The Oxidation of Copper in Air at Temperatures up to 100 °C

J. Aromaa, M. Kekkonen, M. Mousapour, A. Jokilaakso, M. Lundström
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引用次数: 14

Abstract

The aim of this study was to investigate the oxidation kinetics of copper at low temperatures (60 °C to 100 °C) in air by isothermal thermogravimetric analysis (TGA) and quartz crystal microbalance (QCM). The weight change in thermogravimetric tests showed periodic weight increase and decrease. In thermogravimetric tests the mass of the copper sample increased until the oxidation gradually slowed down and finally started to decrease due to cracking and spalling of the oxide formed on the surface. In QCM tests using electrodeposited copper film, the weight change was rapid at the beginning but slowed to a linear relationship after few minutes. Temperature and exposure time appeared to have a large effect on oxide film thickness and composition. With QCM, oxidation at 60–80 °C produced less than 40 nm films in 10 days. Oxidation at 90–100 °C produced 40 nm thick films in a day and over 100 nm films in a week. Although SEM-EDS analyses in TGA tests indicated that oxygen was adsorbed on the copper surface, neither XRD patterns nor Raman spectroscopy measurements showed any trace of Cu2O or CuO formation on the copper surface. Electrochemical reduction analysis of oxidized massive copper samples indicated that the oxide film is mostly Cu2O, and CuO develops only after several days at 90–100 °C.
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铜在温度高达100°C的空气中的氧化
采用等温热重分析(TGA)和石英晶体微天平(QCM)研究了铜在低温(60 ~ 100℃)空气中的氧化动力学。热重试验的重量变化表现为周期性的重量增加和减少。在热重测试中,铜样品的质量增加,直到氧化逐渐减慢,最终由于表面形成的氧化物的开裂和剥落而开始减少。在使用电沉积铜膜的QCM测试中,重量变化在开始时很快,但在几分钟后减慢到线性关系。温度和曝光时间对氧化膜厚度和成分有较大影响。使用QCM,在60-80°C氧化,在10天内生成小于40 nm的薄膜。在90-100°C的氧化条件下,一天可生成40 nm厚的薄膜,一周可生成超过100 nm的薄膜。虽然SEM-EDS分析和TGA测试表明,铜表面吸附了氧气,但XRD和拉曼光谱测量都没有显示铜表面有Cu2O或CuO形成的痕迹。氧化块状铜样品的电化学还原分析表明,氧化膜主要是Cu2O,在90-100℃下经过几天才形成CuO。
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