This work aims to investigate the effects of current density, electrolyte temperature and substrate composition on the morphology of porous anodic films formed on AA 2024-T3 alloy in sulphuric acid electrolytes and the factors that determine the transition between linear and sponge-like film porosities. Comparisons were made with pure aluminium. Particular attention is given to understanding the rising voltage that occurs during galvanostatic hard anodizing of the alloy and the role of oxygen in the anodizing process. Conditions were selected to be representative of typical hard and conventional anodizing processes. SEM was employed to observe the film morphology, which was then correlated with the voltage-time responses. The anodic film composition was investigated by TEM/EDX and SEM/EDX to determine the effect of alloy element enrichment and cell diameter on the distribution of copper species in the film. A real-time gravimetric method was developed to measure the rate of oxygen evolution during anodizing and its influence on the anodizing voltage and film morphology. Results showed that hard anodic films on AA 2024-T3 alloy formed at relatively high voltages have linear pores and cells, contrasting with sponge-like porosity under conventional anodizing. The linear porosity is shown to depend on the voltage, with a morphological transition occurring in the range 25 to 30 V, with linear cells promoted by a high current density and/or low electrolyte temperature. As the film thickens with time, pore blockage by oxygen bubbles, impedes oxidation of the alloy leading to current re-distribution and hence localized increases in the current density producing a rise of the anodizing voltage as anodizing proceeds. The rise of the anodizing voltage, which leads to an increasing call diameter and barrier layer thickness, has a minor influence on the rate of oxygen evolution, which typically consumes about 20 % of the applied current density. In contrast, the voltage rise in the presence of sponge-like films is comparatively negligible, which is suggested to be due to easier escape of oxygen from the film. The films comprising linear cells contain more copper than the sponge-like films, with copper being enriched at the cell boundaries. Moreover, a model is proposed to explain the enrichment of copper, suggesting that above a critical cell diameter, an alloy enrichment sufficient for oxidation of the alloying element can be maintained across the alloy/film interface. Below this diameter, the enrichment is less than that necessary for oxidation, and the alloying element is then incorporated into the film at the cell boundaries.

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