Formation mechanism of nanopores in dense films of anodic alumina

Constant-current anodization of pure aluminum was carried out in non-corrosive capacitor working electrolytes to study the formation mechanism of nanopores in the anodic oxide films.Through comparative experiments,nanopores are found in the anodic films formed in the electrolytes after high-temperature storage(HTS)at 130°C for 240 h.A comparison of the voltage-time curves suggests that the formation of nanopores results from the decrease in formation efficiency of anodic oxide films rather than the corrosion of the electrolytes.FT-IR and UV spectra analysis shows that carboxylate and ethylene glycol in electrolytes can easily react by esterification at high temperatures.Combining the electronic current theory and oxygen bubble mold effect,the change in electrolyte composition could increase the electronic current in the anodizing process.The electronic current decreases the formation efficiency of anodic oxide films,and oxygen bubbles accompanying electronic current lead to the formation of nanopores in the dense films.The continuous electronic current and oxygen bubbles are the prerequisites for the formation of porous anodic oxides rather than the traditional field-assisted dissolution model.

Electrode Potential Explaining the Growth of Anodic Oxides

The formation mechanism of porous anodic oxides remains unclear till now.The classical field-assisted dissolution(FAD)theory cannot explain the relationship between the current curve and FAD reaction,and the influence of the electrode potential on anodization is rarely reported.The electrode potential theory,oxygen bubble model and the ionic current and electronic current theories were introduced to explain the growth of porous anodic oxides of three metals(Ti,Zr and Fe).Taking the anodization of Ti in aqueous solution containing 0.5wt% NH_(4)F as an example,the electrode potential was calculated,and the morphology of porous anodic oxides was investigated at low voltages.Results show that the growth of porous anodic oxides is determined by the ratio of the ionic current to the electronic current.During the anodization,metals are classified into two groups:one is easy to form the compact oxide layer,and the other is easy to induce oxygen releasing,thus forming oxygen bubbles.The electrolyte is also classified into two groups correspondingly:compact oxide layer-assisted electrolyte and releasing oxygen-assisted electrolyte.