Surface modification of Ti–6Al–4V alloy for biomineralization and specific biological response: Part I,inorganic modification

Titanium and its alloys represent the gold standard for orthopaedic and dental prosthetic devices, because of their good mechanical properties and biocompatibility. Recent research has been focused on surface treatments designed to promote their rapid osteointegration also in case of poor bone quality. A new surface treatment has been investigated in this research work, in order to improve tissue integration of titanium based implants. The surface treatment is able to induce a bioactive behaviour, without the introduction of a coating, and preserving mechanical properties of Ti6Al4V substrates (fatigue resistance). The application of the proposed technique results in a complex surface topography, characterized by the combination of a micro-roughness and a nanotexture, which can be coupled with the conventional macro-roughness induced by blasting. Modified metallic surfaces are rich in hydroxyls groups: this feature is extremely important for inorganic bioactivity (in vitro and in vivo apatite precipitation) and also for further functionalization procedures (grafting of biomolecules). Modified Ti6Al4V induced hydroxyapatite precipitation after 15 days soaking in simulated body fluid (SBF). The process was optimised in order to not induce cracks or damages on the surface. The surface oxide layer presents high scratch resistance.     

In vivo and in vitro response to electrochemically anodized Ti-6Al-4V alloy

Tissues’ reactions to metals depend on a variety of properties of the metal, most notably surface structure. Anodizing has been shown to alter the surface properties of metal, thus eliciting a change in the biocompatibility of the metal. In order to evaluate the biocompatibility of unoxidized titanium alloy (Ti-6Al-4V) and anodized titanium alloy samples, the samples were implanted in murine abdominal subcutaneous tissues, and maintained for 2 and 4 weeks. The reaction of the abdominal subcutaneous connective tissues to the samples was then assessed. Fibrous connective tissue capsules were observed around the vicinity of the sample, and these capsules were shown to harbor fibroblasts, fibrocytes, and other cells, including neutrophils, macrophages, and giant multinucleated cells. The average thickness of the fibrous capsules observed around the anodized alloy samples was less than that of the capsules seen around samples of the unoxidized titanium alloy. Blood was obtained from the tails of the experimental mice, and blood cell analyses were conducted in order to assess the levels of leukocytes, red blood cells, and thrombocytes. The blood analysis results of the unoxidized control group and treatment group were all within normal ranges. In addition, the biocompatibility of the titanium alloy samples was evaluated using cell culture techniques. The numbers of MG-63 cells cultured on oxidized samples tended to be greater than those in the controls; however, these increases were not statistically significant. The alkaline phosphatase activity of the sample oxidized at 310 V evidenced significantly higher activity than was observed in the control group. These results indicate that the anodized Ti-6Al-4V alloy will be of considerable utility in biomedical applications.     

Types of superplasticm-δ curves of Ti-6Al-4V alloy and their intertransformation

The superplasticm- curves of Ti-6Al-4 alloy have been determined at different temperatures and strain rates; all were of them _L=m _max type, and were of either fundamental, descending or ascending types. The latter two types were transformed from the former through the processes ofm _Lm _O, _LO andm _Lm _F, _LF, respectively. The highest total elongation, _F, was 1150% obtained at 950C and 1.55×10^–3 s^–1. The Chin Liu equation has been applied to all types ofm- curves. The parameters characteristic of all types ofm- curves have been obtained and were found to vary with temperature and strain rate. The total elongation, _F, is determined by the resultant effects of all other parameters, not by a singlem value, theoretically considered to be constant and determined practically by a tensile strain of about 30%–50% (m _30%–50%) as usual.Nomenclature C (=k/k _o ) the normalized slope ofm- curve corresponding to - a material constant corresponding to - m strain-rate sensitivity index corresponding to - m _max maximum on them- curve corresponding to _L - m _min minimum on them- curve corresponding to _L - crosshead speed during the tensile test - the strain of the entire stretching process (has same significance as ordinarily adopted ) - _F total elongation at fracture chosen for the present work - _I intermediate strains including _I1, _I2, _I3, ..., _I(i–1), _Ii , _I(i+1), ..., chosen for the present work - _L limit strain separatingm- curves into sections - _O (=0) starting strain - strain rate - flow stress     

Laser Surface Modification of Ti-6Al-4V with Addition of Pr

The behaviour of oxidation at elevated tem-peratures and fretting in the laser-alloyed layer ofTi-6Al-4V with the addition of Pr was studied.The results show that the addition of Pr changes thestructure of oxide scale of Ti-6Al-4V,controls theshort-range diffusion of oxygen to thescale/substrate interface and increases the adhe-sion and ductility of the scale,thus changing theoxidation kinetics and considerably reducingoxidation rate.The analysis of fretting test showsthat the existence of high hardness layer in the al-loyed zone,fine dendrites perpendicular to the sur-face of the high hardness layer and the oxide scaleproduced during fretting at elevated temperaturesare all beneficial to the improvement of wear resist-ance.     

