In-Situ Gravimetrical Study on Corrosion Reaction of Metal Thin Film by a Quartz Oscillator

1.空气中金属薄膜大气腐蚀的原位重量法：本研究建立了由石英振荡器谐振频率的变化自动监测空气中金属薄膜大气腐蚀重量变化的系统和空气中相对湿度和污染物气体浓度恒温可控的大气腐蚀加速试验装置。根据石英振荡器谐振频率的变化，监测了30℃时铜薄膜在含20ppm SO2或H2S的空气中的腐蚀行为随空气相对湿度的变化。H_2S的存在而不是SO_2的存在使铜膜的腐蚀环境更加恶劣。腐蚀速率随相对湿度的增加而迅速增加，空气中的氧气促进了腐蚀速率的提高，说明铜薄膜的大气腐蚀是在铜表面形成多个单分子膜的水膜中进行的电化学机理。金属薄膜在水溶液中微腐蚀的原位重量法：为稳定石英在水溶液中的振荡，专门设计了振荡电路。通过同时测量石英振荡器谐振频率的变化和阳极电流的时间变化，研究了铜膜在pH 8.4的硼酸盐溶液中的阳极氧化过程。通过现场重量和电化学数据的对比，确定了铜离子在阳极氧化膜中的溶解速率和膜生长过程中氧离子的吸收速率。从分离出的两个速率组分之间的关系，详细揭示了铜膜的阳极氧化机理。

1. In-Situ Gravimetry of Atmospheric Corrosion of Metal Thin Film in Air: The system in which the weight change due to atmospheric corrosion of metal thin film in air was capable of monitoring automatically from the change in resonance frequency of quartz oscillator and the atmospheric corrosion-accelerated test apparatus in which the relative humidity and the concentration of pollutant gas in air were capable of controlling at constant temperature were constructed for this research. The corrosion behaviors of copper thin film in air containing 20 ppm of SO_2 or H_2S at 30C were monitored as a function of relative humidity in air from the change in resonance frequency of quartz oscillator. The presence of H_2S rather than SO_2 gave the more severe corrosion environment for copper thin film. The corrosion rate increased rapidly with increasing the relative humidity and oxygen in air promoted the corrosion rate.It is made clear that the atmospheric corrosion of copper thin film proceeds with an electrochemical mechanism operative in a water film with several monolayers formed on the copper surface.2. In-Situ Gravimetry of Minute Corrosion of Metal thin Film in Aqueous solution: The specially designed oscillating circuit was constructed to stabilize the oscillation of quartz in aqueous solution. The anodic oxidation of copper thin film in pH 8.4 borate solution was investigated by simultaneous measurements of change in resonance frequency of quartz oscillator and time-variation of anodic current. The separation of the dissolution rate of copper ions through the anodic oxide film and the uptake rate of oxygen ions into the film during the film growth was made from the comparison of the in-situ gravimetrical and electrochemical data. The anodic oxidation mechanism of copper thin film was revealed in detail from the relation between the separated two rate components.