Preparation,scratch adhesion and anti-corrosion performance of TiO2-MgO-BHA coating on Ti6Al4V implant by plasma electrolytic oxidation technique

Bovine hydroxyapatite (BHA) (from cortical bone), was selected as the main electrolyte for plasma electrolytic oxidation (PEO) on Ti6Al4V implant. The prepared PEO coatings were examined by X-ray diffraction, field emission scanning electron microscope and energy-dispersive X-ray spectroscopy. The surface roughness, adhesion strength, wettability, surface energy and corrosion behaviour of the film were also investigated. The results show that the oxide layer (26 μm) formation on the Ti6Al4V was rough and porous. The micro-pores were filled with anatase TiO₂, cubic MgO and hexagonal BHA particles. The porous structures and the compound particles were mainly composed of Mg, O, Ca, P, Ti, Na and Al. Unlike previous coatings produced from calcium and phosphorus inorganic solutions, the coating formation from a newly developed bovine bone-derived HA electrolyte revealed an additional MgO phase in the coating layer. Moreover, higher amount of single phase hexagonal crystalline BHA phase with a Ca/P ratio of 1.1 was achieved with a single PEO process. A film-to-substrate adhesion strength of 1862.24 mN and scratch hardness of about 4.1 GPa was achieved from this method. The TiO₂/MgO/BHA film exhibited better wettability, higher surface energy and superior corrosion resistance compared to the bare Ti6Al4V substrate.     

Microstructures,mechanical properties and corrosion resistance of sprayed Ca–P coating for micropatterning carbon/carbon substrate surface

Carbon/carbon (C/C) surface micropatterning is a method of modifying the surface into the complete and regular geometry. In this work, we introduce a positive effect on bonding strength between sprayed Ca–P coating and surface micropatterning C/C substrate. Interestingly, C/C substrate coated by Ca–P coating provides textured surface for a new bone ingrowth. The sprayed Ca–P coating is then subjected to microwave-hydrothermal (MH) treatment with the aim of eliminating surface defects and obtaining a uniform purity phase. These objectives were achieved in our previous study by the MH method. The molar ratio of Ca/P in the coatings is nearly close to 1, which is far below that of Ca/P for hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA, 1.67). The purpose of this article is to transform the phases in the sprayed Ca–P coating, which owns the better bioactivity and high corrosion resistance. In order to raise the molar ratio of Ca/P, the coatings are treated under high-temperature (around 700 °C). They are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and a fourier transform infrared spectra (FTIR). The bonding strength (coating/substrate), biological activity and corrosion resistance of the coatings are investigated. The resulting coatings own the different microstructures and phase compositions from the original sprayed Ca–P coating. Especially, results show that the shear strength of the sprayed Ca–P coating deposited on surface micropatterning C/C substrate increases by 61% which is more than that of the coating on non-surface micropatterning C/C substrate. Additionally, high-temperature treated coating presents a good biological activity and an excellent corrosion resistance of current density (1.3078 × 10^-6 A/cm²) and potential (−0.17 V_SCE).     

Electrodeposition of graphene oxide-hydroxyapatite composite coating on titanium substrate

In this work, graphene oxide (GO)/hydroxyapatite (HA) composite coatings were successfully prepared on titanium substrate by electrophoretic deposition technology. Subsequently, microstructure, phase composition, adhesion strength, hydrophilicity, corrosion resistance, bioactivity, antibacterial activity and biocompatibility of the coating were evaluated. The adhesion strength of coating increased by 76% from 6.46 MPa to 17.81 MPa with 0 wt% GO to 12 wt% GO and the corrosion rate of coating with 8 wt% GO was achieved at the minima of (1.493 × 10^-3mm/a). Biomineralization experiment indicated the excellent bioactivity of GO/HA composite coatings. The water contact angle of the composite coatings increased from 20.6°(0 wt% GO) to 38.1°(12 wt%GO). The antibacterial rates of coating with 5 wt% GO was 96.7%, while declined to 25% after thermal treatment. In-vitro L929 cell culture experiments indicated the composite coatings with 5 wt% GO exhibited good biocompatibility.     

