Recent innovations in laser additive manufacturing of titanium alloys

Titanium(Ti)alloys are widely used in high-tech fields like aerospace and biomedical engineering.Laser additive manufacturing(LAM),as an innovative technology,is the key driver for the development of Ti alloys.Despite the significant advancements in LAM of Ti alloys,there remain challenges that need further research and development efforts.To recap the potential of LAM high-performance Ti alloy,this article systematically reviews LAM Ti alloys with up-to-date information on process,materials,and properties.Several feasible solutions to advance LAM Ti alloys are reviewed,including intelligent process parameters optimization,LAM process innovation with auxiliary fields and novel Ti alloys customization for LAM.The auxiliary energy fields(e.g.thermal,acoustic,mechanical deformation and magnetic fields)can affect the melt pool dynamics and solidification behaviour during LAM of Ti alloys,altering microstructures and mechanical performances.Different kinds of novel Ti alloys customized for LAM,like peritecticα-Ti,eutectoid(α+β)-Ti,hybrid(α+β)-Ti,isomorphousβ-Ti and eutecticβ-Ti alloys are reviewed in detail.Furthermore,machine learning in accelerating the LAM process optimization and new materials development is also outlooked.This review summarizes the material properties and performance envelops and benchmarks the research achievements in LAM of Ti alloys.In addition,the perspectives and further trends in LAM of Ti alloys are also highlighted.

Tribological Behaviors of Electroless Nickel-Boron Coating on Titanium Alloy Surface

Titanium alloys are excellent structural materials in engineering fields,but their poor tribological properties limit their further applications.Electroless plating is an effective method to enhance the tribological performance of alloys,but it is difficult to efficiently apply to titanium alloys,due to titanium alloy’s strong chemical activity.In this work,the electroless Nickel-Boron(Ni-B)coating was successfully deposited on the surface of titanium alloy(Ti-6AL-4V)via a new pre-treatment process.Then,linearly reciprocating sliding wear tests were performed to evaluate the tribological behaviors of titanium alloy and its electroless Ni-B coatings.It was found that the Ni-B coatings can decrease the wear rate of the titanium alloy from 19.89×10^(−3)mm^(3)to 0.41×10^(−3)mm^(3),which attributes to the much higher hardness of Ni-B coatings.After heat treatment,the hardness of Ni-B coating further increases corresponding to coating crystallization and hard phase formation.However,heat treatment does not improve the tribological performance of Ni-B coating,due to the fact that higher brittleness and more severe oxidative wear exacerbate the damage of heat-treated coatings.Furthermore,the Ni-B coatings heat-treated both in air and nitrogen almost present the same tribological performance.The finding of this work on electroless coating would further extend the practical applications of titanium alloys in the engineering fields.

Hot Deformation Behavior of Ti-6Al-4V-0.5Ni-0.5Nb Titanium Alloy

Characterization of hot deformation behavior of Ti-6Al-4V-0.5Ni-0.5Nb titanium alloy was investigated through isothermal compression at various temperatures from 750 to 1050℃and strain rate from 0.01 to 10 s^(-1).The isothermal compression experiment results showed that the peak stress of Ti-6Al-4V-0.5Ni-0.5Nb titanium alloy decreased with the temperature increasing and the strain rate decreasing.The softening mechanism was dynamic recovery below T_(β)and changed to dynamic recrystallization above T_(β).The arrheniustype relationship was used to calculate the constitutive equation of Ti-6Al-4V-0.5Ni-0.5Nb alloy in two-phase regions.It was found that the apparent activation energies were 427.095 kJ·mol^(-1)in theα+βphase region and 205.451 kJ·mol^(-1)in theβphase region,respectively.On the basis of dynamic materials model,the processing map is generated,which shows that the highest peak efficiency of power dissipation of 56%occurs at about 1050℃/0.01 s^(-1).It can be found in the processing maps that the strain had significant effect on the peak region of power dissipation efficiency of Ti-6Al-4V-0.5Ni-0.5Nb alloy.Furthermore,optimized hot working regions were investigated and validated through microstructure observation.The optimum thermo mechanical process condition for hot working of Ti-6Al-4V-0.5Ni-0.5Nb titanium alloy was suggested to be in the temperature range of 950-1000℃with a strain rate of 0.01-0.1 s^(-1).

