块体纳米晶工业纯铁化学镀镍磷
|
摘要
块体纳米晶工业纯铁(BNⅡ)是将普通工业纯铁(CPⅡ)通过深度轧制技术制得的块状纳米材料。
化学镀镍磷是一项表面处理技术,是化学镀技术最具代表性且应用最广泛的一种。化学镀镍磷是利用次磷酸钠为还原剂,使镀液中的镍离子直接在具有催化活性的基体表面还原,同时磷共沉积而形成镍磷镀层的一种镀镍工艺。
本文采用高温(88℃)酸性(pH 4.4-4.5)化学镀Ni-P合金的方法制得了高磷(12-14 wt%)非晶镀层,并利用其高硬度、耐磨性、抗腐蚀性对BNⅡ进行修饰和保护。研究内容包括最佳施镀工艺的研究,采用扫描电镜形貌分析仪、能谱分析仪、X射线衍射分析仪、X射线光电子能谱、金相显微镜、硬度计、电化学工作站等仪器对镍磷镀层的结构形貌、孔隙率、硬度、结合力、腐蚀性能等相关性能的研究。同时对BNⅡ与CPⅡ化学镀镍磷的性能及沉积机理进行对比研究,以期使用BNⅡ较适用CPⅡ在化学镀镍磷性能方面有所改善。
制备了光泽度及平整度优良的高磷(P wt%11-13%)镀层,厚度为24±1μm,具有零孔隙率,结合力良好,化学镀镀态的硬度为HV 506,经390℃热处理1h后可达HV 936。镀膜为非晶结构,加热可使其晶化,生成Ni和Ni3P两相,BNⅡ镀层晶化温度为340℃,镀层在883℃时熔化。由Tafel极化实验知,在5% NaCl和0.5 mol/LHC1溶液中,BNⅡ镀层与BNⅡ相比,自腐蚀电位Ecorr分别正移216 mV和197 mV；CPⅡ镀层Ecorr与CPⅡEcorr相比,分别正移50 mV和118 mV；BNⅡ镀层自腐蚀电流密度icorr(8.956×10-6A/cm2,4.215×10-5A/cm2),较BNⅡ的icorr(1.303×10-5A/cm2,1.326×10-4A/cm2)明显减小。
X射线光电子能谱分析表明,在化学镀最初期,BNⅡ与CPⅡ相比,其化学镀Ni-P镀层中P 2p3结合能高出0.9 eV；Ni 2p3结合能降低0.1 eV,Ni 2p1结合能降低0.3 eV；Fe 2p3结合能降低0.2 eV,Fe 2p1结合能降低0.4 eV。
Bulk nanocrystalline ingot iron (BNII) was produced from conventional polycrystalline ingot iron (CPII) by the severe rolling technique.
Electroless nickel-phosphorus (Ni-P) is a technique for solid surface treatment. It has been adopted as representative chemical plating and widely applied in industry. Electroless Ni-P using sodium hypophosphite as a reducing agent, therefore the nickel ion is reduced directly on the catalytic reducting surface of the substrate from Ni-plating solution, and phosphorus is co-deposited simultaneously. Thus chemical Ni-P plating is performed.
In this paper, high phosphorus (Pwt% 11%-13%) amorphous plating was obtained by optimum Ni-P electrless plating process at high temperatures of 88℃The acidity of the plating solution was controlled as 4.4-4.5 in pH with a buffer solution. Characterization of nickel-phosphorus plating including the structure and morphology, porosity, hardness, bonding strength, and corrosion resistance properties was made by using scanning electron micrograph, X-ray diffraction analyzer, X-ray photoelectron spectroscopy, metallographic microscope, hardness tester, chi660c electrochemical workstation equipment, respectively. The deposition mechanism of electroless Ni-P on BNII and CPII was studied, and improvement of electroless Ni-P plating on BNII was expected.
