In situ composite coating of titania-hydroxyapatite on titanium substrate by micro-arc oxidation coupled with electrophoretic deposition processing

In situ composite coating of hydroxyapatite (HA)/TiO₂ were produced on titanium (Ti) substrate by micro-arc oxidation coupled with electrophoretic deposition (MAO&EPD) technique with different concentrations of HA particles in the 0.2 M NaOH electrolyte solution. The surface morphology and chemical composition of the hybrid coating were effected by HA concentration. The amount of HA particles incorporated into coating layer increased with increasing HA concentration used in the electrolyte solution. The corrosion behavior of the coating layer in simulated body fluids (SBF) was evaluated using a potentiodynamic polarization test. The corrosion resistance of the coated sample was increased compared to the untreated Ti sample. The in vitro bioactivity assessment showed that the MAO&EPD treated Ti substrate possessed higher apatite-forming ability than the untreated Ti. Moreover, the apatite-forming ability had a positive correlation with HA concentration. In addition, the cell behavior was also examined using cell proliferation assay and alkaline phosphatase ability. The coating formed at HA concentration of 5 g/L exhibited the highest cell ability.     

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating fabricated by a modified electrochemical deposition

Fluoridated hydroxyapatite/titanium dioxide nanocomposite coating was successfully fabricated by a modified electrochemical deposition technique. F⁻ ions, nanoscaled TiO₂ particles and 6% H₂O₂ was added into the electrolyte, and ultrasonication was also performed to prepare this nanocomposite coating. The microstructure, phase composition, dissolution rate, bonding strength and in vitro cellular responses of the composite coating were investigated. The results show that the composite coating was uniform and dense owing to the effects of H₂O₂ and ultrasonication. The thickness of the composite coating was ~5 μm and scanning electron microscopy revealed that nanoscaled TiO₂ particles were imbedded uniformly between FHA crystals. The addition of F⁻ and TiO₂ reduced the crystallite size and increased the crystallinity of HA in FHA/TiO₂ composite coating. In addition, the composite coating shows higher bonding strength and lower dissolution rate than pure HA coating, and the in vitro bioactivity of FHA/TiO₂ composite coating was not affected as compared with pure HA coating.     

Growth and characterization of hydroxyapatite nanorice on TiO2 nanofibers

Hydroxyapatite (HA) coating with nanoparticles like nanorice is fabricated on chemically pretreated titanium (Ti) surface, through an electrochemical deposition approach, for biomaterial applications. The Ti surface was chemically patterned with anatase TiO₂ nanofibers. These nanofibers were prepared by in situ oxidation of Ti foils in a concentrated solution of H₂O₂ and NaOH, followed by proton exchange and calcinations. Afterward, TiO₂ nanofibers on Ti substrate were coated with HA nanoparticles like nanorice. The obtained samples were annealed at high temperature to produce inter diffusion between TiO₂ and HA layers. The resultant layers were characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS), X-ray Diffraction (XRD), Infrared Spectroscopy (FTIR), corrosion tests in SBF solution, and Electron Probe Micro Analysis (EPMA). It was found that only Ti from the titanium substrate diffuses into the HA coating and a good corrosion resistance in simulated body fluid was obtained.     

Nano-structural bioactive gradient coating fabricated by computer controlled plasma-spraying technology

The poor mechanical property of hydroxyapatite was the major problem for load bearing and implant coating in clinical applications. To overcome this weakness, a bioactive gradient coating with a special design composition of hydroxyapatite (HA), ZrO₂, Ti, bioglass was developed. This 120 μm coating with an upper layer of 30–50 μm porous HA produced by computer controlled plasma spraying which maintained energy level of the plasma which ensure proper melting of powder. The crystal size of the coating was 18.6–26.2 nm. Transformation of t-ZrO₂ to m-ZrO₂ reduced the thermal stress that weakened the coating and lowered down interfacial strength of the coating and metal substrate. Thermal stress of sprayed coating was 16.4 MPa which was much smaller than the sample without thermal treatment of 67.1 MPa. Interfacial strength between the coating and metal substrate was 53 MPa which is much higher than conventional Hydroxyapatite coating. Based on XRD analysis crystallinity of HA approached 98%. Therefore, high temperature treatment improved long term stability of the coating through improved crystallinity of hydroxyapatite and reduced other impure calcium phosphate phase.     