Effect of ZrO2 nanoparticles addition to PEO coatings on Ti–6Al–4V substrate: Microstructural analysis,corrosion behavior and antibacterial effect of coatings in Hank's physiological solution

In this study, plasma electrolyte oxidation (PEO) method was employed to modify the surface of Ti–6Al–4V. Effects of different concentrations of ZrO₂ nanoparticles (0, 1, 3 and 5 g/l) into a phosphate-based electrolyte on the morphology, wettability, antibacterial and corrosion behaviors of coatings were investigated. Microstructural analyses of coatings were evaluated using scanning electron microscopy with an energy dispersive spectrometer. Also, X-ray diffraction, contact angle instrument and profilometry were respectively used to perform phase analysis, wettability, and surface roughness of the coatings. The antibacterial test was conducted with spot inoculation method on four pathogenic bacteria. Polarization and impedance spectroscopy measurements were performed in Hank's solution to investigate the corrosion behavior of coatings. The results revealed that PEO coatings without nanoparticles and by increasing the concentration of the ZrO₂ nanoparticles up to 3 g/l in the electrolyte led to a significant improvement in the antibacterial activities of gram-negative bacteria (P. aeruginosa and E. Coli). In the case of gram-positive bacteria, the PEO coated samples demonstrated improved antibacterial effects but addition of ZrO₂ nanoparticles in the PEO coatings resulted in deterioration of antibacterial effect. The sample coated with 3 g/l ZrO₂ nanoparticles showed the peak corrosion resistance compared to its counterparts.     

Preparation and bioactivity of apatite coating on Ti6Al4V alloy by microwave assisted aqueous chemical method

To improve the bioactivity of titanium and its alloys, dense and uniform apatite coatings were prepared on Ti6Al4V titanium substrates using microwave assisted aqueous chemical method. The influence of the pretreatment to the titanium substrates and the Ca/P molar ratio of the microwave solution on the coating deposition and morphology, as well as the bioactivity of the coated samples were studied. Results showed that during the microwave process, alkali treatment followed by heat treatment to the titanium substrates would promote the rapid deposition of hydroxyapatite to form coating. And the morphologies of the apatite coatings could be adjusted by the Ca/P molar ratio of the microwave solution. After immersion test in simulated body fluid (SBF), the coated titanium alloy exhibits a good bioactivity by inducing the formation of apatite depositions.     

Effect of titania particles preparation on the properties of Ni–TiO2 electrodeposited composite coatings

In this paper, the effect of titania particles preparation on the properties of Ni–TiO₂ electrocomposite coatings has been addressed. Titania particles were prepared by precipitation method using titanium tetrachloride as the precursor. The titanyl hydroxide precipitate was subjected to two different calcinations temperatures (400 and 900 °C) to obtain anatase and rutile titania particles. These particles along with commercial anatase titania particles were separately dispersed in nickel sulfamate bath and electrodeposited under identical electroplating conditions to obtain composite coatings. The electrodeposited coatings were evaluated for their microhardness, wettability, corrosion resistance, and tribological behavior. The variation of microhardness with current density exhibited a similar trend for all the three composite coatings. The composite coating containing anatase titania particles exhibited higher microhardness and improved wear resistance. However, the corrosion resistance of the composite coating containing commercial titania powder was superior to that of plain nickel, Ni–TiO₂ composite coatings containing anatase and rutile titania particles. The poor corrosion resistance of these composite coatings was attributed to the higher surface roughness of the coatings. This problem was alleviated by incorporating ball-milled titania powders. The composite coatings with higher surface roughness were modified with a low surface energy material like fluoroalkyl silane to impart hydrophobic and superhydrophobic properties to the coatings. Among these coatings, Ni–TiO₂–9C coating exhibited the highest water contact angle of 157°.     