The experimental results indicated that the prepared Ni-P plating has excellent gloss smoothness, zero porosity, and nice binding force. The thickness of the Ni-P plating was 24±1μm. The hardness was increased from HV 506 at the very beginning of chemical plating to HV 936 after treating at 390℃for 1h. The structure of Ni-P plating is amorphous at room temperature. A crystallized structure with two-phase Ni and Ni3P could be formed at elevated temperatures. The crystallization temperature of the plating on BNII was 340℃, and the melting point was about 883℃. According to the Tafel polarization analysis,in 5% NaCl and in 0.5 mol/L HCl solutions, the corrosion potential Ecorr of BNII with the plating is 216 mV and 197 mV higher than that without plating, respectively; The corrosion potential Ecorr of CPII with the plating is 50 mV and 118 mV higher than that without plating, respectively; Meanwhile, corrosion current density icorr of BNII with the plating (1.303×10-5 A/cm2,4.215×10-5 A/cm2, respectively) are obviously lower than those of BNII without plating (1.303×10-5 A/cm2,1.326×10-4 A/cm2, respectively).
According to the X-ray photoelectron spectroscopy, the binding energy of the earlier plating was increased in 0.9 eV for P 2p3; decreaded in 0.1 eV for Ni 2p3 and 0.3 eV for Ni 2p1; decreased in 0.2 eV for Fe 2p3 and 0.4 eV for Fe 2p1, respectively, by comparing the results obtained from BNII plating with those from CPII plating.
化学镀镍磷是一项表面处理技术,是化学镀技术最具代表性且应用最广泛的一种。化学镀镍磷是利用次磷酸钠为还原剂,使镀液中的镍离子直接在具有催化活性的基体表面还原,同时磷共沉积而形成镍磷镀层的一种镀镍工艺。
本文采用高温(88℃)酸性(pH 4.4-4.5)化学镀Ni-P合金的方法制得了高磷(12-14 wt%)非晶镀层,并利用其高硬度、耐磨性、抗腐蚀性对BNⅡ进行修饰和保护。研究内容包括最佳施镀工艺的研究,采用扫描电镜形貌分析仪、能谱分析仪、X射线衍射分析仪、X射线光电子能谱、金相显微镜、硬度计、电化学工作站等仪器对镍磷镀层的结构形貌、孔隙率、硬度、结合力、腐蚀性能等相关性能的研究。同时对BNⅡ与CPⅡ化学镀镍磷的性能及沉积机理进行对比研究,以期使用BNⅡ较适用CPⅡ在化学镀镍磷性能方面有所改善。
制备了光泽度及平整度优良的高磷(P wt%11-13%)镀层,厚度为24±1μm,具有零孔隙率,结合力良好,化学镀镀态的硬度为HV 506,经390℃热处理1h后可达HV 936。镀膜为非晶结构,加热可使其晶化,生成Ni和Ni3P两相,BNⅡ镀层晶化温度为340℃,镀层在883℃时熔化。由Tafel极化实验知,在5% NaCl和0.5 mol/LHC1溶液中,BNⅡ镀层与BNⅡ相比,自腐蚀电位Ecorr分别正移216 mV和197 mV；CPⅡ镀层Ecorr与CPⅡEcorr相比,分别正移50 mV和118 mV；BNⅡ镀层自腐蚀电流密度icorr(8.956×10-6A/cm2,4.215×10-5A/cm2),较BNⅡ的icorr(1.303×10-5A/cm2,1.326×10-4A/cm2)明显减小。
X射线光电子能谱分析表明,在化学镀最初期,BNⅡ与CPⅡ相比,其化学镀Ni-P镀层中P 2p3结合能高出0.9 eV；Ni 2p3结合能降低0.1 eV,Ni 2p1结合能降低0.3 eV；Fe 2p3结合能降低0.2 eV,Fe 2p1结合能降低0.4 eV。
Bulk nanocrystalline ingot iron (BNII) was produced from conventional polycrystalline ingot iron (CPII) by the severe rolling technique.
Electroless nickel-phosphorus (Ni-P) is a technique for solid surface treatment. It has been adopted as representative chemical plating and widely applied in industry. Electroless Ni-P using sodium hypophosphite as a reducing agent, therefore the nickel ion is reduced directly on the catalytic reducting surface of the substrate from Ni-plating solution, and phosphorus is co-deposited simultaneously. Thus chemical Ni-P plating is performed.
