Plasma electrolytic oxidation was undertaken on Zircaloy-4 in alkaline silicate and pyrophosphate electrolytes, with a square waveform AC current regime. The resultant coatings were examined using scanning electron spectroscopy, X-ray diffraction and nanoindentation. The coatings formed in silicate electrolyte comprised mainly a porous inner layer and a more compact outer layer, with characteristic solidification structures being evident following prolonged treatment. The coatings contained monoclinic and tetragonal ZrO2, the latter being mainly present in the outer layer, which was of hardness up to similar to 8 GPa. In contrast, extensively cracked coatings resulted from use of pyrophosphate electrolyte; the coating integrity was improved by the addition of silicate to the pyrophosphate electrolyte. The different morphologies of the coatings appeared to be related to the differing nature of the microdischarges and to the incorporation of silicon species that enhanced the formation of t-ZrO2. (C) 2011 Elsevier Ltd. All rights reserved.