Silicon-substituted hydroxyapatite composite coating by using vacuum-plasma spraying and its interaction with human serum albumin

The incorporation of silicon can improve the bioactivity of hydroxyapatite (HA). Silicon-substituted HA (Ca₁₀(PO₄)_6−x (SiO₄) _x (OH)_2−x , Si-HA) composite coatings on a bioactive titanium substrate were prepared by using a vacuum-plasma spraying method. The surface structure was characterized by using XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated and XRD patterns showed that Ti/Si-HA coatings were similar to patterns seen for HA. The only different XRD pattern was a slight trend toward a smaller angle direction with an increase in the molar ratio of silicon. FTIR spectra showed that the most notable effect of silicon substitution was that –OH group decreased as the silicon content increased. XRD and EDS elemental analysis indicated that the content of silicon in the coating was consistent with the silicon-substituted hydroxyapatite used in spraying. A bioactive TiO₂ coating was formed on an etched surface of Ti, and the etching might improve the bond strength of the coatings. The interaction of the Ti/Si-HA coating with human serum albumin (HSA) was much greater than that of the Ti/HA coating. This might suggest that the incorporation of silicon in HA can lead to significant improvements in the bioactive performance of HA.     

Sol–gel derived hydroxyapatite/titania biocoatings on titanium substrate

A simple sol–gel method was successfully developed for a hydroxyapatite (HA)/TiO₂ double layer deposition on a pure titanium substrate. Phase formation, surface morphology, and interfacial microstructure were investigated by differential scanning calorimetry analysis (DSC), X-ray diffraction (XRD) and scanning electron microscopy (SEM). The TiO₂ layer was coated by a spin coating method at a speed of 1500 rpm for 15 s, followed by a heat treatment at 560 °C for 20 min. The HA film was subsequently spin coated on the outer surface at the same speed and then heat-treated at difference temperatures. Results indicated that the HA phase began to crystallize after a heat treatment at 580 °C; and the crystallinity increased obviously at a temperature of 780 °C. The HA film showed a porous structure and a thickness of 5–7 μm after the heat treatment at 780 °C. SEM observations revealed no delamination and crack at the interfaces of HA/TiO₂ and TiO₂/Ti. The HA film with a porous structure is expected to be more susceptible to the natural remodeling processes when it is implanted in a living body.     

Hydroxyapatite-anatase-carbon nanotube nanocomposite coatings fabricated by electrophoretic codeposition for biomedical applications

In order to eliminate micro-cracks in the monolithic hydroxyapatite (HA) and composite hydroxyapatite/carbon nanotube (HA/CNT) coatings, novel HA/TiO₂/CNT nanocomposite coatings on Ti6Al4V were attempted to fabricate by a single-step electrophoretic codeposition process for biomedical applications. The electrophoretically deposited layers with difference contents of HA, TiO₂ (anatase) and CNT nanoparticles were sintered at 800°C for densification with thickness of about 7–10 μm. A dense and crack-free coating was achieved with constituents of 85 wt% HA, 10 wt% TiO₂ and 5 wt% CNT. Open-circuit potential measurements and cyclic potentiodynamic polarization tests were used to investigate the electrochemical corrosion behavior of the coatings in vitro conditions (Hanks’ solution at 37°C). The HA/TiO₂/CNT coatings possess higher corrosion resistance than that of the Ti6Al4V substrate as reflected by nobler open circuit potential and lower corrosion current density. In addition, the surface hardness and adhesion strength of the HA/TiO₂/CNT coatings are higher than that of the monolithic HA and HA/CNT coatings without compromising their apatite forming ability. The enhanced properties were attributed to the nanostructure of the coatings with the appropriate TiO₂ and CNT contents for eliminating micro-cracks and micro-pores.     

Highly porous titanium (Ti) scaffolds with bioactive microporous hydroxyapatite/TiO2 hybrid coating layer

Highly porous Ti scaffolds with a bioactive microporous hydroxyapatite (HA)/TiO₂ hybrid coating layer were fabricated using the sponge replication process and micro-arc oxidation (MAO) treatment to produce the porous Ti scaffold and hybrid coating layer, respectively. In particular, the morphology and chemical composition of the hybrid coating layer were controlled by carrying out the MAO treatment in electrolyte solutions containing various concentrations of HA, ranging from 0 to 30 wt.%. The fabricated sample showed high porosity of approximately 70 vol.% with interconnected pores and reasonably high compressive strength of 18 ± 0.3 MPa. Furthermore, the surfaces could be coated successfully with a bioactive microporous HA/TiO₂ hybrid layer. The amount of HA particles in the hybrid coating layer increased with increasing HA content in the electrolyte solution, while preserving the microporous morphology. This hybrid coating improved the osteoblastic activity of the porous Ti scaffolds significantly.     