Multiple α sub-variants and anisotropic mechanical properties of an additively-manufactured Ti-6Al-4V alloy

Additive manufacturing(AM)is a promising material processing method which gains significant momen-tum in the aerospace and biomedical industries.However,the anisotropy in the mechanical properties of additively-manufactured materials is still poorly understood.This study was aimed at elucidating crys-tallographic feature-anisotropy-mechanical property relationship for a Ti-6Al-4V alloy manufactured via selective electron beam melting(SEBM).Abundant α lamellae with six variants were present inside the columnar prior-β grains with a<100>fiber texture during β→α phase transformation.The six αvariants followed the Burgers orientation relationship of{110}β//{0001}α and<1-11>β//<11-20>α.Mul-tiple sub-variants in each α variant were observed for the first time.The anisotropy in the mechanical properties was mainly related to the relative amount of six α variants.While the horizontally-oriented samples had a lower yield strength,they exhibited a higher ductility and longer fatigue life than the vertically-oriented samples.Cyclic softening occurred at higher strain amplitudes,and cyclic stabiliza-tion sustained at lower strain amplitudes.Fatigue crack mainly initiated from the specimen surface at lower strain amplitudes,while multiple crack initiation tended to occur at higher strain amplitudes.Crack propagation was characterized by fatigue striations along with some secondary cracks.     

Modelling the optimum hot workability of TiB reinforced Ti-6Al-4 V alloy by stability maps

Hot workability of Ti-6%Al-4%V and two whisker discontinuously reinforced materials, Ti-6%Al-4%V/1.2%TiB and Ti-6%Al-4%V/8.9%TiB, have been investigated. Hot uniaxial compression tests were carried out using a computer controlled thermomechanical simulator Gleeble machine at temperatures in the range 850 °C to 950 °C and strain rates ranging from 1 to 50 s^?1. The microstructures and the compression test results were compared among the three materials. The Ti-6%Al-4%V/8.9%TiB material presented extensive cracking after deformation. In contrast, the Ti-6%Al-4%V/1.2%TiB material showed an interesting compromise between flow stress and workability. The parameters of the Garofalo equation were calculated for the three materials revealing apparent activation energies that increased with increasing TiB content. The modelling is carried out by stability maps that gives the temperature at a given strain rate to obtain optimal workability and the stresses that has to bear the equipment. Taken 5 s^?1 as a reference strain rate, the temperature required to obtain a quality product increased from about 1143 K (870 °C) for the Ti-6-4 alloy without TiB to 1228 K (955 °C) for the 1.2%TiB and to 1283 K (1010 °C) for the 8.9%TiB material. Therefore, the production of parts of the TiB composites should be conducted at a higher forming temperature to avoid the presence of cracks.     

Thermomechanical Behavior of Ti-6Al-4V Alloy

Ti-6Al-4V, among the Ti alloys, is the most widely used. In the present work, the behavior of Ti-6Ak-4V alloy has beeninvestigated by the uniaxial hot isothermal compression tests and a series of dilatometric experiments were also carried out todetermine the transformation temperatures at different cooling rates. Specimens for hot compression tests were homogenizedat 1050℃ for 10 min and then quickly cooled to different straining temperatures from 1050 to 850℃. Cooling rates were chosenfast enough to prevent high temperature transformation during cooling. Compression tests were conducted at temperaturesfrom 1050 to 850℃ in steps of 50℃ at constant true strain rates of 10~(-3) or 10~(-2) s~(-1). The apparent activation energy forcompression in two-phase region was calculated 420 kJ·mol~(-1). Partial globularization of cr phase was observed in the specimendeformed at low strain rates and at temperatures near the transformation zone and annealed after deformation.     

Influence of alloy element partitioning on strength of primary α phase in Ti-6Al-4V alloy

The partitioning effect of Al(α-phase stabilizer) and V elements(β-phase stabilizer) on strength of the primary α phases in the α/β Ti-6 Al-4 V alloy with the bimodal microstructure was investigated.It was found that partitioning of Al and V elements took place in the Ti-6 Al-4 V alloy during the recrystallization process,leading to the variation of the content of Al and V elements in the primary α phases with changing the volume fraction of the primary α phase.Nanoindentation tests reveal a general trend that the strength of the primary α phases increases with decreasing the volume fraction of the primary α phases,and such trend is independent on the loading direction relative to the c-axis of the α phase.The enhanced strength is attributed to the increase of the content of Al element in the primary α phase,but it is not dominated evidently by the change of the V content.The solid solution strengthening contributed from both the elastic strain introduced by the solute atoms and the variation of the density of states was estimated theoretically.     