Fabrication of Ti/TiO2(Ca)/hydroxyapatite bioceramic material by micro-arc oxidation and electrochemical deposition

Titanium with a bioceramic hydroxyapatite (HA) coating has been widely used in biomaterials owing to its excellent mechanical characteristics and high osteoconductivity. However, the interfacial strength of Ti/HA prepared by electrochemical deposition (ED) is relatively low because the physical combination is typically inadequate. In this study, to improve the interfacial strength, a micro-arc oxidation (MAO) process with calcium was introduced for preparing a connecting interlayer known as the MAO coating. Pulsed ED was employed to synthesise the HA coating on the MAO surface using an electrolyte with 6 wt% H₂O₂. Sample characterisations revealed that the MAO coating comprised porous TiO₂ (rutile and anatase) with Ca or CaTiO₃. The formation of CaTiO₃ depends on the current density, reaction time, and concentration of Ca²⁺, in addition to voltage. The MAO coatings exhibited a higher corrosion resistance than that exhibited by Ti substrates. Furthermore, the HA coating on the MAO coating was confirmed to be plate-like Ca-deficient HA. The final sample had a Ti/TiO₂(Ca)/HA structure, and its adhesive strength was approximately double that of the Ti/HA sample. In particular, the MAO coating synthesised at a high Ca²⁺ concentration exhibited an improved adhesive strength (2.326 MPa). The application of the MAO coating containing Ca as a connecting interlayer is a promising strategy for improving the HA adhesion strength.     

Synthesis and photocatalysis of TiO2 hollow spheres by a facile template-implantation route

Process variables such as reaction temperature (55 to 90 °C), calcination temperature (450 to 750 °C), and concentration of TiCl₄ precursor (26 to 105 mM) have been examined in order to tailor the surface area, crystallite size, and the anatase/rutile ratio of the polycrystalline TiO₂ microcapsules prepared by a template-implantation route in heptane solvent. The hollow capsules are all non-aggregating with nanoporous shell structure. Among the process variables examined, the Brunauer–Emmett–Teller (BET) surface area and the anatase/rutile ratio are found critically dependent on the reaction temperature, in which a reduced reaction temperature (from 90 to 55 °C) leads to a higher BET value (from 8.4 to 36.4 m^?2 g^?1), a predominant anatase phase (weight fraction of the anatase phase increases from 0.20 to 0.84), and an improved photodegradation of aqueous methylene blue (MB) dye under UV exposure (the degradation rate increases from 0.5×10^?2 to 5.5×10^?2 min^?1).     

Electrophoretic deposition (EPD) of nanohydroxyapatite - nanosilver coatings on Ti13Zr13Nb alloy

Titanium and its alloys are the biomaterials most frequently used in medical engineering, especially as parts of orthopedic and dental implants. The surfaces of titanium and its alloys are usually modified to improve their biocompatibility and bioactivity, for example, in connection with the deposition of hydroxyapatite coatings.The objective of the present research was to elaborate the technology of electrophoretic deposition (EPD) of nanohydroxyapatite (nanoHAp) coatings decorated with silver nanoparticles (nanoAg) and to investigate the mechanical and chemical properties of these coatings as determined by EPD voltage and the presence of nanoAg. The deposition of nanoHAp was carried out at two voltage values, 15 and 30 V. The decoration of nanoHAp coatings with nanoAg was carried out using the EPD process at a voltage value of 60 V and a deposition time of 5 min. The thickness of the undecorated coatings was found to be 2.16 and 5.14 µm for applied EPD voltages of 15- and 30-V, respectively. The release rate of silver nanoparticles into an artificial saliva solution increased with exposure time and EPD voltage. The corrosion current, between 1 and 10 nA/cm², was significantly higher for undecorated nanoHAp coatings and close to that of the substrate for decorated nanoHAp coatings. The hardness of the undecorated nanoHAp coatings obtained at 15 and 30 V of EPD voltage attained 0.2245±0.036 and 0.0661±0.008 GPa, respectively. Resistance to nanoscratching was higher for thicker coatings. The wettability angle was lower for coatings decorated with nanoAg.     