Microstructure evolution and strengthening mechanism of high -performance powder metallurgy TA15 titanium alloy by hot rolling

Hot deformation of sintered billets by powder metallurgy(PM)is an effective preparation technique for titanium alloys,which is more significant for high-alloying alloys.In this study,Ti–6.5Al–2Zr–Mo–V(TA15)titanium alloy plates were prepared by cold press-ing sintering combined with high-temperature hot rolling.The microstructure and mechanical properties under different process paramet-ers were investigated.Optical microscope,electron backscatter diffraction,and others were applied to characterize the microstructure evolution and mechanical properties strengthening mechanism.The results showed that the chemical compositions were uniformly dif-fused without segregation during sintering,and the closing of the matrix craters was accelerated by increasing the sintering temperature.The block was hot rolled at 1200℃ with an 80%reduction under only two passes without annealing.The strength and elongation of the plate at 20–25℃ after solution and aging were 1247 MPa and 14.0%,respectively,which were increased by 24.5%and 40.0%,respect-ively,compared with the as-sintered alloy at 1300℃.The microstructure was significantly refined by continuous dynamic recrystalliza-tion,which was completed by the rotation and dislocation absorption of the substructure surrounded by low-angle grain boundaries.After hot rolling combined with heat treatment,the strength and plasticity of PM-TA15 were significantly improved,which resulted from the dense,uniform,and fine recrystallization structure and the synergistic effect of multiple slip systems.

Comparison of electrochemical behaviors of Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe and Ti-6Al-4V titanium alloys in NaNO_(3) solution

The Ti-5Al-2Sn-4Zr-4Mo-2Cr-1Fe(β-CEZ)alloy is considered as a potential structural material in the aviation industry due to its outstanding strength and corrosion resistance.Electrochemical machining(ECM)is an efficient and low-cost technology for manufacturing theβ-CEZ alloy.In ECM,the machining parameter selection and tool design are based on the electrochemical dissolution behavior of the materials.In this study,the electrochemical dissolution behaviors of theβ-CEZ and Ti-6Al-4V(TC4)alloys in NaNO3solution are discussed.The open circuit potential(OCP),Tafel polarization,potentiodynamic polarization,electrochemical impedance spectroscopy(EIS),and current efficiency curves of theβ-CEZ and TC4 alloys are analyzed.The results show that,compared to the TC4 alloy,the passivation film structure is denser and the charge transfer resistance in the dissolution process is greater for theβ-CEZ alloy.Moreover,the dissolved surface morphology of the two titanium-based alloys under different current densities are analyzed.Under low current densities,theβ-CEZ alloy surface comprises dissolution pits and dissolved products,while the TC4 alloy surface comprises a porous honeycomb structure.Under high current densities,the surface waviness of both the alloys improves and the TC4 alloy surface is flatter and smoother than theβ-CEZ alloy surface.Finally,the electrochemical dissolution models ofβ-CEZ and TC4 alloys are proposed.

Preparation of micro-nanostructure on titanium implants and its bioactivity

Surface modification of medical implants was considered as an effective method to improve the cellular behaviors and the integration of tissue onto materials. The micro-nanostructured surface on the titanium alloy was prepared by laser treatment and multiple acid etching. The surface morphologies of different titanium alloy substrates were characterized by scanning electron microscopy (SEM). The effects of micro-nanostructured surfaces on the cellular responses were investigated in vitro by observing hydroxyapatite formation, cell morphology and cell adhesion. The results indicate that the micro-sized structure promoted the adhesion and proliferation of cultured osteoblasts. Furthermore, the micro-nanostructured surface was more conducive to cell adhension stretching compared with the micro-structured surface. All results suggest that the micro-nanostructured surface improved the biocompatibility and integration of tissue onto titanium alloy implants.

