Harumi Tsutsumi

Calcification by MC3T3-E1 cells on RGD peptide immobilized on titanium through electrodeposited PEG.

The effect of a cell-adhesive peptide containing Arg-Gly-Asp (RGD) immobilized through poly(ethylene glycol) (PEG) on titanium (Ti) on calcification by MC3T3-E1 cells was investigated to develop a new surface modification technique using biofunctional molecules. RGD was immobilized on Ti through PEG, both terminals of which were terminated with -NH(2) and -COOH to combine with the Ti surface and RGD. PEG was immobilized on Ti with electrodeposition, and RGD, with immersion. For comparison, glycine was employed because it is the simplest molecule containing both -NH(2) and -COOH at its terminals. MC3T3-E1 cells were cultured and differentiation-induced on each specimen, and the cell calcification properties were investigated. As a result, there was no significant difference in the morphology and extension of MC3T3-E1 cells cultured on each specimen, while the number of cells cultured on RGD/PEG/Ti was the largest. After differentiation-induction, there was no significant difference in the ALP activity among all specimens. On the other hand, the level of cell calcification on RGD/PEG/Ti was the highest. Therefore, the hard tissue compatibility of Ti is improved by immobilizing RGD through functional molecules which have a long molecular chain.

Development of biomedical porous titanium filled with medical polymer by in-situ polymerization of monomer solution infiltrated into pores

Porous metallic materials can have a low Youngs modulus, which is approximately equal to that of human bone, by controlling the porosity. On the other hand, certain medical polymers exhibit biofunctionalities that are not intrinsically present in metallic materials. Therefore, a composite consisting of these materials is expected to possess both these advantages for biomedical applications. However, in the case of using porous metallic materials, the deterioration of mechanical properties should of concern because a stress concentration may be induced near the pores. In this study, for the fabrication of the abovementioned composite, a versatile process for filling a medical polymer into a porous metallic material has been developed using porous pure titanium (pTi) and polymethylmethacrylate (PMMA). Then, the tensile strength and Youngs modulus of pTi filled with PMMA (pTi/PMMA) fabricated using this process are systematically investigated. The tensile strength of pTi can be improved by the PMMA filling. Particularly, the improvement in the tensile strength of pTi pretreated using a silane coupling agent before PMMA filling is greater than that of the non-pretreated pTi because the stress concentration near the pores may be reduced by the improvement in the interfacial adhesiveness between the titanium particles and the PMMA. In contrast, the effect of the PMMA filling on the Youngs modulus of pTi is smaller than that on the tensile strength because the Youngs modulus of PMMA is considerably lower than that of pTi. Further, tensile strengths and Youngs moduli comparable to the tensile strength and Youngs modulus of the human bone are successfully obtained in the case of some pTi/PMMA samples.

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.

Improvement of adhesive strength of segmented polyurethane on Ti–29Nb–13Ta–4.6Zr alloy through H2O2 treatment for biomedical applications

The number of hydroxyl groups on a Ti-29Nb-13Ta-4.6Zr (TNTZ) alloy surface was controlled through H₂O₂ treatment for further improvement of the adhesive strength and durability against water of TNTZ/silane layers (SILs)/segmented polyurethane (SPU) composites. The effect of the terminal functional groups on the adhesive strength of SPU on TNTZ, and the adhesiveness of SPU on TNTZ against water was investigated. Three types of silane-coupling agents were used to bind TNTZ and SPU: methacryloxypropyltrimethoxysilane (γ-MPTS), aminopropyltriethoxysilane (APS), and mercaptopropyltrimethoxysilane (γ-MPS). The adhesive strength of each composite was evaluated by shear bonding tests. The number of hydroxyl groups increases with an increase in treatment time at a H₂O₂ concentration of 5% (v/v). On the other hand, an increase from 5% (v/v) to 30% (v/v) in H₂O₂ concentration leads to a decrease in the number of hydroxyl groups on the TNTZ surface because at higher H₂O₂ concentrations, the reaction that consumes the hydroxyl groups is dominant. The shear bonding strength is doubled compared with the untreated TNTZ/SIL/SPU interface. Although the shear bonding strength decreases after immersion in water for 30 days when APS and γ-MPS are used, TNTZ/γ-MPTS/SPU composites exhibit good durability to water and maintain an equivalent shear bonding strength before immersion in water.

Effect of Oxygen Addition on Isothermal Omega Phase Stability in Ti-29Nb-13Ta-4.6Zr

A peculiar effect of oxygen on ω-phase stability, i.e., the enhancement of the isothermal ω-phase formation during aging due to oxygen addition was observed in the Ti-29Nb-13Ta-4.6Zr; this effect is contradictory to that reported conventionally. The effect was analyzed from the viewpoint of distribution of alloying elements. Oxygen and/or zirconium may dissolve in the ω phase during aging, resulting in the stabilization of the ω phase in this alloy.