In this paper, high phosphorus (Pwt% 11%-13%) amorphous plating was obtained by optimum Ni-P electrless plating process at high temperatures of 88℃The acidity of the plating solution was controlled as 4.4-4.5 in pH with a buffer solution. Characterization of nickel-phosphorus plating including the structure and morphology, porosity, hardness, bonding strength, and corrosion resistance properties was made by using scanning electron micrograph, X-ray diffraction analyzer, X-ray photoelectron spectroscopy, metallographic microscope, hardness tester, chi660c electrochemical workstation equipment, respectively. The deposition mechanism of electroless Ni-P on BNII and CPII was studied, and improvement of electroless Ni-P plating on BNII was expected.
The experimental results indicated that the prepared Ni-P plating has excellent gloss smoothness, zero porosity, and nice binding force. The thickness of the Ni-P plating was 24±1μm. The hardness was increased from HV 506 at the very beginning of chemical plating to HV 936 after treating at 390℃for 1h. The structure of Ni-P plating is amorphous at room temperature. A crystallized structure with two-phase Ni and Ni3P could be formed at elevated temperatures. The crystallization temperature of the plating on BNII was 340℃, and the melting point was about 883℃. According to the Tafel polarization analysis,in 5% NaCl and in 0.5 mol/L HCl solutions, the corrosion potential Ecorr of BNII with the plating is 216 mV and 197 mV higher than that without plating, respectively; The corrosion potential Ecorr of CPII with the plating is 50 mV and 118 mV higher than that without plating, respectively; Meanwhile, corrosion current density icorr of BNII with the plating (1.303×10-5 A/cm2,4.215×10-5 A/cm2, respectively) are obviously lower than those of BNII without plating (1.303×10-5 A/cm2,1.326×10-4 A/cm2, respectively).
According to the X-ray photoelectron spectroscopy, the binding energy of the earlier plating was increased in 0.9 eV for P 2p3; decreaded in 0.1 eV for Ni 2p3 and 0.3 eV for Ni 2p1; decreased in 0.2 eV for Fe 2p3 and 0.4 eV for Fe 2p1, respectively, by comparing the results obtained from BNII plating with those from CPII plating.
引文
1.张立德,牟季美.纳米材料和纳米结构[M],北京：科学出版社,2001：164-169.
2.程军胜,杨滨,张济山等.块体金属纳米材料成形技术研究进展[J],材料导报,2004,18(11)：63-65.
3.张振忠,宋广生,杨根仓,周尧和.块状金属纳米材料的制备技术进展及展望[J],兵器材料科学与工程,1999,22(3)：46-50.
4.赵廷凯,柳永宁,朱杰武.纳米材料概述[J],功能材料,2004,35：2675-2678.
5. Gleiter H. Nano-structured materials:basic concepts and micro-structure [J], Acta Materialia,2000,48(1):1-29.
6. Langdon G. Recent. Development in high strain rate super plasticity [J], Materials Transactions,1999,40(8):716-722.
7.张立德,牟季美.纳米材料和纳米结构[M],北京：科学出版社,2001：170-171.
8. Xu B S, Tanaka S I. Formation and bonding of platinum nanoparticles controlled by high energy beam irradiation [J], Nanostructured Materials,2000,20(12):915-917.
9.曹茂盛,关长斌,徐甲强.纳米材料导论[M],哈尔滨：哈尔滨工业大学出版社,2001：5-14.
10.居志兰,戈晓岚,许晓静.块体纳米材料的研究现状与发展思路[J],江苏大学学报,2002,23(4)：47-51.
11. Gleiter H V. Synthesis of nanostructured materials by the use of a thermophoretic forced flux system [J], Nanostructured Materials,1986,27(8):43.
12.王胜刚,龙康,龙期威.深度轧制细化工业纯铁晶粒[J],金属学报,2003,39(12)：1247-1250.
13. Wang S G, Shen C B, Long K, Yang H Y, Wang F H, Zhang Z D. Preparation and electrochemical corrosion behavior of bulk nanocrystalline ingot iron in HCl acid solution [J], Jurnal of Physical Chemistry B,2005,109(8):2499-2503.
14. Wang S G, Shen C B, Long K, Zhang T, Wang F H, Zhang Z D. The electrochemical corrosion of bulk nanocrystalline ingot iron in acidic sulfate solution [J], Jurnal of Physical Chemistry B,2006,110(9):377-382.
15.吕晓仁,王胜刚,刘阳,李曙.纳米化纯铁在干摩擦及油润滑条件下的磨损行为研究[J],摩擦学学报,2007,27(1)：20-27.