Influence of precursor characteristics on properties of porous calcium phosphate-titanium dioxide composite bioceramics

Highly porous (macroporosity 76–90%) bioceramics containing interconnected pores (>100 μm) with compressive strength between 0.54 and 0.32 MPa were prepared by polyurethane foam replica method. Effect of following variables, i.e., calcium phosphate/anatase ratio (30/70, 50/50, 70/30 wt%) in the ceramic slurry, anatase particle size (15 nm, 180 nm), Ca/P molar ratio of calcium phosphate (1.67 and 1.50 for hydroxyapatite and apatitic-tricalcium phosphate (ap-TCP), respectively), on the bioceramics properties was investigated. Bioceramics prepared using anatase and hydroxyapatite consisted of three high-temperature crystalline phases - β-tricalcium phosphate (β-TCP), rutile and CaTiO₃. In case of anatase and ap-TCP, two phases (β-TCP and rutile) were obtained. Interaction of anatase and hydroxyapatite during sintering caused formation of CaTiO₃ at β-TCP and rutile grain boundaries thus contributing to a denser grain packing. Combination of ap-TCP and nanosized anatase facilitated decrease of grain sizes. Correlation was found between compressive strength and calcium phosphate precursor in the ceramic slurry.     

The microstructural features and corrosion behavior of Hydroxyapatite/ZnO nanocomposite electrodeposit on NiTi alloy: Effect of current density

In the present study, hydroxyapatite/ZnO nanocomposite coatings were developed on NiTi superelastic alloy via pulse electrodeposition technique under three different current densities. The morphological observations (FESEM) indicated that under 6 mA/cm², a compact, uniform composite layer could form, whereas lower or higher current densities resulted in non-uniform, porous coatings with uneven distribution of nanoparticles. XRD and FTIR studies revealed that pure hydroxyapatite was not achieved below 6 mA/cm². Topographic features (AFM) were assessed and demonstrated a continuous rise in roughness parameters as current density increased. The corrosion behavior was investigated through potentiodynamic polarization as well as impedance spectroscopy techniques. According to the extracted data, the porosity and non-uniformity of coatings formed under 3 and 9 mA/cm² caused a detrimental effect on the corrosion resistance of surfaces. The layer obtained under 6 mA/cm² showed resistance (R_c) which was almost two times greater than those deposited under 3 and 9 mA/cm² current densities. Last but not least, the bioactivity of coatings was evaluated in simulated body fluid. It was observed that more compact deposits offered more active sites for apatite nucleation, resulting in refined cauliflower-like grains. Accordingly, it can be asserted that the best composite coating was achieved under 6 mA/cm² current density.     

Surface,Biocompatible and Hemocompatible Properties of Meta‐Amorphous Titanium Oxide Film

This study involved modification of the surface of Ti by micro‐arc oxidation (MAO). A rough and porous oxide film with good wettability was formed on the Ti surface. This MAO‐treated film exhibited a meta‐amorphous structure comprising crystalline anatase and rutile TiO₂ as well as amorphous phases. In addition, the incorporation of Ca and P in the MAO‐treated film was induced by micro‐arc discharge. The biological responses of the MAO‐treated surfaces were evaluated by observing the adhesion of MG63 osteoblast‐like cells and platelets. The MAO‐treated Ti had a considerably better biocompatibility and blood compatibility than untreated Ti.     

Low-Temperature Preparation of Anatase and Rutile Layers on Titanium Substrates and Their Ability To Induce in Vitro Apatite Deposition

Surface modification of titanium and its alloys to induce apatite deposition within a short period is of practical importance in clinical applications. In this study, titanium substrates were treated with hydrogen peroxide solutions at low temperatures to yield titania layers consisting of anatase and rutile. Those titania layers, regardless of the fraction of anatase and rutile, were bioactive to induce deposition of apatite in Kokubo's simulated body fluid within 24 h. The bioactivity was attributed to both the epitaxial effect and the abundant Ti–OH group of the titania layer.     

