TC4钛合金硅酸钠−氢氧化钠微弧氧化电解液优化与膜层性能

Optimization of Na ₂SiO ₃–NaOH electrolyte for micro-arc oxidation on TC4 titanium alloy and properties of coatings

摘要

[目的]采用以 Na ₂SiO ₃ 和 NaOH 为主成分的电解液对 TC4 钛合金进行微弧氧化(MAO)处理，以提升其耐蚀性。[方法]通过正交试验研究了硅酸钠、氢氧化钠和三乙醇胺质量浓度对 MAO 膜层厚度、表面粗糙度和显微硬度的影响。采用扫描电镜(SEM)、X 射线衍射仪(XRD)及电化学工作站表征了膜层的微观形貌、相组成及耐蚀性。[结果] Na ₂SiO ₃浓度对膜层厚度和显微硬度的影响最大，NaOH 浓度对膜层表面粗糙度的影响最显著；较优的电解液配方为：硅酸钠 45 g/L，氢氧化钠 2.0 g/L，硼酸 6.0 g/L，三乙醇胺 5 mL/L，双氧水 5 mL/L，乙二胺四乙酸二钠 5 g/L。该配方所得 MAO 膜层的厚度为 56.3 μm，表面粗糙度 Ra 为 3.514 μm，显微硬度为 796.6 HV。膜层主要由金红石型 TiO ₂、非晶态 SiO ₂ 和少量锐钛矿型 TiO ₂ 组成，结构致密，能够有效阻隔腐蚀介质。[结论]采用优化的电解液可在 TC4 钛合金表面制备出厚度大、硬度高且结构致密的微弧氧化陶瓷膜层，显著改善基材的耐腐蚀性能。研究结果可为 TC4 钛合金的表面防护处理提供理论依据和技术支持。

Abstract

[Objective] TC4 titanium alloy was treated by micro-arc oxidation (MAO) in an electrolyte primarily composed of Na ₂SiO ₃ and NaOH to improve its corrosion resistance. [Method] Orthogonal tests were conducted to study the effects of mass concentration of sodium silicate, sodium hydroxide, and triethanolamine on the thickness, surface roughness, and microhardness of the MAO coatings. The microstructure, phase structure, and corrosion resistance of the MAO coatings were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), and an electrochemical workstation. [Result] The concentration of Na ₂SiO ₃ exhibited the most significant influence on coating thickness and microhardness, while the concentration of NaOH had the most pronounced effect on surface roughness. The optimized electrolyte formulation was determined as follows: sodium silicate 45 g/L, sodium hydroxide 2.0 g/L, boric acid 6.0 g/L, triethanolamine 5 mL/L, hydrogen peroxide 5 mL/L, and EDTA-2Na 5 g/L. The MAO coating prepared with this formulation possessed a thickness of 56.3 μm, a surface roughness ( Ra) of 3.514 μm, and a microhardness of 796.6 HV. The coating was primarily composed of rutile TiO ₂, amorphous SiO ₂, and a small amount of anatase TiO ₂. Its dense structure effectively acted as a barrier against corrosive media. [Conclusion] Micro-arc oxidation of TC4 titanium alloy in the optimized electrolyte produced a compact ceramic coating with substantial thickness and high hardness, significantly enhancing the corrosion resistance of the substrate. These findings provide a theoretical basis and technical support for surface protection treatment of TC4 titanium alloys.

关键词

钛合金 / 微弧氧化 / 硅酸钠 / 氢氧化钠 / 耐蚀性 / 显微硬度 / 组织结构

Key words

titanium alloy / micro-arc oxidation / sodium silicate / sodium hydroxide / corrosion resistance / microhardness / microstructure

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基金资助

2024年台州市科技计划项目(24GYB21)

2023年度台州职业技术学院高层次人才项目(2023GCC10)

2025年度上海电子信息职业技术学院高层次与紧缺人才科研项目(GCC2025012)