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Hydroxyapatite (HA) coating has been carried out on a titanium alloy Ti–29Nb–13Ta-4.6Zr (TNTZ) to improve the biocompatibility and bioactivity of the alloy in order to attain a high degree of osseointegration and low inflammatory reactions in bone tissue after implantation in orthopedic implant applications. The coating process was carried out using the electrophoretic deposition (EPD) method. TNTZ implants with and without HA coating were installed in the tibia of the Rattus norvegicus Wistar test rats; the test animals were then terminated after two weeks. The degree of osseointegration was measured using a removal torque tester, the Tumor Necrosis Factor-Alpha (TNF-α) level was measured by using the Enzyme-Linked Immunosorbent Assay (ELISA) method, and a histopathological analysis was carried out on the implanted tissue. TNTZ implants with HA coating exhibit significantly higher osseointegration compared to those without HA coating, whereas TNTZ implants without HA coating can trigger significantly higher TNF-α levels. Greater osteogenesis occurs in a bone tissue fitted with TNTZ implants with HA layers. The HA coating on the surface of the TNTZ implant can reduce excessive inflammation, enhance the osteogenesis process, and then improve osseointegration in the bone tissues of test animals. It is also expected to be suitable for orthopedic implant applications.

Li Q., Qi Q., Li J., et al. Low springback and low Young’s modulus in Ti-29-Nb-13Ta-4.6Zr alloy modified by Mo addition. Materials Transactions 60, 1755 (2019); https://doi.org/10.2320/matertrans.ME201912., Deformation-induced higher Young’s modulus can satisfy the contradictory requirements of Ti alloys for spinal-fixation applications, which demand a high Young’s modulus to reduce springback during operations and a low Young’s modulus to prevent stress shielding effect for patients after surgeries. In this study, TNTZ-(1, 3, 5)Mo are designed by adding Mo and Ti to Ti-29-Nb-13Ta-4.6Zr (TNTZ) in order to maintain low initial Young’s modulus and achieve low springback. All the solutionized alloys show single β phase with increasing the β stability by Mo addition. They show low Young’s moduli less than 65 GPa, similar ultimate tensile strength of 650 MPa and elongation around 20%. The springback of TNTZ-3Mo and TNTZ-5Mo is lower than that of TNTZ and TNTZ-1Mo owing to their more stable β phase. After cold rolling, TNTZ-3Mo shows the largest increasing ratio of 25% in Young’s modulus and the highest ultimate tensile strength owning to the appearance of deformation-induced ω phase. With the low initial Young’s modulus of 59 GPa, TNTZ-3Mo is a potential candidate to make the spinal rods in spinal fixation devices.

Oxygen is considered to be an impurity in titanium and its alloys, and it enhances their brittleness. However, oxygen has also been recognized as a useful ingredient to improve the mechanical performance of titanium alloys for biomedical applications, because oxygen is a lightweight interstitial element that is non-toxic and non-allergenic. Some reports show that adding oxygen improves both the strength and the ductility of titanium alloys for biomedical applications. The effects of oxygen addition on the mechanical performance of titanium alloys for biomedical aplications are described.

The growth process of α phase in β-type bio-Titanium alloy TNTZ during aging at 723 K is investigated. The results show that acicular α phase has a Burgers orientation relationship with β matrix of {1−10}β//(0001)α, 〈111〉β//〈11−20〉α. The kinetics equation of acicular α phase length meets l = 333(t-3.95)^0.0764, while the kinetics equation of diameter meets d = 7.50(t-2.83)^0.353. The growth process of α phase can be divided into three stages. During stage I, α phase grows rapidly along both the long direction and the diameter. At beginning of stage I, fine acicular α phase grows with the long direction parallel to each other. Subsequently, α phase grows with another long direction beside the former one in a ‘V-shape’ or in a ‘near perpendicular shape’. During stage II, α phase grows slowly along the diameter, while, the growth along long direction will be gradually restricted with the other α around it. The phase distributes more homogeneously, and present 5 classic possible orientations between α variants. During stage III, α phase grows slowly along the diameter, and stops growing along long direction. The growth of α phase is affected by distortion energy, interface energy and diffusion anisotropy, and it is mainly controlled by Nb diffusion through the ledge riser of the interface between α and β phases.

Deformation-induced ω-phase transformation during tensile deformation was investigated in the developed spinal-support alloy, Ti-9Cr-0.2O. Both preferential single-variant ω transformation along its [0001] direction and growth and/or assembling of uniformly distributed ω particles undergo in the alloy during tensile deformation. It is confirmed that this deformation-induced ω-phase transformation can be triggered by elastic strain or stress without plastic deformation. Furthermore, a re-orientation process works for this transformation; that is, the ω1 variant may re-orientate into the ω2 variant via {001} ⟨110〉 twinning-type mechanism probably related to the external loading condition and the orientations of ω and β phases.

The microstructural evolution and its effect on biocompatibility of TNTZ through HPT processing were investigated systematically in this study. TNTZAHPT shows an enhanced mechanical biocompatibility, which is characterized by a higher tensile strength (1375 MPa) and hardness (450 HV) than those of TNTZST, TNTZAT, and Ti64 ELI while maintaining a relatively low Young’s modulus. In this study, such microstructural refinement of TNTZ and its effect on electrochemical biocompatibility through HPT processing are investigated systematically in this study. The microstructure of TNTZAT consists of randomly distributed needle-like α precipitates in the equiaxed β grains with a diameter of approximately 40 m. The microstructure of TNTZAHPT consists of nanograined (NG) elongated β grains that have subgrains of non-uniform morphologies resulting from distortion by severe torsional deformation. Furthermore, the β grains and subgrains are surrounded by non-equilibrium grain boundaries. The needle-like α precipitates are completely refined to a nanograined. TNTZAHPT exhibits an enhanced combination of excellent corrosion performance and improved cellular response compared to TNTZST, TNTZAT, and Ti64 ELI.