Effect of niobium alloying level on the oxidation behavior of titanium aluminides at 850°C

This work addresses the alloying of titanium aluminides used in aircraft engine applications and automobiles. The oxidation resistance behavior of two titanium aluminides of α2 ＋ γ （Ti3Al ＋ TiAl） and orthorhombic Ti2NbAl, recognized as candidates for high-temperature applications, was investigated by exposure of the alloys for 100 h in air. Thus, oxidation resistance was expressed as the mass gain rate, whereas surface aspects were analyzed using scanning electron microscopy in conjunction with energy-dispersive X-ray spectroscopy, and the type of oxidation products was analyzed by X-ray diffraction and Raman spectroscopy. The orthorhombic Ti2NbAl alloy was embrittled, and pores and microcracks were formed as a result of oxygen diffusion through the external oxide layer formed during thermal oxidation for 100 h.

Alloying elements characterization in a Ti-5.6Al-4.8Sn-2Zr-1Mo-0.35Si-1Nd titanium alloy by carbon addition

The effects of carbon addition (0.01wt%-0.43wt%) on a Ti-5.6Al-4.8Sn-2Zr-1Mo-0.35Si-1Nd (wt%) alloy with a bimodal microstructure were investigated. Electron probe microanalysis was carried out to examine the partitioning behavior of carbon and the relation of carbon content to the distributions of Al and Mo in the primary αp phase (α p) and β transformed structure (β). It was found that interstitial carbon is enriched in the α p phase and its content slightly reduces with the increase of the volume fraction of α p. The measurements of carbon content in the present alloy with an α p of 15vol% showed that the carbon content in the α p phase increases with the increment of carbon addition until a maximum but keeps almost constant in the β phase. The addition of carbon reduces the solubility of Al and Mo in the α p phase and leads to the increment of Mo partitioning to the β phase. When the carbon content is over 0.17wt% (0.67at%), carbide precipitation occurs in the matrix and its volume fraction is related to the volume fraction of α p which can be explained in term of the difference of carbon solubility in the α p and β phases.

Structure and properties of micro-arc calcium phosphate coatings on pure titanium and Ti-40Nb alloy

The microstructure, physical and mechanical, and chemical properties of micro-arc calcium phosphate （CAP） coatings deposited under different process voltages in the range of 150-400 V on the commercially pure titanium （Ti） and Ti-40%Nb （Ti-40Nb） （mass fraction） alloy were investigated by the SEM, TEM, XRD and EDX methods. The coating thickness, roughness, and sizes of structural elements were measured and showed similar linear character depending on the process voltage for the coatings on both substrates. SEM results showed the porous morphology with spherical shape structural elements and rough surface relief of the coatings. XRD and TEM studies exhibited the amorphous structure of the CaP coating. With increasing the process voltage to 300-400 V, the crystalline phases, such as CaHPO4 and β-Ca2P207, were formed onto the coatings. The annealing leads to the formation of complex poly-phase structure with crystalline phases： CaTi4（PO4）6, β-Ca2P2O7, TiP2O7, TiNb（PO4）3, TiO2, NbO2, and Nb2O5. The applied voltage and process duration in the ranges of 200-250 V and 5-10 min, respectively, revealed the coating formed on Ti and Ti-40Nb with optimal properties： thickness of 40-70μm, porosity of 20%-25%, roughness （Ra） of 2.5-5.0 μm, adhesion strength of 15-30 MPa, and Ca/P mole ratio of 0.5-0.7.

Plasma Niobium Surface Alloying of Pure Titanium and its Oxidation at 900 ℃

A niobium-modified layer on pure titanium surface was obtained by means of double glow plasma surface alloying technique. The modified layer was uniform, continuous, compact and well adhered to the substrate. The niobium composition in the modified layer decreased gradually from the surface to the substrate. The oxidation behavior of the niobium-modified layer was investigated and com- pared with the untreated surface at 900 ~C for 100 h. Characterization of the layers was performed using X-ray diffraction and scanning electron microscope, respectively. The test results show that the oxidation behavior of pure titanium was improved by niobium alloying process. Niobium has a positive influence on the oxidation resistance.

