Biomedical Β-type Titanium Alloy Research Articles

Exceptional improvement in the wear resistance of biomedical β-type titanium alloy with the use of a biocompatible multilayer Si/DLC nanocomposite coating

A silicon/diamond-like carbon (Si/DLC) multilayer nanocomposite coating (MNC) was applied to the Ti–29Nb–13Ta‒4.6Zr (TNTZ) alloy to improve its wear resistance and durability. The Si/DLC MNC on the TNTZ alloy demonstrated an extremely low wear rate of 6.2 × 10−10 mm3N−1mm−1. Moreover, the wear track depth after one million wear cycles was found to be only 220 nm, while the thickness of the entire coating was 370 nm. Furthermore, cell culture tests demonstrated that the Si/DLC MNC samples exhibited better biocompatibility than the TNTZ alloy samples. A quantitative comparison of the cell adhesion behavior of the TNTZ and Si/DLC MNC samples indicated that 60% of the surface of the Si/DLC MNC sample was covered with cells, which was approximately twice the surface of the TNTZ alloy sample covered with cells. In addition, no dead cells were observed on the Si/DLC MNC samples, indicating that the Si/DLC MNC samples exhibited no toxic effects against the MC3T3 cells. These results indicate that the Si/DLC MNC enhances the wear resistance of the TNTZ alloy and improves its biofunctionality, thus making it a potential candidate for use in long-term implant applications.

Effect of Thermo-Mechanical Treatments on the Microstructure and Mechanical Properties of the Metastable β-type Ti-35Nb-7Zr-5Ta Alloy

In this work, theoretical composition design and thermo-mechanical treatments were combined in order to improve the mechanical compatibility of a biomedical β-type titanium alloy. By applying a composition design theory, cold rolling and low temperature aging, a metastable β-type Ti-35Nb-7Zr-5Ta (wt%) alloy with an elastic modulus of 47 GPa and a yield strength of 730 MPa was successfully fabricated. This combination of high yield strength and low elastic modulus resulted in enhanced elastic recoverable strain of 1.7%, which is much higher than that of the conventional metallic biomaterials. The microstructure responsible for the much sought-after mechanical properties was observed to be mainly consisted of a homogeneous distribution of nanometer-sized ω- and α-precipitates in a β-phase matrix obtained via cold rolling plus short-time aging at low temperature, i.e. aging at 673 K for 20 min. These precipitates increase the strength of the material by hindering the motion of dislocations while the β-matrix with relatively low content of β-stabilizers gives rise to the observed low elastic modulus. By extending aging time, a higher strength is reached at the expense of an undesirable increasing in elastic modulus.

Significant improvement in cell adhesion and wear resistance of biomedical β-type titanium alloy through ultrasonic nanocrystal surface modification

A novel β-type Ti–29Nb–13Ta–4.6Zr (TNTZ) alloy with a low Young's modulus, high bio-corrosion resistance, and excellent biocompatibility has been recently introduced for implant applications. Here, ultrasonic nanocrystal surface modification (UNSM) treatment was applied to TNTZ alloy to improve its wear resistance and biofunctionality. Application of UNSM to a TNTZ alloy resulted in the generation of a nanostructured surface layer. The wear resistance of the UNSM-treated specimen was observed to be more than 7 times higher than that of the untreated one. Cell culture tests indicated that MC3T3 cells adhered and spread more readily on the UNSM-treated specimen than on the untreated one. MTT assays after 1 and 4 days in culture also indicated enhancement of cell proliferation on the UNSM-treated specimen than that of the untreated one. Live/dead assay revealed no significant cytotoxicity in either substrate. The significant improvement of cell adhesion, spreading, and proliferation on the UNSM-treated TNTZ alloy specimen were attributed to both grain refinement and micro-patterned surface effects. These results demonstrate that UNSM-treatment not only improves the wear resistance of TNTZ alloy, but also enhances its biocompatibility, which makes it a strong candidate for applications in medical implants.

Microstructure and superelasticity of a biomedical β-type titanium alloy under various processing routes

The influences of various processing routes including cold forging, suction casting, cold rolling, hot compression and hot forging on the microstructure, mechanical properties and superelasticity of Ti-7.5Nb-4Mo-2Sn alloy were investigated. It has been found that, the alloy processed by cold rolling, hot forging, cold forging and suction casting contained a single β phase, but the alloy after hot compression consisted of a duplex structure of α and β phases. The alloy exhibited an average grain size of about 4μm after suction casting processing, indicating excellent grain refining effect. A strong recrystallization texture {111}〈110〉 was well developed in the cold rolled and hot forged alloys; while cold forged and hot compressed alloys exhibited strong multiple textures in different directions associated with their deformation. Superelastic behavior was observed in the cold rolled, suction casted, hot forged and hot compressed alloys, in which the casted alloy exhibited the highest strain recovery rate which reached nearly 75%, and the hot compressed alloy showed higher stress for inducing martensitic transformation but lower recovery rate due to the complex multiple textures formed during hot compressing processing among the alloys after different processing routes.