Metastable β-type titanium alloys are highly suitable for use as structural biomaterials applied to hard tissue, i.e., as cortical bone (hereafter, bone) replacing implants. However, their mechanical biocompatibitities, such as the Young’s modulus, strength and ductility balance, fatigue strength, resistance against fatigue crack propagation and fracture toughness, require improvenent for increased compatibility with bone. Through deformation, the metastable β-phase in a metastable β-type titanium alloy is transformed into various phases, such as α’ martensite, α” martensite, and ω-phases with exact phase depending by metastable β-phase stability. In addition, twinning is also induced by deformation. Deformation twinning effectively enhances the work hardening in the metastable β-type titanium alloy, leading to increased strength and ductility. This improvement is accompanied by with other deformation-induced transformations including the appearance of deformation-induced martensite and ω-phase transformation. The enhancement of the mechanical biocompatibility of various materials using the abovementioned deformation-induced transformation is described in this paper, for both newly developed metastable β-type Ti-Mo and Ti-Cr alloys for biomedical applications.

Titanium (Ti) and its alloys are currently getting much attention for structural biomaterials, because they are much advantageous as compared with other metallic biomaterials such as biomedical stainless steels and Co-based alloys, and their practical uses in implant devices are widely spreading. In this paper, types of Ti alloys for biomedical applications are first described. Pure Ti, (α + β)-type, and β-type Ti alloys for biomedical applications including general β-type Ti alloys, superelastic and shape-memory β-type Ti alloys, Young’s modulus self-adjustable β-type Ti alloys, and β-type Ti alloys for reconstructive implants are then described.

Metallic materials are mainly employed for the orthopaedic and dental implants because of high strength and appropriate ductility. Further, the implants are used for long term so that high fatigue strength is one of the most important properties in practical use. In addition, these implants are exposed to human body fluid, which is composed of corrosive liquid for metallic materials. In the case of metallic materials, corrosion sometimes accelerates the fatigue failure, that is, corrosion fatigue. Therefore, the effect of testing environment on fatigue strength should be also considered. In this chapter, the mechanical properties such as tensile properties and fatigue properties of the representative metallic materials for biomedical applications such as stainless steels, cobalt–chromium alloys, and titanium alloys in air and simulated body fluid are reviewed.

Mouthpieces made for brass instruments cause allergic problems to the user, because the ions of the harmful metallic elements are dissolved into the blood via saliva due to corrosion. Therefore, mouthpieces made of nontoxic and allergy-free elements are required. Ti and its alloys are expected to efficiently solve this problem, because they are nontoxic and allergy-free metallic materials. For instance, Ti-Nb and Ti-Ta alloys are selected for making the mouthpiece of the trumpet. Herein, their vibration and sound-damping characteristics are discussed and compared with those for mouthpieces made of pure Ti and brass. Subsequently, the vibration and sound characteristics of the trumpet mouthpiece, with the practical size made of Ti-10Nb by precision casting, are compared with mouthpieces made of pure Ti and brass. Brass instruments, acoustic characteristics, generation principle of sound and role of mouthpiece, development of Ti alloys for trumpet mouthpieces including Young’s modulus (E) and density (ρ), resonant frequency and internal friction, relationship between E/ρ and resonant frequency, and corrosion resistance are discussed in this chapter. Furthermore, fabrication of trumpet mouthpieces using the developed Ti alloys for brass and sound characteristics of the trumpet mouthpiece made of Ti alloy are also discussed in this chapter.

In this chapter, the general behavior of titanium and its alloys is described, with an emphasis on strength level and corrosion resistance. This is followed by a brief discussion of the consumer applications of titanium alloys. Consumer uses are defined as automotive use, sporting applications, backpacking, architecture, firearms and laptops, tools and jewelry, as well as watches and drones.

The effect of oxygen on stability of isothermal omega precipitates in Ti-29Nb-13Ta-4.6Zr was examined using X-ray powder diffraction, transmission electron microscopy, and atom probe tomography. Two alloys with 0.1 and 0.4 mass% oxygen were subjected to single step, and two-step annealing heat-treatments to respectively promote omega and alpha formation. After second step annealing, large volume fraction of omega precipitates was retained in 0.4 mass% O alloy while mainly alpha phase was observed in TNTZ-0.1O. The enhanced stability of omega in the higher oxygen containing TNTZ alloys questions the conventionally accepted understanding that oxygen destabilizes the omega phase in titanium alloys.

In order to develop new low-cost and high-strength β-type titanium alloys, a Ti–13Mn was fabricated by metal injection molding. For improving its tensile strength, Ti–13Mn was subjected to cold-rolling at reduction ratios of 60% and 90%, respectively. The solutionized Ti–13Mn has pores and titanium carbide (Ti carbide) precipitates and consists of a β phase and an athermal ω phase. The porosity of the alloy decreases from 6.1% to 0.01% after cold-rolling at a reduction ratio of 90%. Moreover, during cold-rolling, the Ti carbides are fragmented and a deformation-induced ω phase is formed. The ultimate tensile strength, 0.2% proof stress, Vickers hardness, and Young's modulus of Ti–13Mn increase from 888 MPa to 1852 MPa, from 827 MPa to 1823 MPa, from 279 Hv to 461 Hv, and from 96 GPa to 108 GPa, respectively, after cold-rolling at a reduction ratio of 90%. On the other hand, the elongations of both the solutionized and cold rolled Ti–13Mn are less than 2%. Although the elongation of Ti–13Mn is less than 2%, the tensile strength of the cold rolled Ti–13Mn is extremely high compared with that of existing titanium alloys. This large-improvement in the tensile strength of the cold rolled Ti–13Mn is attributed to the increase in the dislocation density, decrease in grain size, decrease in porosity, and formation of a deformation-induced ω phase.

