I wish I was 21 now beyond doping in the Australian peloton

An investigation into the reasons for doping among professional athletes (cyclists) and attitudes towards and assessments of current attempts and form of legislation and regulation of doping, inlcuding prospects for reform, and types of reform required.

Corrosion of mg alloy ZE41 and its mitigation using ionic liquids

Magnesium alloy ZE41 (Mg-Zn-RE-Zr), which is used extensively in the aerospace industry, possesses excellent mechanical properties albeit poor corrosion resistance. This work investigates the mechanism of corrosion, and the interaction between the grain boundary intermetallic phases, the zirconium (Zr)-rich regions within the grains and the bulk Mg rich matrix in both the as-cast and heat-treated conditions. The results of optical and scanning electron microscopy (SEM) show the importance of the microstructure in the initiation and propagation of corrosion in an aqueous environment. The Zr-rich regions play a distinct role in the early stages of corrosion with this alloy. The second part of this work investigates the interaction of two different ionic liquids (ILs) with the surface of the ZE41 alloy. ILs based on trihexyltetradecylphosphonium (P 6,6,6,14) coupled with either diphenylphosphate (DPP) or bis(trifluoromethanesulfonyl) amide (Tf 2N) have been shown to react with Mg alloy surfaces, leading to the formation of a surface film that can improve the corrosion resistance of the alloy. The interaction of the ILs with the ZE41 surface has been investigated by optical microscopy and SEM. Surface characterization has been performed using Time of Flight-Secondary Ion Mass Spectrometry (ToF-SIMS) and X-ray Photoelectron Spectroscopy (XPS). The surface characterization and microscopy revealed the preferential interaction with the grain boundaries and grain boundary phases. Thus the morphology and microstructure of the Mg surface seems critical in determining the nature of the interaction with the IL. The corrosion protection of the IL films formed on the ZE41 surface was investigated by SEM and potentiodynamic polarisation.

Roles of additives in the trihexyl(tetradecyl) phosphonium chloride ionic liquid electrolyte for primary mg-air cells

As reported previously, water saturated trihexyl(tetradecyl)phosphonium chloride ([P6,6,6,14][Cl]) ionic liquid (IL) is a promising electrolyte for magnesium-air batteries. The added water plays an important role in enabling high rate and high efficiency Mg dissolution while stabilizing the Mg interphase. In this work, the role of the water was investigated by replacement with other additives such as toluene and tetrahydrofuran to specifically target the assumed roles of water, namely: (i) enhancement of transport properties; (ii) complexation and stabilization of the Mg anode; (iii) provision of active protons for the cathodic reaction. Discharge tests show that ethylene glycol supports comparable performance to that provided by water. Examination of the viscosity and conductivity of different [P6,6,6,14][Cl]/additive mixtures indicates that a simple consideration of solution characteristics cannot explain the observed trends. Rather, other factors, such as the presence of active protons and/or oxygen-donor groups, are also key features for the development of IL electrolytes for practical magnesium-air cells. Finally, the presence of ethylene glycol in the electrolyte results in a complex gel on the Mg interface, similar to that found in the presence of water. This may also play a role in enabling stable discharge of the Mg anode. © 2014 The Electrochemical Society.

Contribution of twinning to low strain deformation in a Mg alloy

Deformation twinning plays an important role in the yielding of extruded magnesium alloys, especially when loaded in compression along the extrusion axis. The magnitude of this contribution is not accurately known. The present study employs electron backscatter diffraction to reveal the influence of grain orientation on twin-volume fraction for alloy AZ31 tested in compression to strains between 0.008 and 0.015. For these strains, it is seen that approximately 45 pct of the deformation can be attributed to "tensile" twinning. The variation of twin-volume fraction over different orientation classes correlates closely with the maximum Schmid factors for both tensile twinning and basal slip. These effects are readily explained quantitatively using a mean field crystal plasticity model without recourse to stochastic effects. Encouraged by this, we introduce an analytical approximation based on the uniformity of (axial) work. © 2013 The Minerals, Metals & Materials Society and ASM International.

Highly sensitive SnO2 nanofiber chemiresistors with a low optimal operating temperature: synergistic effect of Cu2+/Au co-doping

Metal oxide chemiresistors (MOCs) with a low optimal operating temperature, high sensitivity and fast response/recovery are highly promising for various applications, but remain challenging to realize. Herein, we demonstrate that SnO2 nanofibers after being co-doped with Cu2+ and Au show considerably enhanced sensing performances at an unexpectedly decreased operating temperature. A synergistic effect occurs when the two dopants are introduced together. Co-doping may form a novel strategy to the development of ultrasensitive MOCs working at a low optimal temperature. This journal is © the Partner Organisations 2014.

A double inclusion homogenization scheme for polycrystals with hierarchal topologies: Application to twinning in Mg alloys

The present work introduces a double inclusion elasto-plastic self-consistent (DI-EPSC) scheme for topologies in which crystals can contain subdomains (i.e. twins, etc.). The approach yields a direct coupling between the mechanical response of grains and their subdomains via a concentration relationship on mean fields derived from both the Eshelby and the Tanaka-Mori properties. The latent effect caused by twinning on the mechanical response is observed on both initially extruded and non-textured Mg alloys. For twinned grains, it is shown that deformation system activities and plastic strain distributions within twins drastically depend on the interaction with parent domains. Moreover, a quantitative study on the coupled influence of secondary slip activities on the material response is proposed. © 2014 Published by Elsevier Ltd.

