Effect of Spray Distance on Microstructure and Tribological Performance of Suspension Plasma-Sprayed Hydroxyapatite–Titania Composite Coatings

Hydroxyapatite (HA)–titania (TiO₂) composite coatings prepared on Ti6Al4V alloy surface can combine the excellent mechanical property of the alloy substrate and the good biocompatibility of the coating material. In this paper, HA–TiO₂ composite coatings were deposited on Ti6Al4V substrates using suspension plasma spray (SPS). X-ray diffraction, scanning electron microscopy, Fourier infrared absorption spectrometry and friction tests were used to analyze the microstructure and tribological properties of the obtained coatings. The results showed that the spray distance had an important influence on coating microstructure and tribological performance. The amount of decomposition phases decreased as the spray distance increased. The increase in spray distance from 80 to 110 mm improved the crystalline HA content and decreased the wear performance of the SPS coatings. In addition, the spray distance had a big effect on the coating morphology due to different substrate temperature resulting from different spray distance. Furthermore, a significant presence of OH^? and CO₃ ^2? was observed, which was favorable for the biomedical applications.     

钛合金表面GO/HA/MAO复合膜层的制备及其性能

为了改善钛合金种植体在体液中的腐蚀及摩擦腐蚀行为,延长其在人体环境中的服役时间,在微弧氧化 (MAO)膜层上采用溶胶凝胶(Sol-gel)法于羟基磷灰石(HA)和氧化石墨烯(GO)的混合溶胶中浸渍提拉成膜,从而在 Ti6Al4V 合金表面成功地制备了 GO/ HA/ MAO 复合膜层。 结果表明,MAO 膜层表面的微孔及微球被 GO/ HA 薄膜有效的覆盖且较为致密;膜层的物相组成主要为金红石相及锐钛矿相的 TiO₂、HA、SiO₂ 和GO;根据电化学腐蚀和摩擦腐蚀结果分析知,GO/ HA/ MAO 复合膜层在模拟体液(SBF)中的耐蚀性及耐摩擦腐蚀性相比于 MAO 膜层和 Ti6Al4V 基体均得到了显著提高。     

Investigations on composition and morphology of electrochemical conversion layer/titanium dioxide deposit on stainless steel

In this study, the formation and characterization of conversion coatings modified by a sol-gel TiO₂ deposit were investigated as a way to develop a new photocatalyst for water and air depollution. The conversion coating, characterised by strong interfacial adhesion, high roughness and high surface area facilitates the sol-gel deposition of titania and enhances its adhesion to the substrate. The conversion treatment is carried out in an acid solution. Observation by Scanning Electron Microscopy (SEM) reveals a rough surface with pores and cavities. According to SIMS measurements, the thickness of the initial conversion layer is evaluated at about 1.5 μm. On this pre-functionalised support, the titanium dioxide was deposited by the sol-gel method. The roughness measurements coupled with SIMS analysis allowed a precise evaluation of the surface state of the final layers. The coating consists of two layers: a TiO₂ outer layer and an inner layer containing iron chromium oxides. Characterization by X-ray diffraction (XRD) showed the existence of the TiO₂ anatase structure as the main compound.     

Novel hydroxyapatite coating on new porous titanium and titanium-HDPE composite for hip implant

Porous titanium (Ti) and Ti-high density polyethylene (Ti-HDPE) composite were investigated as new hip implant materials to increase the biomechanical compatibility by promoting a matching modulus of elasticity between hip stem and human bone. Surfaces of both materials were modified to increase its bioactivity and biocompatibility through electrochemical activation treatment and deposition of hydroxyapatite (HA) coating. The electrochemical activation treatment of both materials in 10 M NaOH solution created a bone-like porous nanostructure across the surfaces, thus enhancing the growth of natural bone. A top layer with nanometer-pores and TiO₂ was formed during the activation process, creating a favorable and prerequisite condition conducive to the formation of hydroxyapatite coating. Furthermore, a layer of hydroxyapatite, a bioactive and biocompatible bioceramics that is the main component of natural bone, was deposited on the porous Ti and Ti-HDPE composite through a novel chemo-biomimetic method. The formed coating was characterized through TEM as a nanometer scale crystalline.     