The alloy Ti–9Cr–0.2O has been developed as a potential material for implant rods used in spinal fixation applications, since it exhibits good mechanical properties and a remarkably “changeable Young's modulus”, which is achieved by suppressing the athermal ω-phase formed upon quenching and enhancing the deformation-induced ω-phase transformation. In this study, athermal and deformation-induced ω-phase transformations in Ti–9Cr–0.2O were investigated systematically by transmission electron microscopy. This was done in order to understand the nature of these ω-phase transformations, as well as the specific functionality—the “changeable Young's modulus”—resulting from them. In solution-treated alloy samples, in addition to ideal ω-structures, structures considered as initial ω-structures associated with incommensurate ω-phase were observed. This might be attributed to the composition heterogeneity, heterogeneity of oxygen distribution, and/or the inhomogeneous distribution of defects such as vacancies and locally strained areas. Following cold rolling, some of the selected area electron diffraction patterns of the alloy showed that the reflections of one ω-variant had increased significantly in intensity while those of the other ω-variant had decreased sharply. This vanishing of one type of variant ω-structures is attributable to two possible mechanisms: (i) a reversal mechanism, under which the particular partial dislocations transform the corresponding ω-variants back into β-phase or (ii) a re-orientation mechanism, according to which the ω-variants unfavorable with regard to the loading direction re-orient and turn into the preferred ω-variants.

Biomedical titanium alloys with Young’s moduli close to that of cortical bone, i.e., low Young’s modulus titanium alloys, are receiving extensive attentions because of their potential in preventing stress shielding, which usually leads to bone resorption and poor bone remodeling, when implants made of their alloys are used. They are generally β-type titanium alloys composed of non-toxic and allergy-free elements such as Ti–29Nb–13Ta–4.6Zr referred to as TNTZ, which is highly expected to be used as a biomaterial for implants replacing failed hard tissue. Furthermore, to satisfy the demands from both patients and surgeons, i.e., a low Young’s modulus of the whole implant and a high Young’s modulus of the deformed part of implant, titanium alloys with changeable Young’s modulus, which are also β-type titanium alloys, for instance Ti–12Cr, have been developed. In this review article, by focusing on TNTZ and Ti–12Cr, the biological and mechanical properties of the titanium alloys with low Young’s modulus and changeable Young’s modulus are described. In addition, the titanium alloys with shape memory and superelastic properties were briefly addressed. Surface modifications for tailoring the biological and anti-wear/corrosion performances of the alloys have also been briefly introduced.

Although Electron Beam Melting (EBM) is an innovative technology, the fatigue properties of materials manufactured by EBM may be lower than those of casted and wrought materials due to defects and surface roughness. In order to enhance the fatigue life of components or structures manufactured by EBM, a mechanical surface treatment technology, e.g., peening, would be effective because peening introduces high compressive residual stress at the surface which can extend the fatigue life considerably. In the present study, specimens were manufactured by EBM using titanium alloy Ti-6Al-4V powder. Two types of specimens were prepared: as-built and as-machined specimens. Specimens of each type were treated by cavitation peening or shot peening. The fatigue lives of the specimens were evaluated by a plate bending fatigue tester. The residual stress and surface roughness were also evaluated. The results obtained showed that the fatigue strength of as-built specimens can be improved by 21% by cavitation peening or shot peening, and the fatigue life under particular applied stresses can also be extended by 178% by cavitation peening.

Proper surface characteristics for a titanium implant are crucial for the formation of different cellular protrusions known as filopodia and lamellipodia, both of which have a significant impact on cell attachment, spreading, migration, and proliferation. Microstructural features such as grain boundaries and defects of implant surface can modulate the cellular components and structure at the leading edge of cells. Here, a nano-grained Ti–29Nb–13Ta–4.6Zr (NG TNTZ) substrate was produced by high-pressure torsion (HPT) for improved biofunctionality. Cellular response of human osteoblast cells on nano-grained TNTZ substrates is evaluated and compared with the cellular response of those on coarse-grained TNTZ. High wettability, which depends on high internal energy due to the nano-sized grains that are full of boundaries, interfaces, and high dislocation density, influenced the hOBs cells on NG TNTZ to form highly developed cellular protrusions. Large number of filopodia protrusions resulted in excellent cell attachment as consistent with high level of vinculin and superior cell proliferation. This study demonstrates the advantages of nanocrystalline surface modification using HPT for processing metallic biomaterials that are proper for orthopedic implants.

In this study, beta( )type Ti-29Nb-13Ta-4.6Zr alloys coated with biphasic calcium phosphate (BCP) reinforced with rutile-TiO2 compounds by sol-gel technique to evaluate its possible usage in biomaterial science. Calcium nitrate tetrahydrate (Ca(NO3)(2)center dot 4H(2)O), di-ammonium hydrogen phosphate (NH4)(2)HPO4), ammonium hydroxide (NH4OH), and titanium (IV) propoxide (Ti(OC3H7)(4)) (Merck, Germany) were used as precursors for producing the BCP-only and BCP/TiO2 composite coatings. Synthesis and coating procedure, surface morphology, adhesion strength, and corrosion results of the coated samples have been investigated in details. XRD technique has been used in order to characterization of BCP phases. The morphological observations of coatings were determined by using a scanning electron microscopy (SEM). In-vitro corrosion behaviors of the coatings have been determined with polarization method in Ringer's electrolyte at body temperature. It was found that the BCP/TiO2 coating synthesized on TNTZ alloy has higher scratch resistance than BCP-only coating due to its containing rutile-TiO2 compounds. In addition, it can be said that the BCP/TiO2 coated sample was less susceptibility to corrosion than the BCP-only coatings and uncoated TNTZ sample in simulated body fluid. In this study, β type Ti?29Nb?13Ta?4.6Zr alloys coated with biphasic calcium phosphate (BCP) reinforced with rutile-TiO2 compounds by sol-gel technique to evaluate its possible usage in biomaterial science. Calcium nitrate tetrahydrate (Ca(NO3)2•4H2O), di-ammonium hydrogen phosphate (NH4)2HPO4), ammonium hydroxide (NH4OH), and titanium (IV) propoxide (Ti(OC3H7)4) (Merck, Germany) were used as precursors for producing the BCP-only and BCP/TiO2 composite coatings. Synthesis and coating procedure, surface morphology, adhesion strength, and corrosion results of the coated samples have been investigated in details. XRD technique has been used in order to characterization of BCP phases. The morphological observations of coatings were determined by using a scanning electron microscopy (SEM). In-vitro corrosion behaviors of the coatings have been determined with polarization method in Ringer’s electrolyte at body temperature. It was found that the BCP/TiO2 coating synthesized on TNTZ alloy has higher scratch resistance than BCP-only coating due to its containing rutile-TiO2 compounds. In addition, it can be said that the BCP/TiO2 coated sample was less susceptibility to corrosion than the BCP-only coatings and uncoated TNTZ sample in simulated body fluid.

