This study aims at providing a thorough examination of compositional and microstructural heterogeneities in the porous oxide ceramic surface layers formed on Ti by plasma electrolytic oxidation (PEO). The PEO-titania layers of up to 5um thick were produced using 0.02...0.04M NaH2PU4 electrolyte solutions in the voltage range of 450... 500 V DC. Advanced methods of X-ray diffractometry (XRD), scanning electron microscopy (SEM) and field-emission transmission electron microscopy (FE-TEM) were employed to observe the surface layer morphology and characterise its crystal structure across the whole coating thickness. As revealed by XRD analysis, the surface layers consist of both anatase and rutile evenly distributed across the layer thickness. Detailed TEM studies showed that a continuous amorphous layer exists at the top of the PEO coating, the layer comprises mainly TÍO2, with some phosphorus incorporated from the electrolyte. Underneath, there is a porous crystalline layer with uniformly distributed nano-scale pores (<50nm), anatase nanocrystallites (<100nm) and submicrometer-scale (0.1 to lum) rutile crystallites. Large micrometre size pores (about 1...3um in diameter) surrounded by nanocrystall ine anatase are found to exist at the bottom of the porous crystalline layer, adjacent to the thin interfacial barrier layer. Correlations between thermal-physical properties of the coating material, heat dissipation conditions and microstructural evolution in the surface layer during coating formation are discussed.
INTRODUCTIONPlasma electrolytic oxidation (PEO) is an efficient method for production of functional ceramic surface layers on non-ferrous metals, such as aluminium, 1 2 magnesium/ zirconium 4 and titaniunf alloys. During PEO process the electrochemical reaction of anodic oxidation on the metal surface is assisted by micro-discharge events to promote formation of thick, hard and well-adhered oxide ceramic surface layers with specific morphologies and phase compositions, exhibiting superior protective performance and other useful electro-physical and chemical properties. 6 Titanium currently attracts significant attention due to high specific strength, corrosion-resistance and biocompatibility and application of PEO treatment allows tailoring surface composition, crystallographic structure and morphology to attain a variety of functions that cannot be provided by the substrate metal alone. Versatility of PEO coatings on Ti together with simple processing set-up and low capital costs triggered many attempts of applying PEO to titanium for different purposes, including tribological, 7 gas-sensor," biomedical,'' dielectric,'" photocatalytic" and photovoltaic applications. 12 It has been commonly observed that the microstructure of the PEO layer strongly influences its properties such as mechanical, n photocatalytic behaviour," biological performance 14 as well as many