Influence of deposition temperature on mechanical properties of plasma-sprayed hydroxyapatite coating on titanium alloy with ZrO<Subscript>2</Subscript> intermediate layer

Hydroxyapatite coatings were plasma sprayed on the Ti6A14V substrate with and without an intermediate ZrO₂ layer; meanwhile the temperatures of substrates were varied at 90, 140, and 200 °C. The coatings were subjected to the standard adhesion test per ASTM C633-79. The purpose of the investigation was to study the effects of those processing variables on the bonding strength and failure behavior of the system. It is found that the bonding strengths of HA/ZrO₂ and HA coatings generally decrease with increasing substrate temperature, except for the HA/ZrO₂ coating deposited at 200 °C. The rationale of the results is attributed to the residual stress reported in the literature. Introducing ZrO₂ bond coat is found to significantly promote the bonding strength of HA coating. The possible strengthening mechanism is the rougher surface of ZrO₂ bond coat and the higher toughness of ZrO₂, which provide the mechanical strengthening effects. The slightly denser HA in 200 °C deposited HA coating cannot explain the high bonding strength of the HA/ZrO₂ coating, nor the mechanical strengthening effect of ZrO₂ intermediate layer should apply. It is believed that a stronger diffusion bonding is formed at the interface of HA and ZrO₂, which increases the bonding between them chemically. The bonding strengths of HA/ZrO₂ and HA coatings are correlated with the area fraction of adhesive failure of the coatings. The correlation explains the findings in this study.     

Adhesion of sol-gel derived hydroxyapatite nanocoatings on anodised pure titanium and titanium (Ti6Al4V) alloy substrates

The mechanical properties and adhesion behaviour of sol-gel derived hydroxyapatite (HA) nanocoatings on commercially pure (cp) titanium (Ti) and Ti6Al4V alloy have been determined and related to anodising treatment. The surface roughness, wetting and coating characteristics were examined using profilometry, contact angle, scanning electron microscopy (SEM) and X-ray diffraction (XRD). Nano-indentation was used to determine the Young's modulus and hardness of the coatings, while microtensile tests were used to introduce controlled strains in the coatings through the cp Ti and TiAl6V4 alloy substrates, from which the strength, fracture toughness and adhesion behaviour could be ascertained based on multiple cracking and delamination events. The toughness of the HA coatings is found to be slightly lower to that of equivalent bulk pure HA ceramics. The substrate and the anodized layer thickness have the most influence on the interfacial adhesion of HA, with nanocoatings on Ti6Al4V exhibiting superior interfacial bonding in comparison to cp Ti.     

Synthesis of titanium aluminide coatings on aluminum and titanium surfaces by mechanical alloying and subsequent annealing

Intermetallic Ti-Al-based coatings were synthesized by mechanical alloying in a vibratory ball mill and subsequent annealing. A titanium layer was deposited on aluminum specimens and an aluminum layer and aluminum-titanium mixture were deposited on titanium specimens. Under the effect of milling balls, powder particles deposit at the substrates, forming layers that have a very good cohesion with the substrate. During subsequent heating, diffusion layers on the basis of titanium-aluminum phases are synthesized as a result of the chemical interaction between titanium and aluminum. In the case of titanium layer deposited on aluminum, the temperature interval of transformations is 600–650°C; first, a Ti₃Al₅-based phase is formed; then, as diffusion saturation with Al increases, an Al₂Ti-based layer appears; and finally, the Al₃Ti compound is formed. The reaction rates depend on the temperature and the duration of annealing. On titanium with a (Ti + Al) layer deposited on its surface, the Al₃Ti, Al₂Ti, TiAl, and Ti₃Al compounds are formed in a temperature interval of 600–900°C. In the case of deposition a homogeneous aluminum layer on titanium, only Al₃Ti and Ti₃Al phases were observed after annealing.     

Preparation of titanium oxide and hydroxyapatite on Ti–6Al–4V alloy surface and electrochemical behaviour in bio-simulated fluid solution

In order to improve the bonding strength between hydroxyapatite (HA) coating and Ti–6Al–4V substrate, a uniform titanium oxide film was obtained by controlled anodic oxidation. After that an alkaline treatment with NaOH solution was used to make them more bioactive. Finally hydroxyapatite coating has been prepared on Ti–6Al–4V substrate through electrochemical deposition. Comparative electrochemical behaviour of untreated and surface modified Ti–6Al–4V alloy, in bio-simulated fluid solution was investigated by electrochemical techniques. SEM was used to observe the morphology of modified surfaces and the thicknesses of the oxide films prepared were evaluated on the cross-sections of the samples using SEM–FIB.     

