Green fabrication of ultrafine N-MoxC/CoP hybrids for boosting electrocatalytic water reduction.

Developing non-noble-metal electrocatalysts for hydrogen evolution reactions with high activity and stability is the key issue in green hydrogen generation based on electrolytic water splitting. It has been recognized that the stacking of large CoP particles limits the intrinsic activity of as-synthesized CoP catalyst for hydrogen evolution reaction. In the present study, N-MoxC/CoP-0.5 with excellent electrocatalytic activity for hydrogen evolution reaction was prepared using N-MoxC as decoration. A reasonable overpotential of 106 mV (at 10 mA cm-2) and a Tafel slope of 59 mV dec-1in 1.0 M KOH solution was achieved with N-MoxC/CoP-0.5 electrocatalyst, which exhibits superior activity even after working for 37 h. Uniformly distributed ultrafine nanoclusters of the N-MoxC/CoP-0.5 hybrids could provide sufficient interfaces for enhanced charge transfer. The effective capacity of the hydrogen evolution reaction could be preserved in the complex, and the enlarged electrocatalytic surface area could be expected to offer more active sites for the reaction.

A bilayer biocompatible polycaprolactone/zinc oxide/Capparis spinosa L. ethyl acetate extract/polylactic acid nanofibrous composite scaffold for novel wound dressing applications.

Capparis spinosa L. (CSL) is used in traditional medicinal purposes for wound dressing because it contains natural phenolic and flavonoid active compounds. In the current study, a bilayer of biocompatible and mechanically stable nanofiber scaffolds with polycaprolactone (PCL)/zinc oxide and Capparis spinosa L. ethyl acetate extract (CSLE)/polylactic acid (PLA) layers was successfully prepared by an electrostatic spinning technique. Microstructural observations carried out by scanning electron microscopy (SEM) have shown that the nanofibers with a smooth surface are continuous and bead-free, and that the size distribution is uniform, with an average diameter of 314.15 nm. The results of careful observation further suggested that polymers in the nanofibers have excellent compatibility with drugs. The results of Fourier transform infrared (FTIR) spectroscopy suggested that CSLE and zinc oxide nanoparticles (ZnO) were successfully loaded in the nanofiber membranes. Water contact angle measurements revealed that the bilayer nanofiber membranes exhibited satisfactory wettability (outside layer, 130°; inner layer, 72.4°). Tensile testing showed that the bilayer PCL/ZnO-CSLE/PLA nanofibers remained unbroken until reaching 10.69 MPa, which is much higher than the tensile strengths of the individual layers or the individual components. Moreover, agar disk diffusion assessment confirmed that the bilayer nanofiber membranes obviously hindered bacterial growth. Cytotoxicity studies showed that the bilayer nanofiber membranes effectively accelerated cell proliferation. The investigated PCL/ZnO-CSLE/PLA bilayer nanofibers have potential for use as membranes for wound dressing applications.

The Formation Mechanism of Nanocrystals after Martensitic Transformation.

Understanding the ultrafine substructure in freshly formed Fe-C martensite is the key point to reveal the real martensitic transformation mechanism. As-quenched martensite, whose transformation temperature is close to room temperature, has been investigated in detail by means of transmission electron microscopy (TEM) in this study. The observation results revealed that the freshly formed martensite after quenching is actually composed of ultrafine crystallites with a grain size of 1−2 nm. The present observation result matches well with the suggestion based on X-ray studies carried out one hundred years ago. Such nanocrystals are distributed throughout the entire martensite. The whole martensite shows a uniform contrast under both bright and dark field observation modes, irrespective of what observation directions are chosen. No defect contrast can be observed inside each nanocrystal. However, a body-centered cubic {112}<111>-type twinning relationship exists among the ultrafine α-Fe grains. Such ultrafine α-Fe grains or crystallites are the root cause of the fine microstructure formed in martensitic steels and high hardness after martensitic transformation. The formation mechanism of the ultrafine α-Fe grains in the freshly formed martensite will be discussed based on a new γ → α phase transformation mechanism.

Twinning behavior of orthorhombic-α" martensite in a Ti-7.5Mo alloy.

