Effect of Alloying Elements on the High-Temperature Yielding Behavior of Multicomponent γ'-L12 Alloys.

The exceptional mechanical properties of Ni-based high entropy alloys are due to the presence of ordered L12 (γ') precipitates embedded within a disordered matrix phase. While the strengthening contribution of the γ' phase is generally accepted, there is no consensus on the precise contribution of the individual strengthening mechanisms to the overall strength. In addition, changes in alloy composition influence several different mechanisms, making the assessment of alloying conditions complex. Multicomponent L12-ordered single-phase alloys were systematically developed with the aid of CALPHAD thermodynamic calculations. The alloying elements Co, Cr, Ti, and Nb were chosen to complexify the Ni3Al structure. The existence of the γ' single phase was validated by microstructure characterization and phase identification. A high-temperature compression test from 500 °C to 1000 °C revealed a positive temperature dependence of strength before reaching the peak strength in the studied alloys NiCoCrAl, NiCoCrAlTi, and NiCoCrAlNb. Ti and Nb alloying addition significantly enhanced the high-temperature yield strengths before the peak temperature. The yield strength was modeled by summing the individual effects of solid solution strengthening, grain boundary strengthening, order strengthening, and cross-slip-induced strengthening. Cross-slip-induced strengthening was shown to be the key contributor to the high-temperature strength enhancement.

Thermoelectric Properties of Variants of Cu4Mn2Te4 with Spinel-Related Structure.

Thermoelectric properties of Cu4Mn2Te4, which is antiferromagnetic with a Néel temperature TN = 50 K and crystallizes in a spinel-related structure, have been investigated comprehensively here. The phase transition occurring at temperatures 463 and 723 K is studied by high-temperature X-ray diffraction (XRD) and differential scanning calorimetry (DSC), and its effect on thermoelectric properties is examined. Hypothetically Cu4Mn2Te4 is semiconducting according to the formula (Cu+)4(Mn2+)2(Te2-)4, while experimentally it shows p-type metallic conduction behavior, exhibiting electrical conductivity σ = 2500 Ω-1 cm-1 and Seebeck coefficient α = 20 µV K-1 at 325 K. Herein, we show that the carrier concentration and thus the thermoelectric transport properties could be further optimized through adding electron donors such as excess Mn. Discussions are made on the physical parameters contributing to the low thermal conductivity, including Debye temperature, speed of sound, and the Grüneisen parameter. As a result of simultaneously boosted power factor and reduced thermal conductivity, a moderately high zT = 0.65 at 680 K is obtained in an excess Mn\In co-added sample, amounting to 5 times that of the pristine Cu4Mn2Te4. This value ( zT = 0.65) is the best result ever reported for spinel and spinel-related chalcogenides.

Forging property, processing map, and mesoscale microstructural evolution modeling of a Ti-17 alloy with a lamellar (α+ß) starting microstructure.

This work identifies microstructural conversion mechanisms during hot deformation (at temperatures ranging from 750 °C to 1050 °C and strain rates ranging from 10-3 s-1 to 1 s-1) of a Ti-5Al-2Sn-2Zr-4Mo-4Cr (Ti-17) alloy with a lamellar starting microstructure and establishes constitutive formulae for predicting the microstructural evolution using finite-element analysis. In the α phase, lamellae kinking is the dominant mode in the higher strain rate region and dynamic globularization frequently occurs at higher temperatures. In the ß phase, continuous dynamic recrystallization is the dominant mode below the transition temperature, Tß (880~890 °C). Dynamic recovery tends to be more active at conditions of lower strain rates and higher temperatures. At temperatures above Tß , continuous dynamic recrystallization of the ß phase frequently occurs, especially in the lower strain rate region. A set of constitutive equations modeling the microstructural evolution and processing map characteristic are established by optimizing the experimental data and were later implemented in the DEFORM-3D software package. There is a satisfactory agreement between the experimental and simulated results, indicating that the established series of constitutive models can be used to reliably predict the properties of a Ti-17 alloy after forging in the (α+ß) region.

Extraordinary high strength Ti-Zr-Ta alloys through nanoscaled, dual-cubic spinodal reinforcement.