Preparation and oxidation resistance of a crack-free Al diffusion coating on Ti22Al26Nb

A crack-free Al diffusion coating has been developed to improve the oxidation resistance of Ti22Al26Nb. It was produced by a two-step method; an Al film was deposited on the substrate alloy by arc ion plating followed by a diffusion process conducted at 873 K in pure Ar to form the Al diffusion coating. The two-step method lowers the temperature required to form the diffusion coating, which dramatically decreases the thermal stress developed in the coating and results in it being crack-free. The oxidation resistance of the non-coated Ti22Al26Nb alloy in isothermal and cyclic tests in air at 1073 K was poor, but the coated specimens possessed excellent oxidation resistance because a protective α-Al₂O₃ scale formed. The life of the Al diffusion coating greatly depends upon the rapid initial formation of a protective Al₂O₃ scale and interdiffusion between coating and substrate. Once the stable Al₂O₃ scale has formed and the composition changes from (Ti, Nb)Al₃ into (Ti, Nb)Al₂, the coating has a long life.     

Microstructure and thermal expansion of Ti coated diamond/A1 composites

A titanium coating fabricated via vacuum vapor deposition for diamond/Al composites was used to improve the interfacial bonding strength between diamond particles and Al matrix, and the Ti coated diamond particles reinforced Al matrix composites were prepared by gas pressure infiltration for electronic packaging. The surface structure of the Ti coated diamond particles was investigated by XRD and SEM. The interfacial characteristics and fracture surfaces were observed by SEM and EDS. The coefficient of thermal expansion(CTE) of 50% (volume fraction) Ti coated diamond particles reinforced Al matrix composites was measured. The Ti coating on diamond before infiltration consists of inner TiC layer and outer TiO₂ layer, and the inner TiC layer is very stable and cannot be removed during infiltration process. Fractographs of the composites illustrate that aluminum matrix fracture is the dominant fracture mechanism, and the stepped breakage of a diamond particle indicates strong interfacial bonding between the Ti coated diamond particles and the Al matrix. The measured low CTEs (5.07×10⁻⁶−9.27×10⁻⁶K⁻¹) of the composites also show the strong interfacial bonding between the Ti coated diamond particles and the Al matrix.     

Coating titanium on carbon steel by in-situ electrochemical reduction of solid TiO2 layer

Ti coating on A3 steel was successfully prepared by direct electrochemical reduction of high-velocity oxy-fuel (HVOF) thermally sprayed and room-temperature dip-coating titanium dioxide coating on A3 steel in molten CaCl₂ at 850 °C. The interfacial microstructure and mutual diffusion between coating and steel substrate were investigated using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy. The results show that the precursory TiO₂ coating prepared by HVOF has closer contact and better adhesion with the A3 steel substrate. After electrolysis, all of the electro-generated Ti coatings show intact contact with the substrates, regardless of the original contact situation between TiO₂ layer and the steel substrate in the precursors. The inter-diffusion between the iron substrate and the reduced titanium takes place at the interface. The results demonstrate the possibility of the surface electrochemical metallurgy (SECM) is a promising surface engineering and additive manufacturing method.     

New method for hydroxyapatite coating of titanium by the hydrothermal hot isostatic pressing technique

A new hydrothermal method is proposed, which enables us to prepare thin hydroxyapatite (HA) ceramic coatings on Ti substrates with a curved surface at low temperatures. The method uses double layered capsules in order to produce a suitable hydrothermal condition; the inner capsule encapsulates the coating materials and a Ti substrate, and the outer capsule is subjected to isostatic pressing under the hydrothermal condition. In this study, it is demonstrated that a pure HA ceramic layer with the thickness of 50 μm could be coated to a Ti cylindrical rod at the low temperature as low as 135 °C under the confining pressure of 40 MPa. The HA coating layer had a porous microstructure with the relative density of approximately 60%. Pull-out tests were conducted to obtain an estimate for the adhesion properties of the HA coating prepared by the double capsule method. The shear strength obtained from the pull-out tests was in the range of 4.0–5.5 MPa. It was also shown that the crack propagation occurred within the HA coating layer, not along the HA/Ti interface in the pull-out tests. This observation suggests that the fracture property of the HA/Ti interface was close to or higher than that of the HA ceramics only. It is expected that the low temperature double capsule method may provide a useful method for producing bioactive HA ceramic coatings on curved prostheses surfaces.     