Along with a high strength, ductility, and work hardening rate, a variable Young’s modulus is crucial for materials used as implant rods in spinal fixation surgery. The potential in this context of Ti–(9, 8, 7)Cr–0.2O (mass%) alloys is reported herein. The microstructural and mechanical properties of the alloys were systematically examined as a function of their chromium content, and the ion release of the optimized alloy was investigated to assess its suitability as an implant material. In terms of the deformation-induced ω-phase transformation required for a variable Young’s modulus, the balance between β-phase stability and athermal ω-phase content is most favorable in the Ti–9Cr–0.2O alloy. In addition, this composition affords a high tensile strength (>1000 MPa), elongation at break (∼20%), and work hardening rate to solution-treated (ST) samples. These excellent properties are attributed to the combined effects of deformation-induced ω-phase transformation, deformation twinning, and dislocation gliding. Furthermore, the ST Ti–9Cr–0.2O alloy proves resistant to metal ion release in simulated body fluid. This combination of a good biocompatibility, variable Young’s modulus and a high strength, ductility, and work hardening rate is ideal for spinal fixation applications. Statement of significance Extensive efforts have been devoted over the past decades to developing β-type titanium alloys with low Young’s moduli for biomedical applications. In spinal fixation surgery however, along with excellent mechanical properties, the spinal-support materials should possess high Young’s modulus for showing small springback during surgery to facilitate manipulation but low Young’s modulus close to bone once implanted to avoid stress shielding. None of currently used metallic biomaterials can satisfy these abovementioned requirements. In the present study, we have developed a novel alloy, Ti–9Cr–0.2O. Remarkably variable Young’s modulus and excellent mechanical properties can be achieved in this alloy via phase transformations and complex deformation mechanisms, which makes the Ti–9Cr–0.2O preferred material for spinal fixation surgery.

A β-type Ti–29Nb–13Ta–4.6Zr (TNTZ) alloy containing various amounts of TiB reinforcements has been developed to achieve higher fatigue strength for biomedical applications. Fatigue tests were performed at room temperature, and the effects of TiB on fatigue crack initiation and propagation were investigated. The results indicate that the fatigue limit of the TNTZ alloy was substantially improved by the TiB reinforcements. However, the fatigue strength first increased and subsequently decreased as the B concentration increased. TNTZ alloy with 0.10% B has the largest fatigue limit, which is 67% greater than that of the TNTZ alloy. The effects of TiB on the improvement of the fatigue properties are due to the following two factors. First, sliding of the dislocations can be blocked by TiB particles, which results in resistance to fatigue crack initiation. In addition, the crack deflection and crack bridging by the TiB particles could delay the crack propagation. Conversely, debonding of some larger TiB particles may occur, especially when the B concentration is higher than 0.20%. Therefore, the crack initiates from the debonding of the TiB particles and easily propagates along the voids from the interfacial decohesion, which could exert a deleterious influence on the fatigue strength.

The predominant factor determining the wear properties of a new titanium alloy, Ti–29Nb–13Ta–4.6Zr (TNTZ) and a conventional titanium alloy, Ti–6Al–4V extra-low interstitial (Ti64) was investigated for TNTZ and Ti64 combinations in metal-to-metal contacting bio-implant applications. The worn surfaces, wear debris, and subsurface damages were analyzed using a scanning electron microscopy combined with energy-dispersive spectroscopy and electron-back scattered diffraction analysis. The volume loss of TNTZ is found to be larger than that of Ti64, regardless of the mating material. The wear track of TNTZ exhibits the galled regions and severe plastic deformation with large flake-like debris, indicative of delamination wear, which strongly suggests the occurrence of adhesive wear. Whereas, the wear track of Ti64 have a large number of regular grooves and microcuttings with cutting chip-like wear debris and microfragmentation of fine oxide debris, indicative of abrasive wear combined with oxidative wear. This difference in the wear type is caused by severe and mild subsurface deformations of TNTZ and Ti64, respectively. The lower resistance to plastic shearing for TNTZ compared to that of Ti64 induces delamination, resulting in a higher wear rate.

Ti-29Nb-13Ta-4.6Zr (TNTZ) alloy has been extensively studied as it is promising for use in biomedical applications. Despite its potential, the effects of warm plastic deformation on the alloy have not yet been revealed. This study investigated the differences in phase constitution of two warm-deformed TNTZ alloys and revealed relevant mechanisms with particular attention to martensitic transformation. The influence of phase constituents on mechanical characteristics was discussed as well. The TNTZ alloy deformed at 823 K possessed α, β, and ω phases as well as α″ martensite, and demonstrated a low Young’s modulus and double-yielding phenomenon. In contrast, the alloy deformed at 723 K had no martensite but more ω phase, leading to increased strength, hardness, and Young’s modulus. The absence of α″ martensite in the alloy deformed at 723 K was interpreted in light of β-stability of the parent phase and reduced Ms temperature.