Hydrogen Treatment of Cast Ti-6Al-4V Alloy

This paper presents the results of an investiga-tion of the effect of hydrogen treatment onmicrostructures and tensile and low cycle fatigueproperties of a Ti-6Al-4V cast alloy.The phasetransformation and the refining mechanism of thecast microstructure during the process of hydrogentreatment were studied.It was found that afterhydrogen treatment,the coarse Widmanstttenstructure of the as-cast Ti alloy was transformedinto a very fine and equiaxed α+β microstructurewithout any GBα phase.The tensile strength andductility and the low cycle fatigue life of thehydrogen treated specimens were significantly im-proved.     

TEM study of metastable β-phase decomposition in rapidly solidified Ti-6Al-4V alloy

A new rationale is presented for various decomposition products obtained from the metastable -phase found in Ti-6A1-4V alloy produced by hot isostatic pressing comminuted melt-spun fibres and cooled to room temperature by furnace cooling. This alloy has an -matrix with about 8 vol% retained -phase, which is supersaturated with -stabilizers to such an extent that the martensitic transformation has been suppressed. The metastable -phase decomposes by different modes during continuous cooling, depending on the actual composition of individual -grains. Less enrichment of vanadium and iron favours the direct formation of the equilibrium -phase from the -matrix, while greater enrichment of vanadium and iron leads to a spinodal decomposition of the metastable -phase, resulting in a + two-phase structure. During further continuous cooling, the -phase which is lean in -stabilizers will transform into isothermal -phase. In addition, an unknown phase has also been observed in the -phase, which is typified by the appearance of 1/2{112} reflections in the SAD patterns.     

Laser additive manufactured Ti-6Al-4 V alloy: Anodizing and its effects on mechanical properties and corrosion resistance

Ti-6Al-4 V components were developed in different orientations (horizontal and vertical) using an additive manufacturing technique called direct metal laser sintering process and heat treated under 3 different procedures (heat treatment-1, heat treatment-2 and heat treatment-3). Anodizing was done at different voltages (8 V–12 V and 18 V–22 V) in the as-sintered and heat treated conditions. Corrosion test was carried out in artificial saliva. Mechanical properties like tensile strength, elongation were tested; microstructure was analyzed using scanning electron microscopy and chemistry of corrosion products were analyzed using energy dispersive x-ray spectroscopy. The results of corrosion tests have been correlated with the measured tensile strength and ductility. The same is also correlated with the dry sliding wear results published from our earlier research. Anodized (8 V–12 V) horizontal built-heat treatment-3 specimen and anodized (18 V–22 V) horizontal built-heat treatment-2 outperforms other combinations in terms of corrosion. Nevertheless, considering the outcome of mechanical testing, the specimen built in horizontal orientation and anodized at 18 V–22 V is preferred for biomedical applications that needs the combination of both mechanical property and corrosion resistance.     

Effects of heating rate on the alloy element partitioning and mechanical properties in equiaxed α+β Ti-6Al-4V alloy

The effects of heating rate on the alloy element partitioning and mechanical properties during the phase transformation of α-→β in Ti-6Al-4 V alloy under soluti...     

Application of high-pressure torsion to Al-6 %Cu-0.4 %Zr alloy for ultrafine-grain refinement and superplasticity

An Al-6 %Cu-0.4 %Zr alloy was processed by high-pressure torsion to produce an ultrafine-grained structure with a grain size of ~200 nm at the steady-state level where the hardness remains constant with straining. Tensile testing showed that a maximum elongation of ~530 % was attained at 673 K with an initial strain rate of 1 × 10^?3 s^?1. Evaluation of the strain-rate sensitivity and the activation energy for the deformation confirmed that grain boundary sliding through grain boundary diffusion is the rate-controlling process for the superplastic deformation.     

Effect of Si3N4 Addition on the Mechanical Properties, Microstructures, and Wear Resistance of Ti-6Al-4V Alloy

In order to improve the wear resistance of Ti-6Al-4V, different amounts of Si3N4 powder were added into the alloy powder and sintered at 1250℃. Porous titanium alloy with higher wear resistance was successfully fabricated. At sintering temperature, reaction took place and a new hard phase of Ti5Si3 formed. The mechanical properties of the fabricated alloys with different amounts of Si3N4 addition were investigated. The hardness of Ti-6Al-4V, which is the index of wear resistance, was increased by the addition of Si3N4. Amounts of Si3N4 addition have very significant influences on hardness and compressive strength. In present study,titanium alloy with 5 wt pct Si3N4 addition has 62% microhardness and 45% overall bulk hardness increase,respectively. In contrast, it has a 16.4% strength reduction. Wear resistance was evaluated by the weight loss during wear test. A new phase of Ti5Si3 was detected by electron probe microanalyzer （EPMA） and X-ray diffraction （XRD） method. The original Si3N4 decomposed during sintering and transformed into titanium silicide. Porous structure was achieved due to the sintering reaction.     

