci. , 1994, 5: 345-350
[26] Liu Changsheng, Huang Yue, Shen Wei, et al. , Biomaterials, 2001, 22 (10): 301-306
[27] 郑昌琼，冉均国，尹光福等．成都科技大学学报[J] ，1996，93(5)：67-71
[28] 徐光亮，聂轶霞，赖振宇等．生物陶瓷材料研究[J]．无机材料学报，2002，17(3)：600-604
[29] Kazuyaki Hosoi, Toshiyuki Hashida, Hideaki Talahashi, et al. . J. Am. Ceram. Soc. , 1996, 79(10): 14-25
[30] Weng Wenjian. Baptista J L. J. Am. Ceram. Soc. , 1998, 82 (1): 27-32
[31] 宋云京，温树林，李木森等．溶胶．凝胶法制备HAP的研究[J]．无机材料学报，2002，17(5)：985-991
[32] RamachandraRao R, et al. . J. Mater. Sci. Mater Med. , 1997, 8: 511-518
[33] 刘昌盛，沈卫，崔锦华等．羟基磷灰石生物陶瓷制备的动力学研究[J]．华东理工大学学报，1996，22(10)：530-535
[34] 李新化．羟基磷灰石生物陶瓷糖化粉体制备及其在钛基体上的涂覆[J]．合肥工业大学，2003，12(5)11-28
[35] Knowles J. C. , Callcut S. , Georgiou G. Biomaterials[M] , 2000, 89-100
[36] 戴安邦．元素周期表[M]．南京：南京大学出版社，1980，40-60
[37] 陈天玉．不锈钢表面处理技术[M]．北京：化学工业出版社，2004，77-85
[38] 卜金纬，黄根良．化学复合镀几个关键工艺因素研究[J]．表面技术，2006，35(4)：48-52
[39] N. Guglielmi. J. Elechochem[M]. Soc. , 1972, 119-130
[40] 唐致远，郭鹤桐等．中国电子学会第二届电子电镀年会论文选编(下)，1982
[41] J. Zahavi, J. Hazac. Platingand Surface Finish. , 1983, 70 (2): 57-62
[42] J. Foster, A. M. J. Kadapper. Trans. Inst. [J]. Metal Finish, 1973, 51(1): 27-36
[43] 唐致远，郭鹤桐．复合电镀沉积机理研究[J]．电镀与精饰，1982，10(4)：1-10
[44] 郭鹤桐，刘淑兰．理论电化学[M]．北京：宇航出版社，1984，155-163
[45] N. Guglielmi. J. Elechochem. Soc. , 1972, 119-125
[46] I. Langmuir, J. Amer. Chem. Soe. , 1916, 124-131
[47] R. Narayan, B. H. Narayan. Reviews on Coating and Corrosion, 1981, 5(2): 145-150
[48] J. P. Celis, J. R. Roos. J. Elechochem. Soc. [M] , 1977, 124-142
[49] 内藤邦子．金属表面技术，1979，6(4)：185-190
[50] 郭鹤桐等．Ni-金钢石复合电镀的研究[J]．电镀与精饰．1982，6(1)：1-10
[51] 郭鹤桐，王兆勇．电镀技术[J]．天津大学学报，1985，15(1)：20-30
[52] C. White, J. Foster. Trans. Inst. Metal Finish, 1981, 12 (1): 8-20
[53] 郭鹤桐，覃奇贤，陈一新．复合电镀沉积机理研究[J]．天津大学学报，1986，5(4)：20-36
[54] 陈一新．天津大学应用化学系研究生硕士论文，1985
[55] H. C. Hamaker. Physica, 1937, 21 (4): 10-58
[56] S. G. Ash, D. H. Everett, C. L. Rader, J. Chem. Soc. . Faraday Trans. Ⅱ, 1973, 69-85
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