16.姜晓霞,沈伟.化学镀理论及实践[M],北京：国防工业出版社,2000：3-4.
17. Gutzeit G. An outline of the chemistry involved in the Process of catalytic Nickel deposition from aqueous solution plating [J], Surface and Coatings Technology,1959, 50(4):1275-1278.
18.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,2000,1-3.
19. Hajdu J. Electroless plating:the past is prologue [J], Plating and Surface Finishing, 1996,83(9):29-33.
20.沈伟,沈晓丹,张钦京.化学镀镍行业近年的发展状况[J],材料保护,2007,40(20)：50-54.
21.胡信国,张钦京.美国化学镀镍年会论文综述[J],电镀与涂饰,2003,22(2)：35-37.
22.李宁.化学镀实用技术[M],化学工业出版社,2003,1-4.
23.张钦京,杨德钧.我国化学镀技术交流与发展[J],表面工程资讯,2005,2(5)：5-6.
24. Bayes M W. Electroless nickel in the 90s'[J], Metal Finishing,1990,88(4):27-30.
25. Brenner A, Riddell G E. Niekel plating on steel by chemieal reduetion plating and surface Finishing [J], Plating and Surface Finishing,1946,39(11):385-395.
26.崔国峰.化学镀镍磷合金过程中磷的析出及其对镀层性能的影响[D],哈尔滨工业大学,2006
27.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,2000,11-13.
28. Meerak A. Electroless nickel plating from acid bath [J], Surface and Coatings Technology,2000,123(1):72-77.
29.俞宏英.化学镀镍磷合金镀层在硝酸溶液中的腐蚀机理[D],北京科技大学,1999
30.洪春勇,张萌.化学沉积镍磷合金的扫描电镜研究[J],江西大学学报,1990,14(3)：31-33.
31. Fundo A M, Abrantes L M. The electrocatalytic behaviour of electroless Ni-P alloy [J], Journal of Electroanalytical Chemistry,2007,600(1):63-79.
32. Baskaran I, Sankara T S, Narayanan N. A stephen.properties of electroless and electroplated Ni-P and its application in microgalvanics [J], Materials Chemistry and Physics,2006,99(2):117-126.
33. Mayanna S M, Ramesh L, Sheshadri B S. Electroless nickel plating influence of mixed legands [J]. Transactions of the Institute of Metal Finishing,1996,74(2):66-68.
34.胡文彬.难度基材的化学镀[M],北京：化学工业出版社,2003,10-13.
35. Zhoua Q J, He J Y, Haob X P, Chuan W Y, Qiao L J. The effect of hydrogen on plastic deformation of electroless nickel phosphorous amorphous plating [J], Materials Science and Engineering A,2006,437(2):356-359.
36. Singh D D N. Electroless nickel-phosphorus coatings to protect steel reinforcement bars from chloride induced corrosion [J], Surface and Coatings Technology,2006, 201(1):90-101.
37.张星笃,严文,白真权.化学镀高磷Ni-P合金的研究[J],电镀与环保,2008,28(5)：31-33.
38. Parker K. The effect of nickel salts on electroless nickel plating [J], Surface Finishing and Plating,1996,38(1):70-71.
39.訾炳涛,王辉.块体纳米材料的制备技术现状[J],中国有色金属学会第五届学术年会论文集,2000：184-188.
40. Brenner A, Riddell G E. Niekel Plating on Steel by Chemieal Reduetion Plating and Surface Finishing [J], Surface Finishing and Plating,1996,39(11):385-395.
41. Huang S, Cui F Z. Effect of complexing agent on the morphology and micros-tructure of electroless deposited Ni-P alloy [J], Surface and Coatings Technology,2007,201(9): 5416-5418.
42.李春玲.化学复合镀Ni-P-纳米TiO2工艺及性能研究(D],沈阳东北大学,2007
43.张天顺.化学镀Ni-P合金工艺研究[J],表面技术,1999,12(4)：12-16.
44.郭素枝.扫描电镜技术及其应用[M],厦门：厦门大学出版社,2000,14-15.
