Williams Geraint, Birbilis Nick, McMurray H Neil
Materials Research Centre, College of Engineering, Swansea University, Singleton Park, Swansea, SA2 8PP, UK.
Faraday Discuss. 2015;180:313-30. doi: 10.1039/c4fd00268g. Epub 2015 Apr 24.
The early stages of localised corrosion affecting magnesium (Mg) surfaces when immersed in aqueous sodium chloride (NaCl) solutions involves the propagation of dark regions, within which both anodic metal dissolution and cathodic hydrogen evolution occur. For nominally "pure" Mg, these dark areas can either take the form of discs which expand radially with time, or filiform-like tracks which lengthen with time. For Mg surfaces which display disc-form corrosion features in concentrated NaCl electrolyte, a transition to filiform corrosion (FFC) is observed as the concentration is decreased, indicating ohmic constraints on radial propagation. A similar effect is observed when Mg specimens of different iron impurity are immersed in a fixed, high concentration NaCl solution, where disc-form corrosion is observed on samples having ≥280 ppm Fe, but FFC predominates at ≤80 ppm Fe. An in situ scanning vibrating electrode technique (SVET) is used to determine current density distributions within the propagating corrosion features. Cathodic current density values of between -100 and -150 A m(-2) measured in central areas of disc-like features are sufficient to sustain the radial growth of a local anode at the perimeter of the discs. However, for high purity Mg specimens (≤80 ppm Fe), cathodic current densities of -10 A m(-2) or less are measured over FFC affected regions, indicating that linear propagation arises when there is insufficient cathodic current produced on the corroded surface to sustain radial growth. The results are consistent with surface control of localised corrosion propagation in concentrated electrolyte, but ohmic control in dilute, lower conductivity NaCl solution.
当镁(Mg)表面浸入氯化钠(NaCl)水溶液中时,局部腐蚀的早期阶段涉及暗区的扩展,在暗区内会同时发生阳极金属溶解和阴极析氢。对于标称“纯”镁,这些暗区可以呈随时间径向扩展的圆盘状,也可以呈随时间延长的丝状轨迹。对于在浓氯化钠电解质中呈现圆盘状腐蚀特征的镁表面,随着浓度降低,会观察到向丝状腐蚀(FFC)的转变,这表明径向扩展存在欧姆限制。当将不同铁杂质含量的镁试样浸入固定的高浓度氯化钠溶液中时,也观察到了类似的效应,其中铁含量≥280 ppm的样品上观察到圆盘状腐蚀,但铁含量≤80 ppm时丝状腐蚀占主导。采用原位扫描振动电极技术(SVET)来确定正在扩展的腐蚀特征内的电流密度分布。在圆盘状特征中心区域测得的阴极电流密度值在-100至-150 A m⁻²之间,足以维持圆盘周边局部阳极的径向生长。然而,对于高纯度镁试样(≤80 ppm Fe),在受丝状腐蚀影响的区域测得的阴极电流密度为-10 A m⁻²或更低,这表明当腐蚀表面产生的阴极电流不足以维持径向生长时,就会出现线性扩展。结果表明,在浓电解质中局部腐蚀扩展受表面控制,但在稀的、电导率较低的氯化钠溶液中受欧姆控制。