Fatigue characteristics of a biomedical β-type titanium alloy with titanium boride

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.

Microstructure, elastic deformation behavior and mechanical properties of biomedical β-type titanium alloy thin-tube used for stents

Cold-deformability and mechanical compatibility of the biomedical β-type titanium alloy are the foremost considerations for their application in stents, because the lower ductility restricts the cold-forming of thin-tube and unsatisfactory mechanical performance causes a failed tissue repair. In this paper, β-type titanium alloy (Ti–25Nb–3Zr–3Mo–2Sn, wt%) thin-tube fabricated by routine cold rolling is reported for the first time, and its elastic behavior and mechanical properties are discussed for the various microstructures. The as cold-rolled tube exhibits nonlinear elastic behavior with large recoverable strain of 2.3%. After annealing and aging, a nonlinear elasticity, considered as the intermediate stage between “double yielding” and normal linear elasticity, is attributable to a moderate precipitation of α phase. Quantitive relationships are established between volume fraction of α phase (Vα) and elastic modulus, strength as well as maximal recoverable strain (εmax-R), where the εmax-R of above 2.0% corresponds to the Vα range of 3–10%. It is considered that the “mechanical” stabilization of the (α+β) microstructure is a possible elastic mechanism for explaining the nonlinear elastic behavior.

Biomedical Polymer Surface Modification of Beta-Type Titanium Alloy for Implants through Anodic Oxide Nanostructures

Anodic oxide nanostructures (nanopores and nanotubes) were formed on a biomedical β-type titanium alloy, Ti–29Nb–13Ta–4.6Zr alloy (TNTZ), in order to improve adhesive strength by the anchor effect of a segmented polyurethane (SPU) with soft tissue compatibility. The nanotube structure was formed beneath the nanoporous structure. The adhesive strength between the SPU coating and the nanoporous structure formed on TNTZ by anodization is more than 1.5 times that of an SPU coating on as-polished TNTZ with a mirror finish. After removal of the nanoporous structure by etching with HF solution, the adhesive strength of the SPU coating on the exposed nanotube structure is decreased.

Adhesive strength of medical polymer on anodic oxide nanostructures fabricated on biomedical β-type titanium alloy

Anodic oxide nanostructures (nanopores and nanotubes) were fabricated on a biomedical β-type titanium alloy, Ti–29Nb–13Ta–4.6Zr alloy (TNTZ), by anodization in order to improve the adhesive strength of a medical polymer, segmented polyurethane (SPU), to TNTZ. TNTZ was anodized in 1.0M H3PO4 solution with 0.5 mass% NaF using a direct-current power supply at a voltage of 20V. A nanoporous structure is formed on TNTZ in the first stage of anodization, and the formation of a nanotube structure occurs subsequently beneath the nanoporous structure. The nanostructures formed on TNTZ by anodization for less than 3600s exhibit higher adhesive strengths than those formed at longer anodization times. The adhesive strength of the SPU coating on the nanoporous structure formed on top of TNTZ by anodization for 1200s improves by 144% compared to that of the SPU coating on as-polished TNTZ with a mirror surface. The adhesive strength of the SPU coating on the nanotube structure formed on TNTZ by anodization for 3600s increases by 50%. These improvements in the adhesive strength of SPU are the result of an anchor effect introduced by the nanostructures formed by anodization. Fracture occurs at the interface of the nanoporous structure and the SPU coating layer. In contrast, in the case that SPU coating has been performed on the nanotube structure, fracture occurs inside the nanotubes.

Heterogeneous grain refinement of biomedical Ti–29Nb–13Ta–4.6Zr alloy through high-pressure torsion

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.

Specific characteristics of mechanically and biologically compatible titanium alloy rods for use in spinal fixation applications

For implant rods as spinal fixation system, low Young's modulus, easy bending to an intended shape (low spring-back), and retaining initial bended shape during a long implantation (low aging-back) are essential properties. The rods were fabricated using a biomedical β-type titanium alloy, Ti–29Nb–13Ta–4.6Zr alloy (TNTZ), and their above-mentioned properties were evaluated in comparison with conventional biomaterials, commercially pure titanium, Ti–6Al–4V ELI, and SUS316L stainless steel. In the results of an animal experiment using implant rods made by TNTZ subjected to solution treatment with low Young's modulus, no negative effects are seen in the radiographs, and no inflammatory cells are observed in histological observation. In spite of low Young's modulus, the spring-back of TNTZ subjected to solution treatment is comparable to that of Ti–6Al–4V ELI. Further, its aging-back is quite small among the other materials.