Accelerated flow softening and dynamic transformation of Ti-6Al-4V alloy in two-phase region during hot deformation via coarsening αgrain

The flow softening is an important phenomenon during hot deformation of metallic materials.In the present work,a more evident flow softening of Ti-6 Al-4 V alloy when deformed in two-phase region was observed in coarser a grain sample,which was attributed to an accelerated dynamic transformation from harder α phase into β phases.Notably,full β microstructure was observed in coarse grain samples at strain of 1.2,while retained a phase was observed in fine a grain specimens.In the views of thermodynamics and crystallographic analysis,the in-depth mechanisms of dynamic transformation were further investigated.     

Microstructural refinement of β-sintered and Ti-6Al-4V porous-coated by temporary alloying with hydrogen

A series of thermochemical treatments, in which hydrogen was used as a temporary alloying element to refine the lamellar microstructure of -sintered and porous-coated Ti-6Al-4V was formulated. Each step of the treatment sequence (hydrogenation, eutectoid decomposition and dehydrogenation) was studied separately, on uncoated specimens and then on porous-coated specimens. The resultant microstructures can have -grain sizes less than 1 m, aspect ratios near unity and discontinuous grain boundary (GB), microstructural attributes which increase the fatigue strength. Microstructural refinement occurs because hydrogen-alloying reduces the (+) transition temperature and enables a eutectoid decomposition reaction to occur. The optimal hydrogenation temperature is 850 °C, because hydrogen concentrations of 0.71 to 0.85 wt% are in-diffused and -transformation is achieved. These weight percentages are in the optimal range for efficient eutectoid decomposition kinetics, -transformation obviates the need for a separate -transformation treatment step. A separate eutectoid decomposition treatment step may be used, or eutectoid decomposition may be combined with dehydrogenation. The finest eutectoid microstructures are obtained if hydrogen concentrations are in the range 0.5 to 0.8 wt%. The criteria for dehydrogenation are efficient removal of hydrogen, with minimal grain growth and absence of GB. These criteria are best met by using dehydrogenation temperatures <700 °C. Altering the sintering temperature or adding a porous coating does not affect the parameters of the hydrogen-alloying treatment steps.     

Surface treatment of new type aluminum lithium alloy and fatigue crack behaviors of this alloy plate bonded with Ti–6Al–4V alloy strap

Samples consisting of new aluminum lithium alloy (Al–Li alloy) plate developed by the Aluminum Company of America and Ti–6Al–4V alloy (Ti alloy) plate were investigated. Plate of 400 mm × 140 mm × 2 mm with single edge notch was anodized in phosphoric solution and Ti alloy plate of 200 mm × 20 (40) mm × 2 mm was anodized in alkali solution. Patterns of two alloys were studied at original/anodized condition. And then, aluminum alloy and Ti alloy plates were assembled into a sample with FM 94 film adhesive. Fatigue crack behaviors of the sample were investigated under condition of nominal stress σ = 36 MPa and 54 MPa, stress ratio of 0.1. Testing results show that anodization treatment modifies alloys surface topography. Ti alloy bonding to Al–Li alloy plate effectively retards crack growth than that of Al–Li alloy plate. Fatigue life of sample bonded with Ti alloy strap improves about 62.5% than that of non-strap plate.     

Microstructural Evolution of Localized Shear Bands Induced during Explosion in Ti-6Al-4V Alloy

Microstructures of the localized shear bands generated during explosion with a thick-walled cylinder specimen in Ti-6Al-4V alloy, were characterized by TEM and SEM. The results show that the twinning is a major mode of deformation, and the distortion-free grains in the bands with the size of 10 μm in diameter were proposed to be the re-crystallization during dynamic explosion. The further observations show that the α→α2 phase transformation may occur in the bands, and this kind of transformation could be confirmed by its dark field image and electron diffraction analysis. Analysis shows that there is specified orientation between the α and α2 Phases.     

Thermo-mechanical sheet metal forming of aero engine components in Ti-6Al-4V—PART 2: Constitutive modelling and validation

In this work constitutive models suitable for thermo-mechanical forming of the titanium alloy Ti-6Al-4V are evaluated. A tool concept for thermo-mechanical forming of a double-curved sheet metal component in Ti-6Al-4V is proposed. The virtual tool design is based on finite element (FE) analyses of thermo-mechanical sheet metal forming in which two different anisotropic yield criteria are evaluated and compared with an isotropic assumption to predict global forming force, draw-in, springback and strain localisation. The shape of the yield surface has been found important and the accuracy of the predicted shape deviation could be slightly improved by including the cooling procedure. The predicted responses show promising agreement with the corresponding experimental observations when the anisotropic properties of the material are considered.