Suspension high velocity oxy-fuel spraying of a rutile TiO2 feedstock: Microstructure,phase evolution and photocatalytic behaviour

Nano-structured TiO₂ coatings were produced by suspension high velocity oxy fuel (SHVOF) thermal spraying using water-based suspensions containing 30 wt% of submicron rutile powders (~180 nm). By changing the flame heat powers from 40 kW to 101 kW, TiO₂ coatings were obtained with distinctive microstructures, phases and photocatalytic behaviour. Spraying with low power (40 kW) resulted in a more porous microstructure with the presence of un-melted nano-particles and a lower content of the anatase phase; meanwhile, high powers (72/101 kW) resulted in denser coatings and rougher surfaces with distinctive humps but not necessarily with a higher content of anatase. Linear sweep voltammetry (LSV) was used to evaluate the photocatalytic performance. Surprisingly, coatings with the lowest anatase content (~20%) using 40 kW showed the best photocatalytic behaviour with the highest photo-conversion efficiency. It was suggested that this was partially owing to the increased specific surface area of the un-melted nano-particles. More importantly, the structural arrangement of the similarly sized TiO₂ nano-crystallites between rutile and antase phases also created catalytic “hot spots” at the rutile−anatase interface and greatly improved the photo-activity.     

Photocatalytic activity of titanium dioxide coatings: Influence of the firing temperature of the chemical gel

Heterogeneous photocatalysis can be exploited for the decomposition of micro-organisms which have developed on the surfaces of building materials. In this work, the efficiency of titanium dioxide coatings on fired clay products is examined. The sol–gel method is used to synthesize a fine TiO₂ powder with a specific surface area of 180 m² g^?1. Thermal treatment of the chemical gel at 340 °C leads to crystallisation in the anatase phase and with further temperature increase, crystallite growth. For thermal treatments in the range 580–800 °C, there is a progressive transition from anatase to rutile. However, despite a decrease in specific surface area of the powder attributed to aggregation/agglomeration, the coherent domain size deduced from X-ray diffraction measurements remains almost constant at 23 nm. Once the transition is completed, increase of thermal treatment temperature above 800 °C leads to further crystallite growth in the rutile phase. The thermally treated titania powders were then sprayed onto fired clay substrates and the photocatalytic activity was assessed by the aptitude of the coating to degrade methylene blue when exposed to ultraviolet light. These tests revealed that the crystallite size is the important controlling factor for photocatalytic activity rather than the powder specific surface area or the anatase/rutile polymorph ratio.     

Apatite formation on titania–vaterite powders in simulated body fluid

Titania–hydroxyapatite composites were prepared by soaking compacts of a powder mixture consisting of crystalline titania and calcium carbonate (vaterite) to form apatite in simulated body fluid (SBF). The apatite crystal formed on compacts in SBF at 37 °C within 2 days. The apatite-forming ability of the mixtures was much higher than that of titania crystals such as anatase or rutile on their own. Calcium carbonate (vaterite), which has high solubility in the aqueous solution, plays an important role in the apatite formation; the dissolution is suggested to increase the supersaturation of the apatite in SBF. Formation of titanium hydroxide groups, which may induce the apatite formation, is drastically promoted on the powder-compacts by the soaking in SBF, independently of the structures of the titania crystals (anatase or rutile). The apatite formation on the compact of the titania–calcium carbonate (vaterite) powder mixture containing the anatase phase occurs in a shorter period than that on the one of titania (rutile)–calcium carbonate (vaterite). Crystalline titania (anatase phase) is suggested to be particularly effective in inducing the apatite nucleation.     

Plasma-sprayed TiO2 coatings: Hydrophobicity enhanced by ZnO additions

Titanium dioxide (TiO₂) powder mixed individually with 10 and 30 weight percentage (wt%) ZnO was thermally sprayed onto a grade B API 5 L carbon steel substrate by atmospheric plasma spraying. The effect of the addition of ZnO (10 wt% and 30 wt%) on the microstructures and wettability properties of the TiO₂/ZnO coatings was investigated. The characterization of the coatings was carried out using scanning electron microscopy, X-ray diffraction (XRD), laser confocal microscope, and sessile droplet system. The XRD analysis of the coating revealed that the anatase phase of TiO₂ in the powder state transformed into rutile phases for the produced TiO₂/ZnO coatings. Surface microstructure analysis revealed that the coatings had typical micro-roughened surfaces of plasma spraying products. The coating with 30 wt% ZnO produced a coating with remarkable pores and microcracks compared with the TiO₂ coating and coating with 10 wt% ZnO. Additionally, the increase in the wt% of ZnO increased the surface roughness value of the produced coatings and substantially changed the wettability properties of the TiO₂ coating from hydrophilic to hydrophobic.     

