纳米复合镀层的制备与性能研究
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摘要
纳米复合镀层将纳米颗粒独特的物理及化学性质与金属基体的特性有机的结合在一起，使复合镀层表现出优异的性能。本论文采用电化学复合沉积与化学复合沉积的方法，成功制备了Ni-W/SiC、Ni-W/ZrOB2B、Ni-P/WC纳米复合镀层，对镀层的制备工艺及性能进行了较为系统的研究。Ni-W/SiC纳米复合镀层的硬度高于Ni-W合金镀层的硬度，且随着镀层中纳米颗粒含量的增加而升高。Ni-W/SiC纳米复合镀层的磨损失重低于Ni-W合金镀层，随着镀层中纳米颗粒含量的增加而降低。通过阳极极化曲线、电化学阻抗谱和浸泡实验考察纳米复合镀层在0.5M NaCl溶液中的腐蚀行为，得到一致的结果，发现Ni-W/SiC纳米复合镀层的耐腐蚀性能优于Ni-W合金镀层及Ni-W/SiC微米复合镀层。对Ni-W合金镀层、Ni-W/ ZrOB2B微米复合镀层与Ni-W/ZrOB2B纳米复合镀层进行热重试验发现，纳米复合镀层的氧化增重低于合金镀层，而微米复合镀层的氧化增重却为纳米复合镀层的3倍。DSC测试结果表明，ZrOB2B纳米颗粒的加入使Ni-W/ZrOB2B复合镀层的高温热稳定性较Ni-W合金提高39℃，而微米ZrOB2B颗粒的加入对复合镀层的热稳定性无明显影响。Ni-W/ZrOB2B纳米复合镀层在NaOH溶液中的催化析氢性能优于Ni-W合金镀层，而且随着镀层中ZrOB2B复合量的增加，镀层的催化析氢性能随之提高。Ni-W/ZrOB2B纳米复合镀层在NaOH溶液中的耐蚀性能高于Ni-W合金镀层，而且耐蚀性随着镀层中ZrOB2B纳米颗粒复合量的增大而进一步提高。Ni-P/WC纳米复合镀层在10％NaCl溶液中的耐蚀性能优于Ni-P合金镀层，硬度随着镀层中WC纳米颗粒复合量的增加而增大。在相同载荷下，Ni-P/WC纳米复合镀层的磨损失重与摩擦系数低于Ni-P合金镀层，而且随着镀层中WC纳米颗粒含量的增加，磨损失重与摩擦系数进一步降低。随着载荷增加，Ni-P/WC纳米复合镀层的磨损失重增大，试样经历由轻度磨损向严重磨损的转化。迄今为止，人们普遍认为复合镀层中的SiC、WC微粒被简单地包裹在镀层中，即所谓机械夹杂。本文通过对复合镀层的XPS测试，发现WC、SiC纳米颗粒与周围的基质金属间发生了电荷转移，并形成界面扩散层。即微粒与周围的基质金属间发生了非计量的化学反应。由该化学反应形成的界面扩散层是使纳米复合镀层的耐蚀性能显著提高的主要原因。
Recently, nanocomposite plating technology has received increasing attention in view of the interesting possibilities that the codeposition of the nano-particles with metal phases can bring a remarkable improvement on physical and chemical properties of the coatings. In this thesis, we have investigated the preparation and property of Ni-W/SiC nanocomposite coating, Ni-W/ZrOB2 Bnanocomposite coatings and Ni-P/WC nanocomposite coating. The addition of SiC nano-particles would lead to an increase in hardness of the Ni-W/SiC nanocomposite coatings. The co-deposited SiC nano-particles in deposit increase the wear resistance and reduce the wear weight loss. Moreover, the wear resistance of Ni–W/SiC nanocomposite coatings is closely related with SiC content in deposit. The co-deposition of SiC nano-particles in the composite coatings increased the corrosion resistance. The high temperature oxidation resistance of Ni-W alloy coating, Ni-W/ ZrOB2B nanocomposite coating and Ni-W/ ZrOB2B composite coating is analyzed．The results of thermogravimetry (TG) and differential scanning calorimetry (DSC) show that the addition of ZrOB2B nano-particles can obviously improve the oxidation resistance of the nanocomposite coatings. The hydrogen evolution reaction of Ni–W/ZrOB2B nanocomposite coatings was investigated by the polarization curves and potentiostatic curves. Arrhenius curves of Ni-W/ZrOB2B nanocomposite coating were calculated. The results indicate that the Ni–W/ZrOB2B nanocomposite coatings obtained higher electrochemical activity than Ni-W alloy coating. The hardness of Ni-P/WC nanocomposite coatings increases with the increasing content of the WC nano-particles in the coatings. The Ni-P/WC nanocomposite coating has better corrosion resistance than the Ni-P alloy coating in NaCl solution. Tribological behavior of Ni-P/WC nanocomposite coatings was investigated using a Block-on-Ring test rig; the effect of mass fraction of WC nano-particles on tribological behavior of the composite coatings was examined. The Ni-P/WC nanocomposite coatings revealed a low coefficient of friction compared with the Ni-P alloy coating. Due to the effects of the reinforcement and reduced friction, the wear rate of the nanocomposite coating decreased with increasing mass fraction of WC nano-particles. The valence of Ni, W, P, Si and Zr element in nanocomposite coatings was investigated by using XPS. The result shows that there is chemical interaction among the elements in such nanocomposite coatings. The main possibility of this phenomenon occurrence may result in the large specific surface area and large surface energy of nanoparticles, therefore, the atoms on nano-particles’ surface are apt to interact with the atoms in alloy matrix and chemical shift appears. The chemical interaction between nano-particles and alloy matrix is the main causation that improves the properties of nanocomposite coatings.
