射流电化学放电加工难电解材料机理与工艺研究

射流电化学加工是一种以微细电解液射流为工具，基于电化学阳极溶解原理实现无掩模高定域性微细加工的技术。然而，当将射流电化学加工技术应用于强钝化金属或惰性半导体等难电解材料时，工件表面易发生阳极氧化反应而形成一层高阻抗氧化膜，阻碍电化学溶解反应进行，这极大限制了射流电化学加工技术的应用范围。为解决此问题，本文提出一种将射流电化学与放电等离子体复合的射流电化学放电加工方法。该方法的思想在于局部耦合放电和电化学能场，利用射流电化学放电实现对难电解材料的高效无损伤加工。本文针对此开发了相应的实验系统，基于实验和理论模型对该技术的实现方法和加工特性进行了系统研究。

本文首先对射流电化学放电的产生方法及形成机制展开研究。通过研究难电解材料表面阳极氧化反应和气体析出现象，结合阳极放电现象的可视化观测，阐明了氧化程度强弱、电解液流速和温度对等离子体点燃的影响规律。通过分析电解液成分对等离子体形成及演变过程的影响规律，结合光发射光谱表征，揭示了等离子体的产生条件与理化特性，明确了由高阻抗氧化层和绝缘气体层组成的复合表面边界层模型。为揭示等离子体稳定存在的边界条件，构建了与射流电化学放电加工特性相对应的等效电路模型，基于模型探究了外加电压、电解液成分及极间距等关键工艺参数对等离子体点燃的影响。

进一步，以难电解材料半导体单晶4H-SiC为研究对象验证了射流电化学放电加工的可行性，明确了电脉冲参数对结构特征尺寸和加工表面粗糙度的作用规律。通过电脉冲波形设计实现对放电时空分布规律的调控，获得了亚射流尺寸加工分辨率。为明确射流电化学放电加工的热效应，本文通过牺牲热电偶法对加工区域的温度进行了直接测定，明确了放电能量与加工区域温度之间的正相关特性，揭示了射流电化学放电加工的低温特性。通过探究电解液化学对加工效率的影响规律，揭示了以放电为辅、化学/电化学溶解为主的材料去除机理。特别地，通过使用与基底材料化学溶解反应较弱的电解液，实现了各向异性材料加工。通过分析超短脉冲条件下工件表面放电位置及材料去除的分布特征，确立了以气体电离为主导的放电模型。

然而，射流电化学放电加工过程中不可避免地会产生等离子体电解氧化（PEO）现象，影响加工效率及精度，该现象在加工强钝化性金属时尤为明显。针对此问题，本文以铌和钛合金作为研究对象，分别从电场、化学场和热场探究了PEO的形成规律及其克服方法。首先探究了放电能量及放电位置分布对PEO氧化物的生长和去除行为的影响。通过研究氧化物与电解液离子的化学反应规律，明确了能溶解氧化物的高浓度电解液是获得高加工速率和良好形状精度的优选电解液。通过研究电解液温度对加工特性的影响，明确了高温电解液中通过改善放电均匀性提升加工性能的作用机制。另一方面，由于PEO氧化层无法被完全避免，射流电化学放电加工的表面呈现出典型的PEO形貌，PEO层厚度<1 μm。

为充分利用射流电化学放电的潜力，本文进一步提出了基于射流电化学放电的涂层化微细结构制造方法。该方法通过对PEO过程的精准控制，实现微细结构和涂层的原位一体化分步制造。通过研究双极性脉冲参数对PEO涂层生长速率的影响规律，结合涂层宽度和厚度等几何尺寸表征，确立了基于双极性脉冲波形的高定域性射流PEO工艺方法，实现了微细结构与PEO涂层尺寸的精确匹配。基于实验，成功在钛合金上获得了特征尺寸700 μm和最大涂层厚度10 μm的涂层化微细结构，其表面硬度为原始表面的2倍。

本文的研究首次证明了射流电化学与放电等离子体复合实现微细加工的可行性，在将射流电化学加工技术可加工材料范围扩展至难电解材料的同时，突破了各向异性材料去除和亚射流尺寸加工分辨率等技术瓶颈，对促进射流微细加工技术的进步具有重要意义。

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