Periodic aggregation patterns of oxide particles on corroding metals: chemical waves due to solution feedback...

Chemical waves that produce periodic patterns are common occurrences in nature. The underlying processes involved have been studied in many disciplines of science, but rarely reported in the chemistry of corrosion. In this study of carbon steel corrosion, iron oxide crystals are observed to deposit in concentric wave patterns or in discrete bands, known as Liesegang patterns. We demonstrate that oxide growth in these patterns is preceded by the formation of a hydrogel network, which consists of a semi-stationary phase of loosely connected metal-hydroxide colloids and a mobile phase of solution saturated with metal cations. Once the hydrogel network covers the metal surface, a metal cation produced by corrosion reactions at the metal surface must diffuse through the layer into the bulk solution. While diffusing through the porous network, the metal cation undergoes adsorption-precipitation as metal-hydroxide colloids which later can dissolve back into the solution. When the kinetics of precipitation and dissolution of the metal cation can be effectively coupled with the transport flux of the dissolved metal cation, the precipitation-dissolution-diffusion cycles can be sustained over time which can lead to periodic aggregation patterns of metal-hydroxide colloids at a specific time. We also establish that for transition metal cations the precipitation-dissolution-diffusion process can couple with reversible redox reactions between the soluble and less soluble metal cations, which can affect the overall transport of banded aggregates of metal-hydroxide colloids and the growth and transformation of metal-hydroxides into crystalline oxides. If systemic feedback between different elementary processes is sustained over long durations, iron-oxide crystals of different chemical compositions and shapes aggregate in Liesegang patterns. This work demonstrates unequivocally that non-uniform deposition of metal oxides during corrosion can occur via strongly coupled solution reactions and transport processes, and not simply as a result of metallurgical non-uniformity and/or localized solution environments.