Huihong Liu

Biomedical titanium alloys with Young’s moduli close to that of cortical bone

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.

Deformation-induced changeable Young's modulus with high strength in β-type Ti-Cr-O alloys for spinal fixture.

In order to meet the requirements of the patients and surgeons simultaneously for spinal fixation applications, a novel biomedical alloy with a changeable Youngs modulus, that is, with a low Youngs modulus to prevent the stress-shielding effect for patients and a high Youngs modulus to suppress springback for surgeons, was developed. In this study, the chromium and oxygen contents in ternary Ti(11, 12 mass%)Cr-(0.2, 0.4, 0.6 mass%)O alloys were optimized in order to achieve a changeable Youngs modulus via deformation-induced ω-phase transformation with good mechanical properties. The Youngs moduli of all the examined alloys increase after cold rolling, which is attributed to the deformation-induced ω-phase transformation. This transformation is suppressed by oxygen but enhanced with lower chromium content, which is related to the β(bcc)-lattice stability. Among the examined alloys, the Ti-11Cr-0.2O alloy shows a low Youngs modulus of less than 80GPa in the solution-treated (ST) condition and a high Youngs modulus of more than 90GPa in the cold rolled (CR) condition. The Ti-11Cr-0.2O alloy also exhibits a high tensile strength, above 1000MPa, with an acceptable elongation of ~12% in the ST condition. Furthermore, the Ti-11Cr-0.2O alloy exhibits minimal springback. This value of springback is the closest to that of Ti64 ELI alloy among the compared alloys. Therefore, the Ti-11Cr-0.2O alloy, which has a good balance between large changeable Youngs modulus, high tensile strength, good plasticity, and minimal springback, is considered to be a potential candidate for spinal fixation applications.

Fabrication of low-cost beta-type Ti-Mn alloys for biomedical applications by metal injection molding process and their mechanical properties.

Titanium and its alloys are suitable for biomedical applications owing to their good mechanical properties and biocompatibility. Beta-type Ti-Mn alloys (8-17 mass% Mn) were fabricated by metal injection molding (MIM) as a potential low cost material for use in biomedical applications. The microstructures and mechanical properties of the alloys were evaluated. For up to 13 mass% Mn, the tensile strength (1162-938MPa) and hardness (308-294HV) of the MIM fabricated alloys are comparable to those of Ti-Mn alloys fabricated by cold crucible levitation melting. Ti-9Mn exhibits the best balance of ultimate tensile strength (1046MPa) and elongation (4.7%) among the tested alloys, and has a Youngs modulus of 89GPa. The observed low elongation of the alloys is attributed to the combined effects of high oxygen content, with the presence of interconnected pores and titanium carbides, the formation of which is due to carbon pickup during the debinding process. The elongation and tensile strength of the alloys decrease with increasing Mn content. The Ti-Mn alloys show good compressive properties, with Ti-17Mn showing a compressive 0.2% proof stress of 1034MPa, and a compressive strain of 50%.

Microstructures, mechanical properties and cytotoxicity of low cost beta Ti-Mn alloys for biomedical applications.

UNLABELLED The microstructures, mechanical properties and biocompatibility of low cost β-type Ti-(6-18)Mn alloys were investigated after solution treatment. Ti-9 Mn exhibits the best combination of tensile strength and elongation among the fabricated alloys, and its performance is comparable to or superior to those of Ti-6Al-4V ELI (Ti-64 ELI) in terms of every parameter evaluated. A hardness of 338 HV, a Youngs modulus of 94 GPa, a 0.2% proof stress of 1023 MPa, an ultimate tensile strength of 1048 MPa and elongation of 19% were obtained for Ti-9 Mn. Furthermore, the cell viability and metallic ion release ratios are comparable to those of commercially pure titanium, making this alloy promising for biomedical applications. The Youngs modulus is also lower than that of Ti-64 ELI (110 GPa), which can possibly reduce the stress shielding effect in implanted patients. STATEMENT OF SIGNIFICANCE This study evaluates mechanical and biological performance of low cost solution treated β-type Ti-(6, 9, 13 and 18 mass%)Mn alloys. It includes alloys containing a Mn content range higher than most previously published works (which is around or lower than 8 mass%). Furthermore, the effects of the ω phase and the β phase stability of the alloys over some mechanical properties and microstructures are discussed. Ion release behavior under simulated body fluids and cell viability are also evaluated. For the case of the Ti-9 Mn, a mechanical and biological performance that is comparable to or superior than that of the widely used Ti-6Al-4V ELI and commercially pure Ti was observed.

