Junko Hieda

Development of new metallic alloys for biomedical applications.

New low modulus β-type titanium alloys for biomedical applications are still currently being developed. Strong and enduring β-type titanium alloy with a low Youngs modulus are being investigated. A low modulus has been proved to be effective in inhibiting bone atrophy, leading to good bone remodeling in a bone fracture model in the rabbit tibia. Very recently β-type titanium alloys with a self-tunable modulus have been proposed for the construction of removable implants. Nickel-free low modulus β-type titanium alloys showing shape memory and super elastic behavior are also currently being developed. Nickel-free stainless steel and cobalt-chromium alloys for biomedical applications are receiving attention as well. Newly developed zirconium-based alloys for biomedical applications are proving very interesting. Magnesium-based or iron-based biodegradable biomaterials are under development. Further, tantalum, and niobium and its alloys are being investigated for biomedical applications. The development of new metallic alloys for biomedical applications is described in this paper.

Exotic shapes of gold nanoparticles synthesized using plasma in aqueous solution

Gold nanoparticles with exotic shapes, such as triangle, pentagon, and hexagon, have been synthesized by glow discharge in aqueous solutions. A pulsed power supply was used to generate discharges in the aqueous solutions. Pulse width and frequency were 2 μs and 15 kHz, respectively. Discharges were generated at applied voltages of 1600 and 3200 V. The shapes of the gold nanoparticles and electron diffraction patterns were observed by transmission electron microscopy. The nanoparticles obtained were about 20 nm in diameter. In particular, at the higher voltage of 3200 V, nanoparticles with anisotropic shapes were synthesized. In the initial stages of synthesis, diameter decreased with discharge time as the nanoparticles redissolved in the solution. After discharge for 25 min, nanoparticles with anisotropic shapes appeared. This discharge led to the generation of H2O2 and a decrease in pH as a result of the consumption of OH radicals during the generation of H2O2 and electron donation of H radicals to the s...

Beta type Ti-Mo alloys with changeable Young's modulus for spinal fixation applications.

To develop a novel biomedical titanium alloy with a changeable Youngs modulus via deformation-induced ω phase transformation for the spinal rods in spinal fixation devices, a series of metastable β type binary Ti-(15-18)Mo alloys were prepared. In this study, the microstructures, Youngs moduli and tensile properties of the alloys were systemically examined to investigate the effects of deformation-induced ω phase transformation on their mechanical properties. The springback of the optimal alloy was also examined. Ti-(15-18)Mo alloys subjected to solution treatment comprise a β phase and a small amount of athermal ω phase, and they have low Youngs moduli. All the alloys investigated in this study show an increase in the Youngs modulus owing to deformation-induced ω phase transformation during cold rolling. The deformation-induced ω phase transformation is accompanied with {332}(β) mechanical twinning. This resulted in the maintenance of acceptable ductility with relatively high strength. Among the examined alloys, the Ti-17Mo alloy shows the lowest Youngs modulus and the largest increase in the Youngs modulus. This alloy exhibits small springback and could be easily bent to the required shape during operation. Thus, Ti-17Mo alloy is considered to be a potential candidate for the spinal rods in spinal fixation devices.

Mechanical properties of a medical β-type titanium alloy with specific microstructural evolution through high-pressure torsion

The effect of high-pressure torsion (HPT) processing on the microstructure and mechanical biocompatibility includes Youngs modulus, tensile strength, ductility, fatigue life, fretting fatigue, wear properties and other functionalities such as super elasticity and shape memory effect, etc. at levels suitable for structural biomaterials used in implants that replace hard tissue in the broad sense (Sumitomo et al., 2008 [4]). In particular, in this study, the mechanical biocompatibility implies a combination of great hardness and high strength with an adequate ductility while keeping low Youngs modulus of a novel Ti-29Nb-13Ta-4.6Zr (TNTZ) for biomedical applications at rotation numbers (N) ranging from 1 to 60 under a pressure of 1.25 GPa at room temperature was systematically investigated in order to increase its mechanical strength with maintaining low Youngs modulus and an adequate ductility. TNTZ subjected to HPT processing (TNTZHPT) at low N exhibits a heterogeneous microstructure in micro-scale and nano-scale consisting of a matrix and a non-etched band, which has nanosized equiaxed and elongated single β grains, along its cross section. The grains exhibit high dislocation densities, consequently non-equilibrium grain boundaries, and non-uniform subgrains distorted by severe deformation. At high N which is N>20, TNTZHPT has a more homogeneous microstructure in nano-scale with increasing equivalent strain, εeq. Therefore, TNTZHPT at high N exhibits a more homogenous hardness distribution. The tensile strength and 0.2% proof stress of TNTZHPT increase significantly with N over the range of 0≤N≤5, and then become saturated at around 1100 MPa and 800 MPa at N≥10. However, the ductility of TNTZHPT shows a reverse trend and a low-level elongation, at around 7%. And, Youngs modulus of TNTZHPT decreases slightly to 60 GPa with increasing N and then becomes saturated at N≥10. These obtained results confirm that the mechanical strength of TNTZ can be improved while maintaining a low Youngs modulus in single β grain structures through severe plastic deformation.