Recently, nanocomposite plating technology has received increasing attention in view of the interesting possibilities that the codeposition of the nano-particles with metal phases can bring a remarkable improvement on physical and chemical properties of the coatings. In this thesis, we have investigated the preparation and property of Ni-W/SiC nanocomposite coating, Ni-W/ZrOB2 Bnanocomposite coatings and Ni-P/WC nanocomposite coating. The addition of SiC nano-particles would lead to an increase in hardness of the Ni-W/SiC nanocomposite coatings. The co-deposited SiC nano-particles in deposit increase the wear resistance and reduce the wear weight loss. Moreover, the wear resistance of Ni–W/SiC nanocomposite coatings is closely related with SiC content in deposit. The co-deposition of SiC nano-particles in the composite coatings increased the corrosion resistance. The high temperature oxidation resistance of Ni-W alloy coating, Ni-W/ ZrOB2B nanocomposite coating and Ni-W/ ZrOB2B composite coating is analyzed．The results of thermogravimetry (TG) and differential scanning calorimetry (DSC) show that the addition of ZrOB2B nano-particles can obviously improve the oxidation resistance of the nanocomposite coatings. The hydrogen evolution reaction of Ni–W/ZrOB2B nanocomposite coatings was investigated by the polarization curves and potentiostatic curves. Arrhenius curves of Ni-W/ZrOB2B nanocomposite coating were calculated. The results indicate that the Ni–W/ZrOB2B nanocomposite coatings obtained higher electrochemical activity than Ni-W alloy coating. The hardness of Ni-P/WC nanocomposite coatings increases with the increasing content of the WC nano-particles in the coatings. The Ni-P/WC nanocomposite coating has better corrosion resistance than the Ni-P alloy coating in NaCl solution. Tribological behavior of Ni-P/WC nanocomposite coatings was investigated using a Block-on-Ring test rig; the effect of mass fraction of WC nano-particles on tribological behavior of the composite coatings was examined. The Ni-P/WC nanocomposite coatings revealed a low coefficient of friction compared with the Ni-P alloy coating. Due to the effects of the reinforcement and reduced friction, the wear rate of the nanocomposite coating decreased with increasing mass fraction of WC nano-particles. The valence of Ni, W, P, Si and Zr element in nanocomposite coatings was investigated by using XPS. The result shows that there is chemical interaction among the elements in such nanocomposite coatings. The main possibility of this phenomenon occurrence may result in the large specific surface area and large surface energy of nanoparticles, therefore, the atoms on nano-particles’ surface are apt to interact with the atoms in alloy matrix and chemical shift appears. The chemical interaction between nano-particles and alloy matrix is the main causation that improves the properties of nanocomposite coatings.
引文
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