AZ91D镁合金在硫酸镍镀液中化学镀镍工艺的研究
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摘要
由于镁合金具有质轻、高导热性、高的比强度和比刚度、抗电磁干扰、抗震和易于回收等优点，现已被广泛应用于航空航天工业、汽车行业、光学仪器、电讯、音响材料等领域。但其耐蚀性差是制约其应用的主要原因之一。
本文综述了镁合金防护方法及化学镀镍的研究进展，并以AZ91D镁合金为实验材料，研究了NiSO_4化学镀镍的工艺条件、工艺流程，以及镀液pH值、施镀温度、主盐NiSO_4、还原剂NaH_2PO_2、配合剂柠檬酸等因素对化学镀镍的影响；利用卧式金相显微镜(HMM)、等离子体原子发射光谱仪(ICP-AES)、X射线衍射仪(XRD)、显微硬度仪(MHT)等技术测试了镀层的性能。研究结果表明：
(1) 通过对镁合金化学镀镍酸洗、活化、浸锌、镀铜和化学镀镍的研究，得到了最佳的配方，确定化学镀镍的工艺流程为：超声波清洗→酸洗→活化→浸锌→活化液退除→二次浸锌→化学镀镍→钝化(各步间水洗)。
(2) 在pH值为3.0～7.0、温度为70℃-95℃范围内进行化学镀镍，得到镀液最佳酸度为4.0，最佳施镀温度为95℃。随着主盐NiSO_4和还原剂NaH_2PO_2浓度的增加，沉积速率先增加后减少，在浓度分别为25g·dm~(-3)和30g·dm~(-3)时沉积速率达最大值。随着配合剂柠檬酸浓度的增加，沉积速率减小，镀层厚度减少，镀层的耐蚀性能降低。延长镀镍时间有助于提高其耐蚀性，镀镍时间一般采用1～2h。在化学镀镍过程中施加超声波能细化晶粒，能使颗粒分散均匀，从而改善镀层的均镀能力，提高镀层的耐蚀性。
(3) 通过正交试验进一步确定了镁合金化学镀镍的最佳实验条件。在此条件下得到的镀层的磷含量为7.9％，为非晶体结构，镀层硬度为640HV，镀层与基体间结合力强，耐蚀性比镁合金明显提高了。
(4) 实验发现在工艺施镀温度下镁合金基体不会受到NiSO_4主盐配制的镀液的腐蚀，并从热力学和化学动力学的角度分析了镁合金化学镀镍的机理。
(5) 采用EDTA配合滴定法和间接碘量法分别测定化学镀镍镀液中Ni~(2+)和H_2PO_2~-浓度，通过PdCl_2试验及镀液稳定常数来评定镀液的使用寿命。
研究的以NiSO_4为主盐配制的镀液比以NiCO_3·2Ni(OH)_2·4H_2O为主盐镀液镀镍工艺价格低廉，镀层质量优良，在生产中具有实际意义。
Magnesium alloys have many advantages such as lightness, good thermal conductivity, high strength to weight ratio and impact strength, ability to dampen electromagnetism and shock waves and being reclaimed easily, so they have been widely used in many fields such as aerospace, automobile, optics apparatus, telecommunication, acoustics materials and so on. However poor corrosion resistance is one of main causes to restrict their applications.
Recent advances in corrosion control measures and electroless nickel plating of magnesium alloys were reviewed in this thesis. The condition and flow of eletroless nickel plating technology on magnesium alloy AZ91D as well as the main influencing factors of bath pH, plating temperature, main salt of nickel sulfate, reducing agent sodium hypophosphite, complexing agent citric acid and so forth were studied. Techniques, such as horizontal metallographic microscopy (HMM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), microhardness tester (MHT) and so on, were employed to determine the properties of the coating. The results are indicated as follows:
(1) The formulations of acid pickling, activation, immersing zinc, copper plating and electroless nickel plating in electroless nickel plating process on magnesium alloys were studied. The optimal formulations were gained as well as the operation sequence of electroless nickel plating, i.e. ultrasonic degreasing, acid pickling, activation, immersing zinc, stripping in activation solution, then the second immersing zinc, electroless nickel plating , finally passivation treatment(water rinse with each other).
