TY - JOUR

T1 - In situ spatiotemporal solute imaging of metal corrosion on the example of magnesium

AU - Wagner, Stefan

AU - Hummel, Christina

AU - Santner, Jakob

AU - Puschenreiter, Markus

AU - Irrgeher, Johanna

AU - Wenzel, Walter W.

AU - Borisov, Sergey M.

AU - Prohaska, Thomas

N1 - Publisher Copyright: © 2022 The Authors

PY - 2022/5/6

Y1 - 2022/5/6

N2 - Visualization and quantification of corrosion processes is essential in materials research. Here we present a new approach for 2D spatiotemporal imaging of metal corrosion dynamics in situ. The approach combines time-integrated Mg 2+ flux imaging by diffusive gradients in thin films laser ablation inductively coupled plasma mass spectrometry (DGT LA-ICP-MS) and near real-time pH imaging by planar optodes. The parallel assessment of Mg 2+ flux and pH distributions on a fine-structured, bare Mg alloy (b-WE43) showed intense Mg dissolution with Mg 2+ flux maxima up to 11.9 ng cm −2 s −1 and pH increase >9 during initial corrosion (≤15 min) in aqueous NaNO 3 solution (c = 0.01 mol L −1). The techniques visualized the lower initial corrosion rate in buffered synthetic body fluid (Hank's balanced salt solution; pH 7.6) compared to unbuffered NaNO 3 (pH 6.0), but precise localization of Mg corrosion remains challenging under these conditions. To further demonstrate the capability of DGT LA-ICP-MS for spatiotemporal metal flux imaging at the microscale, a coated Mg alloy (c-WE43) with lower reactivity was deployed for ≤120 min. The high spatial resolution (∼10 μm × 80 μm) and low limits of detection (≤0.04 ng cm −2 s −1, t = 60 min) enabled accurate in situ localization and quantification (U rel = 20%, k = 2) of distinct Mg 2+ flux increase, showing micro-confined release of Mg 2+ from surface coating defects on c-WE43 samples. The presented approach can be extended to other metal species and applied to other materials to better understand corrosion processes and improve material design in technological engineering.

AB - Visualization and quantification of corrosion processes is essential in materials research. Here we present a new approach for 2D spatiotemporal imaging of metal corrosion dynamics in situ. The approach combines time-integrated Mg 2+ flux imaging by diffusive gradients in thin films laser ablation inductively coupled plasma mass spectrometry (DGT LA-ICP-MS) and near real-time pH imaging by planar optodes. The parallel assessment of Mg 2+ flux and pH distributions on a fine-structured, bare Mg alloy (b-WE43) showed intense Mg dissolution with Mg 2+ flux maxima up to 11.9 ng cm −2 s −1 and pH increase >9 during initial corrosion (≤15 min) in aqueous NaNO 3 solution (c = 0.01 mol L −1). The techniques visualized the lower initial corrosion rate in buffered synthetic body fluid (Hank's balanced salt solution; pH 7.6) compared to unbuffered NaNO 3 (pH 6.0), but precise localization of Mg corrosion remains challenging under these conditions. To further demonstrate the capability of DGT LA-ICP-MS for spatiotemporal metal flux imaging at the microscale, a coated Mg alloy (c-WE43) with lower reactivity was deployed for ≤120 min. The high spatial resolution (∼10 μm × 80 μm) and low limits of detection (≤0.04 ng cm −2 s −1, t = 60 min) enabled accurate in situ localization and quantification (U rel = 20%, k = 2) of distinct Mg 2+ flux increase, showing micro-confined release of Mg 2+ from surface coating defects on c-WE43 samples. The presented approach can be extended to other metal species and applied to other materials to better understand corrosion processes and improve material design in technological engineering.

UR - http://www.scopus.com/inward/record.url?scp=85130080520&partnerID=8YFLogxK

U2 - 10.1016/j.aca.2022.339910

DO - 10.1016/j.aca.2022.339910

M3 - Article

VL - 1212.2022

JO - Analytica chimica acta

JF - Analytica chimica acta

SN - 0003-2670

IS - 15 June

M1 - 339910

ER -