Oxidation Resistant Ce-modified Silicide Coatings Prepared on Ti–6Al–4V Alloy by Pack Cementation Process

Cerium-modified silicide coatings were prepared on Ti–6Al–4V by pack cementation. The effects of different kinds of activators (NaCl, AlF₃, AlCl_3, and NH₄Cl) and pack CeO₂ concentrations (1, 3, and 5 wt%) on the coating structures were studied. The results show that the coatings were mainly composed of a TiSi₂ outer layer, a TiSi middle layer, a Ti₅Si₄ inner layer and a 1–2 μm thick Ti₅Si₃ interdiffusion zone. NH₄Cl was a more suitable activator for preparing the Ce-modified silicide coating on Ti–6Al–4V, based on the coating microstructure and growth rate. The coating thickness decreased with increasing CeO₂ concentration in the pack. Oxidation tests at 800 °C in air showed that the Ce-modified silicide coating showed improved oxidation resistance compared to both the uncoated alloy and the pure silicide coating. A dense, but thick oxide scale formed that was composed of a TiO₂ outer layer and a SiO₂ inner layer.     

Electrophoretic deposition of hydroxyapatite coatings on titanium from dimethylformamide suspensions

Hydroxyapatite powders were prepared by a chemical precipitation method and electrophoretically deposited on pure Ti surgical substrates. The powders were suspended in dimethylformamide (DMF). The zeta potential, electromobility and the conductivity of the HA suspension was characterized at various pH values to identify the most stable dispersion conditions. The effect of applied voltage and deposition time on deposition rate, deposition thickness and coating morphology were studied. The coating morphology and composition were characterized by scanning electron microscopy (SEM). The crystalline phase of HA before and after electrophoretic deposition was examined using X- ray diffraction (XRD). Transition electron microscope (TEM) indicated that HA consisted of needle-shaped crystallites.     

The Effect of Deposition Conditions on Adhesion Strength of Ti and Ti6Al4V Cold Spray Splats

Cold spray is a complex process where many parameters have to be considered in order to achieve optimized material deposition and properties. In the cold spray process, deposition velocity influences the degree of material deformation and material adhesion. While most materials can be easily deposited at relatively low deposition velocity (<700 m/s), this is not the case for high yield strength materials like Ti and its alloys. In the present study, we evaluate the effects of deposition velocity, powder size, particle position in the gas jet, gas temperature, and substrate temperature on the adhesion strength of cold spayed Ti and Ti6Al4V splats. A micromechanical test technique was used to shear individual splats of Ti or Ti6Al4V and measure their adhesion strength. The splats were deposited onto Ti or Ti6Al4V substrates over a range of deposition conditions with either nitrogen or helium as the propelling gas. The splat adhesion testing coupled with microstructural characterization was used to define the strength, the type and the continuity of the bonded interface between splat and substrate material. The results demonstrated that optimization of spray conditions makes it possible to obtain splats with continuous bonding along the splat/substrate interface and measured adhesion strengths approaching the shear strength of bulk material. The parameters shown to improve the splat adhesion included the increase of the splat deposition velocity well above the critical deposition velocity of the tested material, increase in the temperature of both powder and the substrate material, decrease in the powder size, and optimization of the flow dynamics for the cold spray gun nozzle. Through comparisons to the literature, the adhesion strength of Ti splats measured with the splat adhesion technique correlated well with the cohesion strength of Ti coatings deposited under similar conditions and measured with tubular coating tensile (TCT) test.     

In situ composite coating of titania-hydroxyapatite on commercially pure titanium by microwave processing

Microwave (MW) processing has been studied as an alternative method of hydroxyapatite (HA) based composite coatings on commercially pure titanium (CPTi) to enhance the bioactivity for orthopaedic and dental implant applications. The coating was formed by processing CPTi metal packed in HA and at 800 W microwave power for 22 min. The composition of the coating was found to be TiO₂ (rutile) as major phase along with HA as minor phase. The MW absorption of non-stoichiometric TiO₂ layer, which was grown during the initial hybrid heating, resulted in sintering of apatite particles interfacing them. The non-stoichiometric nature of TiO₂ was evident from the observed mid-gap bands in ultraviolet-visible diffusive reflectance (UV-VIS-DR) spectrum. The lamellar α structure of the substrate suggests that the processing temperature was above β transus of CPTi (1155 K). The oxygen stabilized α phase whose thickness increased with microwave processing time, was likely to be the reason for the increase in Young's Modulus and hardness of the substrate. The coating induced apatite precipitation in bioactivity test. The osteoblast cell adhesion test demonstrated cell spreading which is considered favourable for cell proliferation and differentiation. Thus, in situ composite coating of titania and HA on CPTi was obtained by a simple one-step process.     

