【作者】 崔国峰；

【导师】 李宁；

【作者基本信息】 哈尔滨工业大学 ， 应用化学， 2006， 博士

【摘要】 化学镀镍镀层中磷的含量对镀层的物理化学性质有很大的影响。明确化学镀镍过程中磷的析出机理及影响因素,是控制磷含量的先决条件。然而,目前对此尚没有深入的研究。本文采用电化学及量子化学手段,对化学镀镍磷过程中磷的析出机理及影响因素进行了深入的探讨。镀层的磷含量采用X射线荧光光谱仪（XRF）进行检测,确保了数据的可靠性。并采用电化学噪声研究了化学镀镍的沉积过程。根据实验结果建立了相关的模型,探讨了磷的析出机理。同时,为了使所获得的镀层在工业中得到广泛的应用,又对化学镀镍光亮剂的作用机理及不同磷的含量对黑镍镀层耐腐性的影响进行了深入的研究。采用电化学测试手段考察了络合剂的种类和用量对镀层中磷含量的影响。在对仅含有次亚磷酸盐、硫酸镍、同时含有两种物质及在含有两种物质的溶液中加入不同络合剂的循环伏安曲线的测试发现,化学镀镍过程中磷的析出是受镍离子的诱导作用影响发生的,并且不同络合剂的结构对磷的析出有不同程度的影响。在实际施镀过程中也得到了一致的结论。在此基础上,提出了络合剂界面异相催化机理。同时研究发现,在络合体系相同的情况下,次亚磷酸盐和硫酸镍的浓度比对化学镀镍层中磷的含量有很大的影响。由此提出了次亚磷酸盐的界面异相催化机理,在这两个假说的指导下,设计了不同磷含量的化学镀镍液,并且获得了磷含量不同的镀层,验证了所提出的两个假说的正确性。化学镀镍过程中,镀层中磷原子的析出来源于次亚磷酸的还原。利用量子化学软件高斯03（G03）分子轨道理论中的从头计算法（ab initio）,计算了次亚磷酸在还原过程中可能的中间产物和过渡态的振动频率和总能量。计算方法是采用二阶微扰理论（MP2）,与在曾经用于计算化学镀镍反应机理的6-311G（d,p）基组水平上进行计算的。计算路径是根据在电镀镍磷中提出的磷的直接析出机理（H₃PO₂→P）和间接析出机理（H3PO2→PH3）进行设计。计算结果表明,间接机理的能量体系相对较低。次亚磷酸盐的还原是通过RP3路径来实现的,即间接机理H₃PO₂→PH₃→P实现的。为了确保计算的准确性,采用更高级的混合基组（CBS-QB3）对此结果进行了进一步的计算。计算结果与MP2得到的数据是一致的。更多还原

【Abstract】 Physical and chemical properties of electroless plating nickel （EN） coatings can be greatly affected by phosphorus content in electroless Ni-P alloy. In order to control phosphorus content in coatings effectively, phosphorus generation mechanism and influencing factors should be realized fully. However, there are no detail researches to report that process.Thus, electrochemical and quantum chemical methods were applied to deeply study phosphorus generation mechanism and influencing factors in this paper. The measurement results were obtained by X-ray fluorescence spectrometer （XRF）, in order to ensure accuracy of phosphorus content data. Furthermore, the electrochemical noise （ENA） measure was applied to monitor electroless plating nickel process. According experimental and measuring results, the phosphorus generation models were established. Moreover, the effect mechanism of electroless plating nickel brightener on nickel deposition and the effect of phosphorus content on corrosion property of electroless plating black nickel were discussed in this paper.The effect of complexing agents on phosphorus content of electroless nickel deposits was investigated by electrochemical measurement and composition analysis of Ni-P deposits by XRF. Phosphorus generation was induced by nickel species, and was greatly affected by the structures of nickel complexing agents, according to the cyclic voltammograms of NiSO4, NaH₂PO₂, NiSO₄ and NaH₂PO₂, and NiSO₄ and NaH₂PO₂ added complexing agents. The plating measuring results were agreed well with the conclusion. Thus, phosphorus generation mechanism of complex heterocatalysis was proposed. Meanwhile, concentration ratio of NiSO₄ and NaH₂PO₂ also greatly affects the phosphorus content. Then direct generation mechanism of phosphorus incorporating with nickel was proposed. The low, middle and high-phosphorus EN baths were obtained based on both mechanisms.Phosphorus generation fully originates from reduction reaction of hypophosphorous during EN process. The reduction reaction was detailed discussed by ab initio method according to molecular orbital theory using更多还原