(2) Electroless nickel plating was investigated at the plating temperature from 70 C to 95 C and the pH from 3.0 to 7.0. It showed that the optimal pH value and plating temperature were 4.0 and 95 C respectively. The deposition rate increased at first and decreased subsequently with the increasing concentrations of main salt nickel sulfate and reducing agent sodium hypophosphite. The deposition rate reached the maximum when the concentrations of nickel sulfate and sodium hypophosphite were 25 g dm-3 and 30 g-dm3 respectively. The deposition rate and the coating thickness decreased with the increasing concentration of complexing agent citric acid, and therefore the corrosion resistance of the coating became worse. Prolonging the plating time could improve the corrosion resistance of the coating. The plating time was usually 1 to 2
hours. When ultrasonic was performed during electroless nickel plating, it could diminish and disperse uniformly the grain, improving the uniformity and the corrosion resistance of the coating accordingly.
(3) The optimal condition of eletroless nickel plating on magnesium alloys was obtained by the orthogonal test. The phosphorus content of the coating gained under this condition was 7.9% and the coating was non-crystal. The Vickers microhardness value of it was 640. The specimen showed good adhesion and better corrosion resistance than magnesium alloys.
(4) Magnesium alloys substrate was not corroded in the bath of nickel sulfate at plating temperature. The reaction mechanism of electroless nickel plating on magnesium alloys was described based on the principles of thermodynamics and chemical dynamics.
(5) The concentrations of nickel ion and hypophosphite in the electroless nickel bath were determined with the methods of the EDTA complexing titration and indirect iodimetry respectively. The life-span of bath could be evaluated by palladium chloride test and determination of steady constant of the bath.
Investigation results showed that the coating obtained in the bath of nickel sulfate is better than that in the bath of basic nickel carbonate. Meanwhile, the cost of nickel sulfate is lower. So the plating process of nickel sulfate has more practical significance in the production.
本文综述了镁合金防护方法及化学镀镍的研究进展，并以AZ91D镁合金为实验材料，研究了NiSO_4化学镀镍的工艺条件、工艺流程，以及镀液pH值、施镀温度、主盐NiSO_4、还原剂NaH_2PO_2、配合剂柠檬酸等因素对化学镀镍的影响；利用卧式金相显微镜(HMM)、等离子体原子发射光谱仪(ICP-AES)、X射线衍射仪(XRD)、显微硬度仪(MHT)等技术测试了镀层的性能。研究结果表明：
(1) 通过对镁合金化学镀镍酸洗、活化、浸锌、镀铜和化学镀镍的研究，得到了最佳的配方，确定化学镀镍的工艺流程为：超声波清洗→酸洗→活化→浸锌→活化液退除→二次浸锌→化学镀镍→钝化(各步间水洗)。
(2) 在pH值为3.0～7.0、温度为70℃-95℃范围内进行化学镀镍，得到镀液最佳酸度为4.0，最佳施镀温度为95℃。随着主盐NiSO_4和还原剂NaH_2PO_2浓度的增加，沉积速率先增加后减少，在浓度分别为25g·dm~(-3)和30g·dm~(-3)时沉积速率达最大值。随着配合剂柠檬酸浓度的增加，沉积速率减小，镀层厚度减少，镀层的耐蚀性能降低。延长镀镍时间有助于提高其耐蚀性，镀镍时间一般采用1～2h。在化学镀镍过程中施加超声波能细化晶粒，能使颗粒分散均匀，从而改善镀层的均镀能力，提高镀层的耐蚀性。
(3) 通过正交试验进一步确定了镁合金化学镀镍的最佳实验条件。在此条件下得到的镀层的磷含量为7.9％，为非晶体结构，镀层硬度为640HV，镀层与基体间结合力强，耐蚀性比镁合金明显提高了。
(4) 实验发现在工艺施镀温度下镁合金基体不会受到NiSO_4主盐配制的镀液的腐蚀，并从热力学和化学动力学的角度分析了镁合金化学镀镍的机理。
(5) 采用EDTA配合滴定法和间接碘量法分别测定化学镀镍镀液中Ni~(2+)和H_2PO_2~-浓度，通过PdCl_2试验及镀液稳定常数来评定镀液的使用寿命。
研究的以NiSO_4为主盐配制的镀液比以NiCO_3·2Ni(OH)_2·4H_2O为主盐镀液镀镍工艺价格低廉，镀层质量优良，在生产中具有实际意义。
Magnesium alloys have many advantages such as lightness, good thermal conductivity, high strength to weight ratio and impact strength, ability to dampen electromagnetism and shock waves and being reclaimed easily, so they have been widely used in many fields such as aerospace, automobile, optics apparatus, telecommunication, acoustics materials and so on. However poor corrosion resistance is one of main causes to restrict their applications.