Synthesis of TiC Powder by Mechanical Alloying of Titanium and Asphalt

Abstract TiC powder was synthesized by mechanical alloying of titanium and asphalt in this paper. Deoiled asphalt as a carbon source not only provided element C in the fabrication of TiC but also cracked itself by the mechanical alloying process. The results of X-ray diffraction demonstrated the synthesis of cubic TiC. Gas phase chromatography showed that the discharged gas was composed of low molecular weight hydrocarbons, including H2, CH4 and C2H6. The formation mechanism of titanium carbide by mechanical alloying, and the thermodynamic and kinetics were discussed. These results showed that mechanical alloying is a promising method to prepare TiC and to crack asphalt with some light fraction byproducts.

Influence of Electrolyte Composition on the Calcium-Phosphorus compound Coating on Titanium Substrate by Micro-arc Oxidation

The compound bioceramic coating containing calcium (Ca) and phosphorus (P) on titanium alloy substrate was prepared by means of micro-arc oxidation (MAO) treatment. The results show that under the different electrolyte the coating with the color of gray or black and surface morphology of cauliflower or honeycomb, where Ca content and P contain can attain 30% and 20% respectively, can be obtained. Meanwhile, the influences of electrolyte temperature, current density and discharge time on morphology and thickness of coating are also discussed here.

Experimental Study on Titanium Alloy Cutting Property and Wear Mechanism with Circular-arc Milling Cutters

Titanium alloy has been applied in the field of aerospace manufacturing for its high specific strength and hardness.Nonetheless,these properties also cause general problems in the machining,such as processing inefficiency,serious wear,poor workpiece face quality,etc.Aiming at the above problems,this paper carried out a comparative experimental study on titanium alloy milling based on the CAMCand BEMC.The variation law of cutting force and wear morphology of the two tools were obtained,and the wear mechanism and the effect of wear on machining quality were analyzed.The conclusion is that in contrast with BEMC,under the action of cutting thickness thinning mechanism,the force of CAMC was less,and its fluctuation was more stable.The flank wear was uniform and near the cutting edge,and the wear rate was slower.In the early period,the wear mechanism of CAMC was mainly adhesion.Gradually,oxidative wear also occurred with milling.Furthermore,the surface residual height of CAMC was lower.There is no obvious peak and trough accompanied by fewer surface defects.

Effect of hot isostatic pressing processing parameters on microstructure and properties of Ti60 high temperature titanium alloy

Hot isostatic pressing parameters are critical to Ti60 high temperature titanium alloy castings which have wide application perspective in aerospace.In order to obtain optimal processing parameters,the effects of hot isostatic pressing parameters on defects,composition uniformity,microstructure and mechanical properties of Ti60 cast high temperature titanium alloy were investigated in detail.Results show that increasing temperature and pressure of hot isostatic pressing can reduce defects,especially,the internal defects are substantially eliminated when the temperature exceeds 920℃or the pressure exceeds 125 MPa.The higher temperature and pressure can improve the microstructure uniformity.Besides,the higher pressure can promote the composition uniformity.With the temperature increases from 880℃to 960℃,α-laths are coarsened.But with increasing pressure,the grain size of prior-βphase,the widths ofα-laths andα-colony are reduced.The tensile strength of Ti60 alloy is 949 MPa,yield strength is 827 MPa,and the elongation is 11%when the hot isostatic pressing parameters are 960℃/125 MPa/2 h,which exhibits the best match between the strength and plasticity.

Relationships between the precipitation of α_2 ordered phase and alloying elements/electron concentration in α+α_2 titanium alloys

Some experimental α+α2 alloys were prepared by the addition of tin or aluminum elements into Ti-55 alloy. These alloys were designed with varied electron concentration values and named as Sn-rich alloys and Al-rich alloys, respectively. The precipita- tion and growth of α2 ordered phase in the tested alloys under various heat treatment conditions were investigated. Some compari- sons among the experimental results were performed and discussed in detail. Stronger precipitation and growth of α2 ordered phase were caused in Al-rich alloys but relatively weak change in Sn-rich alloys with increasing the electron concentration. The precipita- tion of α2 ordered phase in Al-rich alloys is stronger than that in Sn-rich alloys when the electron concentration value is the same for the two alloys.

