Kenta Yamanaka

Nanoarchitectured Co-Cr-Mo orthopedic implant alloys: nitrogen-enhanced nanostructural evolution and its effect on phase stability.

Our previous studies indicate that nitrogen addition suppresses the athermal γ (face-centered cubic, fcc)→ε (hexagonal close-packed, hcp) martensitic transformation of biomedical Co-Cr-Mo alloys and ultimately offers large elongation to failure while maintaining high strength. In the present study, structural evolution and dislocation slip as an elementary process in the martensitic transformation in Co-Cr-Mo alloys were investigated to reveal the origin of their enhanced γ phase stability due to nitrogen addition. Alloy specimens with and without nitrogen addition were prepared. The N-doped alloys had a single-phase γ matrix, whereas the N-free alloys had a γ/ε duplex microstructure. Irrespective of the nitrogen content, dislocations frequently dissociated into Shockley partial dislocations with stacking faults. This indicates that nitrogen has little effect on the stability of the γ phase, which is also predicted by thermodynamic calculations. We discovered short-range ordering (SRO) or nanoscale Cr2N precipitates in the γ matrix of the N-containing alloy specimens, and it was revealed that both SRO and nanoprecipitates function as obstacles to the glide of partial dislocations and consequently significantly affect the kinetics of the γ→ε martensitic transformation. Since the formation of ε martensite plays a crucial role in plastic deformation and wear behavior, the developed nanostructural modification associated with nitrogen addition must be a promising strategy for highly durable orthopedic implants.

Effects of nitrogen addition on microstructure and mechanical behavior of biomedical Co–Cr–Mo alloys

In the present study, the microstructures and tensile deformation behaviors of biomedical Co-29Cr-6Mo (wt%) alloys containing different concentrations of nitrogen (0-0.24wt%) were systematically investigated. As the nitrogen concentration increased, the volume fraction of athermal ε martensite decreased, because nanoprecipitates hindered the formation of stacking faults (SFs) by acting as obstacles to Shockley partial dislocation formation, and athermal ε martensite usually forms through the regular overlapping of SFs. The formation of the athermal ε martensite was completely suppressed when the nitrogen concentration exceeded 0.10wt%, resulting in a simultaneous improvement in the strength and ductility of the alloys. It was found that the glide of the Shockley partial dislocations and the strain-induced γ (fcc)→ε (hcp) martensitic transformation (SIMT) operated as the primary deformation mechanisms. However, adding nitrogen reduced the work hardening by suppressing the formation of the SFs and preventing the SIMT from taking place. This resulted in an intrinsic decrease in the tensile ductility of the alloys. It is also shown that all the alloys exhibited premature fractures owing to the SIMT. The formation of annealing twins in the γ grains is found to be enhanced by nitrogen addition and to promote the SIMT, resulting in a reduction in the elongation-to-failure due to nitrogen addition. These results should aid in the design of alloys that contain nitrogen.

Origin of Significant Grain Refinement in Co-Cr-Mo Alloys Without Severe Plastic Deformation

We have previously reported that ultrafine-grained (UFG) microstructures can be obtained in a Co-29Cr-6Mo (wt pct) alloy by utilizing dynamic recrystallization (DRX) that occurs during conventional hot deformation (Yamanaka et al.: Metall. Mater. Trans. A, 2009, vol. 40A, pp. 1980−94). The present study investigates the novel DRX mechanism of this alloy in detail. The microstructure evolution during hot deformation under relatively high Zener–Hollomon (Z) parameter conditions for which ultrafine grains can develop was systematically investigated by electron backscatter diffraction (EBSD) and transmission electron microscopy. This alloy exhibited a different flow stress behavior and microstructural development from conventional DRX mechanisms. The deformation microstructure contained a large number of stacking faults, which implies that planar dislocation slip is the primary deformation mechanism in the hot deformation of the Co-29Cr-6Mo alloy due to its abnormally low stacking fault energy (SFE) at elevated temperatures. Inhomogeneities in local strain distributions induced by planar slip will enhance grain subdivision by geometrically necessary (GN) dislocation boundaries. Deformation twinning may also contribute to grain refinement. The DRX mechanism operating in the Co-29Cr-6Mo alloy is discussed by considering the relationships between anomalous dislocation structures, flow stress behavior, texture development, and nucleation behavior.