In order to elucidate the microstructural refinement mechanism and the effect of secondary phase on the microstructural evolution of β -type titanium alloy, severe plastic deformation was conducted on samples of a precipitation-hardened Ti–29Nb–13Ta–4.6Zr (TNTZ). Specifically, TNTZ that was precipitation-hardened through an aging treatment (TNTZ AT ) was subjected to high-pressure torsion (HPT) processing (TNTZ AHPT ). The microstructure of TNTZ AHPT , which has been evaluated as a function of the torsional rotation number, N , exhibits ultrafine elongated β grains. The needle-like α precipitates in TNTZ AT , which exhibit a diameter of approximately 12 nm, are homogeneously distributed within the β grains. The dislocation density and subgrain diameter, estimated by X-ray line profile analysis, saturate at approximately 4.2 × 10 16 m −2 and 12.2 nm, respectively, at N ⩾ 10. The β grains contain nanostructured subgrains having non-uniform morphologies surrounded by blurred and wavy boundaries. A saturated hardness distribution at approximately 450 HV indicates that microstructural homogeneity has been achieved at N ⩾ 10. The α precipitates enhance the β grain refinement and microstructural homogeneity is achieved in TNTZ AHPT at N ⩾ 10, whereas this occurs at later stages ( N > 20) in TNTZ which is solution-treated and therefore does not contain any α precipitates.

A novel β-type titanium alloy Ti–29Nb–13Ta–4.6Zr (TNTZ) has been developed and extensively researched to achieve highly desirable mechanical properties such as a high strength while maintaining a low Young’s modulus that is close to that of bone, as an alternative candidate for conventional titanium metallic biomaterials such as Ti-6Al-4V ELI. Therefore, strengthening by grain refinement and increasing dislocation density is expected to provide TNTZ high mechanical strength while keeping a low Young’s modulus because they keep the original β phase. In this case, severe plastic deformation, such as high-pressure torsion (HPT) processing, is a potential treatment for obtaining these properties. Furthermore, HPT processing is effective for producing ultrafine-grained TNTZ having high dislocation density in single β structure. The obtained promising results, which are a tensile strength of around 1100 MPa and a Young's modulus of around 60 GPa, motivated that the above mentioned mechanical properties can be achieved by microstructural refinement through HPT processing However, the mechanism of microstructural refinement is unclear for TNTZ during HPT processing. Therefore, the aim of this study is to investigate microstructural changes of TNTZ through HPT processing by X-ray diffraction analysis and transmission electron microscopy. The microstructures of TNTZ subjected to cold rolling (TNTZCR) and HPT processing (TNTZHPT) comprised single β grains; however, the intense β {110} peak reveals that the preferred orientation is β for TNTZHPT. While the microstructure of TNTZCR shows a comparatively high dislocation density (2.3 x 10

Materials used for implant rods in spinal fixation systems must show changeable Young’s moduli, high strength and large elongation-to-failure. A d-electron design method was used to determine the chemical composition of Ti–10Cr, which showed all these properties and significant work-hardening characteristics owing to multiple plastic deformation mechanisms, such as deformation-induced ω-phase transformation, {3 3 2} mechanical twinning and dislocation gliding. Therefore, Ti–10Cr exhibits great potential for use in spinal fixation applications.

The wear mechanisms of conventional Ti–6Al–4V extra-low interstitial (Ti64) and the new Ti–29Nb–13Ta–4.6Zr (TNTZ) were studied to investigate the wear properties of Ti64/TNTZ for application in spinal fixation devices. Ti64 and TNTZ balls and discs were first prepared as wear-test specimens. A ball-on-disc frictional wear-testing machine was used in air to perform the frictional wear tests of the Ti64 and TNTZ discs mated against Ti64 and TNTZ balls. The wear mechanisms were investigated using a scanning electron microscopy to analyze the worn surfaces and wear debris. The volume losses for the TNTZ discs were larger than those for the Ti64 ones, regardless of the mating ball material. Furthermore, the morphologies of the wear tracks and the debris of the Ti64 and TNTZ discs were different, suggesting that the wear mechanisms for the Ti64 and TNTZ discs were abrasive and delamination wear caused by mild and severe subsurface deformations of the Ti64 and TNTZ, respectively, regardless of the mating ball material.

Recently, low-modulus β-type titanium alloys have been the focus of considerable attention because of their high biocompatibility and their low moduli that make them effective for inhibiting bone atrophy and for enhancing bone remodeling. However, the biofunctinalities of titanium alloys, such as bone conductivity, blood compatibility, and soft tissue compatibility, are poor. Therefore, surface modification techniques such as bioactive ceramic surface modification and blood-and soft-tissue-compatible polymer surface modification are applied to titanium alloys. Hydroxyapatite (HAp) surface modification via metal organic chemical vapor deposition (MOCVD) and segmented polyurethane (SPU) surface modification via silane coupling treatment are effective techniques to add biofunctionalites to titanium alloys. HAp surface modification via MOCVD and SPU surface modification using three kinds of silane coupling agents on a low modulus beta-type titanium alloy, namely, TNTZ, are discussed. Moreover, the bonding strengths of HAp and SPU on the surface of TNTZ, which are important parameters, are also discussed.

Beta-type Ti-29Nb-13Ta-4.6Zr (TNTZ) was recently developed as a representative biomedical Ti alloy. As-solutionized TNTZ has a low Young’s modulus less than 60 GPa close to that of cortical bone along with very low cytotoxicity and good bone biocompatibility. Solution treatment and aging (STA) is a typical heat treatment for improving the mechanical properties of beta-type titanium alloys. However, STA also drastically increases the Young’s modulus. Therefore, this study investigated the effects of surface modification, micro-shot peening, on the mechanical properties of TNTZ subjected to severe thermomechanical treatment in order to maintain a relatively low Young’s modulus. The bone contact characteristics of TNTZ samples subjected to surface modification and cancellous bone were also compared. The Vickers hardness of cold-swaged TNTZ (TNTZSW) subjected to micro-shot peening was significantly increased within 20 mm from the very edge of the specimen surface. The fatigue strength of TNTZSW subjected to micro-shot peening increased especially in the high cycle fatigue life region. The fatigue limit was around 400 MPa. The bone formations on TNTZSW subjected to micro-shot peening and TNTZSW with the mirror surface as comparison material were almost identical to each other. However, the relative bone contact ratio of TNTZSW subjected to micro-shot peening was better than that of TNTZSW with the mirror surface.

