目的 探究Nb-30Ti-20W合金的室温耐蚀性能。方法 采用激光增材制造技术制备Nb-30Ti-20W合金块体,用电化学工作站分别测试合金在质量分数3.5%的NaCl溶液、1 mol/L的HCl溶液、0.5 mol/L的H2SO4溶液、1 mol/L的NaOH溶液中的开路电位、动电位极化曲线及交流阻抗。采用X射线衍射（XRD）、扫描电子显微镜（SEM）、X射线光电子能谱（XPS）等手段表征合金表面腐蚀形貌及钝化膜成分。结果 合金在质量分数3.5%的NaCl溶液、1 mol/L的HCl溶液、0.5 mol/L的H2SO4溶液、1 mol/L的NaOH溶液中均出现钝化,但仅在NaCl溶液中出现点蚀击穿现象。合金在4种腐蚀介质中生成的钝化膜的成分均为TiO2、Nb2O5、WO3,在NaCl溶液中的点蚀坑内主要生成TiO2、TiCl3。通过Tafel曲线获得了腐蚀电流密度,计算得到Nb-30Ti-20W合金在质量分数3.5%的NaCl溶液、1 mol/L的HCl溶液、0.5 mol/L的H2SO4溶液、1 mol/L的NaOH溶液中的平均腐蚀速率分别为0.017、0.009 7、0.006 2、0.172 mm/a,合金在NaCl、HCl、H2SO4溶液中的腐蚀速率远小于在NaOH溶液中。用软件拟合交流阻抗曲线电路图,并通过动电位极化曲线外推法计算极化电阻Rp,推测合金在NaOH溶液中的电荷转移阻力较小。此合金相较于其他耐蚀合金,它在质量分数3.5%的NaCl溶液中呈现出更高的点蚀电位（Epit）和更低的维钝电流密度（Jpass）,在1 mol/L的HCl溶液、0.5 mol/L的H2SO4溶液、1 mol/L的NaOH溶液中呈现更高的自腐蚀电位（Ecorr）和更低的自腐蚀电流密度（Jcorr）,因而合金在此4种溶液中具有更优异的室温耐蚀性能。结论 在室温环境下,Nb-30Ti-20W合金在耐酸碱盐水溶液中的腐蚀性能良好,在NaCl、HCl溶液中可生成钝化膜,从而阻止反应进一步进行,具有在海洋等严苛工况下服役的应用价值和发展潜力。
Abstract
Due to the high melting point, Nb-based alloys are regarded as an ideal alternative to Ni-based superalloys and the most suitable materials for developing a new generation of turbine blades. Since the turbine blades are expensive, the applied alloys should withstand the test of long service. However, the corrosion resistance of the Nb-based alloys is still insufficient. Thus, the researches on the corrosion resistance of the Nb-based alloys are of great importance. In present work, Nb-30Ti-20W alloy was designed to enhance the performance of the traditional Nb-based alloy. Due to its high melting point and relative high hardness, the Nb-30Ti-20W alloy was hard to be processed by traditional methods. To overcome this shortcoming, the Nb-30Ti-20W samples were prepared by laser melting deposition (LMD) method at argon atmosphere. The LMD prepared Nb-30Ti-20W alloy exhibited a body centered cube (BCC) structure and equiaxed crystals with average grain size of ~50 μm. Then, the corrosion rates and mechanisms under different environments of the prepared Nb-30Ti-20W alloy were investigated after grinding and polishing. The open-circuit potential, dynamic polarization curves and alternating current impedance of the alloy in 3.5% NaCl solution, 1 mol/L HCl solution, 0.5 mol/L H2SO4 solution and 1 mol/L NaOH solution were measured with an electrochemical workstation. After the corrosion test, the morphologies of the corroded surface of the samples and the composition of the passivating membrane components were characterized through X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Combined with the analysis of the polarization curves, the alloy was passivated in the four corrosive media. Passivation breakdown only occurred in NaCl solution. The passivating membrane components of the alloy in 3.5% NaCl solution, 1 mol/L NaOH solution, 1 mol/L HCl solution and 0.5 mol/L H2SO4 solution were all TiO2, Nb2O5 and WO3. The low X-ray photoelectron spectroscopy (XPS) peak intensity of the corrosion products after NaCl corrosion indicated lower oxide content in these products. Cl element was observed in the pitting on the corroded surface in NaCl solution, while it was absent on the uncorroded surface. Based on the reaction principles and the chemical properties of the products, this phenomenon suggested the formation of chlorides such as TiCl3 and NbCl5 in the pitting. The average corrosion rates of the alloy, calculated from the Tafel extrapolation of self-corrosion current density, were 0.017 8 mm/a (NaCl), 0.009 7 mm/a (HCl), 0.006 2 mm/a (H2SO4) and 0.172 mm/a (NaOH). The polarization resistance Rp value was fitted by fitting the circuit diagram with the AC impedance curve. By combining equivalent circuit fitting of electrochemical impedance spectroscopy (EIS) data with extrapolation of Rp values from potentiodynamic polarization curves, it was indicated that the alloy exhibited significantly lower charge transfer resistance in NaOH solution. The Nb-30Ti-20W alloy demonstrated good corrosion resistance to acid, alkali and saline solutions at room temperature. The alloy formed a passivation film to prevent further reaction. The present work indicates that the Nb-30Ti-20W alloy exhibits excellent corrosion resistance in different environments, and may be a promising candidate for the development of next-generation turbine blade structural materials.
关键词
Nb-Ti-W合金 /
激光增材制造 /
室温腐蚀 /
酸碱盐溶液腐蚀 /
电化学腐蚀评价 /
化学成分分析
Key words
Nb-Ti-W alloy /
laser additive manufacturing /
room-temperature corrosion /
acid-alkali-salt solution corrosion /
electrochemical corrosion evaluation /
chemical composition analysis
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基金
表面物理与化学重点实验室基金（JCKYS2023120204）
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