Electrophoretic enhanced micro arc oxidation of ZrO2–HAp–TiO2 nanostructured porous layers

Micro arc oxidation (MAO) and electrophoretic deposition (EPD) processes were simultaneously employed to grow ZrO2–HAp–TiO2 porous layers on titanium substrates under different conditions. Influence of the electrolyte composition and the growth time on surface morphology, topography, phase structure, and stoichiometry of the layers was investigated. The utilized electrolytes consisted of β-glycerophosphate, calcium acetate, sodium phosphate, and micron sized yttria-stabilized zirconia with different concentrations. AFM and SEM evaluations revealed a rough surface with a porous structure with a pores size of 50–750 nm. The pores size increased with the time and the electrolyte concentration. Based on the XRD and XPS results, the layers consisted of anatase, hydroxyapatite, monoclinic ZrO2, tetragonal ZrO2, ZrO, CaTiO3, and α-TCP phases whose fractions were observed to change depending on the synthesis conditions. The average crystalline size of the HAp phase was determined as ∼54 nm. The nano-sized zirconia particles (d = 20–60 nm) were dispersed not only on surface, but also in depth of the layers. Utilizing thicker electrolytes and prolonging the growth time resulted in decomposition of hydroxyapatite as well as tetragonal ZrO2 to monoclinic ZrO2. EDX results also showed that the zirconium wt% in the layers increased with the time. EPD-enhanced MAO (EEMAO) technique was expressed as an efficient route to fabricate ZrO2–HAp–TiO2 multiphase systems within short times and only in one step.

► ZrO2–HA–TiO2 composite layers were synthesized via EPD/MAO hybrid technique.
► Effect of the growth time on properties of the layers was studied.
► Effect of the electrolyte composition on properties of the layers was studied.