While titanium alloys represent the current state-of-the-art for orthopedic biomaterials, concerns still remain over their modulus. Circumventing this via increased porosity requires high elastic admissible strains, yet also limits traditional thermomechanical strengthening techniques. To this end, a novel ß-type Ti-Zr-Ta alloy system, comprised of Ti-45Zr-10Ta, Ti-40Zr-14Ta, Ti-35Zr-18Ta and Ti-30Zr-22Ta, was designed and characterized mechanically and microstructurally. As-cast, this system displayed extremely high yield strengths and elastic admissible strains, up to 1.4GPa and potentially 1.48%, respectively. This strength was attributed to a nanoscaled, cuboidal structure of semi-coherent, dual body-centered cubic (BCC) phases, arising from the thermodynamics of interaction between Ta and Zr; this morphology occurring with dual BCC-phases is heretofore unreported in Ti-based alloys. Further, cell proliferation investigated by MTS assay suggests this was achieved without sacrificing biocompatibility, with no significant difference to either empty-well or commercially-pure Ti controls noted. STATEMENT OF SIGNIFICANCE: The current research details microstructural, mechanical, and biological investigations into four novel biomedical alloys in a hitherto uninvestigated region of the Ti-Zr-Ta alloy system; Ti-45Zr-10Ta, Ti-40Zr-14Ta, Ti-35Zr-18Ta and Ti-30Zr-22Ta. We find that the investigated alloys display 0.2% yield strengths of up to 1.40GPa and elastic admissible strains of up to 1.48%, along with biological properties comparable to that seen in the conventional metallic biomaterial ASTM Grade-2 CP-Ti, achieved in the complete absence of traditional thermomechanical processing techniques. This is attributed to the presence of a dual-BCC cuboidal nanostructure, achieved via spinodal decomposition; while similar structures have been reported in e.g. Ni-based superalloys, we believe this is the first such structure investigated in a Ti-based material. As such, this work is felt to be of great interest in aiding the design and manufacture of highly-biocompatible, porous, metallic biomaterials for orthopedic application.

Impact of ruthenium on mechanical properties, biological response and thermal processing of ß-type Ti-Nb-Ru alloys.

In this paper, we present further work on the influence of minor additions of Ru to the Ti-20Nb alloy system, with a primary focus on mechanical properties of the as-cast material, along with microstructural response to elevated temperatures. Findings include high as-cast strengths and admissible strain values, up to 920MPa and 1.5% respectively, along with moduli down to approximately 65GPa in the as-cast state. Together with a significant increase in cell proliferation under MTS assay relative to controls, this indicates the chosen alloy system has significant promise for application in porous orthopaedic biomaterials, in particular those alloys with 0.5-1.0% Ru are deemed most suitable. Given their promise, preliminary investigation of the alloy system's response to thermal treatment was also undertaken. STATEMENT OF SIGNIFICANCE: The presented research, an investigation into the mechanical properties and response to thermal treatments of Ru-containing Ti-20Nb-base alloys, holds significance in the field of metallic biomaterials due to the heretofore limited investigation into the impact of Ru on the properties of biomedical, ß-phase, Ti-based alloys. Given Ru's known beneficial impact on corrosion resistance, experimental confirmation of the impact of addition on mechanical properties was needed; that suitable mechanical properties, including yield strengths up to ∼930MPa along with elastic admissible strains approaching 1.5%, were achieved is both promising in and of itself, and of significant note for further research into the field. Preliminary thermal and cell-proliferation studies are additionally provided to inform further studies.

Investigations into Ti-(Nb,Ta)-Fe alloys for biomedical applications.

