Microstructure and Tribological Properties of TiB2/TiB/TiNx（x=1,0.3）/Ti Composite Coating Produced on Pure Ti by Laser Surface Alloying

TiB2/TiB/TiNx(x=1,0.3)/Ti composite coating was prepared on pure Ti by laser surface alloying by using powders of boron as starting materials.The composite coating was examined by X-ray diffraction(XRD),high-resolution transmission electron microscopy(HRTEM)and scanning electron microscopy(SEM).The friction and wear properties of the composite coating were examined using a pin-on-disk tester under dry sliding wear condition.The results showed that the top surface of the composite coating was mainly composed of TiB2,TiB,TiN0.3,TiN and Ti phases,while the interface of the composite coating was composed of TiB and Ti phases.The composite coating showed sticklike structure near the top surface,and dendrites structure near the interface.The friction and wear test showed that the composite coating had better wear resistance than pure Ti due to their higher microhardness than that of pure Ti substrate.     

Microstructure evolution and liquid phase separation in Ta-O hypermonotectic melts during laser-cladding

A three-layer Ta_2O_5-containing coating was successfully fabricated by laser cladding on a pure Ta substrate. The maximum thickness of such a coating is about 1.6 mm. The microstructure, phase constitution and elemental distribution in the coating were investigated. Results show that the coating has been metallurgically bonded to the Ta substrate and the microstructure exhibits a graded change along the deposition direction from Ta substrate to the top of coating. In the layers I and II of the graded coating, the microstructure evolution can be confi rmed as a result of hypomonotectic reaction, but in the layer Ⅲ it was formed by hypermonotectic reaction. At the top of coating, the microstructure was still homogeneous although liquid phase separation had occurred, which can be attributed to the fact that the O-rich droplets do not have enough time to fl oat at high cooling rate. The theoretical calculation results show that during laser cladding, the solidifi cation time of the melt pool was less than 0.1 s, which fi ts well with the results from the experiment.     

Hot Corrosion Behavior of SiO_2–Al_2O_3–Glass Composite Coating on Ti–47Al–2Cr–2Nb Alloy: Diffusion Barrier for S and Cl

Type Ⅰ hot corrosion behavior of SiO_2-Al_2O_3-glass composite coating based on Ti-47 Al-2 Cr-2 Nb substrate was investigated in the mixture salt of 25 wt%NaCl + 75 wt%Na_2SO_4 at 850 °C. The results showed that there was a bidirectional ion exchange between composite coating and the film of mixed salts, and the sodium ion in the molten salts penetrated into the glass matrix of composite coating, while the potassium ion in the glass matrix dissolved into the molten salts. A decrease in hot corrosion rate was achieved for the coated alloy in comparison with the bared substrate due to the composite coating acting as a diffusion barrier to sulfur and chlorine and preventing the molten salts from diffusing to the coating/alloy interface during the hot corrosion exposure. Additionally, the composite coating decreased the oxygen partial pressure at the coating/alloy interface and promoted the selective oxidation of Al to form a protective Al_2O_3 layer.     

Study on the subsonic speed flame spraying coating of hydroxyapatite

A new method of preparation of biomaterial composite coating by the technique of subsonic thermal spraying was discussed in this paper. Ti6Al4V and pure Ti were chosen as substrate and sublayer material respectively and the working layer was sprayed with biomaterial hydroxyapatite (HAP), forming the composite coating. The experiments of heat shock and tensile strength showed that the bonding strength between coating and substrate is almost as same as that of specimen in which Ni/Al powder was adopted as sublayer. The phases of TiN, TiO2, and Ti2O3 were formed in the sublayer, which are free of toxic and have no side effects. The powder of working layer HAP was decomposed partly during spraying, but it can be solved by later treatment.     

