(Invited) Growth of Self-Ordered Porous Anodic Oxide Nanomaterials By Coupled Ion Migration and Viscous Flow

Abstract

Porous anodic oxide (PAO) films are self-organized porous oxide nanomaterials formed by electrochemical oxidation. PAO includes porous anodic alumina and TiO2 nanotube layers. These films eventually evolve into a hexagonally-ordered array of parallel cylindrical pores or nanotubes of order 100 nm diameter, with a characteristic interpore spacing that scales directly with the cell voltage.We explore the roles of mechanical stress and oxide flow in self-ordering, through a modeling analysis of stress-driven viscous flow of oxide (1). The model is based on coupled viscous flow of oxide and stress- and electric field-driven migration of metal and oxygen ions (2). Stress at the film interfaces is generated by ion-transfer processes and relaxed by viscous flow, resulting in layers with elevated compressive or tensile stress within a few nm of the interfaces (3,4). Experimental evidence for these layers has been found from in situ stress measurements (5,6). We present linear stability analysis incorporating the surface stress boundary conditions in the coupled oxide flow-electrical migration model of Houser and Hebert (2).For porous alumina, the calculations reveal self-organized pattern formation with steady-state pore spacing-voltage scaling ratios that compare favorably to those found experimentally (1). The scaling ratios are independent of oxide viscosity or uncertainties in the values of any other model parameters. The stress driving oxide flow arises at the oxide-solution interface due to strong electrolyte anion adsorption, which blocks direct oxide deposition on the surface itself. New results for TiO2 nanotube layers are presented. Near-surface stress is not present in TiO2 nanotube layers (6); instead, compressive stress driving flow arises at the metal-oxide interface from the volume change upon conversion of metal to oxide.REFERENCES P. Mishra and K. R. Hebert, Electrochim. Acta, 340, 135879 (2020).J. E. Houser and K. R. Hebert, Nature Mater., 8, 415 (2009).K. R. Hebert, P. Mishra, J. Electrochem. Soc., 165, E737 (2018).K. R. Hebert, P. Mishra, J. Electrochem. Soc., 165, E744 (2018).Ö. Ö. Çapraz, P. Shrotriya, P. Skeldon, G. E. Thompson, K. R. Hebert, Electrochim. Acta, 167, 404 (2015).Q. Dou, P. Shrotriya, W. F. Li, K. R. Hebert, Electrochim. Acta, 292, 676 (2018).Q. Dou, P. Shrotriya, W. F. Li, K. R. Hebert, Electrochim. Acta, 295, 418 (2019).