Deformation microstructure of orthorhombic-α" martensite in a Ti-7.5Mo (wt.%) alloy was investigated by tracking a local area of microstructure using scanning electron microscopy, electron back-scattered diffraction, and transmission electron microscopy. The as-quenched α" plates contain {111}α"-type I transformation twins generated to accommodate transformation strain from bcc-ß to orthorhombic-α" martensite. Tensile deformation up to strain level of 5% induces {112}α"-type I deformation twins. The activation of {112}α"-type I deformation twinning mode is reported for the first time in α" martensite in ß-Ti alloys. {112}α"-type I twinning mode was analyzed by the crystallographic twinning theory by Bilby and Crocker and the most possible mechanism of atomic displacements (shears and shuffles) controlling the newly reported {112}α"-type I twinning were proposed.

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.

Novel Ti-Ta-Hf-Zr alloys with promising mechanical properties for prospective stent applications.

Titanium alloys are receiving increasing research interest for the development of metallic stent materials due to their excellent biocompatibility, corrosion resistance, non-magnetism and radiopacity. In this study, a new series of Ti-Ta-Hf-Zr (TTHZ) alloys including Ti-37Ta-26Hf-13Zr, Ti-40Ta-22Hf-11.7Zr and Ti-45Ta-18.4Hf-10Zr (wt.%) were designed using the d-electron theory combined with electron to atom ratio (e/a) and molybdenum equivalence (Moeq) approaches. The microstructure of the TTHZ alloys were investigated using optical microscopy, XRD, SEM and TEM and the mechanical properties were tested using a Vickers micro-indenter, compression and tensile testing machines. The cytocompatibility of the alloys was assessed using osteoblast-like cells in vitro. The as-cast TTHZ alloys consisted of primarily ß and ω nanoparticles and their tensile strength, yield strength, Young's modulus and elastic admissible strain were measured as being between 1000.7-1172.8 MPa, 1000.7-1132.2 MPa, 71.7-79.1 GPa and 1.32-1.58%, respectively. The compressive yield strength of the as-cast alloys ranged from 1137.0 to 1158.0 MPa. The TTHZ alloys exhibited excellent cytocompatibility as indicated by their high cell viability ratios, which were close to that of CP-Ti. The TTHZ alloys can be anticipated to be promising metallic stent materials by virtue of the unique combination of extraordinarily high elastic admissible strain, high mechanical strength and excellent biocompatibility.

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.

A new nanoscale metastable iron phase in carbon steels.

Metastable ω phase is common in body-centred cubic (bcc) metals and alloys, including high-alloying steels. Recent theoretical calculations also suggest that the ω structure may act as an intermediate phase for face-centred cubic (fcc)-to-bcc transformation. Thus far, the role of the ω phase played in fcc-bcc martensitic transformation in carbon steels has not been reported. In previous investigations on martensitic carbon steels, extra electron diffraction spots were frequently observed by transmission electron microscopy (TEM), and these spots were historically ascribed to the diffraction arising from either internal twins or carbides. In this paper, an intensive TEM investigation revealed that the extra spots are in fact attributed to the metastable ω phase in particle-like morphology with an overall size of several or dozens of nanometres. The strict orientation relationships between the ω phase and the ferrite matrix are in good agreement with those of the hexagonal (P6/mmm) ω phase in other bcc metals and alloys. The identification of the ω phase as well as the extra diffraction spots might provide a clue to help understand the physical mechanism of martensitic transformation in steels.

Controlled photocatalytic growth of Ag nanocrystals on brookite and rutile and their SERS performance.

Ag nanocrystals (NCs) were photocatalytically grown on the surfaces of brookite and rutile nanocrystals, respectively, and their surface-enhanced Raman scattering (SERS) performance was evaluated. The resultant Ag NCs exhibit different morphologies owing to the different photocatalytic capabilities of the two types of TiO2 under otherwise identical synthetic conditions. The effects of AgNO3 concentration, UV irradiation time, and UV light power on the morphology evolution and growth kinetics of the Ag NCs were systematically investigated. Moreover, PVP was found to serve as both a reductant and a capping agent in the photocatalytic reaction systems, and its presence allows morphological control of the Ag NCs. A proper amount of PVP was confirmed to favor Ag nanoplates of larger sizes and to produce SERS substrates of substantially better performance.