Effect of alloying and extrusion temperature on the microstructure and mechanical properties of Mg-Zn and Mg-Zn-RE alloys

Extruded Mg-Zn-RE alloys have been shown to exhibit excellent combinations of yield strength and ductility, but it is not completely clear how adding rare earth metals to Mg-Zn alters the microstructure and affects the mechanical properties. Microstructural changes and the resulting mechanical properties from changes in composition and extrusion temperature have been investigated for Mg-. x Zn-. y RE (. x=2.5 and 5. wt.%, y=0 and 1. wt. %, and RE=Gd and Y) alloys. Adding RE to Mg-Zn increased the strength and reduced the ductility, while increasing the zinc concentration in the Mg-Zn-RE alloys had the reverse effect.

Collagen type-I leads to in vivo matrix mineralization and secondary stabilization of Mg-Zr-Ca alloy implants

Biodegradable magnesium-zirconia-calcium (Mg-Zr-Ca) alloy implants were coated with Collagen type-I (Coll-I) and assessed for their rate and efficacy of bone mineralization and implant stabilization. The phases, microstructure and mechanical properties of these alloys were analyzed using X-ray diffraction (XRD), optical microscopy and compression test, respectively, and the corrosion behavior was established by their hydrogen production rate in simulated body fluid (SBF). Coll-I extracted from rat tail, and characterized using fourier transform infrared (FT-IR) spectroscopy, was used for dip-coating the Mg-based alloys. The coated alloys were implanted into the femur bones of male New Zealand white rabbits. In vivo bone formation around the implants was quantified by measuring the bone mineral content/density (BMC/BMD) using dual-energy X-ray absorptiometry (DXA). Osseointegration of the implant and new bone mineralization was visualized by histological and immunohistochemical analysis. Upon surface coating with Coll-I, these alloys demonstrated high surface energy showing enhanced performance as an implant material that is suitable for rapid and efficient new bone tissue induction with optimal mineral content and cellular properties. The results demonstrate that Coll-I coated Mg-Zr-Ca alloys have a tendency to form superior trabecular bone structure with better osteoinduction around the implants and higher implant secondary stabilization, through the phenomenon of contact osteogenesis, compared to the control and uncoated ones in shorter periods of implantation. Hence, Coll-I surface coating of Mg-Zr-Ca alloys is a promising method for expediting new bone formation in vivo and enhancing osseointegration in load bearing implant applications.

Supplementing cold plasma with heat enables doping and nano-structuring of metal oxides

Nitrogen doped SnO2 polycrystalline nanostructures were produced from commercial SnO powders in a new system that combines a low-temperature plasma with heating. The method has the potential to improve the initial efficiency and the cycling performance of SnO2 anodes in Li-ion batteries. With this system, the temperature of the SnO to SnO2 conversion was lowered from 430 to 320 °C, up to 5 at% of doped nitrogen was detected and a nano-scale polycrystalline structure was observed in the product. Combining heat and low-pressure plasma is a promising approach for the production and treatment of enhanced energy storage materials.

The effect of treatment temperature on corrosion resistance and hydrophilicity of an ionic liquid coating for mg-based stents

Mg alloys are attractive candidate materials for biodegradable stents. However, there are few commercially available Mg-based stents in clinical use because Mg alloys generally undergo rapid localized corrosion in the body. In this study, we report a new surface coating for Mg alloy AZ31 based on a low-toxicity ionic liquid (IL), tributyl(methyl)phosphonium diphenyl phosphate (P1,4,4,4 dpp), to control its corrosion rate. Emphasis is placed on the effect of treatment temperature. We showed that enhancing the treatment temperature provided remarkable improvements in the performances of both corrosion resistance and biocompatibility. Increasing treatment temperature resulted in a thicker (although still nanometer scale) and more homogeneous IL film on the surface. Scanning electron microscopy and optical profilometry observations showed that there were many large, deep pits formed on the surface of bare AZ31 after 2 h of immersion in simulated body fluid (SBF). The IL coating (particularly when formed at 100 °C for 1 h) significantly suppressed the formation of these pits on the surface, making corrosion occur more uniformly. The P1,4,4,4 dpp IL film formed at 100 °C was more hydrophilic than the bare AZ31 surface, which was believed to be beneficial for avoiding the deposition of the proteins and cells on the surface and therefore improving the biocompatibility of AZ31 in blood. The interaction mechanism between this IL and AZ31 was also investigated using ATR-FTIR, which showed that both anion and cation of this IL were present in the film, and there was a chemical interaction between dpp(-) anion and the surface of AZ31 during the film formation.