One-step synthesis of petal-like apatite/titania composite coating on a titanium by micro-arc oxidation

Petal-like apatite/titania (TiO₂) coating was prepared on commercially pure titanium (Ti) by micro-arc oxidation in electrolyte containing calcium and phosphate for the first time. The surface morphology, crystalline structure, chemical composition and binding state of the apatite/TiO₂ composite coating were characterized. The coating consists of a double-layer (apatite layer and TiO₂ layer) structure. The average thickness of the inner TiO₂ layer and the outer apatite layer is about 6 μm and 16 μm respectively. The outer apatite layer is porous and exhibits petal-like pattern. The apatite layer consists of hydroxyapatite (HA) and carbonate-apatite and the inner TiO₂ layer consists of anatase and rutile.     

Preparation of TiO2/NiO composite particles and their applications in dye-sensitized solar cells

This study investigates the applicability of n-type TiO₂ and p-type NiO on the FTO-glass (Fluorine doped tin oxide, SnO₂:F) substrate of the working electrode in a dye-sensitized solar cell (DSSC). The working electrode was designed and fabricated by depositing a film of TiO₂/NiO composite particles, which were prepared by mixing the Ni powder with TiO₂ particles using dry mixing method, on a FTO-glass substrate using a spin coating process. The working electrode was then immersed in the solution of N-719 (Ruthenium) dye at a temperature of 70 °C for 6 h. Moreover, a thin film of platinum (Pt) was deposited on the FTO-glass substrate of the counter electrode using an E-beam evaporator. Finally, the DSSC was assembled, and the short-circuit photocurrent, the open-circuit photovoltage and the power conversion efficiency of DSSC were measured using an I–V measurement system. This study also examined the effects of the mass ratio of TiO₂ to Ni and the number of coating of TiO₂ particles (or TiO₂/NiO composite particles) colloid on the power conversion efficiency of the DSSC. Most importantly, this study shows that the power conversion efficiency of the DSSC with TiO₂/NiO composite particles (3.80%) substantially exceeds that of the conventional DSSC (3.27%) due to the effects of the NiO barrier and the n–p junction.     

Interfacial titanium oxide between hydroxyapatite and TiAlFe substrate

The interface between nano-crystalline hydroxyapatite (HA) thin films and a titanium alloy (Ti5Al2.5Fe) has been studied by means of Fourier transform infrared spectrophotometry and X-ray diffraction at grazing incidence. The HA thin films were deposited by radio-frequency magnetron sputtering in low pressure dry argon on substrates kept at low temperature or heated at 550 °C. The effect of film treatment by sputtering and annealing in humid air, as a simple, effective way of restoring the crystallinity and stoichiometry of the HA bulk, was studied in correlation with the development of a titanium oxide layer at the film-substrate interface. An interfacial TiO₂ film grew at the interface during annealing in moist air, while a TiO₂ layer diffused into the HA films when directly sputtered at 550 °C. The formation of an interfacial titanium oxide layer was inhibited by the insertion of a crystalline TiN buffer interlayer between the substrate and the HA film. Separately, the mechanical characteristics of the different HA films were monitored by nanoindentation to find out how they had been affected.     

Synthesis and conductive performance of antimony-doped tin oxide-coated TiO2 by the co-precipitation method

The synthesis of Sb–SnO₂/TiO₂ (SST) composites by assembling antimony-doped tin oxide (Sb–SnO₂) nanoparticles on the surface of titanium dioxide (TiO₂) is systematically investigated. X-ray diffraction data show that the SST composite materials with good crystallinity can be indexed as anatase TiO₂ phase and cassiterite SnO₂ phase. The scanning electron microscopy and transmission electron microscopy indicate that Sb–SnO₂ particles with average diameter of 25 nm have been successfully coated on the surface of TiO₂. In addition, the Ti–O–Sn band can be detected on the surface of TiO₂ through Fourier translation infrared spectroscopy. The influences of pH, Sn/Ti mole ratio, hydrolysis temperature and calcination temperature on the electrical resistivity of the SST powders are studied. Under the optimum experimental conditions, the electrical resistivity of the composite conductive powders is 2.546 × 10³ Ω cm. Therefore, the SST composite conductive powders are useful as conductive fillers for the application in antistatic materials.     