Effects of carbon concentration on microstructure and mechanical properties of as-cast nickel-free Co–28Cr–9W-based dental alloys

We determined the effects of carbon concentration on the microstructures and tensile properties of the Ni-free Co-29Cr-9W-1Si-C (mass%) cast alloys used in dental applications. Alloy specimens prepared with carbon concentrations in the range 0.01-0.27 mass% were conventionally cast. Scanning electron microscopy (SEM) and electron probe microanalysis (EPMA) revealed that precipitates had formed in all the alloy specimens. The σ phase, a chromium-rich intermetallic compound, had formed in the region between the dendrite arms of the low-carbon-content (e.g., 0.01 C) alloys. Adding carbon to the alloys increased the amount of interdendritic precipitates that formed and changed the precipitation behavior; the precipitated phase changed from the σ phase to the M23C6 carbide with increasing carbon concentration. Adding a small amount of carbon (i.e., 0.04 mass%) to the alloys dramatically enhanced the 0.2% proof stress, which subsequently gradually increased with increasing content of carbon in the alloys. Elongation-to-failure, on the other hand, increased with increasing carbon content and showed a maximum at carbon concentrations of ~0.1 mass%. The M23C6 carbide formed at the interdendritic region may govern the tensile properties of the as-cast Co-Cr-W alloys similar to how it governed those of the hot-rolled alloys prepared in our previous study.

Local strain evolution due to athermal γ→ε martensitic transformation in biomedical CoCrMo alloys

Locally developed strains caused by athermal γ face-centered cubic (fcc)→ε hexagonal close-packed (hcp) martensitic transformation were investigated for the γ matrix of Ni-free Co-29Cr-6Mo (wt%) alloys prepared with or without added nitrogen. Electron-backscatter-diffraction-(EBSD)-based strain analysis revealed that in addition to ε-martensite interiors, the N-free alloy that had a duplex microstructure consisting of the γ matrix and athermal ε-martensite plates showed larger magnitudes of both elastic and plastic strains in the γ phase matrix than the N-doped counterpart that did not have a ε-martensite phase. Transmission electron microscopy (TEM) results indicated that the ε-martensite microplates were aggregates of thin ε-layers, which were formed by three different {111}γ〈112¯〉γ Shockley partial dislocations in accordance with a previously proposed mechanism (Putaux and Chevalier, 1996) that canceled the shear strains of the individual variants. The plastic strains are believed to have originated from the martensitic transformation itself, and the activity of dislocations is believed to be the origin of the transformation. We have revealed that the elastic strains in the γ matrix originate from interactions among the ε-martensite phase, extended dislocations, and/or thin ε-layers. The dislocations highly dissociated into stacking faults, making stress relaxation at intersections difficult and further introducing local strain evolution.

Influence of carbon addition on mechanical properties and microstructures of Ni-free Co-Cr-W alloys subjected to thermomechanical processing.

We report the effects of carbon concentration on the microstructures and tensile deformation behaviors of thermomechanically processed Ni-free Co-29Cr-9W-1Si-C (mass%) alloys designed for use as disk materials in CAD/CAM dental technology. The alloy specimens, which contained carbon in different concentrations, were prepared by casting and subsequent hot rolling. Overall, the developed Ni-free alloys with added carbon showed an excellent combination of high strength and high ductility. The precipitates were identified in all of the alloy specimens. Intermetallic compounds, i.e., the Laves and σ phases, were formed in the low-carbon alloys, whereas the precipitates changed to M23C6 carbide when the carbon concentration exceeded 0.1mass%. Carbon concentrations less than 0.1mass% exhibited minimal contribution to strengthening, but the formation of the M23C6 carbide particles increased the alloy strength. On the other hand, elongation-to-failure increased with increasing carbon content when the carbon concentration is relatively low. However, the coarse M23C6 carbide particles formed by higher concentrations of carbon were detrimental to ductility. Thus, a maximum elongation-to-failure was obtained at carbon concentrations of around 0.1mass%. The results of the current study can aid in the design of biomedical Co-28Cr-9W-1Si-based alloys containing carbon.

Assessment of precipitation behavior in dental castings of a Co–Cr–Mo alloy

This study investigated solute portioning and precipitation in dental castings of a Co-Cr-Mo alloy and discussed their effects on alloy performance, in particular, the mechanical properties. Samples of a commercial Co-29Cr-6Mo (mass%) alloy were prepared using a dental-casting machine. The precipitates formed owing to the partitioning behaviors of the alloying elements were investigated using scanning electron microscopy, electron backscatter diffraction analysis, electron probe microanalysis, and transmission electron microscopy. The prepared samples exhibited a very coarse face-centered-cubic γ-phase dendritic structure with an average grain size of a few millimeters. A large number of precipitates, which decomposed further into complex interdendritic constituents (σ- and M23C6 carbide phases) were observed in the interdendritic regions rich in Cr, Mo, Si, and C. A reaction between the σ-phase and carbon is probably responsible for the carbide M23C6; however, this reaction did not occur to completion in the current case in spite of slow cooling (i.e., long exposure to elevated temperatures) in dental casting. While these precipitates result in high strength (hardness) and/or brittleness, the properties can be improved further by optimizing the alloy composition and the manufacturing process. The results of this study shed light on the significance of precipitation control in dental castings of Co-Cr-Mo alloys and should aid in the design of novel biomedical Co-Cr-based dental alloys that exhibit better performances.

