14 Search Results

Thin films grown on mineral surfaces can immobilize toxic metals in natural systems, but the effects of epitaxy and film thickness on dissolution rates of the overgrowth are typically unknown. To explore these effects, otavite (CdCO₃) films were grown on dolomite (104) surfaces from aqueous solutions containing [Cd] = [Ca] = [CO₃] = 0.2 mM for 1–48 h and then dissolved in deionized water. Films of various thicknesses and strain states were obtained by varying the growth reaction time. Growth for up to 3 h produced strained thin films with Cd coverages of <4.3 ± 0.6 equivalent monolayers (ML) (correspondingmore » to a thickness of up to 17 Å), whereas reaction times of up to 48 h produced thicker films with as many as 114 ± 14 equivalent ML of Cd. Intrinsic dissolution rates were measured as a function of otavite film thickness by a combination of synchrotron X-ray fluorescence, specular X-ray reflectivity, and atomic force microscopy. As a result, the initial dissolution rates for unstrained films were comparable to those reported for synthetic otavite powders, whereas the thinnest films (<3.1 ± 1.1 ML) dissolved at a 50% slower rate, indicating that epitaxial strain effectively enhanced their stability. We discuss potential reasons for this difference.« less

The Cl¯-induced corrosion of metals and alloys is of relevance to a wide range of engineered materials, structures, and systems. Because of the challenges in studying pitting corrosion in a quantitative and statistically significant manner, its kinetics remain poorly understood. Herein, by direct, nano- to micro-scale observations using vertical scanning interferometry (VSI), we examine the temporal evolution of pitting corrosion on AISI 1045 carbon steel over large surface areas in Cl¯-free, and Cl¯-enriched solutions. Special focus is paid to examine the nucleation and growth of pits, and the associated formation of roughened regions on steel surfaces. By statistical analysis ofmore » hundreds of individual pits, three stages of pitting corrosion, namely, induction, propagation, and saturation, are quantitatively distinguished. By quantifying the kinetics of these processes, we contextualize our current understanding of electrochemical corrosion within a framework that considers spatial dynamics and morphology evolutions. In the presence of Cl¯ ions, corrosion is highly accelerated due to multiple autocatalytic factors including destabilization of protective surface oxide films and preservation of aggressive microenvironments within the pits, both of which promote continued pit nucleation and growth. Furthermore these findings offer new insights into predicting and modeling steel corrosion processes in mid-pH aqueous environments« less