Compound Ceramic Coatings on Ti-6AI-4V by Micro-Plasma Oxidation in NaAlO2 Solution

Micro-plasma oxidation (MPO) technique is a new technique by which compound ceramic coating can be grown in situ on AI, Ti, Mg and many other valve-metals. Compound ceramic coatings on Ti-6Al-4V alloy were prepared for different time by pulsed bi-polar MPO in NaAlO2 solution. The phase composition, morphology and the element distribution of the coatings were studied by XRD, SEM and JEOL SUPERPROBE 733 electric probe, respectively. Electrochemical Impedance Spectra (EIS) of the coatings were measured to study the structure character of the coatings. Through the proper EIS interpreting software, the “equivalent circuit“ of the coatings was established, and the fitting values of equivalent element were calculated. The coating is mainly composed of Al2TiO5, α-Al2O3 and futile TiO2. The content of Ti element in the coating is less than that of substrate; its distribution is relatively uniform, and Ti in the outer layer is less than that in the inner layer. The content of A1 in the coating is more than that of substrate, and its distribution is not even: Al in the middle part is more than that on both sides of the coating; And the EIS analysis has illustrated the double-layer structure of the coatings, and the outside layer is loosen and the inner layer compact; with the increase of the oxidizing time, the surface roughness of the coatings, and the porosity of the outer layer of the coating are increased while the compactness of the inner layer of the coatings are improved.     

Effects of additives on corrosion and wear resistance of micro-arc oxidation coatings on TiAl alloy

Ceramic coating was deposited on TiAl alloy substrate by micro-arc oxidation(MAO)in a silicate-aluminate electrolyte solution with additives including sodium citrate,graphite and sodium tungstate.The microstructures and compositions were analyzed by SEM,EDX and XRD.The corrosion and wear properties of the coatings were investigated by potentiodynamic polarization and ball-on-disc wear test,respectively.The results show that the MAO coatings consist of WO3,Ti2O3,graphite and Al2O3 besides Al2TiO5 and Al2SiO5.With additives in the electrolyte,the working voltage at the micro-arc discharge stage decreases,and the ceramic coating gets smoother and more compact.The corrosion current density of MAO coating is much lower than that of TiAl substrate.It can be reduced from 9.81×10-8A/cm 2to 3.02×10-10A/cm 2 .The MAO coatings composed of hard Al2O3,WO3 and Ti2O3 obviously improve the wear resistance of TiAl alloy.The wear rate is-3.27×10-7g/(N·m).     

Electrodeposition of nanostructured Ti/(Ru+Ti+Ce)O_2 coatings

A nanostructured ternary coating of Ti/(Ru + Ti + Ce)O_2 was prepared by the conventional electrodeposition on the titanium substrate as the cathode with different numbers of coating layers. The main objective of this work was to study nanostructured coatings of ceramic materials. For this purpose, the amount of precursor materials in the electrolyte was a variable parameter. Furthermore, the salt of TiCl_4/RuCl_3·xH_2 O/Ce(NO_3)_3·6 H_2 O with different amounts, hydrogen peroxide, methanol, and distilled water were used as an aqueousunaqueous bath. In addition, the coated samples were put to heat at 300, 450, 650, and 850℃ in an electric furnace for1 h. The crystalline phase of the coating was characterized by X-ray diffraction(XRD). The chemical composition and microstructure of the coating were studied using energydispersive spectroscopy(EDS) and scanning electron microscopy analysis(SEM). Moreover, the electrochemical measurement of Ti/(Ru + Ti + Ce)O_2 coatings was carried out. Results show that with the increase in the number of coating layers, the quality of morphology is improved.Then, the best quality of coatings is obtained at six layers on the titanium substrate with electrolyte including TiO_2/RuO_2/CeO_2 with the molar ratio of 70:5:25 after heat treatment at 450 ℃ for 1 h. Besides,with the increase in Ce02 content from 5 wt% to 25 wt% and the number of coating layers, higher thickness of about(20.0±0.1) μm and minimum over potential for chlorine evolution were obtained.     

Plasma spray forming of tungsten coatings on copper electrodes

Both direct current dc plasma and radio frequency induction plasma were used to deposit tungsten coatings on copper electrodes. Fine tungsten powder with mean particle size of 5 um and coarse tungsten powder with particle size in the range from 45 um to 75 um were used as plasma spray feedstock. It is found that dc plasma is only applicable to spray the fine tungsten powder and induction plasma can be used to spray both the coarse powder and the fine powder. The tungsten coating deposited by the induction plasma spraying of the coarse powder is extremely dense. Such a coating with an interlocking structure and an integral interface with the copper substrate demonstrates high cohesion strength and adhesion strength.     