β-Type titanium alloys for spinal fixation surgery with high Young's modulus variability and good mechanical properties.

UNLABELLED Along with a high strength, ductility, and work hardening rate, a variable Youngs 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 Youngs 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 (>1000MPa), 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 Youngs 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 Youngs moduli for biomedical applications. In spinal fixation surgery however, along with excellent mechanical properties, the spinal-support materials should possess high Youngs modulus for showing small springback during surgery to facilitate manipulation but low Youngs 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 Youngs 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.

Bending springback behavior related to deformation-induced phase transformations in Ti-12Cr and Ti-29Nb-13Ta-4.6Zr alloys for spinal fixation applications.

The springback behavior of Ti-12Cr and Ti-29Nb-13Ta-4.6Zr (TNTZ) during deformation by bending was investigated; and the microstructures of the non-deformed and deformed parts of both alloys were systematically examined to clarify the relationship between microstructure and springback behavior. For the deformed Ti-12Cr alloy, deformation-induced ω-phase transformation occurs in both the areas of compression and tension within the deformed part, which increases the Young׳s modulus. With the deformed TNTZ alloy, deformation-induced ω-phase transformation is observed in the area of compression within the deformed part; while a deformation-induced α″ martensite transformation occurs in the area under tension, which is likely to be associated with the pseudoelasticity of TNTZ. Among these two alloys, Ti-12Cr exhibits a smaller springback and a much greater bending strength when compared with TNTZ; making Ti-12Cr the more advantageous for spinal fixation applications.

Abnormal Deformation Behavior of Oxygen-Modified β-Type Ti-29Nb-13Ta-4.6Zr Alloys for Biomedical Applications

Abstract Oxygen was added to the biomedical β-type Ti-29Nb-13Ta-4.6Zr alloy (TNTZ, mass pct) in order to improve its strength, while keeping its Young’s modulus low. Conventionally, with an increase in the oxygen content, an alloy’s tensile strength increases, while its tensile elongation-to-failure decreases. However, an abnormal deformation behavior has been reported in the case of oxygen-modified TNTZ alloys in that their strength increases monotonically while their elongation-to-failure initially decreases and then increases with the increase in the oxygen content. In this study, this abnormal tensile deformation behavior of oxygen-modified TNTZ alloys was investigated systematically. A series of TNTZ-(0.1, 0.3, and 0.7 mass pct)O alloy samples was prepared, treated thermomechanically, and finally solution treated; these samples are denoted as 0.1ST, 0.3ST, and 0.7ST, respectively. The main tensile deformation mechanisms in 0.1ST are a deformation-induced α″-martensitic transformation and {332}〈113〉 mechanical twinning. The large elongation-to-failure of 0.1ST is attributable to multiple deformation mechanisms, including the deformation-induced martensitic transformation and mechanical twinning as well as dislocation glide. In both 0.3ST and 0.7ST, dislocation glide is the predominant deformation mode. 0.7ST shows more homogeneous and extensive dislocation glide along with multiple slip systems and a higher frequency of cross slip. As a result, it exhibits a higher work-hardening rate and greater resistance to local stress concentration, both of which contribute to its elongation-to-failure being greater than that of 0.3ST.

