海洋大气环境中铜基电子材料的腐蚀防护与在线监测方法研究

The breakdown of electronic apparatus serving in oceanic environment, are often attributed to the corrosion and localized corrosion of Cu/Sn/Ag multi-metal components on the print circuit board (PCB), jeopardizing the security of ships and airplanes. Nevertheless, deep recognition was inadequate about the initiation and stabilization of metastable pits, as well as galvanic corrosion of PCB-Cu/Sn/Ag beneath a thin electrolytic layer (TEL). With the help of comprehensive techniques including electrochemical noise, wire beam electrode and quartz crystal microbalance, this project aims at studying the mechanism of initiation, stabilization and rehabilitation of pitting corrosion and galvanic corrosion of PCB-Cu/Sn/Ag without external polarization. The initiation rate, lifespan and the integration of current noise of metastable pits related to the cyclic stress and corrosion products will be emphasized. Then, the diffusion, migration of volatile corrosion inhibitors, and the competitive adsorption process between aggressive and inhibitive species under the TEL are also explored via AFM, ATR-IR and micro-Raman. The research is expected to be a guide for the inhibitor protection strategy of PCB in harsh environment. Eventually, we expect to develop a high sensitive sensor for the atmospheric corrosion of electronic material based on the accurate film resistance measurement. The sensor is supposed to serve the online health monitoring of electronic apparatus and therefore improve the efficiency of maintenance and attendance of the equipment in the end.

电路板(PCB)上Cu/Sn/Ag多金属体系在海洋大气中的局部腐蚀可导致电子设备严重故障，危害舰船和舰载机的服役安全。然而当前对PCB-Cu/Sn/Ag电子材料在大气吸附薄液膜下的点蚀、电偶腐蚀以及基于缓蚀剂的腐蚀抑制仍缺乏深入认识。本项目以PCB为研究对象，采用电化学噪声、丝束电极和石英晶体微天平技术，于自然状态下研究薄液膜下Cu/Sn/Ag表面的电偶腐蚀以及亚稳态点蚀形核、生长或修复过程；探讨应力和腐蚀产物等因素对点蚀形核速率、平均寿命和积分电量的影响规律。其次， 采用AFM、ATR-IR和显微Raman等方法研究气相缓蚀剂在薄液膜下的扩散、迁移以及与侵蚀性粒子（Cl-、SO2、NOx）的竞争吸附机制，为苛刻环境下电子装备的缓蚀剂保护提供理论参考。最后，基于薄膜电阻精密测量技术，研制一种高灵敏电子材料气相腐蚀监测传感器，用于电子设备健康状态的在线监控，提升海上装备的维修水平和出勤率。

随着海上油气、海上风电和其他海洋资源的开发，大量海上装备不仅需要巨量的耐蚀结构材料，也需要高可靠性的电气控制系统。此外舰船、舰载机和其它海上装备中，火控、航电和导航等装置也离不开精密电子设备。因此以集成电路、印刷电路板（PCB）和航空接插件等为主的电子材料，不仅要有较高的抗盐雾和微生物腐蚀能力，还要有良好的电接触可靠性。本项目用电化学噪声、电化学阻抗、薄膜电阻传感器，石英晶体微天枰（QCM）等技术，并结合微区电化学（SKP，SVET）等方法，研究海洋大气环境下PCB-Cu/Sn/Ag等电子材料的点蚀和电偶腐蚀行为；采用QCM和衰减全反射红外（ATR-IR）等手段，研究气相缓蚀剂分子与侵蚀性粒子在PCB-Cu/Sn/Ag表面的扩散与竞争吸附过程，及其对局部腐蚀的抑制机制等科学问题，采用超疏水涂层技术提高电子装备尤其是电路板的防护能力和服役可靠性。基于本项目支持，共发表署名本基金支持的SCI论文13篇，中文核心论文3篇，申请发明专利3份。培养博士生3人，硕士生3人。本项目还在理论研究基础上，设计了一套适合装备封存质量监控的高灵敏气相腐蚀在线监测传感器，并已经应用在武器装备封存锈蚀监控以及海上风电塔筒和舱室的新风质量监控领域，并形成了具有自主知识产权的设备故障诊断与健康监测系统，提高海上装备的服役安全性,具有十分重要的应用价值。