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金属学报  2019, Vol. 55 Issue (2): 281-290    DOI: 10.11900/0412.1961.2018.00215
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静水压力对金属腐蚀热力学及动力学的影响
马荣耀1,2, 赵林1, 王长罡1, 穆鑫1, 魏欣1, 董俊华1, 柯伟1
1 中国科学院金属研究所 沈阳 110016
2 中国科学院大学 北京 100049
Influence of Hydrostatic Pressure on the Thermodynamics and Kinetics of Metal Corrosion
Rongyao MA1,2, Lin ZHAO1, Changgang WANG1, Xin MU1, Xin WEI1, Junhua DONG1, Wei KE1
1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 University of Chinese Academy of Sciences, Beijing 100049, China
全文: PDF(965 KB)   HTML
摘要: 

以热力学和动力学为基础,分析了静水压力对电极反应中材料的活度、环境中离子的活度、气体的溶解度、活度或逸度的影响,讨论了静水压力对海水环境中的pH值及化学平衡的作用,给出了静水压力与电极反应平衡电极电位和交换电流密度的关系式,并建立了静水压力影响活性金属腐蚀行为的理论模型。研究表明,静水压力可提高材料、环境中离子及溶解气体的活度,且这与其偏摩尔体积密切相关;静水压力对异相材料的活度差异具有放大效应,异相材料的偏摩尔体积相差越大,活度的差异越明显。升高静水压力可降低金属Fe和Al阳极溶解反应的平衡电极电位,同时降低其交换电流密度;升高静水压力可提高吸氧反应的平衡电极电位,降低其交换电流密度;升高静水压力可降低析氢反应的平衡电极电位,增大其交换电流密度。

关键词 静水压力活度逸度溶解度平衡电极电位交换电流密度    
Abstract

In recent years, researches on deep sea corrosion have attracted much attention of many researchers. The high hydrostatic pressure is a distinctive feature of deep-sea environment. The hydrostatic pressure affects the corrosive behavior of metallic materials by modifying the composition, structure and compactness of corrosion products, changing the polarization processes of cathode electrode and anode electrode, altering pitting nucleation rate and growth rate, impacting on chemical reaction rate and equilibrium constant, and varying hydrogen diffusion rate and coverage. However, in essence, the influence of hydrostatic pressure on the corrosion behavior of different metal materials is the manifestation of the thermodynamic and kinetic parameters of the corrosion electrode process caused by hydrostatic pressure. At present, the mechanism of effect of hydrostatic pressure on the thermodynamics and kinetics of corroding electrode processes is unclear yet. In addition, the concerns about the effects of hydrostatic pressure on the chemical properties of materials and seawater are comparatively low. Based on thermodynamics and kinetics, the effects of hydrostatic pressure on the activities of electrode material and ions in environment, including on the solubility, fugacity or activity of gases in environment are analyzed. The influence of hydrostatic pressure on pH value and chemical equilibrium is also discussed. The relationships between hydrostatic pressure and equilibrium electrode potential, as well as the exchange current density, are analyzed. The theoretical model of the effect of hydrostatic pressure on the corrosion behavior of active metals is established. The studies have shown that hydrostatic pressure would increase the activities of materials, ions and dissolved gas in environments, and this is closely related to their partial molar volume. The hydrostatic pressure would magnify the difference in the activity of heterogeneous materials. The larger the partial molar volume difference of the heterogeneous materials, the more obvious the difference in activity. Increasing hydrostatic pressure reduces the equilibrium electrode potential of iron and aluminum anode dissolution reaction while reducing its exchange current density. Increasing hydrostatic pressure increases the equilibrium electrode potential of oxygen reaction and decreases its exchange current density. Increasing hydrostatic pressure reduces the equilibrium electrode potential of hydrogen evolution reaction and increases its exchange current density.

Key wordshydrostatic pressure    activity    fugacity    solubility    equilibrium electrode potential    exchange current density
收稿日期: 2018-05-21     
ZTFLH:  O646.6  
基金资助:资助项目 国家重点研发计划项目No.2017YFB0702302及国家自然科学基金项目Nos.51671200、51501204
作者简介:

作者简介 马荣耀,男,1987年生,博士

引用本文:

马荣耀, 赵林, 王长罡, 穆鑫, 魏欣, 董俊华, 柯伟. 静水压力对金属腐蚀热力学及动力学的影响[J]. 金属学报, 2019, 55(2): 281-290.
Rongyao MA, Lin ZHAO, Changgang WANG, Xin MU, Xin WEI, Junhua DONG, Wei KE. Influence of Hydrostatic Pressure on the Thermodynamics and Kinetics of Metal Corrosion. Acta Metall Sin, 2019, 55(2): 281-290.

链接本文:

https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00215      或      https://www.ams.org.cn/CN/Y2019/V55/I2/281

图1  纯Fe和纯Al的活度随着压力变化的趋势图
图2  0.725 mol/L的NaCl溶液中Cl-活度随压力变化的趋势图
图3  溶解氧活度随压力变化的趋势图
图4  不同压力下纯水电离反应的平衡常数、离子积常数及呈中性时的pH值图
图5  某些电极反应的平衡电极电位随压力变化趋势图
图6  某些电极反应的交换电流密度随压力变化趋势图
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