Morphology and Phase Compositions of Hydroxyapatite Powder Particles Plasma—sprayed into Water

Hydroxyapatite powder particles were plasma sprayed into water,their inner structures and phase compositions were studied by using scanning electron microscope(SEM) and X-ray diffractometer.The results show that the molten HA particles have a central hollow morphology and high crystallinity.The hollow morphology was caused by sublimated P2O5 and H2O, which will have an effect on surface morphology,cohesive and adhesive strength as well as dissolution and degradation of coating.The high crystallinity is attributed to lower cooling speed in water.     

Influence of Coating Parameter and Sintering Atmosphere on the Corrosion Resistance Behavior of Electrophoretically Deposited Composite Coatings

The purpose of this study is to synthesize and characterize nanosized titania (TiO₂), zinc oxide (ZnO), and its composite coating on Ti–6Al–4V to enhance its corrosion protection behavior in Ringer's solution. Nanosized powders of TiO₂ and ZnO was characterized by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (XRD), and scanning electron microscopy - energy dispersive atomic spectroscopy (SEM-EDAX) analysis. As a result of antibacterial activity, both ZnO and TiO₂/ZnO have produce remarkable inhibition zone on Escherichia coli. The antibacterial activity of composites are due to the combined effect of ZnO on TiO₂. The adherence and surface uniformity of TiO₂/ZnO composite film on titanium implant was examined by optical microscopy and Vickers microhardness test. Corrosion resistant behavior of the coating on titanium implant was investigated by tafel polarization and impedance analysis. The composite coatings on Ti–6Al–4V have produced improved corrosion resistance with a pronounced shift in the anodic corrosion potential (E_corr) with a corresponding less corrosion current density (I_corr) compared to monophase coating. Similar results have been obtained for impedance analysis which indicated a reduction in double layer capacitance (C_dl) and with enhancement in charge transfer resistance (R_ct). These observations suggest improved corrosion resistance property of TiO₂/ZnO composite coating on Ti–6Al–4V.     

Hydroxyapatite growth on multiwall carbon nanotubes grown on titanium fibers from a titanium sheet

Nano-hydroxyapatite (HA) was grown on functionalized multiwalled carbon nanotubes (MWCNTs) deposited on TiO₂ nanofibers (NFs) that were hydrothermally grown on Ti metal sheets. The HA was electrochemically grown on the MWCNTs/TiO₂ porous layer. It was found that the HA grows on the MWCNTs/TiO₂ NFs in the form of dense coating with nanorice grain-shaped. The incorporation of MWCNTs between HA and TiO₂ NFs has led to higher adhesion strength as measured by micro-scratching test indicating the benefit of MWCNTs on the improving the bonding strength of HA layer. The obtained coatings exhibit excellent corrosion resistance in simulated body fluid. It is expected that this simple route for preparing the new HA/MWCNTs/TiO₂/Ti-layered structure might be used not only in the biomedical field, but also in catalysis and biological sensing among others.     

Hydrothermal-electrochemical codeposited hydoxyapatite/yttria-stabilized zirconia composite coating

Hydroxyapatite(HA)/yttria-stabilized zirconia(YSZ) composite coatings were deposited on titanium substrates using a hydrothermal electrochemical method in an electrolyte containing calcium, phosphate ions and YSZ particles. HA/YSZ composite coatings were prepared in different conditions with different electrolyte temperatures(100 ∼ 200°C), current densities(0.1 ∼ 10.0 mA/cm²), and particles content in bath(0 ∼ 100 g/L). The effect of YSZ additions on the phase composition, microstructure, thermal stability, corrosion behavior and the bonding strength of HA/YSZ composite coatings were studied. The results show that crystallinity of HA in HA/YSZ composite coatings increase continuously with the electrolyte temperature and close to stoichiometric HA. The n(Ca)/n(P) ratio at 200°C is about 1.67 according with stoichiometric HA. YSZ particles are imbedded uniformly between the HA crystals. The average HA crystal size are reduced owing to the additions of YSZ particles. After annealing at 1200°C, tetragonal phase YSZ tend to react with the released CaO to form cubic phase YSZ and CaZrO₃, which cause destabilization of HA to decompose into more α-TCP phase. The bonding strength between HA/YSZ composite coatings and titanium substrates increase with increasing volume content of YSZ in the composite coatings (V %). HA/YSZ composite coatings exhibit a better electrochemical behavior than pure HA coatings and uncoated Ti metals.     

