Electrochemical oxidation of Ti15Mo alloy : the impact of anodization parameters on surface morphology of nanostructured oxide layers

It is well-known that the structure and composition of the material plays an important role in the processes occurring at the surface. In this paper, a surface morphology of nanostructured oxide layers electrochemically grown on Ti15Mo, tuned by applying different anodization parameters, was investigated in detail. The one-step anodization of Ti15Mo alloy was performed at room temperature in an ethylene glycol-based electrolyte containing 0.11 M NH4F and 1.11 M H2O. Different anodization times (ranging from 5 to 60 min) and applied potentials (40–100 V) were tested, and the surface morphology, elemental content, and crystalline structure were monitored by scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDS), and X-ray diffractometry (XRD), respectively. The results showed that contrary to the multistep anodization of titanium foil, the surface morphology of anodic oxide obtained via the one-step process contains the nanoporous outer layer covering the nanotubular structure. What is more, the pore diameter (Dp) and interpore distance (Dint) of such layers exhibit different trends than those observed for anodization of pure titanium. In particular, at a certain potential range, a decrease in both Dp and Dint with increasing potential was observed. However, independently on the used anodization conditions, the elemental content of oxide layers remained similar, showing the amount of molybdenum at c.a. 15 wt.%. Finally, the amorphous nature of as-anodized layers was confirmed, and their optical band-gap was determined from the diffuse reflectance UV–Vis spectra. It was found that Eg is tunable to some extent by changing the anodizing potential. However, further thermal treatment in air at 400 °C resulted in the anatase phase formation that was accompanied by a significant Eg reduction. Therefore, we believe that the presented results will greatly contribute to the understanding of anodic formation of nanostructured functional oxide layers with tunable properties that can be applied in various fields

The influence of passivation type on corrosion resistance of Ti15Mo alloy in simulated body fluids

This work reports on determination of the influence of passivation type of Ti15wt.%Mo implant alloy surface on its corrosion resistance in simulated body fluids. The alloy under investigation was subjected to natural self-passivation in air, and forced passivation by autoclaving in steam, boiling in 30 % solution of H2O2, and electrochemical passivation in 0.9 % NaCl solution. Resistance of the passivated Ti15Mo alloy to pitting corrosion was studied at 37°C in 0.9 % NaCl solution using open circuit potential method, anodic polarization curves, and electrochemical impedance spectroscopy (EIS). Comparative estimation of the determined parameters of corrosion resistance revealed that the obtained passive layers improve anticorrosive properties of the tested alloy. Surface of the alloy subjected to passivation in steam autoclave reveals the highest protection against pitting corrosion. Anodic potentiodynamic curves showed that the Ti15Mo alloy after different passivation types of the surface is characterized by a lack of susceptibility to pitting corrosion up to potential of 9 V. Based on the EIS investigations, the thickness of the formed oxide layers (TiO2, anatase) was determined to be in the range from 2.0 to 7.8 nm in dependence on the applied type of passivation. It was ascertained that electrochemical properties of the Ti15Mo alloy and possibility of its surface passivation using simple methods, make it an attractive material for use in biomedicine for long-term implants

Innovative bioactive Ag-SiO2/TiO2 coating on a NiTi-shape memory alloy : structure and mechanism of its formation