β-type titanium alloys such as a Ti–29Nb–13Ta–4.6Zr alloy (TNTZ) are potential candidates for next-generation metallic biomaterials. However, the mechanical strength of β-type titanium alloys with a single β phase is not enough to be approved as materials for fabricating medical implant devices that are subjected to heavy loads, such as a spinal fixation device. Therefore, β-type titanium alloys are often subjected to aging treatments in order to improve their mechanical strength through precipitation hardening. However, β-type titanium alloys exhibit a heterogeneous microstructure because of microscale elemental segregation. In this study, the heterogeneous microstructure caused by the microsegregation of secondary phases was characterized by field emission scanning electron microscopy (FESEM) in TNTZ subjected to aging treatments. Furthermore, the influence of the heterogeneous distribution of secondary phases in TNTZ on mechanical properties was revealed by comparing its properties to the homogeneously structured TNTZ subjected to long-term homogenization.

The wear mechanisms of a conventional titanium alloy, Ti–6Al–4V extra-low interstitial (Ti64), and a new titanium alloy, Ti–29Nb–13Ta–4.6Zr alloy (TNTZ) were studied to investigate the wear properties of a Ti64/TNTZ combination for spinal fixation devices. Balls and discs made of Ti64 and TNTZ were prepared to be used as wear-test specimens. Frictional wear tests of Ti64 and TNTZ discs were carried out against Ti64 and TNTZ balls in air using a ball-on-disc frictional wear testing system. The wear mechanisms were investigated by analysis of worn surfaces and wear debris using scanning electron microscopy. Volume losses of the TNTZ discs were found to be larger than those of the Ti64 discs, regardless of mating ball. Furthermore, the morphologies of wear tracks and debris were found to be different between TNTZ and Ti64 discs. It is considered that the wear mechanism for a Ti64 disc is oxidative wear, whereas that for a TNTZ disc is delamination wear, regardless of mating ball material.

A novel β-type, Ti-29Nb-13Ta-4.6Zr, referred to as TNTZ has been developed for biomedical applications. Its fatigue strength is one of the most important mechanical biocompatibilities of TNTZ because, in surgical applications, it will be used under cyclic loading conditions. The effect of the microstructural refinement by high-pressure torsion (HPT) on the fatigue behaviour of TNTZ is systematically investigated in this study. TNTZ subjected to HPT processing where the rotation number (N) is 20 (TNTZAHPT) after aging treatment (AT) shows a unique microstructure having ultrafine elongated grains (285 nm in length and 36 nm in width) with high-density dislocations, a large fraction of blurred and wavy boundaries consisting of non-uniform subgrains with high misorientation and nanostructured precipitated α phase. Remarkably, a good combination of high mechanical strength (1375 MPa) and low Young’s modulus (87 GPa), compared to that of Ti-6Al-4V (Ti64) ELI, is achieved for TNTZAHPT at N = 20. TNTZAHPT a great fatigue strength, which is comparable to those of (Ti64) ELI.

In order to reduce the anisotropy of mechanical properties of a coilable thin sheet of (α+β)-type titanium alloy, Ti–4.5Al–2Mo–1.6V–0.5Fe–0.3Si–0.03C (Ti9), for use in aircraft applications, duplex heat treatments were examined. In each duplex heat treatment, the first heat treatment controls the volume fraction of the primary α phase and orientation of the acicular α phase in (α+β) two-phase area between the primary α grains, whereas the second heat treatment stabilizes the α and β phases. The microstructure of the Ti9 sheet after the duplex heat treatment was analyzed by optical microscopy, pole-figure measurement through X-ray diffraction, and electron backscatter diffraction. The mechanical properties of the duplex heat-treated Ti9 sheet were evaluated by tensile tests. The Ti9 sheet was heat treated to obtain two different types of microstructures. A microstructure consisting of acicular α phase in the β grains was obtained by a first heat treatment above the β transus (1273 K) followed by water quenching and a second heat treatment at 973 K. A microstructure consisting of equiaxed primary α grains and an (acicular α+β) two-phase area between the primary α grains was obtained by heating below the β transus (1123–1223 K) followed by water quenching and a second heat treatment at 973 K. The volume fraction of the primary α grains decreased and the volume fraction of the acicular α phase with 12 variants increased instead of increasing first heat-treatment temperature, suppressing the alignment of the c axis of the α lattice parallel to the transverse direction within the rolling plane (T-texture formation) as a result. Anisotropy of the tensile properties can be decreased by increasing the first heat-treatment temperature because the T texture was decreased.

Some newly developed β-type titanium alloys for biomedical applications exhibit distinctive heterogeneous structures. The formation mechanisms for these structures have not been completely revealed; however, understanding these mechanisms could lead to improving their properties. In this study, the heterogeneous structures of a Ti-29Nb-13Ta-4.6Zr alloy (TNTZ), which is a candidate for next-generation metallic biomaterials, were analyzed. Furthermore, the effects of such heterogeneous structures on the mechanical strength of this alloy, including fatigue strength, were revealed by comparing its strength to that of homogenous TNTZ. The heterogeneous structures were characterized micro-, submicro- and nano-scale wave-like structures. The formation mechanisms of these wave-like structures are found to be different from each other even though their morphologies are similar. It is revealed that the micro-, submicro- and nano-scale wave-like structures are caused by elemental segregation, crystal distortion related to kink band and phase separation into β and β', respectively. However, these structures have no significant effect on both tensile properties and fatigue strength comparison with homogeneous structure in this study.