45.张延东.化学镀镍磷合金工艺优化及络合剂作用的研究(D),北京科技大学,2000
46.卢旭东,邵忠财.化学镀N i-P合金镀层孔隙率的影响因素[J],电镀与精饰,2007,29(6)：1-3.
47.郭东萍,薛士科,王春玉.化学镀镍磷层孔隙率的电化学评价[J],材料保护,2007,40(9)：28-30.
48.王煜明.非晶体及晶体缺陷的X射线衍射[M],北京：科学出版社,1988,55-60.
49.杨于兴,漆睿.X射线衍射分析[M],上海：上海交通大学出版社,1994,1-15.
50.李吉学,国秀珍.化学镀N i-P合金镀层相结构与硬度的研究[J],表面技术,2001,30(1)：6-8.
51.牛振江,沈吉军,李则林,吴廷华.原位XRD研究热处理Ni-P化学镀合金的结构[J],材料保护,2003,36(7)：45-47.
52.王丽丽,管从胜,孙从征.热处理对镍磷合金镀层结合强度和硬度的影响[J],电镀与精饰,2008,30(2)：4-6.
53. Guo X P, Tomoe Y. The effect of corrosion product layers on the anodic and cathodic reations of carbon steel in CO2-saturated MDEA solutions at 100℃ [J], Corrosion science,1999,41:1391-1402.
54.曹楚南,张鉴清.电化学阻抗谱导论[M],北京：科学出版社,2002,151-154.
55.李瑛,王福会.表面纳米化对金属材料电化学腐蚀行为的影响[J],腐蚀与防护,2003,24(1)：7-9.
56.蒋太祥,吴辉煌,毛秉伟,周少民.化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为[J],应用化学,1999,16(3)：21-24.
57.王徐承,王卫东,柳厚田,郁祖湛.化学镀非晶态Ni-P和Ni-B合金在H2SO4溶液中的电化学行为[J],电化学,2003,9(1)：36-39.
58.胡飞,肖静芝,旷亚非.非晶态Ni-P合金电镀层耐蚀性的研究[J],电镀与涂饰,1997,16(4)：17-20.
59.徐瑞东,王军丽,薛方勤,郭忠诚.全光亮镍磷合金镀层的耐蚀性[J],腐蚀科学与防护技术,2004,16(2)：110-112.
60.李振钢,徐景生,王宙,李淑华,赵小京.化学沉积Ni-P合金非晶态形成机制[J],大庆石油学院学报,1993,17(2)：100-102.
61.曹文博,任晨星,关绍康.高锌镁合金化学镀镍磷初始沉积特征的研究[J],材料保护,2006,39(2)：11-13.
62.洪春勇,张萌.化学沉积镍磷合金的扫描电镜研究[J],江西大学学报,1990,14(3)：31-34.
63.朱和国,王恒志.材料科学研究与测试方法[M],南京：东南大学出版社,2007,257-259.
64.王龙彪,吴俊,黄清安.非晶态Ni基合金电极电子结构的XPS研究[J],化学物理学报,2000,13(4)：487-490.
65. Ezaki H, Morinaga M, Watanabe M. Hydrogen overpotential for transition metals and alloys and its interpretation using an electronic model [J], Electrochimica Acta,1993, 38:55-57.
2.程军胜,杨滨,张济山等.块体金属纳米材料成形技术研究进展[J],材料导报,2004,18(11)：63-65.
3.张振忠,宋广生,杨根仓,周尧和.块状金属纳米材料的制备技术进展及展望[J],兵器材料科学与工程,1999,22(3)：46-50.
4.赵廷凯,柳永宁,朱杰武.纳米材料概述[J],功能材料,2004,35：2675-2678.
5. Gleiter H. Nano-structured materials:basic concepts and micro-structure [J], Acta Materialia,2000,48(1):1-29.
6. Langdon G. Recent. Development in high strain rate super plasticity [J], Materials Transactions,1999,40(8):716-722.
7.张立德,牟季美.纳米材料和纳米结构[M],北京：科学出版社,2001：170-171.
8. Xu B S, Tanaka S I. Formation and bonding of platinum nanoparticles controlled by high energy beam irradiation [J], Nanostructured Materials,2000,20(12):915-917.
9.曹茂盛,关长斌,徐甲强.纳米材料导论[M],哈尔滨：哈尔滨工业大学出版社,2001：5-14.