Plasma surface alloying of titanium alloy for enhancing burn-resistant property

Conventional titanium alloy may be ignited and burnt under high temperature, high pressure and high gas flow velocity condition. In order to avoid this problem,burn-resistant alloying layers were made on the surface of Ti-6Al-4V and Ti-6.5Al-0.3Mo-1.5Zr-0.25Si titanium alloys by using double glow plasma surface alloying technology (DG Technology). Two typical burn-resistant layers Ti-Cr and Ti-Mo were made by DG plasma chromizing and DG plasma molybdenizing, respectively. Burn-resistant properties were tested by layer ignition method using 2 kW laser machine. Ignition experiments result reveals that the ignition temperature of alloyed layer with Mo and Cr concentration above 10% is about 200℃higher than ignition temperature of Ti-6Al-4V substrate.

Direct ink writing to fabricate porous acetabular cups from titanium alloy

Acetabular cups,which are among themost important implants in total hip arthroplasty,are usually made from titanium alloys with high porosity and adequate mechanical properties.The current three-dimensional(3D)printing approaches to fabricate customized acetabular cups have some inherent disadvantages such as high cost and energy consumption,residual thermal stress,and relatively low efficiency.Thus,in this work,a direct ink writing method was developed to print a cup structure at room temperature,followed by multi-step heat treatment to form microscale porous structure within the acetabular cup.Our method is facilitated by the development of a self-supporting titanium-6 aluminum-4 vanadium(Ti64)ink that is composed of Ti64 particles,bentonite yield-stress additive,ultraviolet curable polymer,and photo-initiator.The effects of Ti64 and bentonite concentrations on the rheological properties and printability of inks were systematically investigated.Moreover,the printing conditions,geometrical limitations,and maximum curing depth were explored.Finally,some complex 3D structures,including lattices with different gap distances,honeycomb with a well-defined shape,and an acetabular cup with uniformly distributed micropores,were successfully printed/fabricated to validate the effectiveness of the proposed method.

Flow Characteristics Analysis of TC18 Titanium Alloy during Hot Deformation Based on Phase Transformation

An accurate flow stress model was established by considering the parameters of strain rate,strain and temperature as well asβ→a+βphase transformation in order to develop the plastic forming theory of TC18 titanium alloy.Firstly,the phase transition kinetics of TC18 titanium alloy during isothermal and continuous cooling at 1073 and 1273 K was studied by thermodynamic calculation,meanwhile,the relationship of volume fraction of phase transition with temperature and time was obtained.Constitutive models were calculated by investigating flow behaviors under hot compression tests with the strain rates of 0.001-1s^(-1) and temperatures of 973-1223 K in the singleβand a+βregions in TC18 titanium alloy,respectively.By combining the phase transformation dynamic kinetics with constitutive models,an accurate flow stress model was established,providing theoretical basis and data support for the hot forging of TC18 titanium alloy.

Effect of Solution-ECAP-Aging Treatment on the Microstructure and Properties of TB8 Titanium Alloy

The microstructure and mechanical properties of the TB8 titanium alloy were controlled by a secondary processing technology of solution-equal channel angular pressing(ECAP)-aging treatment,which combined strong plastic deformation with heat treatment. The effects of ECAP and heat treatment on the microstructure and properties of the titanium alloy were systematically investigated by optical microscopy(OM), scanning electron microscopy(SEM), hardness tests, and tensile property analysis. The results indicate that the metallographic structure without ECAP treatment is mainly equiaxed β-phase, while that after ECAP treatment is equiaxed β-phase with grain fragmentation, slip bands, and new small grains. After 850 ℃ solutionECAP-520 ℃ aging treatment, the titanium alloy has the smallest grain size, while the directionality of tissue growth along the ECAP direction is the most apparent. Under the same solution-aging conditions, the hardness of the titanium alloy increases from 431.5 to 531.2 HV compared to that without ECAP treatment, i e, increases by 23.11%, and the tensile strength increases from 1 045.30 to 1 176.25 MPa, i e, increases by 12.5%.