Analysis of the Fracture Mechanism of Ti-6Al-4V Alloy Rods That Failed Clinically After Spinal Instrumentation Surgery.

Study Design. Retrieval analysis of 2 Ti-6Al-4V alloy rods that fractured after spinal instrumentation surgery. Objective. To determine the mechanism that underlies fractures of Ti-6Al-4V alloy rods after spinal instrumentation surgery from a materials science viewpoint. Summary of Background Data. Rod failures after spinal instrumentation surgery are often reported and many case-based studies have been published. However, the details of the mechanism that underlies the fractures have not yet been fully elucidated. Methods. Two patients, a 71-year-old female and an 11-year-old male, underwent radiography and removal of their fractured rods. The latter patient had been treated using the growing-rod method. Metallurgical failure analysis of the retrieved rods was conducted, and material properties were compared between the unused and fractured rods. Results. The microstructures and mechanical properties of the Ti-6Al-4V alloy rods that failed after spinal instrumentation surgery were similar to those of unused rods. Analysis of the fracture surfaces clearly identified fatigue cracking in both cases that would have lowered the resistance of the rods to failures caused by external stresses. Shot blasting the surfaces of Ti-6Al-4V alloy rods and bending the rods to fit particular contours, which is always conducted during spinal instrumentation surgery, probably introduced fatigue cracking because the alloy is highly notch sensitive. Conclusion. Improvements should be made to rod design and/or rod material, because the fatigue resistance of titanium alloys is intrinsically lower than that of other commercially available rod materials, including cobalt-chromium alloys. These imperfections may have greater consequences for the growing-rod method and pseudarthrosis, where the rods are not completely fixed, and they subsequently suffer from severe long-arm moments. Level of Evidence: N/A

Developing high strength and ductility in biomedical Co–Cr cast alloys by simultaneous doping with nitrogen and carbon

UNLABELLED There is a strong demand for biomedical Co-Cr-based cast alloys with enhanced mechanical properties for use in dental applications. We present a design strategy for development of Co-Cr-based cast alloys with very high strength, comparable to that of wrought Co-Cr alloys, without loss of ductility. The strategy consists of simultaneous doping of nitrogen and carbon, accompanied by increasing of the Cr content to increase the nitrogen solubility. The strategy was verified by preparing Co-33Cr-9W-0.35N-(0.01-0.31)C (mass%) alloys. We determined the carbon concentration dependence of the microstructures and their mechanical properties. Metal ion release of the alloys in an aqueous solution of 0.6% sodium chloride (NaCl) and 1% lactic acid was also evaluated to ensure their corrosion resistance. As a result of the nitrogen doping, the formation of a brittle σ-phase, a chromium-rich intermetallic compound, was significantly suppressed. Adding carbon to the alloys resulted in finer-grained microstructures and carbide precipitation; accordingly, the strength increased with increasing carbon concentration. The tensile ductility, on the other hand, increased with increasing carbon concentration only up to a point, reaching a maximum at a carbon concentration of ∼0.1mass% and decreasing with further carbon doping. However, the alloy with 0.31mass% of carbon exhibited 14% elongation and also possessed very high strength (725MPa in 0.2% proof stress). The addition of carbon did not significantly degrade the corrosion resistance. The results show that our strategy realizes a novel high-strength Co-Cr-based cast alloy that can be produced for advanced dental applications using a conventional casting procedure. STATEMENT OF SIGNIFICANCE The present study suggested a novel alloy design concept for realizing high-strength Co-Cr-based cast alloys. The proposed strategy is beneficial from the practical point of view because it uses conventional casting approach-a simpler, more cost-effective, industrially friendly manufacturing process than other manufacturing processes such as thermomechanical processing or powder metallurgy. The developed alloys showed the excellent strength-ductility balance and significantly high strength comparable to that of wrought Co-Cr-Mo alloys, while maintaining acceptable ductility and good corrosion resistance. We described the relationship between microstructures and mechanical and corrosion prosperities of the developed alloys; this provides the fundamental aspect of the proposed strategy and will be helpful for further investigations or industrial realization of the proposed strategy.

Superthermostability of nanoscale TIC-reinforced copper alloys manufactured by a two-step ball-milling process

A Cu-TiC alloy, with nanoscale TiC particles highly dispersed in the submicron-grained Cu matrix, was manufactured by a self-developed two-step ball-milling process on Cu, Ti and C powders. The thermostability of the composite was evaluated by high-temperature isothermal annealing treatments, with temperatures ranging from 727 to 1273 K. The semicoherent nanoscale TiC particles with Cu matrix, mainly located along the grain boundaries, were found to exhibit the promising trait of blocking grain boundary migrations, which leads to a super-stabilized microstructures up to approximately the melting point of copper (1223 K). Furthermore, the Cu-TiC alloys after annealing at 1323 K showed a slight decrease in Vickers hardness as well as the duplex microstructure due to selective grain growth, which were discussed in terms of hardness contributions from various mechanisms.