In recent years, more and more emphasis has been placed on the development and functionalization of metallic substrates for medical applications to improve their properties and increase their applicability. Today, there are many different types of approaches and materials that are used for this purpose. Our idea was based on a combination of a chemically synthesized Ag-SiO2 nanocomposite and the electrophoretic deposition approach on a NiTi-shape memory substrate. As a result, silver-silica coating was developed on a previously passivated alloy, which was then subjected to sintering at 700 C for 2 h. The micrometer-sized coat-forming material was composed of large agglomerates consisting of silica and a thin film of submicron- and nano- spherical-shaped particles built of silver, carbon, and oxygen. Structurally, the coatings consisted of a combination of nanometer-sized silver-carbonate that was embedded in thin amorphous silica and siloxy network. The temperature impact had forced morphological and structural changes such as the consolidation of the coat-forming material, and the partial coalescence of the silver and silica particles. As a result, a new continuous complex ceramic coating was formed and was analyzed in more detail using the XPS, XRD, and Raman methods. According to the structural and chemical analyses, the deposited Ag-SiO2 nanocomposite material’s reorganization was due to its reaction with a passivated TiO2 layer, which formed an atypical glass-like composite that consisted of SiO2-TiO2 with silver particles that stabilized the network. Finally, the functionalization of the NiTi surface did not block the shape memory effect

Electrodeposition of copper and brass coatings with olive-like structure

One method of creating a brass coating is through electrodeposition, which is most often completed in cyanide galvanic baths. Due to their toxicity, many investigations focused on the development of more environmentally friendly alternatives. The purpose of the study was to explore a new generation of non-aqueous cyanide-free baths based on 1-ethyl-3-methylimidazolium acetate ionic liquids. The study involved the formation of copper, zinc, and brass coatings. The influence of the bath composition, cathodic current density, and temperature was determined. The obtained coatings were characterized in terms of their morphology, chemical composition, phase composition, roughness, and corrosion resistance. It was found that the structure of the obtained coatings is strongly dependent on the process parameters. The three main structure types observed were as follows: fine-grained, porous, and olive-like. To the best knowledge of the authors, it is the first time the olive-like structure was observed in the case of an electrodeposited coating. The Cu-Zn coatings consisted of 19–96 at. % copper and exhibited relatively good corrosion resistance. A significant improvement of corrosion properties was found in the case of copper and brass coatings with the olive-like structure

Surface modification of biomedical MgCa4.5 and MgCa4.5Gd0.5 alloys by micro-arc oxidation

The aim of this work was to characterize the structure and corrosion properties of the MgCa4.5(Gd0.5) alloys surface treated by the micro-arc oxidation (MAO) process. The MgCa4.5 and MgCa4.5Gd0.5 alloy samples were processed by MAO in an electrolyte composed of NaOH (10 g/dm3), NaF (10 g/dm3), NaH2PO4 (5 g/dm3), Na2SiO2·5H2O (10 g/dm3) and water. Two different voltages (120 V and 140 V) were used in the MAO process. The alloys protected by an oxide layer formed in the MAO were then the subject of corrosion resistance tests in an environment simulating the human body (Ringer’s solution). After the experiments, the resulting samples were investigated with using SEM, XPS and EDS techniques. The addition of Gd affected the fragmentation of the coating structure, thereby increasing the specific surface; higher voltages during the MAO process increased the number and size of surface pores. Corrosion tests showed that the MgCa4.5Gd0.5 alloys were characterized by low polarization resistances and high corrosion current densities. The studies indicated the disadvantageous influence of gadolinium on the corrosion resistance of MgCa4.5 alloys. The immersion tests confirmed lower corrosion resistance of MgCa4.5Gd0.5 alloys compared to the referenced MgCa4.5 ones. The MgCa4.5 alloy with the MAO coating established at voltage 140 V demonstrated the best anticorrosion properties

Physico-chemical and biological evaluation of doxycycline loaded into hybrid oxide-polymer layer on TiMo alloy