10.居志兰,戈晓岚,许晓静.块体纳米材料的研究现状与发展思路[J],江苏大学学报,2002,23(4)：47-51.
11. Gleiter H V. Synthesis of nanostructured materials by the use of a thermophoretic forced flux system [J], Nanostructured Materials,1986,27(8):43.
12.王胜刚,龙康,龙期威.深度轧制细化工业纯铁晶粒[J],金属学报,2003,39(12)：1247-1250.
13. Wang S G, Shen C B, Long K, Yang H Y, Wang F H, Zhang Z D. Preparation and electrochemical corrosion behavior of bulk nanocrystalline ingot iron in HCl acid solution [J], Jurnal of Physical Chemistry B,2005,109(8):2499-2503.
14. Wang S G, Shen C B, Long K, Zhang T, Wang F H, Zhang Z D. The electrochemical corrosion of bulk nanocrystalline ingot iron in acidic sulfate solution [J], Jurnal of Physical Chemistry B,2006,110(9):377-382.
15.吕晓仁,王胜刚,刘阳,李曙.纳米化纯铁在干摩擦及油润滑条件下的磨损行为研究[J],摩擦学学报,2007,27(1)：20-27.
16.姜晓霞,沈伟.化学镀理论及实践[M],北京：国防工业出版社,2000：3-4.
17. Gutzeit G. An outline of the chemistry involved in the Process of catalytic Nickel deposition from aqueous solution plating [J], Surface and Coatings Technology,1959, 50(4):1275-1278.
18.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,2000,1-3.
19. Hajdu J. Electroless plating:the past is prologue [J], Plating and Surface Finishing, 1996,83(9):29-33.
20.沈伟,沈晓丹,张钦京.化学镀镍行业近年的发展状况[J],材料保护,2007,40(20)：50-54.
21.胡信国,张钦京.美国化学镀镍年会论文综述[J],电镀与涂饰,2003,22(2)：35-37.
22.李宁.化学镀实用技术[M],化学工业出版社,2003,1-4.
23.张钦京,杨德钧.我国化学镀技术交流与发展[J],表面工程资讯,2005,2(5)：5-6.
24. Bayes M W. Electroless nickel in the 90s'[J], Metal Finishing,1990,88(4):27-30.
25. Brenner A, Riddell G E. Niekel plating on steel by chemieal reduetion plating and surface Finishing [J], Plating and Surface Finishing,1946,39(11):385-395.
26.崔国峰.化学镀镍磷合金过程中磷的析出及其对镀层性能的影响[D],哈尔滨工业大学,2006
27.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,2000,11-13.
28. Meerak A. Electroless nickel plating from acid bath [J], Surface and Coatings Technology,2000,123(1):72-77.
29.俞宏英.化学镀镍磷合金镀层在硝酸溶液中的腐蚀机理[D],北京科技大学,1999
30.洪春勇,张萌.化学沉积镍磷合金的扫描电镜研究[J],江西大学学报,1990,14(3)：31-33.
31. Fundo A M, Abrantes L M. The electrocatalytic behaviour of electroless Ni-P alloy [J], Journal of Electroanalytical Chemistry,2007,600(1):63-79.
32. Baskaran I, Sankara T S, Narayanan N. A stephen.properties of electroless and electroplated Ni-P and its application in microgalvanics [J], Materials Chemistry and Physics,2006,99(2):117-126.
33. Mayanna S M, Ramesh L, Sheshadri B S. Electroless nickel plating influence of mixed legands [J]. Transactions of the Institute of Metal Finishing,1996,74(2):66-68.
34.胡文彬.难度基材的化学镀[M],北京：化学工业出版社,2003,10-13.
35. Zhoua Q J, He J Y, Haob X P, Chuan W Y, Qiao L J. The effect of hydrogen on plastic deformation of electroless nickel phosphorous amorphous plating [J], Materials Science and Engineering A,2006,437(2):356-359.
36. Singh D D N. Electroless nickel-phosphorus coatings to protect steel reinforcement bars from chloride induced corrosion [J], Surface and Coatings Technology,2006, 201(1):90-101.
37.张星笃,严文,白真权.化学镀高磷Ni-P合金的研究[J],电镀与环保,2008,28(5)：31-33.