Recent advances in corrosion control measures and electroless nickel plating of magnesium alloys were reviewed in this thesis. The condition and flow of eletroless nickel plating technology on magnesium alloy AZ91D as well as the main influencing factors of bath pH, plating temperature, main salt of nickel sulfate, reducing agent sodium hypophosphite, complexing agent citric acid and so forth were studied. Techniques, such as horizontal metallographic microscopy (HMM), inductively coupled plasma atomic emission spectroscopy (ICP-AES), X-ray diffraction (XRD), microhardness tester (MHT) and so on, were employed to determine the properties of the coating. The results are indicated as follows:
(1) The formulations of acid pickling, activation, immersing zinc, copper plating and electroless nickel plating in electroless nickel plating process on magnesium alloys were studied. The optimal formulations were gained as well as the operation sequence of electroless nickel plating, i.e. ultrasonic degreasing, acid pickling, activation, immersing zinc, stripping in activation solution, then the second immersing zinc, electroless nickel plating , finally passivation treatment(water rinse with each other).
(2) Electroless nickel plating was investigated at the plating temperature from 70 C to 95 C and the pH from 3.0 to 7.0. It showed that the optimal pH value and plating temperature were 4.0 and 95 C respectively. The deposition rate increased at first and decreased subsequently with the increasing concentrations of main salt nickel sulfate and reducing agent sodium hypophosphite. The deposition rate reached the maximum when the concentrations of nickel sulfate and sodium hypophosphite were 25 g dm-3 and 30 g-dm3 respectively. The deposition rate and the coating thickness decreased with the increasing concentration of complexing agent citric acid, and therefore the corrosion resistance of the coating became worse. Prolonging the plating time could improve the corrosion resistance of the coating. The plating time was usually 1 to 2
hours. When ultrasonic was performed during electroless nickel plating, it could diminish and disperse uniformly the grain, improving the uniformity and the corrosion resistance of the coating accordingly.
(3) The optimal condition of eletroless nickel plating on magnesium alloys was obtained by the orthogonal test. The phosphorus content of the coating gained under this condition was 7.9% and the coating was non-crystal. The Vickers microhardness value of it was 640. The specimen showed good adhesion and better corrosion resistance than magnesium alloys.
(4) Magnesium alloys substrate was not corroded in the bath of nickel sulfate at plating temperature. The reaction mechanism of electroless nickel plating on magnesium alloys was described based on the principles of thermodynamics and chemical dynamics.
(5) The concentrations of nickel ion and hypophosphite in the electroless nickel bath were determined with the methods of the EDTA complexing titration and indirect iodimetry respectively. The life-span of bath could be evaluated by palladium chloride test and determination of steady constant of the bath.
Investigation results showed that the coating obtained in the bath of nickel sulfate is better than that in the bath of basic nickel carbonate. Meanwhile, the cost of nickel sulfate is lower. So the plating process of nickel sulfate has more practical significance in the production.
引文
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