Microstructural evolution and mechanical properties of biomedical Co-Cr-Mo alloy subjected to high-pressure torsion

The effects of severe plastic deformation through high-pressure torsion (HPT) on the microstructure and tensile properties of a biomedical Co-Cr-Mo (CCM) alloy were investigated. The microstructure was examined as a function of torsional rotation number, N and equivalent strain, εeq in the HPT processing. Electron backscatter diffraction analysis (EBSD) shows that a strain-induced martensitic transformation occurs by the HPT processing. Grain diameter decreases with increasing εeq, and the HPT-processed alloy (CCMHPT) for εeq=45 exhibits an average grain diameter of 47nm, compared to 70μm for the CCM alloy before HPT processing. Blurred and wavy grain boundaries with low-angle of misorientation in the CCMHPT sample for εeq<45 become better-defined grain boundaries with high-angle of misorientation after HPT processing for εeq=45. Kernel average misorientation (KAM) maps from EBSD indicate that KAM inside grains increases with εeq for εeq<45, and then decreases for εeq=45. The volume fraction of the ε (hcp) phase in the CCMHPT samples slightly increases at εeq=9, and decreases at εeq=45. In addition, the strength of the CCMHPT samples increases at εeq=9, and then decrease at εeq=45. The decrease in the strength is attributed to the decrease in the volume fraction of ε phase, annihilation of dislocations, and decrease in strain in the CCMHPT sample processed at εeq=45 by HPT.

Wear transition of solid-solution-strengthened Ti–29Nb–13Ta–4.6Zr alloys by interstitial oxygen for biomedical applications

In previous studies, it has been concluded that volume losses (V loss) of the Ti-29Nb-13Ta-4.6Zr (TNTZ) discs and balls are larger than those of the respective Ti-6Al-4V extra-low interstitial (Ti64) discs and balls, both in air and Ringers solution. These results are related to severe subsurface deformation of TNTZ, which is caused by the lower resistance to plastic shearing of TNTZ than that of Ti64. Therefore, it is necessary to further increase the wear resistance of TNTZ to satisfy the requirements as a biomedical implant. From this viewpoint, interstitial oxygen was added to TNTZ to improve the plastic shear resistance via solid-solution strengthening. Thus, the wear behaviors of combinations comprised of a new titanium alloy, TNTZ with high oxygen content of 0.89 mass% (89O) and a conventional titanium alloy, Ti64 were investigated in air and Ringers solution for biomedical implant applications. The worn surfaces, wear debris, and subsurface damage were analyzed using a scanning electron microscopy and an electron probe microanalysis. V loss of the 89O discs and balls are smaller than those of the respective TNTZ discs and balls in both air and Ringers solution. It can be concluded that the solid-solution strengthening by oxygen effectively improves the wear resistance for TNTZ materials. However, the 89O disc/ball combination still exhibits higher V loss than the Ti64 disc/ball combination in both air and Ringers solution. Moreover, V loss of the disc for the 89O disc/Ti64 ball combination significantly decreases in Ringers solution compared to that in air. This decrease for the 89O disc/Ti64 ball combination in Ringers solution can be explained by the transition in the wear mechanism from severe delamination wear to abrasive wear.

Development and Performance of Low-Cost Beta-Type Ti-Based Alloys for Biomedical Applications Using Mn Additions

The microstructures, mechanical properties, and biocompatibility of various low-cost β-type Ti-Mn alloys fabricated by both cold crucible levitation melting (CCLM) and metal injection molding (MIM) were investigated after solution treatment. Mn was chosen as a potential low-cost alloying element for Ti. Among the alloys fabricated by both methods, Ti-9Mn shows the best combination of tensile strength and elongation, and their performances are mostly comparable to or superior to those of Ti-6Al-4V (Ti-64) ELI. However, alloys fabricated by MIM show a higher O and C content, along with precipitated Ti carbides and pores, which all cause the ductility of the alloys fabricated by MIM to be lower than that of the alloys fabricated by CCLM. Furthermore, the cell viability and metallic ion release ratios of the alloys fabricated by CCLM are comparable to those of commercially pure Ti, making this alloy promising for biomedical applications. The Young’s modulus of the alloys is also lower than that of Ti-64 ELI (which is of approximately 110 GPa), which can possibly reduce the stress shielding effect in implanted patients.