38. Parker K. The effect of nickel salts on electroless nickel plating [J], Surface Finishing and Plating,1996,38(1):70-71.
39.訾炳涛,王辉.块体纳米材料的制备技术现状[J],中国有色金属学会第五届学术年会论文集,2000：184-188.
40. Brenner A, Riddell G E. Niekel Plating on Steel by Chemieal Reduetion Plating and Surface Finishing [J], Surface Finishing and Plating,1996,39(11):385-395.
41. Huang S, Cui F Z. Effect of complexing agent on the morphology and micros-tructure of electroless deposited Ni-P alloy [J], Surface and Coatings Technology,2007,201(9): 5416-5418.
42.李春玲.化学复合镀Ni-P-纳米TiO2工艺及性能研究(D],沈阳东北大学,2007
43.张天顺.化学镀Ni-P合金工艺研究[J],表面技术,1999,12(4)：12-16.
44.郭素枝.扫描电镜技术及其应用[M],厦门：厦门大学出版社,2000,14-15.
45.张延东.化学镀镍磷合金工艺优化及络合剂作用的研究(D),北京科技大学,2000
46.卢旭东,邵忠财.化学镀N i-P合金镀层孔隙率的影响因素[J],电镀与精饰,2007,29(6)：1-3.
47.郭东萍,薛士科,王春玉.化学镀镍磷层孔隙率的电化学评价[J],材料保护,2007,40(9)：28-30.
48.王煜明.非晶体及晶体缺陷的X射线衍射[M],北京：科学出版社,1988,55-60.
49.杨于兴,漆睿.X射线衍射分析[M],上海：上海交通大学出版社,1994,1-15.
50.李吉学,国秀珍.化学镀N i-P合金镀层相结构与硬度的研究[J],表面技术,2001,30(1)：6-8.
51.牛振江,沈吉军,李则林,吴廷华.原位XRD研究热处理Ni-P化学镀合金的结构[J],材料保护,2003,36(7)：45-47.
52.王丽丽,管从胜,孙从征.热处理对镍磷合金镀层结合强度和硬度的影响[J],电镀与精饰,2008,30(2)：4-6.
53. Guo X P, Tomoe Y. The effect of corrosion product layers on the anodic and cathodic reations of carbon steel in CO2-saturated MDEA solutions at 100℃ [J], Corrosion science,1999,41:1391-1402.
54.曹楚南,张鉴清.电化学阻抗谱导论[M],北京：科学出版社,2002,151-154.
55.李瑛,王福会.表面纳米化对金属材料电化学腐蚀行为的影响[J],腐蚀与防护,2003,24(1)：7-9.
56.蒋太祥,吴辉煌,毛秉伟,周少民.化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为[J],应用化学,1999,16(3)：21-24.
57.王徐承,王卫东,柳厚田,郁祖湛.化学镀非晶态Ni-P和Ni-B合金在H2SO4溶液中的电化学行为[J],电化学,2003,9(1)：36-39.
58.胡飞,肖静芝,旷亚非.非晶态Ni-P合金电镀层耐蚀性的研究[J],电镀与涂饰,1997,16(4)：17-20.
59.徐瑞东,王军丽,薛方勤,郭忠诚.全光亮镍磷合金镀层的耐蚀性[J],腐蚀科学与防护技术,2004,16(2)：110-112.
60.李振钢,徐景生,王宙,李淑华,赵小京.化学沉积Ni-P合金非晶态形成机制[J],大庆石油学院学报,1993,17(2)：100-102.
61.曹文博,任晨星,关绍康.高锌镁合金化学镀镍磷初始沉积特征的研究[J],材料保护,2006,39(2)：11-13.
62.洪春勇,张萌.化学沉积镍磷合金的扫描电镜研究[J],江西大学学报,1990,14(3)：31-34.
63.朱和国,王恒志.材料科学研究与测试方法[M],南京：东南大学出版社,2007,257-259.
64.王龙彪,吴俊,黄清安.非晶态Ni基合金电极电子结构的XPS研究[J],化学物理学报,2000,13(4)：487-490.
65. Ezaki H, Morinaga M, Watanabe M. Hydrogen overpotential for transition metals and alloys and its interpretation using an electronic model [J], Electrochimica Acta,1993, 38:55-57.