Papers by Author: Takayuki Narushima

Abstract: The Co-20Cr-15W-10Ni (CCWN, mass%) alloy, registered as American society of testing and materials (ASTM) F90, has been widely used as a balloon-expandable stent because of its excellent balance between its mechanical properties and corrosion resistance. To realize a less invasive stent placement, the stent diameter must be reduced, which implies that the stent strut thickness must be reduced. As such, the CCWN alloy must be high in strength and ductility while maintaining a low yield stress to facilitate the expansion and suppression of stent recoil. In this study, we focus on the effects of the adding Mn/Fe on the microstructure, mechanical properties, and corrosive properties of CCWN alloys. A 6 mass% Mn-added CCWN alloy with a grain size of approximately 20 μm prepared in this study exhibits excellent balance between tensile strength and ductility. In addition, it exhibits a lower yield stress while maintaining a high tensile strength compared with the ASTM F90 alloy. Meanwhile, a 6 mass% Fe-added CCWN alloy exhibits a higher ductility compared with the ASTM F90 alloy. The addition of Mn or Fe to the CCWN alloy increases the stacking fault energy of the alloy and suppresses strain-induced martensitic transformation during plastic deformation, thus improving the ductility of the alloy. Results of polarization tests show that the 6 mass% Mn-or Fe-added CCWN alloys exhibit the same corrosion current density as the ASTM F90 alloy. Mn-added Co-Cr-W-Ni alloys are suitable for use in balloon-expandable stents.

Abstract: The Co-20Cr-15W-10Ni (CCWN, mass%) alloy has excellent corrosion resistance and strength-ductility balance and is applied in almost all balloon-expandable stent platforms. To further reduce the invasiveness of stent placement, it is necessary to reduce the diameter of the stent. That is, both high strength and high ductility should be achieved while maintaining a low yield stress. In our previous studies, it was discovered that low-temperature heat-treatment (LTHT) at 873 K improves the elongation of the CCWN alloy. In this study, we focused on the grain refinement by swaging and static recrystallization to improve the strength of the alloy. The as-swaged alloy was recrystallized at 1373–1473 K for 100–300 s, followed by LTHT. A fine grain structure with an average grain size of 3–17 μm was obtained by static recrystallization. The η-phase (M₁₂X-M₆X type precipitates, M: metallic elements, X: C and/or N) formed during the recrystallization at 1373–1448 K. The alloys recrystallized at 1448 and 1473 K had a homogeneous structure with a small variation in the grain size. On the other hand, the alloys recrystallized at 1373 and 1423 K had an inhomogeneous structure in which fine and coarse grains were mixed. Both the strength and ductility of the CCWN alloy were improved by combining high-temperature short-time recrystallization and LTHT.

Abstract: The effect of high-pressure torsion (HPT) processing on the microstructure and Vickers hardness of Co-Cr-Mo (CCM) alloys were investigated in this study. The microstructure of initial CCM alloy contains equiaxed grains with a grain diameter of approximately 50 μm and twins. The clear grain boundaries of equiaxed grains and twins disappear after HPT processing at a rotation number, N, of 10. The phase maps of initial CCM alloy and CCM alloy subjected to HPT processing at N = 5 measured by electron backscatter diffraction exhibit that the ratio of γ phase decreases from 93.5% to 34.1% and the ratio of ε phase increases from 6.5% to 65.9% by applying HPT processing. These results indicate that the ε phase is formed by high-strain, which is induced by the HPT processing. The Vickers hardness values on the surfaces of the CCM alloys subjected to HPT processing at N = 1, 5, and 10 increase with increasing the equivalent strain, ε_eq. These results suggest that an increase of Vickers hardness is correlated to an increase of the ratio of ε phase and the dislocation density, and grain refinement, which are caused by the high-strain induced by HPT processing.

Abstract: The precipitation behavior during heat treatment and resulting mechanical properties of ASTM F 90 Co-20Cr-15W-10Ni (mass%) alloys were investigated with regards to their biomedical applications. Heat treatment was conducted at temperatures of 873 to 1623 K, for a holding time of 259.2 ks. The precipitates produced were then electrolytically extracted from the alloys and analyzed by X-ray diffraction (XRD). This revealed that the precipitates formed were an M₂₃X₆ type and/or η-phase (i.e., an M₆X-M₁₂X type). The M₂₃X₆-type precipitate was detected across the entire heat-treatment temperature range; however, the η-phase precipitate was only detected at 1073 to 1473 K, becoming dominant at 1173 to 1373 K. The formation of M₂₃X₆ type precipitates at 873 K is shown to improve the mechanical properties of this alloy, whereas the domination by the η-phase precipitate at higher temperatures causes deterioration in the ductility.

Abstract: In this study, the carbide dissolution and formation of biomedical Co-28Cr-6Mo-0.25C-1Si (1Si) and Co-28Cr-6Mo-0.25C-1Mn (1Mn) alloys occurring during solution treatment and aging were investigated. The addition of Si or Mn markedly affected the behavior of precipitates during heat treatment. The alloy with added Si required a longer solution treatment time for complete precipitate dissolution as compared to the alloy with added Mn. Blocky M23C6-type carbide was observed during solution treatment at 1448–1523 K. Starlike precipitates were observed in the 1Si and 1Mn alloys at 1523–1548 K and 1523 K, respectively. The starlike precipitates exhibited two types of morphologies: dense and stripe patterned. The starlike precipitates with dense and stripe-patterned appearances were a -phase and M23C6¬-type carbide + metallic -phase, respectively. An M23C6-type carbide and an -phase were formed during the aging of both the 1Si and the 1Mn alloys. In addition, an intermetallic -phase was detected during the aging of the 1Si alloy at 1373 K.

