Nanometer Resolved Real Time Visualization of Acidification and Material Breakdown in Confinement

Abstract

Localized surface reactions in confinement are inherently difficult to visualize in real-time. Herein multiple-beam-interferometry (MBI) is extended as a real-time monitoring tool for corrosion of nanometer confined bulk metallic surfaces. The capabilities of MBI are demonstrated, and the initial crevice corrosion mechanism on confined nickel and a Ni75Cr16Fe9 model material is compared. The initiation of crevice corrosion is visualized in real time during linear sweep polarization in a 1 x 10(-3) m NaCl solution. Pre- and post-experiment analysis is performed to complementarily characterize the degraded area with atomic force microscopy (AFM), optical microscopy, nano-Laue diffraction (nano-LD), scanning electron microscopy (SEM)/electron backscatter diffraction (EBSD), and X-ray photoelectron spectroscopy (XPS). Overall, Ni75Cr16Fe9 displays a better corrosion resistance; however, MBI imaging reveals 200 nm deep severe localized corrosion of the alloy in the crevice opening. Chromium rich passive films formed on the alloy contribute to accelerated corrosion of the confined alloy by a strongly acidifying dissolution of the passive film in the crevice opening. Nano-LD further reveals preferential crystallographic defect and corrosion migration planes during corrosion. MBI provides nanometer accurate characterization of topologies and degradation in confined spaces. The technique enables the understanding of the initial crevice corrosion mechanism and testing modeling approaches and machine-learning algorithms.