In this study, a Ti-(Ta,Nb)-Fe system was investigated with aims toward the development of high strength, biocompatible titanium alloy suitable for the development of porous orthopedic biomaterials with minimal processing. Notable findings include yield strengths of 740, 1250 and 1360 MPa for the Ti-12Nb-5Fe, Ti-7Ta-5Fe and Ti-10Ta-4Fe alloys, respectively, with elastic moduli comparable to existing Ti-alloys, yielding admissible strains of 0.9 ± 0.3, 1.2 ± 0.2 and 1.13 ± 0.02% for the Ti-12Nb-5Fe, Ti-7Ta-5Fe and Ti-10Ta-4Fe alloys, respectively; more than twice that of human bone. Observed microstructure varied significantly depending on alloy; near pure ß-phase was seen in Ti-12Nb-5Fe, ß with some ω precipitation in Ti-10Ta-4Fe, and a duplex α+ß structure was observed throughout the Ti-7Ta-5Fe. In addition to suitable mechanical parameters, all investigated alloys exhibited promising corrosion potentials on the order of -0.24 V SCE, equalling that seen for a C.P.-Ti control at -0.25V SCE, and substantially more noble than that seen for Ti-6Al-4V. Electrochemical corrosion rates of 0.5-3 µm/year were likewise seen to agree well with that measured for C.P.-Ti. Further, no statistically significant difference could be seen between any of the alloys relative to a C.P.-Ti control regards to cell proliferation, as investigated via MTS assay and confocal microscopy. As such, the combination of high admissible strain and low corrosion indicate all investigated alloys show significant promise as potential porous biomaterials while in the as-cast state, with the Ti-10Ta-4Fe alloy identified as the most promising composition investigated. STATEMENT OF SIGNIFICANCE: The findings of this paper are of significance to the field of metallic biomaterials as they detail the development of alloys of satisfactory biocompatibility and electrochemical behaviour, that furthermore display exceptional mechanical properties. Notably, both extremely high compressive yield strengths and admissible strains, up to 1.36 GPa and 1.2% respectively, are reported, exceeding or rivalling that seen in traditional alloys such as Ti-6Al-4V, which typically displays compressive yield strengths and admissible strains on the order of 895 MPa and 0.81% respectively, as well as modern alloys such as Gum Metal or TNZT. That this is achieved in the absence of thermomechanical processing represents a significant and novel outcome of substantial benefit for application as a porous biomaterial.

Correlation between the surface electronic structure and CO-oxidation activity of Pt alloys.

The surface electronic structure and CO-oxidation activity of Pt and Pt alloys, Pt3T (T = Ti, Hf, Ta, Pt), were investigated. At temperatures below 538 K, the CO-oxidation activities of Pt and Pt3T increased in the order Pt < Pt3Ti < Pt3hHf < Pt3Ta. The center-of-gravity of the Pt d-band (the d-band center) of Pt and Pt3T was theoretically calculated to follow the trend Pt3Ti < Pt3Ta < Pt3Hf < Pt. The CO-oxidation activity showed a volcano-type dependence on the d-band center, where Pt3Ta exhibited a maximum in activity. Theoretical calculations demonstrated that the adsorption energy of CO on the catalyst surface monotonically decreases with the lowering of the d-band center because of diminished hybridization of the surface d-band and the lowest-unoccupied molecular orbital (LUMO) of CO. The observed volcano-type correlation between the d-band center and the CO oxidation activity is rationalized in terms of the CO adsorption energy, which counterbalances the surface coverage by CO and the rate of CO oxidation.

Pt3Ti nanoparticles: fine dispersion on SiO2 supports, enhanced catalytic CO oxidation, and chemical stability at elevated temperatures.

A platinum-based intermetallic phase with an early d-metal, Pt(3)Ti, has been synthesized in the form of nanoparticles (NPs) dispersed on silica (SiO(2)) supports. The organometallic Pt and Ti precursors, Pt(1,5-cyclooctadiene)Cl(2) and TiCl(4)(tetrahydrofuran)(2), were mixed with SiO(2) and reduced by sodium naphthalide in tetrahydrofuran. Stoichiometric Pt(3)Ti NPs with an average particle size of 2.5 nm were formed on SiO(2) (particle size: 20-200 nm) with an atomically disordered FCC-type structure (Fm3m; a = 0.39 nm). A high dispersivity of Pt(3)Ti NPs was achieved by adding excessive amounts of SiO(2) relative to the Pt precursor. A 50-fold excess of SiO(2) resulted in finely dispersed, SiO(2)-supported Pt(3)Ti NPs that contained 0.5 wt % Pt. The SiO(2)-supported Pt(3)Ti NPs showed a lower onset temperature of catalysis by 75 degrees C toward the oxidation reaction of CO than did SiO(2)-supported pure Pt NPs with the same particle size and Pt fraction, 0.5 wt %. The SiO(2)-supported Pt(3)Ti NPs also showed higher CO conversion than SiO(2)-supported pure Pt NPs even containing a 2-fold higher weight fraction of Pt. The SiO(2)-supported Pt(3)Ti NPs retained their stoichiometric composition after catalytic oxidation of CO at elevated temperatures, 325 degrees C. Pt(3)Ti NPs show promise as a catalytic center of purification catalysts for automobile exhaust due to their high catalytic activity toward CO oxidation with a low content of precious metals.