Microstructure and Mechanical Properties of a Biomedical β-Type Titanium Alloy Subjected to Severe Plastic Deformation after Aging Treatment

Strengthening by Grain Refinement and Increasing Dislocation Density through High-Pressure Torsion (HPT), which Is an Attractive Technique to Fabricate Ultrafine Grained and Nanostructured Metallic Materials, Is Expected to Provide β-Type Ti-29Nb-13Ta-4.6Zr (TNTZ) Higher Mechanical Strength while Maintaining Low Young’s Modulus because they Keep the Original β Phase. However, the Ductility Shows Reverse Trend. Greater Strength with Enhanced Ductility Can Be Achieved by Controlling Precipitated Phases through HPT Processing after Aging Treatment. Aged TNTZ Subjected to HPT Processing at HighNExhibits a Homogeneous Microstructure with Ultrafine Elongated Grains Having a High Dislocation Density and Consequently Non-Equilibrium Boundaries and Distorted Subgrains with Non-Uniform Shapes and Nanostructured Intergranular Precipitates of αphases. Therefore, the Effect of HPT Processing on the Microstructure and Mechanical Hardness of TNTZ after Aging Treatment Was Systematically Investigated in this Study. TNTZ, which Was Subjected to Aging Treatment at 723 K for 259.2 Ks in Vacuum Followed by Water Quenching, Subjected to HPT Processing at Rotation Numbers (N) of 1 to 20 under a Pressure of around 1.25 GPa at Room Temperature. The Microstructure of TNTZATConsisted of Precipitated Needle-Like α Phases in β Grains. However, TNTZAHPTatN≥ 10 Comprises Very Fine α and Small Amount ω Phases in Ultrafine β Grains. Furthermore, the Hardness of Every TNTZAHPTWas Totally much Greater than that of TNTZAT. The Hardness Increased from the Center to Peripheral Region of TNTZAHPT. In Addition, the Tensile Strength of Every TNTZAHPTWas Greater than that of TNTZAT. The Tensile Strength of TNTZAHPTIncreased, but the Elongation Decreased with IncreasingNand then both of them Saturated atN≥ 10.

Effect of terminal functional groups of silane layers on adhesive strength between biomedical Ti-29Nb-13Ta-4.6Zr alloy and segment polyurethanes

Composite materials that consisted of a biomedical β-type titanium alloy, Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) with low Young's modulus and segment polyurethane (SPU) have been fabricated for application in biomedical devices. The effects of different kinds of terminal functional groups and the thickness of the silane layers (SIL) on the adhesive strength between TNTZ and SPU were investigated by means of shear bonding tests. The following silane coupling agents were employed in this study: 3-methacryloxypropyltrimethoxysilane (γ-MPTS), aminopropyltriethoxysilane (APS), and 3-mercaptopropyltrimethoxysilane (γ-MPS). Furthermore, the shear bonding strength of the TNTZ/SIL/SPU interface was also characterized after immersion in water for 30d.Silane coupling treatment produces a ten-fold increase in the shear bonding strength, independent of the type of terminal functional groups and the thickness of the silane layers. Scanning electron microscopic evaluation of the fracture surfaces of the TNTZ/SIL/SPU composites after the shear bonding tests coupled with energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the TNTZ/SIL/SPU composites are partially fractured at the interfaces of the TNTZ/SIL while the rest of the fracture occurs at the interfaces of the SIL/SPU in single sample. The shear bonding strength decreases after immersion in water for 30d when APS and γ-MPS are used as the silane coupling agents, because stable chemical bonding is not achieved between the silane layer and SPU, whereas the bonding of the γ-MPTS composite is not affected by exposure to water.

Improvement in Fatigue Strength of Biomedical β-type Ti–Nb–Ta–Zr Alloy While Maintaining Low Young’s Modulus Through Optimizing ω-Phase Precipitation

The improvement in fatigue strength, with maintenance of a low Young’s modulus, in a biomedical β-type titanium alloy, Ti–29Nb–13Ta–4.6Zr (TNTZ), by thermomechanical treatment was investigated. A short aging time at an ω-phase-forming temperature combined with severe cold rolling was employed. A fine ω phase is observed in TNTZ subjected to this thermomechanical treatment. Because the rolling texture of β phase is formed by cold rolling, such as the ω phase may be preferentially oriented to a direction that is effective for inhibiting the increase in Young’s modulus. The samples aged at 573 K (300 °C) for 3.6 ks and 10.8 ks after cold rolling exhibit a good balance between a high tensile strength and low Young’s modulus. In the case of the sample aged for 3.6 ks, the tensile strength is improved, although the fatigue strength is not improved significantly. Both the tensile strength and the fatigue strength of the sample aged for 10.8 ks are improved. This fatigue strength is the highest among the TNTZ samples used in the current and in previous studies with Young’s moduli less than 80 GPa.