Mechanical Performance of Newly Developed Titanium and Zirconium System Alloys for Biomedical Applications

A new -type Ti alloy composed of non-toxic and allergy-free elements like Nb, Ta, and Zr, Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) proposed by present authors, has been developed in order to achieve relatively low Young’s modulus and excellent mechanical performance. On the other hand, Zr has been also paid attention as metallic biomaterial for the next generation because of good biocompatibility nearly equal to Ti or a few GPa smaller Young’s modulus as compared to one. In this study, mechanical performances such as tensile properties and Youngs modulus of TNTZ subjected to thermo-mechanical treatments or severe deformation, and the mechanical properties and biocompatibility of Zr-Nb system alloys were investigated in order to judge their potential for biomedical applications. Young’s modulus of as-solutionized TNTZ, which is around 63 GPa, is pretty similar to that of as-cold-rolled TNTZ. The Young’s moduli of hot-rolled Ti-6Al-4V ELI alloy are respective around 110 GPa. The Young’s moduli of as-solutionized and as-cold-rolled TNTZ are around a half of those, and are twice as large as that of the cortical bone. The tensile strengths of TNTZ aged after solution treatment and those aged after cold rolling decrease with an increase in the aging temperature, although the elongation shows the reverse trend. The tensile strength of as-cold-rolled TNTZ is improved drastically through severe deformation such as high pressure torsion and shows more than 1000 MPa. Zr-XNb system alloy (X: 5-30mass%) shows the smallest value of Young’s modulus (around 58 GPa) at Nb content of 20mass%. In the case of implantation of the bars made of Zr-XNb system alloys into the lateral femoral condyles of Japanese white rabbits, the tendency of contact between the cancellous bone and the bar becomes remarkably at 24 weeks after the implantation according to increasing with Nb content.

Effect of Oxygen on Phase Precipitation and Mechanical Functionality in Ti-29Nb-13Ta-4.6Zr

Oxygen plays very important roles in titanium and its alloys. Solute oxygen in titanium alloys leads to solid solution strengthening, suppressing the precipitation of the athermal omegaor orthorhombic martensite phase, enhancing the formation of the -case, etc. The proper using oxygen is effective to improve the mechanical functionalities of titanium alloys. However, the role of oxygen in titanium alloys is still not well understood. Therefore, the effect of oxygen on the mechanical functionalities such as strength-ductility balance, hardness, and Young’s modulus in Ti-29nb-13Ta-4.6Zr was investigated.

Effect of Y2O3 on Mechanical Properties of Ti-29Nb-13Ta-4.6Zr for Biomedical Applications

Y2O3 was added to β-type Ti-29Nb-13Ta-4.6Zr (TNTZ) in order to achieve excellent mechanical performance and low Young’s modulus. TNTZ specimens with 0.05%–1.0% Y are all found to be composed of a β phase. Young’s moduli of TNTZ with 0.05–1.0% Y are all maintained low, and are almost the same as that of TNTZ without Y2O3. The grain size of TNTZ with 0.05%–1.0% Y is smaller than that of TNTZ without Y2O3. Moreover, Y2O3 precipitates can prevent the texture movement, and this effect becomes more obvious with an increase in the Y concentration. The tensile strength of TNTZ is successfully improved by adding Y2O3. TNTZ specimens with 0.2% and 1.0% Y exhibit good balance between the tensile strength and the elongation.

Anomalous Characteristics of Ti-Nb-Ta-Zr Alloy for Biomedical Applications

Negative thermal expansion, i.e. a type of shrinkage that occurs during heating, was observed in cold-rolled Ti-29Nb-13Ta-4.6Zr alloy (mass%) (TNTZ). The reduction ratio of cold rolling was systematically changed, and then the thermal expansion rate was measured using a dilatometer. The cyclicity of thermal expansion was also examined for the cold-rolled TNTZ. Further, the effect of oxygen content on the thermal expansion behavior of the cold rolled TNTZ was examined. With an increase in the reduction ratio of cold rolling, the thermal expansion rate of TNTZ cold-rolled parallel to the rolling direction (RD) decreases, but it increases in TNTZ cold-rolled parallel to the transverse direction (TD). The cyclicity of above-mentioned anomalous thermal expansion is observed in a temperature range below 473 K, but it is not observed when the specimen is heated to above 573 K in the first cycle. The oxygen suppresses the negative thermal expansion behavior of TNTZ.

Improvement of Mechanical Performance and Biocompatibility of Spinal Implant Rod Made of Beta-Type Ti-Nb-Ta-Zr Alloy

Mechanical properties of beta-type biomedical Ti-29Nb-13Ta-4.6Zr (mass %) (TNTZ), which exhibits non-toxicity and a low modulus similar to that of cortical bone, is improved by thermomechanical treatments, including severe cold swaging. Simultaneously, the biocompatibility of a TNTZ spinal implant rod with living tissue is evaluated using ovines, and TNTZ is proved to show good biocompatibility with bovine tissue.