Analysis of Bonding Features between the Particles and the Substrate during Cold Spraying

Cold spraying is a new coating process and manufacturing technology. The coating quality is upgraded with dense layers, higher bonding force and lower oxidation comparing with thermal spraying. Bonding of particles onto substrate is a result of extensive plastic deformation and related phenomena at the interface. The cold-sprayed copper and aluminum deposits on aluminum and steel substrates were prepared, and the features of interface were observed by using scanning electron microscope (SEM). Then the particle/substrate impact process was modeling through finite-element methods (ANSYS/LS-DYNA software). Numerical results show that the high plastic strain at the interface can result in an adiabatic shear instability at the interface. Due to these extremely high pressure and strain rate, it may be more appropriate to treat the material adjacent to the particle/substrate interface as a viscous ‘fluid-like’ material, various fluid-based phenomena, such as interfacial instabilities and roll-ups and vortices, can lead to interface material mixing. In numerical simulation, adiabatic shear instability both in the particle and the substrate at contact interface is regarded as a criterion for predicting the optimal process parameters and the bonding feature.     

Characterization of microarc oxidation coatings on pure titanium

The morphology, composition, and phase structure of the oxide coatings produced on the surface of pure titanium by alternating-current microarc discharge in aluminate solution were investigated by X-ray diffraction and scanning electron microscopy. The profiles of the hardness H and the elastic modulus E in the coatings were determined using a nanoindenta-tion method. The concentration distributions of Ti, Al, and O in the coating show that this coating over 30 μm thick contains two layers: an outer layer and an inner layer. The oxide coating is mainly composed of TiO2 rutile and Al2TiO5 compounds. During oxidation, the temperature in the microarc discharge channel was very high to make the local coating molten. From the surface to the interior of the coating, H and E increase gradually, and then reach maximum values of 9.78 GPa and 176 GPa respectively at a distance of 7μrn from the coating/titanium interface. They are also rather high near the interface.     

溶胶凝胶法制备TiO_2/HA复合生物活性涂层及其体外活性

通过溶胶凝胶法在纯钛基体上制备了羟基磷灰石(HA)/TiO2复合生物活性涂层。HA和TiO2溶胶由前驱体制得,按不同摩尔比直接混合两种溶胶来制备混合溶胶。HA可以提高钛基的生物活性,TiO2可以提高涂层与基体的物理、化学相容性和结合强度。粘结拉伸结果表明,复合涂层与基体结合良好,比纯HA涂层与基体的结合强度提高约47%。复合涂层试样于SBF中浸泡4、7和14d的SEM分析结果表明,复合涂层表面的类骨磷灰石生成量较高。成骨细胞实验结果表明,复合涂层上细胞铺展良好。     

Electrophoretic deposition of titanium/silicon-substituted hydroxyapatite composite coating and its interaction with bovine serum albumin

Silicon-substituted hydroxyapatite (Ca10(PO4)6-x(SiO4)x(OH)2-x, Si-HA) composite coatings on a bioactive titanium substrate were prepared by electrophoretic deposition technique with the addition of triethanolamine (TEA) to enhance the ionization degree of Si-HA suspension. The surface structure was characterized by XRD, SEM, XRF, EDS and FTIR. The bond strength of the coating was investigated. The results show that the depositing thickness and the images of Si-HA coating can be changed with the variation of deposition time. The XRD spectra of Ti/Si-HA coatings show the characteristic diffraction peaks of HA, and the incorporation of silicon changes the lattice parameter of the crystal. The FTIR spectra shows that the most notable effect of silicon substitution is the decrease of intensities of -OH and PO43- groups with the silicon contents increasing. XRD and EDS element analyses present that the content of silicon in the coating increases with increasing silicon concentration in the suspension. The bioactive TiO2 coating formed may improve the bond strength of the coatings. The interaction of Ti/Si-HA coating with BSA is much greater than that of Ti/HA coating, suggesting that the incorporation of silicon in HA is significant to improve the bioactive performance of HA.     

羟基磷灰石生物涂层材料界面的电镜观察与分析

用扫描电子显微镜和透射电子显微镜对未经热处理的钛合金基体等离子喷涂羟基磷灰石生物材料的显微结构、相组成和界面结合进行了观察与分析. 结果表明 HA涂层的显微结构疏松, 内部有裂纹和孔洞; 涂层的相结构中, HA以结晶态和非晶态两种形态存在; HA和基体的界面结合是以物理结合为主, 界面明显, 没有过渡相, 说明基体和涂层之间化学反应不明显.     