Beta-type Ti-29Nb-13Ta-4.6Zr (TNTZ), which is a recently developed biomedical titanium alloys, shows a relatively low Young’s modulus of around 60GPa when subjected to a solution treatment. However, our focus in this study was on the practical applications of TNTZ in vivo because its mechanical strength decreases with solution treatment progress. Therefore, we investigated the effect of fine particle bombarding (FPB) on the mechanical properties of TNTZ subjected to a cold-swaging treatment in order to maintain its relatively low Young’s modulus and to improve its mechanical properties. The relative bone contact ratios between the cancellous bones of Japanese white rabbits and column-shaped TNTZ samples subjected to FPB were also evaluated. The microstructure of cold-swaged TNTZ showed a single beta-phase with a marble-like structure. Moreover, its Vickers hardness did not increase remarkably with changes in its diameter, although the average diameter of the beta-grains of solutionized TNTZ ranged from 5.0 to 20 μm, depending on the increase in the holding time of the solution treatment. The Vickers hardness and Young’s modulus of TNTZ subjected to FPB increased at the edge of the specimen surface to be around 70% and 15%, respectively, more than those of cold-swaged TNTZ. Further, the fatigue strength of TNTZ subjected to FPB became significantly higher than that of cold-swaged TNTZ in the high-cycle fatigue life region. Lastly, TNTZ with a rough surface texture (Ra: 0.65μm) showed a relative bone contact ratio of more than 80% after undergoing FPB; this value was significantly higher than that of cold-swaged TNTZ with a very smooth surface texture (Ra: 0.07 μm). [doi:10.2320/matertrans.M2014349]

Ti-29Nb-13Ta-4.6Zr (TNTZ) is a novel β-type titanium alloy that has great potential use in biomedical implants because of its relatively low Young’s modulus (around 60 GPa), which minimise bone atrophy due to stress shielding. However, the biocompatibility and bio-functionality of TNTZ is poor. Therefore, a bioactive ceramic surface modification or soft-tissue-compatible polymer surface modification is advantageous for enhancing the biological properties of TNTZ. The bio-functionality of TNTZ itself, and that modified with a coating hydroxyapatite (HAp) using alkali treatment, electrochemical treatment, and dip-coating treatment with calcium phosphate glass ceramic or metal organic chemical vapour deposition (MOCVD) is assessed. In addition, modification of TNTZ with soft-tissue-compatible segmented polyurethane (SPU) using different silane coupling agents is described. The bonding strength of the bioactive ceramic and soft-tissue compatible polymer with the TNTZ is assessed with respect to variations in surface roughness.

Titanium alloy, especially titanium type Ti-12Cr for biomedical application has been a concern of many researchers recently. This titanium has excellent biocompatibility and controllable mechanical properties. Generally, titanium β type contains many alloying elements that lead to a high price. Therefore, it is interesting to develop β type with only one cheap alloying element such as Ti-12Cr that is designed as a low-cost implant material. Initially, Ti-12Cr has been developed, in particular for spinal fixation. Nowadays, the research of Ti-12Cr emphasizes only on mechanical properties. The corrosion behavior of this alloy has not been understood well yet. Therefore, corrosion characteristics of this alloy in any circumstances are necessary to investigate. This paper reports the corrosion behavior of Ti-12Cr in a salted environment using the weight loss method. Ti-12Cr samples were immersed in a 3% NaCl solution for 2, 4, and 6 weeks. Samples consist of Ti-12Cr (as-received), Ti-12Cr (ST) and Ti-12Cr (AT 30 ks). Weight of samples was measured before and after the immersing process using the digital balance. Microstructure and composition of the sample surfaces were examined by using SEM and EDX, respectively. The lowest corrosion rate after exposure for 6 weeks while the highest one is Ti-12Cr (as-received) is Ti-12Cr (AT 30 ks) that is 0,003 mmpy. The microstructure all of the samples shows black spots in the surfaces indicating corrosion has been started to occur on the samples. It was found that the corrosion is due to destruction of the chrome-oxide layer in some weak point as a result of a chemical reaction between the metal (Cr) with Cl- ions. Some oxides are formed on the surface of titanium, as indicated by a significant increment of oxygen content is the corrosive sample surface. This study indicates the corrosion resistance of Ti-12Cr (AT 30 ks) is much better than other materials in this research.

A novel β-type titanium alloy with a changeable Youngs modulus, that is, with a low Young's modulus to prevent the stress-shielding effect for patients and a high Young's modulus to suppress springback for surgeons, should be developed in order to satisfy the conflicting requirements of both the patients and surgeons in spinal fixation operations. In this study, the oxygen content in ternary Ti-11Cr-O alloys was optimized in order to achieve a large changeable Young's modulus with good mechanical properties for spinal fixation applications. The increase in Youngs moduli of all the examined alloys by cold rolling is attributed to the deformation-induced ω-phase transformation which is suppressed by oxygen. Among the examined alloys, the Ti-11Cr-0.2O alloy exhibits the largest changeable Youngs modulus and a high tensile strength with an acceptable plasticity under both solution-treated (ST) and cold-rolled (CR) conditions. Therefore, the Ti-11Cr-0.2O alloy, which shows a good balance among a changeable Youngs modulus, high tensile strength and good plasticity, is considered a potential candidate for spinal fixation applications.

