Study on impact fusion at particle interfaces and its effect on coating microstructure in cold spraying

This paper deals with the impact melting phenomenon at the interfaces between the deposited particles in cold-sprayed coatings and its effect on coating microstructure and particle bonding mechanism. Al-12Si, Al2319, Ti, Ti-6Al-4V, Ni and NiCoCrAlTaY powders were selected as feedstocks, which have various thermal and mechanical properties. The analytical results showed that most of the used materials possibly experienced the local melting at the contact interfaces of particles under certain impact conditions. Low melting point, relatively high gas temperature and chemical reaction with the atmosphere are the main factors contributing to the impact fusion during cold spraying. The results also indicated that the local melting would benefit the formation of a metallurgical bonding between the deposited particles and enhance the coating cohesion.     

XPS study of porous dental implants fabricated by electro-discharge-sintering of spherical Ti-6Al-4V powders in a vacuum atmosphere

A single electro-discharge-sintering (EDS) pulse (0.7-2.0 kJ/0.7 g), from a 300 μF capacitor, was applied to atomized spherical Ti-6Al-4V powder in a vacuum to produce a porous-surfaced implant compact. A solid core surrounded by a porous layer was formed by a discharge in the middle of the compact. X-ray photoelectron spectroscopy was used to study the surface characteristics of the implant material. C, O, and Ti were the main constituents, with smaller amounts of Al, V, and N. The implant surface was lightly oxidized and was primarily in the form of TiO₂ with a small amount of metallic Ti. A lightly etched EDS implant sample showed the surface form of metallic Ti, indicating that EDS breaks down the oxide film of the as-received Ti-6Al-4V powder during the discharge process. The EDS Ti-6Al-4V implant surface also contained small amounts of aluminum oxide in addition to TiO₂. However, V detected in the EDS Ti-6Al-4V implant surface did not contribute to the formation of the oxide film. The small amount of N in the implant surface resulted from nitride material that was also found in the as-received Ti-6Al-4V powders.     

Surface characteristics of self-assembled microporous Ti-6Al-4V compacts fabricated by electro-discharge-sintering in air

A single electro-discharge-sintering (EDS) pulse (1.0 kJ/0.7 g), from a 300 (F capacitor, was applied to atomized spherical Ti-6Al-4V powder in air to produce microporous compact. A solid core surrounded by a porous layer was self-assembled by a discharge in the middle of the compact. X-ray photoelectron spectroscopy was used to study the surface characteristics of the compact material. C, N, O and Ti were the main constituents, with smaller amounts of Al and V. The surface was lightly oxidized and was primarily in the form of TiO₂. A lightly etched EDS sample showed the surface form of metallic Ti, indicating that EDS breaks down the oxide film of the as-received Ti-6Al-4V powder during the discharge process. The EDS Ti-6Al-4V compact surface also contained small amounts of TiN in addition to TiO₂, resulting in the reaction between nitrogen in air and the Ti substrate in times as short as 125 μs.     

Growth characteristics of micro-plasma oxidation ceramic coatings on Ti alloy by inductively coupled plasma-atomic emission spectrometer technique

The aim of this work was to study the growth characteristics of micro-plasma oxidation ceramic coatings on Ti-6Al-4V alloy. Compound ceramic coatings were prepared on Ti-6Al-4V alloy by pulsed micro-plasma oxidation (MPO) in NaAlO₂ solution. The phase composition and surface morphology of the coating were investigated by X-ray diffractometry and scanning electron microscopy. The solution of Ti from the substrate and the content of Al in the electrolyte were studied by inductively coupled plasma-atomic emission spectrometer (ICP-AES) technique. Ti from the substrate dissolved and came into the coating and the electrolyte during MPO process. The content of Ti in the electrolyte under the pulsed bi-polar mode was more than that of the pulsed single-polar mode. The phase composition and structure of the coating was attributable to the space steric hindrance of Al congregated on the electrode surface due to the effect of the electric field and the electrolyte characters. For the pulsed single-polar mode, the coating was mainly composed of a large amount of α-Al₂O₃ and a small amount of γ-Al₂O₃. And the coating was mainly structured by Al from the electrolyte. However, the coating was composed of a large amount of Al₂TiO₅ and a little α-Al₂O₃ and rutile TiO₂ for the pulsed bi-polar mode. And the coating was structured both by Ti from the substrate and Al from the electrolyte.     