Abstract: The phase and morphology of precipitates in heat-treated Co-28Cr-6Mo-xC (x = 0.12, 0.15, 0.25, and 0.35mass%) alloys were investigated. The as-cast alloys were solution-treated in the temperature range of 1473 to 1623 K for 0 to 43.2 ks. Complete precipitate dissolution was observed in all four alloys, each of which had different carbon contents. The holding time for complete dissolution was greater for alloys with greater carbon content. The curve representing the boundary between the complete- and incomplete-dissolution conditions for each alloy is C shaped. Under the incomplete precipitate dissolution conditions of the Co-28Cr-6Mo-0.25C alloy, an M23C6 type carbide and a π-phase (M2T3X type carbide with β-Mn structure) were observed at 1548 to 1623 K, and starlike precipitates with a stripe pattern and with a dense appearance were both observed; the former comprised the M23C6 type carbide + γ-phase, and the latter was the π-phase. In contrast, only a blocky-dense M23C6 type carbide was observed at 1473 to 1523 K.

Abstract: The surface modification of commercially pure titanium (CP Ti) by pack cementation treatment at 973 K using tetracalcium phosphate (Ca4(PO4)2O, TTCP) slurry was investigated. An HAp phase and a CaTiO3 phase were observed on the reaction layer of the CP Ti substrate after pack cementation treatment at 973 K for 86.4 ks. TTCP powder decomposed to HAp and CaO, and CaO reacted with TiO2 to form CaTiO3. The reaction layer on the CP Ti substrate consisted of inner and outer layers and the particles were in the outer reaction layer. The pores observed on the reaction layer were formed by the detachment of particles from the outer layer. The bonding strength of the reaction layer was 68.1 MPa. Apatite completely covered the surface of the pack-cementation-treated CP Ti after immersion in Kokubo solution for 21.6 ks; such rapid apatite formation suggests that pack cementation treatment improves the biocompatibility of titanium.

Abstract: Oxyapatite, amorphous calcium phosphate, and double-layered calcium phosphate coating films were fabricated on mirror-polished commercially pure titanium (CP Ti) and blasted Ti-6Al-4V alloy substrates by radiofrequency (RF) magnetron sputtering; the properties of these films were evaluated in vivo and in vitro. The bonding strength between the calcium phosphate films and the Ti substrates was higher than 50 MPa. This value is higher than the bonding strength reported in the case of plasma-sprayed calcium phosphate coating films fabricated on Ti substrates. The removal torque of screw-type blasted Ti-6Al-4V alloy implants in the femurs of Japanese white rabbits increased with the duration of implantation, and the removal torque values of the coated implants was observed to be higher than those of the non-coated implants. In vitro and in vivo studies indicate that coating Ti implants with calcium phosphate films using RF magnetron sputtering is effective in improving the bone compatibility of Ti implants. Finally, the factors that should be considered in fabricating biomedical coating films were discussed.

Abstract: Microstructural changes occurring in biomedical Co-Cr-Mo alloys with three carbon levels due to solution treatment and aging were investigated. Ingots of Co-Cr-Mo alloys with three different carbon levels were prepared by vacuum furnace melting; their chemical composition was Co-28Cr-6Mo-xC (x = 0.12, 0.25 and 0.35 mass%). Precipitates were electrolytically extracted from as-cast and heat-treated alloys. An M23C6 type carbide and a phase were detected as precipitates in as-cast Co-28Cr-6Mo-0.12C alloy, and an M23C6 type carbide and an  phase (M6C-M12C type carbide) were detected in as-cast Co-28Cr-6Mo-0.25C and Co-28Cr-6Mo-0.35C alloys. Only the M23C6 type carbide was detected during solution treatment. Complete precipitate dissolution occurred in all the three alloys after solution treatment. The holding time required for complete precipitate dissolution increased with increasing carbon content and decreasing solution treatment temperature. Complete precipitate dissolution occurred in the Co-Cr-Mo-C alloys solution treated at 1523 K for 43.2 ks; they were then subjected to aging from 873 to 1473 K for a heating time up to 44.1 ks after complete precipitate dissolution in solution treatment at 1523 K for 43.2 ks. The M23C6 type carbide with a grain size of 0.1–3 m was observed after aging. A time-temperature-precipitation diagram of the M23C6 type carbide formed in the Co-28Cr-6Mo-0.25C alloy was plotted.

Abstract: Calcium phosphate coating films were fabricated on Ti-6Al-4V plates and screw-type implants with a blast-treated surface using radiofrequency (RF) magnetron sputtering and were evaluated in vitro and in vivo. Amorphous calcium phosphate (ACP) and oxyapatite (OAp) films obtained in this study could cover the blast-treated substrate very efficiently, maintaining the surface roughness. For the in vitro evaluations of the calcium phosphate coating films, bonding strength and alkaline phosphatase (ALP) activity were examined. The bonding strength of the coating films to a blast-treated substrate exceeded 60 MPa, independent of film phases except for the film after post-heat-treatment in silica ampoule. When compared with an uncoated substrate, the increase in the ALP activity of osteoblastic SaOS-2 cells on a calcium phosphate coated substrate was confirmed by a cell culture test. The removal torque of screw-type Ti-6Al-4V implants with a blast-treated surface from the femur of Japanese white rabbit increased with the duration of implantation and it was statistically improved by coating an ACP film 2 weeks after implantation. The in vitro and in vivo studies suggested that the application of the sputtered ACP film as a coating on titanium implants was effective in improving their biocompatibility with bones.