Oxide-polymer coatings were formed on the surface of the vanadium-free Ti-15Mo titanium alloy. The Ti alloy surface was modified by the plasma electrolytic oxidation process, and then, the polymer layer of a poly (D, Llactide- co-glycolide) with doxycycline was formed. The polymer evenly covered the porous oxide layer and filled some of the pores. However, the microstructure of the polymer surface was completely different from that of the PEO layer. The surface morphology, roughness and microstructure of the polymer layer were examined by scanning electron microscopy (SEM) and a confocal microscope. The results confirmed the effectiveness of polymer and doxycycline deposition in their stable chemical forms. The drug analysis was performed by highperformance liquid chromatography. The $^{1}$H NMR technique was used to monitor the course of hydrolytic degradation of PLGA. It was shown that the PLGA layer is hydrolysed within a few weeks, and the polyglycolidyl part of the copolymer is hydrolysed to glycolic acid as first and much faster than the polylactide one to lactic acid. This paper presents influence of different microstructures on the biological properties of modified titanium alloys. Cytocompatibility and bacterial adhesion tests were evaluated using osteoblast-like MG-63 cells and using the reference S. aureus and S. epidermidis strains. The results showed that the optimum concentration of doxycycline was found to inhibit the growth of the bacteria and that the layer is still cytocompatible

Antibacterial and cytocompatible coatings based on poly(adipic anhydride) for a Ti alloy surface

This paper describes a formation of hybrid coatings on a Ti–2Ta–3Zr–36Nb surface. This is accomplished by plasma electrolytic oxidation and a dip-coating technique with poly(adipic anhydride) ((C$_{6}$H$_{8}$O$_{3}$)n) that is loaded with drugs: amoxicillin (C$_{16}$H$_{19}$N$_{3}$O$_{5}$S), cefazolin (C$_{14}$H$_{14}$N$_{8}$O$_{4}$S$_{3}$) or vancomycin (C$_{6}6$H$_{75}$Cl$_{2}$N$_{9}$O$_{24}$ · xHCl). The characteristic microstructure of the polymer was evaluated using scanning electron microscopy and confocal microscopy. Depending on the surface treatment, the surface roughness varied (between 1.53 μm and 2.06 μm), and the wettability was change with the over of time. X-ray photoelectron spectroscopy analysis showed that the oxide layer did not affect the polymer layer or loaded drugs. However, the drugs lose their stability in a phosphate-buffered saline solution after 6.5 h of exposure, and its decrease was greater than 7% (HPLC analysis). The stability, drug release and concentration of the drug loaded into the material were precisely analyzed by high-performance liquid chromatography. The results correlated with the degradation of the polymer in which the addition of drugs caused the percent of degraded polymer to be between 35.5% and 49.4% after 1 h of material immersion, depending on the mass of the loaded drug and various biological responses that were obtained. However, all of the coatings were cytocompatible with MG-63 osteoblast-like cells. The drug concentrations released from the coatings were sufficient to inhibit adhesion of reference and clinical bacterial strains (S. aureus). The coatings with amoxicillin showed the best results in the bacterial inhibition zone, whereas coatings with cefazolin inhibited adhesion of the above bacteria on the surface

Atomic and electronic structure of graphene oxide/Cu interface

The results of X-ray photoemission (XPS) and valence bands spectroscopy, optically stimulated electron emission (OSEE) measurements and density functional theory based modeling of graphene oxide (GO) placed on Cu via an electrophoretic deposition (EPD) are reported. The comparison of XPS spectra of EPD prepared GO/Cu composites with those of as prepared GO, strongly reduced GO, pure and oxidized copper demonstrate the partial (until C/O ratio about two) removal of oxygen-containing functional groups from GO simultaneously with the formation of copper oxide-like layers over the metallic substrate. OSEE measurements evidence the presence of copper oxide phase in the systems simultaneously with the absence of contributions from GO with corresponding energy gap. All measurements demonstrate the similarity of the results for different thickness of GO cover of the copper surface. Theoretical modeling demonstrates favorability of migration of oxygen-containing functional groups from GO to the copper substrate only for the case of C/O ratio below two and formation of Cu-O-C bonds between substrate and GO simultaneously with the vanishing of the energy gap in GO layer. Basing on results of experimental measurements and theoretical calculations we suggest the model of atomic structure for Cu/GO interface as Cu/CuO/GO with C/O ratio in gapless GO about two.Comment: 22 pages, 14 figures, accepted to Thin Solid Films journa