Effect of carbonate content on the in vitro bioactivity of carbonated hydroxyapatite

The effect of carbonate content on the apatite-forming ability of carbonated hydroxyapatite (CHA) in simulated body fluid (SBF) has been investigated. Five different nanocrystalline B-type CHA with carbonate content ranged from 2.01 to 5.25 wt% were prepared, sintered, and assessed for their in vitro bioactivity in SBF solution for 7-weeks under static conditions at 36.5 °C. The formation of the apatite layer and the surface morphology of CHA were examined by using a scanning electron microscope (FESEM) at week 1, 3, and 7 of SBF immersion, respectively. The Ca/P molar ratio of the CHA was determined by X-ray fluorescence (XRF). In addition, the sample weight changes and the pH of the SBF solution were measured. The results show that the formation of apatite layer depends on the carbonate content of CHA. Increasing the carbonate content caused significant increases in the surface area of CHA and the rate of apatite formation. Weight loss was observed for all CHA samples during the first week of SBF immersion, and thereafter followed by weight regain weekly until week 7. The changes in the pH of SBF and the Ca/P molar ratio were proportional to the carbonate content of CHA. This study thus highlights the importance of determining carbonate content aspect that govern the bioactivity of CHA.     

Chrome-free qandilite (Mg2TiO4) refractory aggregates: Role of titania source and evaluation of thermal expansion coefficient

As used chrome-based refractories may contain toxic Cr⁶⁺, the chrome-free Mg₂TiO₄ phase is being considered which is known to improve hot strength and resistance to thermal shock and slag corrosion. As in situ Mg₂TiO₄ formation generates porosity, preformed aggregates are desirable. Dilatometric studies revealed that when dead burned magnesia is combined with industrial anatase instead of rutile, it expanded less (1 % versus 7.2 %) and the reaction occurred earlier (965 ℃ compared to 1120 ℃). After sintering at 1,600 ℃, rutile produced an aggregate with 3.8 % open porosity, whereas anatase led to 0 % porosity and a bulk density of 3.24 g/cm³ with a thermal expansion coefficient (70–1,600 ℃) of 13.5 × 10^?6 K^?1. Moreover, replacing rutile by anatase eliminates the undesirable MgTiO₃ phase. The anatase-based aggregate consisted of a Mg₂TiO₄ matrix with residual unreacted MgO and an intergranular, refractory CaTiO₃ phase. The rutile-based aggregate was deemed unsuitable due to a low-melting microstructure of forsterite contiguous with CaTiO₃.     

The influence of pulse plating parameters on microstructure and properties of Ni-W-Si3N4 nanocomposite coatings

Nanosized silicon nitride (Si₃N₄) particles reinforced Nickel-tungsten composite coatings were deposited on the surface of C45 steel sheet by pulse electrodeposition. The effect of duty cycle, frequency, current pattern and presence of Si₃N₄ nanoparticles on microstructure, phases and corrosion resistance and mechanical properties of the coatings were investigated. The Si₃N₄ phase was incorporated into Ni-W alloy matrix uniformly and the inclusion content of in the coating was analyzed by energy dispersive x-ray spectrometer (EDS). The structure, microhardness and surface roughness of the coatings was analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), Vickers micro-indenter and atomic force microscopy (AFM). The corrosion protection of steel by the coatings was evaluated by weight loss and electrochemical impedance spectroscopy (EIS). Corrosion rates of the coatings were determined using the Tafel polarization test. The results indicated that the duty cycle of 60%, pulse frequency of 1000 Hz, average current density of 5 A/dm⁻², and Si₃N₄ nanoparticles concentration of 30 g/L were the optimal plating conditions. The amount of Si₃N₄ particles incorporated into the coating that were produced under the optimum plating conditions was 2.1 wt%, and the microhardness was 1031 Hv as well as the crystallite size of this coating was 27 nm.