Analysis of the interface between a pulsed laser deposited calcium phosphate coating and a titanium alloy substrate

Calcium phosphate coatings deposited on titanium alloy are intended to add a bioactive surface to medical implants. This work presents the characterisation of the interface between Ti-6Al-4V and a crystalline calcium phosphate coating obtained by pulsed laser deposition, with a KrF excimer laser, at 575 °C and under a 45 Pa water-vapour atmosphere. The coating–substrate system was studied by secondary-ion mass spectrometry, scanning electron microscopy, X-ray diffractometry, Raman spectroscopy and X-ray photoelectron spectroscopy. The results show that the deposition process promotes the interdiffusion of substrate elements into the coating and coating elements into the substrate oxide layer. Thus, a graded layer of mixed calcium phosphate and amorphous titanium oxide is formed. For the substrate, a hydroxyapatite coating acts more as a barrier for oxygen incoming from a gas than as an oxygen source during deposition. Moreover, oxygen diffusion into the substrate occurs. Thus, the content of oxygen of this oxide layer diminishes with depth. When the oxygen concentration is low enough it is incorporated in solid solution in the titanium alloy . PACS 81.15.Fg; 68.55.-a; 87.68.+z     

The effect of thermal aging on the strength and the thermoelectric power of the Ti-6Al-4V alloy

When the Ti-6Al-4V alloy is overaged at 500-600°C, nanometer-sized α₂ (Ti₃Al) particles can be homogeneously precipitated inside a phases, thereby leading to strength improvement. Widmanstätten and equiaxed microstructures containing fine α₂ (Ti₃Al) particles were obtained by overaging the Ti-6Al-4V alloy. Precipitation of α₂ (Ti₃Al) particles was monitored using thermoelectric power measurements for different aging conditions in the Ti-6Al-4V alloy. Overaging heat treatments were conducted at 515, 545 and 575°C for different aging times. In addition, overaging samples were examined by optical microscopy, scanning electron microscopy and hardness measurements. It was found that the thermoelectric power is very sensitive to the aging process in the two studied Ti-6Al-4V structures.     

The effects of anodic and cathodic processes on the characteristics of ceramic coatings formed on titanium alloy through the MAO coating technology

This paper reports on the investigation into the effects of the different anodic j_a and cathodic j_c current densities on the variations of the anodic and cathodic processes and the associated changes in the characteristics of the coatings synthesized on Ti-6Al-4V alloy substrate by microarc oxidation technique. The coated samples were subjected to coating thickness and cross-section fracture observation. Phase and elemental composition at different depth of the coatings were evaluated through X-ray diffraction and energy dispersive spectrum analyses. The experimental results indicate that the increase of j_a leads to the increasing slope of anodic voltage U₊ versus oxidation time plots, the larger coating thickness and the more coarse surface morphology of MAO coatings; while the aggrandizement of the cathodic process results in the lower growth rate and more uniform structure of coatings. The changes of the elements distribution from the interface towards the coating surface with variation of j_a and j_c are affected by the Ti anodic dissolution and the electromigration of electriferous particles, such as Al(OH)₄⁻, in electrolytes.     

Microstructure and properties of TiB2–TiB reinforced titanium matrix composite coating by laser cladding

TiB₂ particle and TiB short fiber reinforced titanium matrix composite coatings were prepared utilizing in situ synthesized technique by laser cladding on the surface of Ti6Al4V alloy. Through the experiment, it was found that the surface of the single-track coatings appeared in the depression, but it can be improved by laser track overlapping. With the increase of laser power density, the amount of TiB short fiber was increased, and the distribution of TiB₂ and TiB became more uniform from the top to bottom. The micro-hardness of TiB₂/TiB coating showed a gradient decreasing trend, and the average micro-hardness of the coatings was two-fold higher than that of the substrate. Due to the strengthening effect of TiB₂ particle and TiB short fiber, the wear volume loss of the center of the coating was approximately 30% less than that of the Ti–6Al–4V substrate, and the wear mechanism of the coating was mild fatigue particle detachment.     

Ti6Al4V合金表面激光沉积复合涂层的组织和性能

为了增强Ti6Al4V钛合金的耐磨性,采用激光沉积制造方法在其表面上制备了以原位生成的TiC颗粒和直接添加的WC颗粒为增强相的耐磨涂层,观察了各涂层的微观组织,并测量了涂层的显微硬度和涂层在室温大气条件下的摩擦磨损性能。结果表明各涂层和基体呈现冶金结合,原位自生的TiC和部分熔化的WC颗粒均能够均匀弥散分布于基体上,由于增强相颗粒的弥散强化及激光沉积组织的细晶强化作用,基材的硬度和耐磨性均得到了提高。原位自生的TiC涂层比WC涂层硬度梯度分布平缓,但耐磨性稍差。     