The fatigue strength of the newly developed β-type titanium alloy Ti-29Nb-13Ta-4.6Zr (referred to as TNTZ) is important for its applications in spinal fixation rods. Enhancements in the fatigue strength of TNTZ upon solution treatmnet and thermo-mechanical processing (aging after severe cold-caliber rolling or sever cold-swaging) have been investigated. Aging the rods at 723 K for 259.2 ks after cold-swaging is shown to be the optimal thermo-mechanical processing method for the TNTZ rod , yeilding a high 0.2% proof stress of about 1200 MPa, high elongation of 18%, and high fatigue strength of 950 MPa. High springback is undesirable for application of TNTZ spinal-fixation rods. To reduce springback, a High Youngs modulus is required; on the other hand, a low Youngs modulus is beneficial to reduce bone absorption and obtain good bone remodeling. To achieve a balance between these two factors, TNTZ has been modified by adding Cr to obtain an alloy with a high Youngs modulus at the deformed region and a low Youngs modulus throughout the undeformed region. TNTZ-8Ti-2Cr and TNTZ-16Ti-4Cr are novel alloys whose β phase is more stable than that of TNTZ. Only the β phase is present in these alloys, which exhibit relatively low Youngs moduli of

For spinal-fixation applications, implants should have a high Young's modulus to reduce springback during operations, though a low Young's modulus is required to prevent stress shielding for patients after surgeries. In the present study, Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) with a low Young's modulus was modified by adding Cr to obtain a higher deformation-induced Young's modulus in order to satisfy these contradictory requirements. Two newly designed alloys, TNTZ-8Ti-2Cr and TNTZ-16Ti-4Cr, possess more stable β phases than TNTZ. These alloys consist of single β phases and exhibit relatively low Young's moduli of65GPa after solution treatment. However, after cold rolling, they exhibit higher Young's moduli owing to a deformation-induced ω-phase transformation. These modified TNTZ alloys show significantly less springback than the original TNTZ alloy based on tensile and bending loading-unloading tests. Thus, the Cr-added TNTZ alloys are beneficial for spinal-fixation applications.

The biomedical β -type titanium alloy Ti–29Nb–13Ta–4.6Zr (TNTZ) exhibits non-toxicity and a low Young’s modulus that is similar to that of bone. This alloy has a low Young’s modulus because it contains a metastable β phase. Strengthening due to grain refinement tends to provide high mechanical strength, while keeping the Young’s modulus low, because it maintains the original β phase. In this case, severe plastic deformation, such as High-Pressure Torsion (HPT), is a potential treatment for obtaining these properties simultaneously. Thus, in this study, the effect of HPT on the microstructure and hardness of TNTZ was systematically investigated. On the cross sections of TNTZ subjected to HPT, heterogeneous microstructures, consisting of a matrix and an unetched band not corroded by an etching solution, were observed. Both the matrix and the unetched band were comprised of a single β phase with submicron-sized grains, but their grain geometries differed: equiaxed grains and elongated grains are observed in the matrix and the unetched band, respectively. The hardness distribution in the cross section of TNTZ subjected to HPT is also heterogeneous; the hardness is higher in the matrix than in the unetched band, when the number of HPT rotations is small.

This paper is a review of results for Ti-Mn [1], Ti-Mn-Al [2] and Ti-Mn-Fe [3] alloys that have been previously published. Titanium alloys, especially beta-type titanium alloys, have high specific strength, excellent corrosion resistance and good biocompatibility. Unfortunately, applications of titanium alloys are limited by their relatively higher cost. One reason is the use of rare and expensive metallic elements, such as vanadium and molybdenum, as a beta stabilizer. In order to reduce the cost, inexpensive and abundantly available metallic elements should be used as beta stabilizers. Manganese was adopted as a beta stabilizer because it is an abundant metallic element in the Earth’s crust and is relatively low in cost. The heat treatment behavior of Ti-Mn, Ti-Mn-Al and Ti-Mn-Fe alloys was investigated through electrical resistivity and Vickers hardness measurements, X-ray diffraction measurements to identify phase constitution, and observations using a light microscope [1], [2] and [3].

β-type titanium alloys comprising low cost elements such as Fe, Mn, Cr, Sn, Al, O and N and having low Young’s modulus are currently being developed. Examples of such alloys include Ti-10Cr-Al, Ti-Mn, Ti-Mn-Fe, Ti-Mn-Al, Ti-Cr-Al, Ti-Sn-Cr, Ti-Cr-Sn-Zr, Ti-(Cr, Mn)-Sn, and Ti-12Cr. Ti-5Fe-3Nb-3Zr belongs to that class of titanium alloys in which rare metals such as Nb, Ta, and Zr have been reduced using Fe. Ti-5Fe-3Nb-3Zr has a Young’s modulus of around 76 GPa and has greater strength than that of Ti-6Al-4V ELI for biomedical applications. The characteristics of Ti-5Fe-3Nb-3Zr and other low-cost beta-type titanium alloys with low Young’s moduli are discussed from the viewpoint of biomedical applications.

Hydroxyapatite (HAp) films were deposited on a β-type titanium alloy, Ti-29Nb-13Ta-4.6Zr (TNTZ), by metal organic chemical vapor deposition (MOCVD) in order to improve its hard-tissue compatibility. The surface morphologies of TNTZ substrates were changed by acid treatments and mechanical polishing prior to the HAp film deposition. The adhesive strength of the HAp films formed on TNTZ substrates treated with an HF solution increased to twice that of the HAp film deposited on a TNTZ substrate with a mirror-like finish. Complex microstructures with deeply etched grain boundaries, formed on the TNTZ substrates after immersion in the HF solution, were responsible for the increase in the adhesive strength of the HAp film caused by an interlocking effect. The HAp films on TNTZ substrates treated with a H(2)SO(4) solution exhibited lower adhesive strength than HAp films on TNTZ substrates treated with HF solution, regardless of the surface roughness of the substrates. Additionally, acid treatments using HNO(3) and H(2)O(2) solutions did not change the surface morphologies of the TNTZ substrates. The complex microstructures with deeply etched grain boundaries and nanosized asperities formed on the TNTZ substrates are important factors in the improvement of the adhesive strengths of HAp films deposited on TNTZ substrates.