微细电化学组合加工技术构建超疏油表面悬臂结构基底的基础研究

The lack of an effective method to fabricate micro re-entrant structures which are wide at the top and narrow at the bottom is the bottleneck that restricts the development and application of superoleophobic surfaces on metal substrates. The re-entrant structures are proposed to be divided into two parts: upper roof structures and lower pillar structures. The superhydrophobic micro pillar structure arrays can be fabricated by mask electrochemical micro-etching. The shape and curvature of the solid-gas-liquid triphase interface on the top of micro pillar structures can be regulated because of superhydrophobicity. Then the micro roof structure arrays can be fabricated on the top of pillars by electrochemical micro-deposition. Thus, the re-entrant structures will be fabricated. Based on the study of the influence of electrochemical etching parameters on the size of pillar structures and water wettability, the regulation mechanism of the shape of the solid-gas-liquid triphase interface and the influence of electrochemical deposition parameters on the size of roof structures will be studied. The regulation model of triphase interface shape and the reaction dynamic model which describes the movement rule of electrochemical deposition interface will be established. The structure-activity relationship between micro re-entrant structures and oil wettability will be studied and revealed. We intend to make breakthroughs in the theory and technology of constructing and regulating micro re-entrant structures on metal substrates by electrochemical composite micromachining technology composed of electrochemical etching and electrochemical deposition. The research is important for enriching the theory and technology of micromachining and for promoting the practical applications of superoleophobic surfaces.

缺乏加工上宽下窄形微观悬臂结构的有效方法，是制约金属基体超疏油表面发展和应用的瓶颈。提出将悬臂结构分为上部顶盖结构和下部底柱结构两部分，借助掩膜微细电化学刻蚀技术加工超疏水微观柱状结构阵列，并利用超疏水微观柱状结构顶部固-气-液三相界面形状可调控的特点，借助微细电化学沉积技术加工微观顶盖结构阵列，由此实现超疏油表面悬臂结构基底的构建。在研究电化学刻蚀工艺参数对柱状结构尺寸和水润湿性影响规律的基础上，进而研究固-气-液三相界面形状的调控机理及电化学沉积工艺参数对顶盖结构尺寸的影响规律，建立三相界面形状调控模型及描述电化学沉积界面移动规律的反应动力学模型，最后研究并揭示微观悬臂结构与油润湿性的构效关系。力争在利用由电化学刻蚀和电化学沉积组成的微细电化学组合加工技术构建、调控表面微观悬臂结构的相关理论及关键技术上有所突破。研究结果将对丰富微细加工理论与技术，促进超疏油表面的实际应用具有重要意义。

缺乏加工上宽下窄形微观悬臂结构的有效方法，是制约金属基体超疏油表面发展和应用的瓶颈。本项目提出将悬臂结构分为上部顶盖结构和下部底柱结构两部分，先借助掩膜电解技术、电化学线切割技术、纳秒激光刻蚀技术加工超疏水微柱阵列，再利用超疏水微柱顶部液-气界面形状可调控的特点，借助微细电化学沉积技术加工微观顶盖阵列，由此实现超疏油表面悬臂结构基底的构建。主要研究进展有：（1）建立了掩膜电解技术加工超疏水微柱阵列的试验装置，研究了金属基体上光刻胶掩膜的制备工艺以及电解加工参数对微柱阵列尺寸参数和润湿性的影响规律，证明了掩膜电解技术加工超疏水微柱阵列的可行性和有效性；（2）建立了掩膜电解技术加工微柱阵列的仿真模型，仿真研究了电流密度、加工时间对微柱阵列尺寸参数的影响规律，并试验验证了仿真结果的准确性；（3）建立了电化学线切割技术加工超疏水微柱阵列的试验装置，研究了冲液速度、电解液浓度、加工电流等工艺参数对窄缝宽度和表面微观形貌的影响规律，在此基础上加工出了超疏水微柱阵列并研究了柱间距对润湿性的影响规律；（4）研究了纳秒激光频率、功率、扫描速度等工艺参数对铝、钢、钛合金及铜等金属基体表面微观形貌和润湿性的影响规律，通过正交试验获得了在多种金属基体上加工超疏水表面的最佳工艺参数，在此基础上再通过控制扫描轨迹和刻蚀时间成功获得超疏水锥形微柱阵列；（5）建立了液-气界面形状调控电化学沉积技术在超疏水微柱结构顶部加工顶盖结构的试验装置，研究了超疏水微柱顶部液-气界面形状的调控方法、电化学沉积参数与液-气界面形状对沉积层形状和尺寸的影响规律，加工出了5°～59°局部几何角度的微观悬臂结构，并最终获得超疏油表面。研究成果对丰富微细加工的相关理论和技术、促进金属基体超疏油表面的实际应用具有重要意义。在Advanced Functional Materials (IF15.6)、ACS Nano (IF13.9)、Journal of Materials Chemistry A (IF10.7)、ACS Applied Materials & Interfaces (IF8.4)、Nanoscale (IF6.9)、Lab on a Chip (IF6.9)等期刊上发表SCI论文18篇（中科院一区Top论文7篇，影响因子大于10的有3篇），获辽宁省自然科学学术成果一等奖2项，授权中国发明专利2项。