Niobium based coatings for dental implants

Niobium based thin films were deposited on stainless steel (SS) substrates to evaluate them as possible biocompatible surfaces that might improve the biocompatibility and extend the life time of stainless steel dental implants. Niobium nitride and niobium oxide thin films were deposited by reactive unbalanced magnetron sputtering under standard deposition conditions without substrate bias or heating. The biocompatibility of the surfaces was evaluated by testing the cellular adhesion and viability/proliferation of human cementoblasts during different culture times, up to 7 days. The response of the films was compared to the bare substrate and pieces of Ti6Al4V; the most commonly used implant material for orthopedics and osteo-synthesis applications. The physicochemical properties of the films were evaluated by different means; X-ray diffraction, Rutherford backscattering spectroscopy and contact angle measurements. The results suggested that the niobium oxide films were amorphous and of stoichiometric Nb₂O₅ (a-Nb₂O₅), while the niobium nitride films were crystalline in the FCC phase (c-NbN) and were also stoichiometric with an Nb to N ratio of one. The biological evaluation showed that the biocompatibility of the SS could be improved by any of the two films, but neither was better than the Ti6Al4V alloy. On the other hand, comparing the two films, the c-NbN seemed to be a better surface than the oxide in terms of the adhesion and proliferation of human cemetoblasts.     

Numerical simulation of deformation behavior of Al particles impacting on Al substrate and effect of surface oxide films on interfacial bonding in cold spraying

In this study, a comprehensive examination of the deformation behavior of Al particles impacting on Al substrate was conducted by using the Arbitrary Lagrangian Eulerian (ALE) method to clarify the deposition characteristics of Al powder and the effect of surface oxide films in cold spraying. It was found that the deformation behavior of Al particles is different from that of Cu particles under the same impact conditions owing to its lower density and thus less kinetic energy upon impact. The results indicated that a higher velocity was required for Al particles to reach the same compression ratio as that of Cu particles. On the other hand, the numerical results showed that the oxide films at particle surfaces influenced the deformation and bonding condition between the particle and substrate. The inclusions of the crushed oxide films at the interfaces between the depostied particles inhibit the deformation.     

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.     

激光熔覆TiC陶瓷涂层的组织和摩擦磨损性能研究

采用激光熔覆技术在TC4合金表面上制备了TiC陶瓷涂层,分析了熔覆层的微观组织,测试了熔覆层的硬度和摩擦磨损性能。结果表明:TiC激光熔覆层分为熔覆区和稀释区两个区域,熔覆区未受到基底的稀释,由TiC颗粒和TiC树枝晶组成;稀释区受到了基底的稀释,由TiC树枝晶和钛合金组成;TiC激光熔覆层的显微硬度在HV700~1500之间,明显地改善了TC4合金表面的摩擦和磨损性能。     

Microstructure effect on microtopography of chemically etched α + β Ti alloys

Microstructure effect on chemical etching behavior of the annealed Ti-6Al-4V and Ti-3Al-2.5V titanium (Ti) alloys was compared with that of unalloyed commercially pure titanium. The microstructural evolution of structure phases after annealing the titanium and its alloys at temperature near and above β transus and followed by furnace cooling to room temperature was studied using optical microscope, scanning electron microscope and X-ray diffraction techniques. The microstructure study illustrates that the heat treatment enhanced partitioning effect allows extensive formation of hemispherical and near spherical pits roughened surface to be readily acquired by chemically etching the annealed α + β titanium alloys. The kinetics of the chemical etching reaction process show a linear dependence on time. The annealed α + β titanium alloys that exhibit relatively lower weight loss and thickness reduction rate illustrate less chemical activity than the annealed unalloyed titanium.     

Dielectric properties of anodic films on sputter-deposited Ti-Si porous columnar films

For electrolytic capacitor application of the single-phase Ti alloys containing supersaturated silicon, which form anodic oxide films with superior dielectric properties, porous Ti-7 at% Si columnar films, as well as Ti columnar films, have been prepared by oblique angle magnetron sputtering on to aluminum substrate with a concave cell structure to enhance the surface area and hence capacitance. The deposited films of both Ti and Ti-7 at% Si have isolated columnar morphology with each column revealing nanogranular texture. The distances between columns are ∼500 nm, corresponding to the cell size of the textured substrate and the gaps between columns are 100-200 nm. When the porous Ti-7 at% Si film is anodized at a constant current density in ammonium pentaborate electrolyte, the growth of a uniform amorphous oxide film continues to ∼35 V, while it is limited to less than 6 V on the porous Ti film. The maximum voltage of the growth of uniform amorphous oxide films on the Ti-7 at% Si films is similar for both the flat and porous columnar films, suggesting little influence of surface roughness on the amorphous-to-crystalline transition of growing anodic oxide under the high electric field. Due to the suppression of crystallization to sufficiently high voltages, the anodic oxide films formed on the porous Ti-7 at% Si film shows markedly improved dielectric properties, in comparison with those on the porous Ti film.     