The characterization of shape memory effect for low elastic modulus biomedical β-type titanium alloy

This work investigates the textures of biomedical TiNbTaZr alloy rolled by 99% cold reduction ratios in thickness. The relationship between textures and superelasticity of the specimens treated at 873 K and 1223 K for 1.2 ks is studied. The microstructure of tensile specimen is investigated by transmission electron microscopy. Textures of cold-rolled and heat-treated specimens are studied. During unloading, the anisotropy of superelastic strain and pure elastic strain in the heat-treated specimens is observed. Superelastic strain along rolling direction and transverse direction is larger than those along 45° from rolling direction while pure elastic strain shows the highest value along 45° from rolling direction in the specimen treated at 873 K. For the specimen treated at 1223 K, higher pure elastic strain is obtained along rolling direction. The maximum recovered strain around 2.11% is obtained along rolling direction.

Bending Fatigue and Spring Back Properties of Implant Rods Made of β-Type Titanium Alloy for Spinal Fixture

Implanting a spinal fixture using metallic rods is one of the effective treatments for spinal diseases. Because cyclic bending stress is loaded on the implant rods when patients move their upper bodies in daily life, bending fatigue properties are important for the implant rod. Further, the implant rods are bended plastically into a curved shape of spine by hand in a surgical operation. In that case, keeping shape is important, namely bending spring back properties are important factors. On the other hand, a biomedical β-type titanium alloy, Ti-29Nb-13Ta-4.6Zr (mass %) alloy (TNTZ), has been developed by the authors. Currently, this alloy are investigated to be applied to the above mentioned implant rod practically. Therefore, four-point bending fatigue and three point-bending spring back properties of TNTZ subjected various heat treatments were examined in this study. TNTZ rods were subjected to solution treatment, and then some of them were subjected to aging treatment at 673 K or 723 K for 259.2 ks, followed by water quenching. Then, four-point bending fatigue and three-point bending spring back tests were carried out on TNTZ rods subjected to the various heat treatments mentioned above. The bending fatigue strength at 2.5 million cycles in the high cycle fatigue region are not much different among any TNTZ rod. However, the bending fatigue strength of the Ti-6Al-4V ELI (Ti64) rod exceeds the fatigue strengths of every TNTZ rods in both low and high cycle fatigue regions. On the other hand, the lower spring back, which is a favorable property, was obtained for some TNTZ rod than Ti64 rod.

S0201-2-4 加工熱処理によるTi-29Nb-13Ta-4.6Zr合金製ロッドの疲労特性の改善(骨再生と骨再建のためのバイオマテリアル(2),社会変革を技術で廻す機械工学)

A biomedical β-type titanium alloy, Ti-29Nb-13Ta-4.6Zr (TNTZ) (mass%), which is composed of non-toxic and allergy-free elements and exhibits low Young's modulus similar to that of cortical bone, has been developed by the authors. According to our previous reports, the mechanical properties including fatigue property of TNTZ can be improved significantly by thermomechanical treatments. On the other hand, fatigue property is one of the most important properties when TNTZ is practically employed as a material of metallic rod for spinal fixation. Therefore, in order to improve the fatigue property of TNTZ, the thermomechanical treatment was optimized for this application in this study.

Change in Fatigue Strength of Biomedical β-Type Titanium Alloy through Heat Treatment Processes

Relationships between fatigue properties and microstructures of hot-forged Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) in under aged, peak aged, and over aged conditions at aging temperatures of 673K and 723K are investigated. The changes in the fatigue properties of TNTZ subjected to thermomechanical treatments, which includes an aging treatment at 673K or 723K for 259.2ks after a severe deformation process by cold rolling, are also investigated.At an aging temperature of 673K, ω phase precipitates at the early stage of aging, but α phase precipitates at relatively longer aging time. The precipitation site of α phase changes from intra-grain to grain boundary at around peak aging time when TNTZ is aged at 673K and 723K. The elastic modulus of TNTZ increases simply with increasing aging time at both 673K and 723K. The fatigue strength of TNTZ increases considerably when α phase precipitates compared with when ω + α phases co-exist. The fatigue strength of TNTZ decreases slightly due to the coarsening of α phase precipitated in β grain and its grain boundary. TNTZ aged at 723K for 259.2ks after cold rolling exhibits the highest fatigue strength in both the low- and high-cycle fatigue life regions. Furthermore, the fatigue limitof about 770MPa (fatigue raito : 0.71) is nearly equal to that of hot-forged Ti-6Al-4V ELI alloy subjected to aging after solution treatment with equiaxed α structure.

OS7-1-2 Mechanical Performance of Biomedical β-type Titanium Alloy Subjected to Surface Hardening Treatment

OS7-1-2 Mechanical Performance of Biomedical β-type Titanium Alloy Subjected to Surface Hardening Treatment