Control of the quantum size effect of TiO2-SiO2 hybrid particles

This paper describes the control of the quantum size effect by controlling the coating layer thickness in TiO₂-SiO₂ core-shell hybrid particles obtained by the liquid phase deposition (LPD) method. The coating layer thickness of TiO₂ on SiO₂ nano-particles was controlled by changing the [Ti]/[Si] ratio. The titania coating thickness and crystallite size were estimated by transmission electron microscope (TEM) and X-ray diffraction (XRD), respectively. The quantum size effect of the obtained nano-hybrid particles was estimated by the band gap energy shift, using ultraviolet-visible spectroscopy (UV-vis). As a result, we successfully controlled the degree of the quantum size effect by controlling the coating layer thickness in core-shell TiO₂-SiO₂ hybrid particles.     

Nanostructured leaf like hydroxyapatite/TiO2 composite coatings by simple sol-gel method

We demonstrate an approach for the coating of nanostructured leaf like hydroxyapatite (HAp)/TiO₂ composite on glass substrate by sol-gel dip coating process. HAp/TiO₂ nanocomposite thin film was obtained by controlling the dipping rate and the dipping cycle. It was observed from Scanning Electron Microscope that leaf like nanostructured film was deposited on the glass substrate. However, the structure of the film was changed with the dipping cycle and dipping rate. Transmission Electron Microscopic analysis further confirms the morphology of the nanostructured coatings. The presence of Ti, O, Ca and P was detected by Energy Dispersive X-ray Analysis. We further confirmed the composite by X-ray diffraction analysis. Atomic Force Microscope analysis indicates that the films are composed of nanoparticles ranging from 100 to 200 nm and the films were observed to present well-defined grain boundaries. It has been shown that nanocomposite coatings are dependent on the sol concentration, dipping parameters, and the composition of HAp and TiO₂.     

Characterization of electrolytic HA/ZrO2 double layers coatings on Ti–6Al–4V implant alloy

Hydroxyapatite (HA) coating was proved having bioactive property and hence improving the bonding strength on bone tissue without inducing the growth of fiber tissue. However, the weak adhesion between HA and metal implants is still the major problem. In this study, a novel method of electrolytic HA/ZrO₂ double layers coating was successfully conducted on F-136 Ti–6Al–4V implant alloy in ZrO₂(NO₃)₂ aqueous solution and subsequently in the mixed solution of Ca(NO₃)₂ and NH₄H₂PO₄. After annealing at 400 °C, 500 °C and 600 °C for 4 h in air, the coated specimens were evaluated by X-ray diffraction analyses, surface morphology observations, scratch tests, dynamic polarization tests, immersion tests and cell culture assays. In addition to corrosion resistance, the adhesion strength of electrolytic deposited HA on Ti alloy was dramatically improved from the critical scratch load 2 N to 32 N by adding the intermediate electrolytic deposition of ZrO₂, which showed the strong bonding effects between Ti alloy substrate and HA coating. Based on the cell morphology and cell proliferation data, HA/ZrO₂ double layers coating revealed the better substrate for the adhesion and proliferation of osteoblasts than the others. It was also found that the crystallization of HA had positive effect on the proliferation of osteoblasts.     

Composite hydroxyapatite/TiO2 materials for photocatalytic oxidation of NOx

Hydroxyapatite/TiO₂ composite photocatalysts were obtained from sol–gel prepared TiO₂ and commercial hydroxyapatite (HA) powders. Composites with different HA/TiO₂ ratio were studied to assess the influence of HA on the morphology and the photocatalytic behavior of the materials. Morphological SEM analysis revealed that the presence of HA diminishes the aggregation of TiO₂ particles and leads to their higher dispersion in the composites that was confirmed by the N₂ adsorption–desorption isotherms and Barret–Joyner–Halenda analysis. The photocatalytic activity of the prepared catalysts was examined by monitoring photocatalytic oxidation of NO_x model gases over catalysts under UV illumination. The NO_x oxidation over the composite catalysts was improved in comparison with pure TiO₂ powder. Moreover, the decrease of the TiO₂ content, which is the photocatalytically active component in the composites, resulted in enhanced NO_x removal. Maximum activity was recorded for composites with HA/TiO₂ ratios 1 and 2 that was related to improved TiO₂ dispersion and NO₂ trapping by the composite materials.