Y and Al modified silicide coatings on an Nb–Ti–Si based ultrahigh temperature alloy prepared by pack cementation process

Y and Al modified silicide coatings were prepared on an Nb–Ti–Si based ultrahigh temperature alloy by co-depositing Si, Al and Y at 1150 °C for up to 10 h, respectively. The deposition of Al and Si occurred in a sequential manner during the pack cementation process. At the initial stage, the element deposited was primarily Al with very little Si and an Al₃(Nb,X) (X represents Ti, Cr and Hf elements) layer formed preferentially. After a short period of holding time, Si started depositing and Si–Al co-deposition took place. However, this Si–Al co-deposition period was not long. When the holding time was longer than 1 h at 1150 °C, Si deposition dominated the coating growth process. The coating growth kinetics at 1150 °C followed a parabolic law. The coating prepared at 1150 °C for 10 h had a multi-layer structure, with a thick (Nb,X)Si₂ outer layer, a thin (Ti,Nb)₅Si₄ middle layer and an Al, Cr-rich inner layer. The coating could protect the Nb–Ti–Si based alloy from oxidation at 1250 °C in air for at least 100 h. The excellent oxidation resistance of the coating was attributed to the formation of a dense scale mainly consisted of TiO₂, SiO₂ and Al₂O₃.     

Deposition of thick TiAlN coatings on 2024 Al/SiCp substrate by Arc ion plating

Aluminum-matrix composites with particulate SiC ceramic reinforcements (Al/SiC_p) have received much attention for space and aircraft propulsion applications. It is imperative to deposit thick hard coatings on these composites for protection. TiAlN coatings with a Ti interlayer were deposited by arc ion plating (AIP) on 2024 Al/SiC_p substrates at various nitrogen flow rates. It was found that when the nitrogen flow rate is increased from 100 sccm to 250 sccm, the deposition rate decreases, the coating hardness increases and the adhesion strength decreases. Based on the above results and the principle of gradient materials, the thick gradient TiAlN coatings with a Ti interlayer were successfully deposited on a 2024 Al/SiC_p substrate to a thickness of 60 μm by continuously increasing the nitrogen flow rate during deposition. Such an achievement can be attributed to the gradient distribution of elements, hardness, and stresses across the coating thickness.     

Pack Cementation Coatings for High-Temperature Oxidation Resistance of AISI 304 Stainless Steel

Aluminum and titanium are deposited on the surface of steel by the pack cementation method to improve its hot-corrosion and high-temperature oxidation resistance. In this research, coatings of aluminum and titanium and a two-step coating of aluminum and titanium were applied on an AISI 304 stainless steel substrate. The coating layers were examined by carrying out scanning electron microscopy (SEM) and x-ray diffraction (XRD). The SEM results showed that the aluminized coating consisted of two layers with a thickness of 450???m each, the titanized coating consisted of two layers with a thickness of 100???m each, and the two-step coatings of Al and Ti consisted of three layers with a thickness of 200???m each. The XRD investigation of the coatings showed that the aluminized coating consisted of Al₂O₃, AlCr₂, FeAl, and Fe₃Al phases; the titanized layers contained TiO₂, Ni₃Ti, FeNi, and Fe₂TiO₅ phases; and the two-step coating contained AlNi, Ti₃Al, and FeAl phases. The uncoated and coated specimens were subjected to isothermal oxidation at 1050?°C for 100?h. The oxidation results revealed that the application of a coating layer increased the oxidation resistance of the coated AISI 304 samples as opposed to the uncoated ones.     

Preparation and characterization of silicon-substituted hydroxyapatite coating by a biomimetic process on titanium substrate

A biomimetic method has been used to prepare silicon-substituted hydroxyapatite coatings on titanium substrates. The surface structures of the coatings were characterized by X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and Fourier transformed infrared spectroscopy (FTIR). Si substituted hydroxyapatite (Si-HA) coatings with different Si contents were deposited successfully on the titanium substrate by immersing the pretreated titanium substrate into silicon containing supersaturated solutions (SSS) with different SiO₃²⁻ concentrations. The pretreatment of the Ti substrate in a mixed alkaline (NaOH + Ca(OH₂)) followed by a heat treatment produced a 3D porous surface structure with rutile and CaTiO₃ as main phases, which contributed mainly to the fast precipitation and deposition of Si-HA. FTIR results showed that Si in the Si-HA coating existed in the form of SiO₄⁴⁻ groups. The cross-section microstructure was observed by scanning electronic microscopy and the shear strength was tested. The coating was about 5-10 μm in thickness and no interval was observed at the interface between the coating and the substrate. Shear strength testing showed that Si-HA/Ti exhibited higher shear strength than HA/Ti due to the existence of the SiO₄⁴⁻ group in the coating.