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.     

电解液成分对纯钛表面微弧氧化膜结构与生物活性的影响

采用微弧氧化处理技术,在纯钛TA2表面制备了含钙磷的多孔复合氧化膜,用SEM、XRD、EPMA等分析了电解液成分对氧化膜形貌、成分、相构成及生物活性的影响。结果表明:纯钛表面微弧氧化后原位生成的含钙磷多孔性复合氧化膜由锐钛矿相TiO2,金红石相TiO2和基体Ti组成;随电解液中钙磷摩尔比(Ca/P)值的增大,表面孔洞数量增多、直径变小,膜中Ca/P值增大,锐钛矿相TiO2减少、金红石相TiO2增多;当电解液中Ca/P=5时得到的氧化膜的Ca/P值为1.528,将该样品经碱液处理后再在快速钙化溶液(FCS)中浸泡2 d后即有羟基磷灰石HA形成,表明其具有良好的生物活性。     

Hydroxyapatite coating on titanium substrate by electrophoretic deposition method: Effects of titanium dioxide inner layer on adhesion strength and hydroxyapatite decomposition

Nanosized hydroxyapatite (HA) powders were prepared by a chemical precipitation method and electrophoretically deposited on Ti6Al4V substrates. The powders were calcined before the deposition process in order to obtain crack-free coating surfaces. As an inner layer between Ti6Al4V substrate and HA coating, nanosized titanium dioxide (TiO₂) powders were deposited, using different coating voltages, in order to connect substrate and HA tightly. Moreover, this layer is considered to be acting as a diffusion barrier, reducing the HA decomposition due to ion migration from the metal substrate into the HA. After the sintering stage, adhesion strengths of coatings were measured by shear testing, phase changes were studied by X-ray diffraction, and coating morphology was analyzed through scanning electron microscopy observations. Results showed that usage of the TiO₂ inner layer prevented HA decomposition. Furthermore, decreasing the voltage used in TiO₂ deposition resulted in crack-free surfaces and increased adhesion strength of the overall coating.     

Measurements of residual stresses in plasma-sprayed hydroxyapatite coatings on titanium alloy

In an attempt to investigate the stress state and stress distribution in hydroxyapatite coatings (HAC), the residual stresses in thick HACs on titanium alloy were studied by the materials removal method, as a function of cooling media during spraying. In addition, the X-ray diffraction sin²ψ method was adopted as a comparison. The Young's moduli of hydroxyapatite coatings were measured on separated free coating by a three-point bending test. The results show that the measured Young's modulus of the HACs with an average of 22.8 GPa was found to be much lower than the theoretical value of bulk HA. During measurements by the materials removal method, on the three types of HACs using different cooling media, the interface between the HAC and Ti substrate displays higher residual stress than the top surface of HAC. The residual stresses in all the HACs measured by both methods were in a compressive mode, and the residual stresses on the top surface obtained from the two methods are consistent. It was also found that the compressive residual stresses on the top surface of HAC and at the interface between the coating and the substrate both increased with increasing temperature of the HAC. Therefore, the coating temperature, and the effect of varying the cooling media during plasma spraying, had a significant effect on the residual stress states of the HACs.     

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。     

钛表面微弧氧化+碳膜的制备与表征

为提升钛金属与碳膜的界面结合,增强涂层的防护作用,利用微弧氧化(MAO)技术在钛表面快速简易制备出与基体为冶金结合的多孔层结构,并以此为基采用离子束复合磁控溅射技术制备碳膜。采用SEM+EDS、AFM分析所制备膜层的微观结构,借助划痕仪、磨损试验机和电化学工作站表征膜层的结合力和性能。结果表明：表层碳膜并不能完全覆盖微弧氧化层的微孔,同时Ti基体表面微弧氧化层可有效增加表层碳膜与Ti基体的结合力;Ti基体/MAO层/碳膜的膜基体系在摩擦磨损过程中,摩擦系数小且波动很小,磨痕宽度最小,表现出最为优异的摩擦学性能;而新设计复合膜层的耐蚀性较传统的Ti基体/Ti打底层/碳膜的膜基体系要差,这与表层碳膜较薄,复合膜层仍呈现出微弧氧化层多孔特征有关,其导致腐蚀介质易于通过微孔而降低耐蚀性。