Grain growth and β-Mg17Al12 intermetallic phase dissolution during heat treatment and its impact on deformation behavior of AZ80 Mg-alloy

Microstructure evolution after solutionizing and ageing treatment of cast AZ80 Mg alloy were investigated using optical and scanning electron microscopy. Effect of these treatments on grain size, β-Mg17Al12 intermetallic phase, mechanical behavior, and flow asymmetry were investigated. The initial continuous network of β-phase found to be reduced after solutionizing. The dissolution of β-phase and simultaneous grain growth are found to be interrelated. Mechanical properties including yield strength, maximum strength (ultimate compressive strength), and maximum strain attainable in compressive found almost twice than the corresponding values obtained in tension. The asymmetry in compressive and tensile properties is found to decrease with grain size at certain solutionizing duration. Particular heat treatment found to offer best combination of tensile compressive flow properties in AZ80 Mg alloy. Aging under certain conditions found to minimize the strength asymmetry. © ASM International.

In-situ and tunable nitrogen-doping of MoS2 nanosheets.

Molybdenum disulfide (MoS2) nanosheets have unique physical and chemical properties, which make it a perfect candidate for next generation electronic and energy storage applications. Herein, we show the successful synthesis of nitrogen-doped MoS2 nanosheets by a simple, effective and large-scale approach. MoS2 nanosheets synthesised by this method show a porous structure formed by curled and overlapped nanosheets with well-defined edges. Analysis of the nanosheets shows that they have an enlarged interlayer distance and high specific surface area. X-ray photoelectron spectroscopy analysis shows the nanosheets have Mo-N bond indicating successful nitrogen doping. The nitrogen content of the product can be modulated by adjusting the ratio of starting materials easily within the range from ca. 5.8 to 7.6 at%.

Corrosion behavior of Mg-5Al-xZn alloys in 3.5 wt.% NaCl solution

Five types of Mg-5Al alloys with different weight percentages of Zn ranging from 0 to 4 wt.% were examined using electrochemical techniques and surface analysis. The electrochemical results indicated that the Mg-5Al alloys containing Zn have a lower corrosion and hydrogen evolution rates than the Mg-5Al based specimens with a decrease of value being observed with the decrease in Zn content. Zn addition induced the precipitation of Mg-Al and Mg-Zn phases in the Mg matrix along with grain refinement and increased an interaction of Zn oxide with Mg and Al products serving as a corrosion barrier. © 2014 Elsevier B.V. All rights reserved.

A potential anti-corrosive ionic liquid coating for MG alloy AZ31 in simulated body fluids

Magnesium alloys are attractive materials for biomedical applications, due to their excellent biocompatibility. However, these alloys show fast corrosion rates in the body that limits their clinical applications. Low-toxic ionic liquid (IL) trimethyl(butyl)phosphonium diphenyl phosphate P1444dpp has been investigated to provide corrosion protection for magnesium alloy AZ31 in simulated body fluids (SBFs). This work reports a preliminary exploration of the influence of different treatment temperatures on the corrosion protection properties of IL films for the magnesium alloy AZ31 in SBFs. Results show that the IL treatment at room temperature did not bring significant improvement in the corrosion performance of the AZ31 in SBF. However, when the treatment temperature was increased to 75°C, the IL treatment resulted in a substantial reduction of the corrosion, in particular the reduction of localized pitting corrosion. The influence of ionic liquid treatment on the corrosion performance of the magnesium alloys AZ31 in SBFs has been investigated by electrochemical impedance spectroscopy (EIS) tests and immersion tests.

Development of a laboratory-based transmission diffraction technique for in situ deformation studies of Mg alloys

A laboratory-based transmission X-ray diffraction technique was developed to measure elastic lattice strains parallel to the loading direction during in situ tensile deformation. High-quality transmission X-ray diffraction data were acquired in a time frame suitable for in situ loading experiments by application of a polycapillary X-ray optic with a conventional laboratory Cu X-ray source. Based on the measurement of two standard reference materials [lanthanum hexaboride (NIST SRM 660b) and silicon (NIST SRM 640c)], precise instrumental alignment and calibration of the transmission diffraction geometry were realized. These results were also confirmed by the equivalent data acquired using the standard Bragg-Brentano measurement geometry. An empirical Caglioti function was employed to describe the instrumental broadening, while an axis of rotation correction was used to measure and correct the specimen displacement from the centre of the goniometer axis. For precise Bragg peak position and hkil intensity information, a line profile fitting methodology was implemented, with Pawley refinement used to measure the sample reference lattice spacings (d o (hkil)). It is shown that the relatively large X-ray probe size available (7 × 714mm) provides a relatively straightforward approach for improving the grain statistics for the study of metal alloys, where grain sizes in excess of 114μm can become problematic for synchrotron-based measurements. This new laboratory-based capability was applied to study the lattice strain evolution during the elastic-plastic transition in extruded and rolled magnesium alloys. A strain resolution of 2 × 10-4 at relatively low 2θ angles (20-65° 2θ) was achieved for the in situ tensile deformation studies. In situ measurement of the elastic lattice strain accommodation with applied stress in the magnesium alloys indicated the activation of dislocation slip and twin deformation mechanisms. Furthermore, measurement of the relative change in the intensity of 0002 and 10 3 was used to quantify {10 2} 011 tensile twin onset and growth with applied load.