Optimization of Cr content of metastable β-type Ti–Cr alloys with changeable Young’s modulus for spinal fixation applications

Metallic implant rods used in spinal fixtures should have a Youngs modulus that is sufficiently low to prevent stress shielding for the patient and sufficiently high to suppress springback for the surgeon. Therefore, we propose a new concept: novel biomedical titanium alloys with a changeable Youngs modulus via deformation-induced ω phase transformation. In this study, the Cr content in the range of 10-14 mass% was optimized to produce deformation-induced ω phase transformation, resulting in a large increase in the Youngs modulus of binary Ti-Cr alloys. The springback and cytotoxicity of the optimized alloys were also examined. Ti-(10-12)Cr alloys exhibit an increase in Youngs modulus owing to deformation-induced ω phase transformation. In this case, such deformation-induced ω phase transformation occurs along with {332}(β) mechanical twinning, resulting in the maintenance of acceptable ductility with relatively high strength. Among the examined alloys, the lowest Youngs modulus and largest increase in Youngs modulus are obtained from the Ti-12Cr alloy. This alloy exhibits smaller springback than and comparable cytocompatibility to the biomedical Ti alloy Ti-29Nb-13Ta-4.6Zr.

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.

Functionalization of Multiwalled Carbon Nanotubes by Solution Plasma Processing in Ammonia Aqueous Solution and Preparation of Composite Material with Polyamide 6

Solution plasma processing (SPP) has been performed on multiwalled carbon nanotubes (MWCNTs) in ammonia aqueous solution. The MWCNTs, which do not disperse in aqueous solution, uniformly dispersed after the SPP. Only 2 h was required to obtain 10 g of the dispersed MWCNTs, while 7 days and additional chemicals were required for 185 mg in a previous study. The X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy of the SPP-treated MWCNTs revealed that nitrogen- and oxygen-containing groups are formed on the MWCNTs. Serious damage to the MWCNT structure was not observed in the Raman spectrum or transmission electron microscopy images of the SPP-treated MWCNTs. The composite materials prepared using polyamide 6 with the SPP-treated MWCNTs showed better tensile, bending, and impact strength than those prepared with nontreated MWCNTs.

Development of thermo-mechanical processing for fabricating highly durable β-type Ti–Nb–Ta–Zr rod for use in spinal fixation devices

The mechanical strength of a beta titanium alloy such as Ti-Nb-Ta-Zr alloy (TNTZ) can be improved significantly by thermo-mechanical treatment. In this study, TNTZ was subjected to solution treatment, cold caliber rolling, and cold swaging before aging treatment to form a rod for spinal fixation. The {110}(β) are aligned parallel to the cross-section with two strong peaks approximately 180° apart, facing one another, in the TNTZ rods subjected to cold caliber rolling and six strong peaks at approximately 60° intervals, facing one another, in the TNTZ rods subjected to cold swaging. Therefore, the TNTZ rods subjected to cold swaging have a more uniform structure than those subjected to cold caliber rolling. The orientation relationship between the α and β phases is different. A [110](β)//[121](α), (112)(β)//(210)(α) orientation relationship is observed in the TNTZ rods subjected to aging treatment at 723 K after solution treatment and cold caliber rolling. On the other hand, a [110](β)//[001](α), (112)(β)//(200)(α) orientation relationship is observed in TNTZ rod subjected to aging treatment at 723 K after cold swaging. A high 0.2% proof stress of about 1200 MPa, high elongation of 18%, and high fatigue strength of 950 MPa indicate that aging treatment at 723 K after cold swaging is the optimal thermo-mechanical process for a TNTZ rod.

Deformation-induced ω phase in modified Ti-29Nb-13Ta-4.6Zr alloy by Cr addition.

For spinal-fixation applications, implants should have a high Youngs modulus to reduce springback during operations, though a low Youngs modulus is required to prevent stress shielding for patients after surgeries. In the present study, Ti-29Nb-13Ta-4.6Zr alloy (TNTZ) with a low Youngs modulus was modified by adding Cr to obtain a higher deformation-induced Youngs modulus in order to satisfy these contradictory requirements. Two newly designed alloys, TNTZ-8Ti-2Cr and TNTZ-16Ti-4Cr, possess more stable β phases than TNTZ. These alloys consist of single β phases and exhibit relatively low Youngs moduli of <65GPa after solution treatment. However, after cold rolling, they exhibit higher Youngs moduli owing to a deformation-induced ω-phase transformation. These modified TNTZ alloys show significantly less springback than the original TNTZ alloy based on tensile and bending loading-unloading tests. Thus, the Cr-added TNTZ alloys are beneficial for spinal-fixation applications.

Fastest Formation Routes of Nanocarbons in Solution Plasma Processes

Although solution-plasma processing enables room-temperature synthesis of nanocarbons, the underlying mechanisms are not well understood. We investigated the routes of solution-plasma-induced nanocarbon formation from hexane, hexadecane, cyclohexane, and benzene. The synthesis rate from benzene was the highest. However, the nanocarbons from linear molecules were more crystalline than those from ring molecules. Linear molecules decomposed into shorter olefins, whereas ring molecules were reconstructed in the plasma. In the saturated ring molecules, C–H dissociation proceeded, followed by conversion into unsaturated ring molecules. However, unsaturated ring molecules were directly polymerized through cation radicals, such as benzene radical cation, and were converted into two- and three-ring molecules at the plasma–solution interface. The nanocarbons from linear molecules were synthesized in plasma from small molecules such as C2 under heat; the obtained products were the same as those obtained via pyrolysis synthesis. Conversely, the nanocarbons obtained from ring molecules were directly synthesized through an intermediate, such as benzene radical cation, at the interface between plasma and solution, resulting in the same products as those obtained via polymerization. These two different reaction fields provide a reasonable explanation for the fastest synthesis rate observed in the case of benzene.