A study on wear resistance and microcrack of the Ti3Al/TiAl + TiC ceramic layer deposited by laser cladding on Ti-6Al-4V alloy

Laser cladding of the Al + TiC alloy powder on Ti-6Al-4V alloy can form the Ti₃Al/TiAl + TiC ceramic layer. In this study, TiC particle-dispersed Ti₃Al/TiAl matrix ceramic layer on the Ti-6Al-4V alloy by laser cladding has been researched by means of X-ray diffraction, scanning electron microscope, electron probe micro-analyzer, energy dispersive spectrometer. The main difference from the earlier reports is that Ti₃Al/TiAl has been chosen as the matrix of the composite coating. The wear resistance of the Al + 30 wt.% TiC and the Al + 40 wt.% TiC cladding layer was approximately 2 times greater than that of the Ti-6Al-4V substrate due to the reinforcement of the Ti₃Al/TiAl + TiC hard phases. However, when the TiC mass percent was above 40 wt.%, the thermal stress value was greater than the materials yield strength limit in the ceramic layer, the microcrack was present and its wear resistance decreased.     

Microstructure evolution of laser solid forming of Ti-Al-V ternary system alloys from blended elemental powders

Morphology evolution of prior β grains of laser solid forming (LSF) Ti-xAl-yV (x 11,y 20) alloys from blended elemental powders is investigated. The formation mechanism of grain morphology is revealed by incorporating columnar to equiaxed transition (CET) mechanism during solidification. The morphology of prior β grains of LSF Ti-6Al-yV changes from columnar to equiaxed grains with increasing element V content from 4 to 20 wt.-%. This agrees well with CET theoretical prediction. Likewise, the grain morphology of LSF Ti-xAl-2V from blended elemental powders changes from large columnar to small equiaxed with increasing Al content from 2 to 11 wt.-%. The macro-morphologies of LSF Ti-8Al-2V and Ti-11Al-2V from blended elemental powders do not agree with CET predictions. This is caused by the increased disturbance effects of mixing enthalpy with increasing Al content, generated in the alloying process of Ti, Al, and V in the molten pool.     

Study on the microstructure and wear resistance of the composite coatings fabricated on Ti-6Al-4V under different processing conditions

Composite coatings mainly containing titanium carbides and borides were produced by laser surface alloying of Ti-6Al-4V with graphite and boron mixed powders. The test results show that the coatings have higher hardness (1600-1700 HV_0.1) and are more resistant to wear than the as-received sample. Laser scanning speed and the content of alloying elements (weight ratio of graphite to boron) have an effect on both the microstructure and the wear resistance of the coatings. TEM results show that strip titanium carbides and borides grow alternately and thus restrain the formation of coarse needle-like TiB and dendritic TiC crystals produced by laser alloying of titanium alloys with boron and graphite separately.     

Effect of microgravity and a high magnetic field on hydroxyapatite deposition and implications for bone loss in space

The microgravity and high magnetic field simulated by a superconducting magnet were used to investigate the dynamics of deposition mechanisms of hydroxyapatite (HAp) on the surface of Ti-6Al-4V samples. The HAp coatings were derived by a self-assembly-induced biomineralization method in simulated body fluid. The experimental results showed that the amount and growth rate of HAp deposition in the simulated microgravity condition were far less than those in the gravity field, as were those in the high magnetic field compared with those outside the magnet. This may provide insight into the bone loss of astronauts in spaceflight from the viewpoint of the dynamic balance between HAp nucleation, deposition and decomposition on the surface of substrates.     

Interaction behaviors at the interface between liquid Al–Si and solid Ti–6Al–4V in ultrasonic-assisted brazing in air

Power ultrasonic vibration (20 kHz, 6 μm) was applied to assist the interaction between a liquid Al–Si alloy and solid Ti–6Al–4V substrate in air. The interaction behaviors, including breakage of the oxide film on the Ti–6Al–4V surface, chemical dissolution of solid Ti–6Al–4V, and interfacial chemical reactions, were investigated. Experimental results showed that numerous 2–20 μm diameter-sized pits formed on the Ti–6Al–4V surface. Propagation of ultrasonic waves in the liquid Al–Si alloy resulted in ultrasonic cavitation. When this cavitation occurred at or near the liquid/solid interface, many complex effects were generated at the small zones during the bubble implosion, including micro-jets, hot spots, and acoustic streaming. The breakage behavior of oxide films on the solid Ti–6Al–4V substrate, excessive chemical dissolution of solid Ti–6Al–4V into liquid Al–Si, abnormal interfacial chemical reactions at the interface, and phase transformation between the intermetallic compounds could be wholly ascribed to these ultrasonic effects. An effective bond between Al–Si and Ti–6Al–4V can be produced by ultrasonic-assisted brazing in air.