The aim of the paper is to study and determine the effect of voltage increasing from 500 up to 650 V DC on chemical and electrochemical properties of the obtained porous coatings with plasma electrolytic oxidation (PEO) processes, known also as micro arc oxidation (MAO). In the present paper, the chemical and electrochemical characterization of porous phosphate coatings enriched with magnesium or zinc on commercially pure (CP) Titanium Grade 2 under DC-PEO obtained in electrolytes based on concentrated 85% analytically pure H 3 PO 4 (98 g/mole) acid with additions of 500 g•L −1 of zinc nitrate Zn(NO 3) 2 •6H 2 O or magnesium nitrate Mg(NO 3) 2 •6H 2 O, are described. These materials were characterized using scanning electron microscope (SEM) with energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and glow discharge optical emission spectroscopy (GDOES). It was found that the voltage of PEO process has influence on the chemical composition and thickness of the obtained porous coatings as well as on their electrochemical behavior. The higher the potential of PEO treatment, the higher the amount of zinc-to-phosphorus ratio for zinc enriched coatings was obtained, whereas in magnesium enriched coatings, the average amount of magnesium detected in PEO coating is approximately independent of the PEO voltages. Based on XPS studies, it was found out that most likely the top 10 nm of porous coatings is constructed of titanium (Ti 4+), magnesium (Mg 2+), zinc (Zn 2+), and phosphates PO 4 3− and/or HPO 4 2− and/or H 2 PO 4 − and/or P 2 O 7 4−. On the basis of GDOES studies, a four-sub-layer model of PEO coatings is proposed. Analysis of the potentiodynamic corrosion curves allowed to conclude that the best electrochemical repeatability was noted for magnesium and zinc enriched coatings obtained at 575 V DC .

Abstract:In the paper, Scanning Electron Microscopy (SEM), Energy-dispersive X-ray Spectroscopy (EDS), X-ray Photoelectron Spectroscopy (XPS), and Glow Discharge Optical Emission Spectroscopy (GDOES) analyses of calcium-and phosphorus-enriched coatings obtained on commercial purity (CP) Titanium Grade 2 by plasma electrolytic oxidation (PEO), known also as micro arc oxidation (MAO), in electrolytes based on concentrated phosphoric acid with calcium nitrate tetrahydrate, are presented. The preliminary studies were performed in electrolytes containing 10, 300, and 600 g/L of calcium nitrate tetrahydrate, whereas for the main research the solution contained 500 g/L of the same hydrated salt. It was found that non-porous coatings, with very small amounts of calcium and phosphorus in them, were formed in the solution with 10 g/L Ca(NO 3 ) 2 ·4H 2 O, whereas the other coatings, fabricated in the consecutive electrolytes containing from 300 up to 650 g/L Ca(NO 3 ) 2 ·4H 2 O, were porous. Based on the GDOES data, it was also found that the obtained porous PEO coating may be divided into three sub-layers: the first, top, porous layer was the thinnest; the second, semi-porous layer was about 12 times thicker than the first; and the third, transition sub-layer was about 10 times thicker than the first. Based on the recorded XPS spectra, it was possible to state that the top 10-nm layer of porous PEO coatings included chemical compounds containing titanium (Ti 4+ ), calcium (Ca 2+ ), as well as phosphorus and oxygen (PO 4 3− and/or HPO 4 2− and/or H 2 PO 4 − , and/or P 2 O 7 4− ).

Abstract:In the paper, the effect of voltage increase (from 500 V DC up to 650 V DC ) on the structure and chemical composition of the porous coating on titanium made by Plasma Electrolytic Oxidation is presented. Phosphates-based coatings enriched with calcium, magnesium, zinc, and copper in electrolyte based on 1 L of 85% concentrated H 3 PO 4 , with additions of Ca(NO 3 ) 2 ·4H 2 O, and Mg(NO 3 ) 2 ·6H 2 O, and Zn(NO 3 ) 2 ·6H 2 O, and Cu(NO 3 ) 2 ·3H 2 O, are described. The morphology and chemical and phase composition are evaluated using SEM, EDS, XRD, XPS, GDOES, and CLSM. Based on these analyses, it was found that PEO coatings are porous and enriched with calcium, magnesium, zinc and copper. They consist mainly of the amorphous phase, which is more visible for higher voltages; this is correlated with an increase in the total PEO coating thickness (the higher the voltage, the thicker the PEO coating). However, for 650 V DC , an amorphous phase and titanium substrate were also recorded, with a signal from Ti 2 P 2 O 7 crystalline that was not observed for lower voltages. It was also found that all obtained coatings may be divided into three sub-layers, i.e., porous, semiporous, and transitional.

The present paper covers the possible ways to fabricate advanced porous coatings that are enriched in copper on a titanium substrate through Direct Current Plasma Electrolytic Oxidation (DC-PEO) with voltage control, in electrolytes made of concentrated orthophosphoric acid with the addition of copper(II) nitrate(V) trihydrate. In these studies, solutions containing from 0 to 650 g salt per 1 dm3 of acid and anodic voltages from 450 V up to 650 V were used. The obtained coatings featuring variable porosity could be best defined by the three-dimensional (3D) parameter Sz, which lies in the range 9.72 to 45.18 μm. The use of copper(II) nitrate(V) trihydrate in the electrolyte, resulted, for all cases, in the incorporation of the two oxidation forms, i.e., Cu+ and Cu2+ into the coatings. Detailed X-Ray Photoelectron Spectroscopy (XPS) studies layers allowed for stating that the percentage of copper in the surface layer of the obtained coatings was in the range of 0.24 at% to 2.59 at%. The X-Ray Diffraction (XRD) studies showed the presence of copper (α-Cu2P2O7, and Cu3(PO4)2) and titanium (TiO2-anatase, TiO3, TiP2O7, and Ti0.73O0.91) compounds in coatings. From Energy-Dispersive X-Ray Spectroscopy (EDS) and XPS studies, it was found that the Cu/P ratio increases with the increase of voltage and the amount of salt in the electrolyte. The depth profile analysis by Glow-Discharge Optical Emission Spectroscopy (GDOES) method showed that a three-layer model consisting of a top porous layer, a semi-porous layer, and a transient/barrier layer might describe the fabricated coatings.

In this paper, the characteristics of new porous coatings fabricated at three voltages in electrolytes based on H3PO4 with calcium nitrate tetrahydrate, magnesium nitrate hexahydrate, and copper(II) nitrate trihydrate are presented. The SEM, energy dispersive spectroscopy (EDS), glow discharge optical emission spectroscopy (GDOES), X-ray photoelectron spectroscopy (XPS), and XRD techniques for coating identification were used. It was found that the higher the plasma electrolytic oxidation (PEO) (micro arc oxidation (MAO)) voltage, the thicker the porous coating with higher amounts of built-in elements coming from the electrolyte and more amorphous phase with signals from crystalline Ca(H2PO4)2∙H2O and/or Ti(HPO4)2∙H2O. Additionally, the external parts of the obtained porous coatings formed on titanium consisted mainly of Ti4+, Ca2+, Mg2+ and PO43−, HPO42−, H2PO4−, P2O74− as well as Zn2+ or copper Cu+/Cu2+. The surface should be characterized by high biocompatibility, due to the presence of structures based on calcium and phosphates, and have bactericidal properties, due to the presence of zinc and copper ions. Furthermore, the addition of magnesium ions should accelerate the healing of postoperative wounds, which could lead to faster patient recovery.