Titanium anodizing in a choline dihydrogencitrate salt-oxalic acid deep eutectic solvent: a step towards green chemistry in surface finishing of titanium and its alloys

Abstract

Deep Eutectic Solvents (DESs) are "green" competitors for some conventional plating baths and electrolytes used for surface modification. Their use allows a material to be obtained with a structure different from that observed in conventional plating or finishing technologies. In this work the titanium anodizing process was investigated in a bath based on a choline dihydrogencitrate salt and oxalic acid (1 : 1 molar ratio) green solvent. Titanium anodized at the lowest voltage applied (10 V) was a deep yellow color, which turned to deep blue at 30 V. The surface morphology and topography of titanium, both anodized and untreated, were monitored by optical, scanning electron (SEM and HR-SEM) and atomic force (AFM) microscopy. Anodizing at 10 V produced a fine granular morphology of the oxide layer, while anodizing at 30 V led to the formation of a probably thicker and quite uneven oxide layer, characterized by a distinct and coarse granular morphology. The average size of the micro-nodules was higher than those at 10 V and porous structures have been also identified. According to X-ray photoelectron spectroscopy (XPS) the stoichiometric TiO₂, regardless of the applied voltage during anodizing, was practically the only component of the oxide layer produced on titanium in the DES bath. At 10 V, the oxide layer was thicker (>10 nm) than the natural Ti passive layer (approx. 2.2 nm), which, apart from TiO₂, also contained oxides of titanium at lower oxidation states, i.e. +2 and +3. Moreover, the XPS technique was supported by electrochemical impedance spectroscopy (EIS), especially in the context of the structure of the oxide layer and its interaction with a corrosive environment. The corrosion resistance of anodized titanium was assessed in 0.05 mol dm^-3 solution of NaCl by the linear polarization resistance (LPR) technique and polarization curves. During interpretation of the impedance spectra, the layers produced by the anodizing process were described using the two-layer model. It was assumed that the inner layer formed directly on the surface of metallic titanium was responsible for the barrier properties (resistance of 2.8 MΩ cm²). The porous outer layer formed on it has a much lower corrosion resistance, i.e. 800-1300 Ω cm².