Rapid microwave synthesis of the iron arsenides NdFeAsO and NdFe0.9Co0.1AsO

The future of iron pnictide superconductors in technology is still undecided. While these materials are now known to possess relatively high critical temperatures and critical magnetic fields, processing methods for these superconductors are still in the development stage. Recently we have been investigating possible ways to speed up the synthetic process for obtaining polycrystalline iron arsenide superconductors and other transition metal pnictides. Here we report the synthesis of NdFeAsO and NdFe_0.9Co_0.1AsO in less than 1 h total exposure to microwave radiation using an additional microwave susceptor to surround the reaction ampoule. Structure and property measurements reveal the samples to be of high quality and superconducting when Co doped.     

Macro- and microscale variables regulate stent haemodynamics,fibrin deposition and thrombomodulin expression

Drug eluting stents are associated with late stent thrombosis (LST), delayed healing and prolonged exposure of stent struts to blood flow. Using macroscale disturbed and undisturbed fluid flow waveforms, we numerically and experimentally determined the effects of microscale model strut geometries upon the generation of prothrombotic conditions that are mediated by flow perturbations. Rectangular cross-sectional stent strut geometries of varying heights and corresponding streamlined versions were studied in the presence of disturbed and undisturbed bulk fluid flow. Numerical simulations and particle flow visualization experiments demonstrated that the interaction of bulk fluid flow and stent struts regulated the generation, size and dynamics of the peristrut flow recirculation zones. In the absence of endothelial cells, deposition of thrombin-generated fibrin occurred primarily in the recirculation zones. When endothelium was present, peristrut expression of anticoagulant thrombomodulin (TM) was dependent on strut height and geometry. Thinner and streamlined strut geometries reduced peristrut flow recirculation zones decreasing prothrombotic fibrin deposition and increasing endothelial anticoagulant TM expression. The studies define physical and functional consequences of macro- and microscale variables that relate to thrombogenicity associated with the most current stent designs, and particularly to LST.     

Mg2FeH6–LiBH4 and Mg2FeH6–LiNH2 composite materials for hydrogen storage

Two composite hydrogen storage materials based on Mg₂FeH₆ were investigated for the first time. The Mg₂FeH₆–LiBH₄ composite of molar ratio 1:5 showed a hydrogen desorption capacity of 5.6 wt.% at 370 °C, and could be rehydrogenated to 3.6 wt.% with the formation of MgH₂, as the material was heated to 445 °C and held at this temperature. The Mg₂FeH₆–LiNH₂ composite of 3:10 molar ratio exhibited a hydrogen desorption capacity of 4.3 wt.% and released hydrogen at 100 °C lower then the Mg₂FeH₆–LiBH₄ composite, but this mixture could not be rehydrogenated. Compared to neat Mg₂FeH₆, both composites show enhanced hydrogen storage properties in terms of desorption kinetics and capacity at these low temperatures. In particular, Mg₂FeH₆–LiNH₂ exhibits a much lower desorption temperature than neat Mg₂FeH₆, but only Mg₂FeH₆–LiBH₄ re-absorbs hydrogen.     

Anaerobic methane oxidation and aerobic methane production in an east African great lake (Lake Kivu)

We investigated CH₄ oxidation in the water column of Lake Kivu, a deep meromictic tropical lake with CH₄-rich anoxic deep waters. Depth profiles of dissolved gases (CH₄ and N₂O) and a diversity of potential electron acceptors for anaerobic CH₄ oxidation (NO₃^?, SO₄^2?, Fe and Mn oxides) were determined during six field campaigns between June 2011 and August 2014. Denitrification measurements based on stable isotope labelling experiments were performed twice. In addition, we quantified aerobic and anaerobic CH₄ oxidation, NO₃^? and SO₄^2? consumption rates, with and without the presence of an inhibitor of SO₄^2?-reducing bacteria activity. Aerobic CH₄ production was also measured in parallel incubations with the addition of an inhibitor of aerobic CH₄ oxidation. The maximum aerobic and anaerobic CH₄ oxidation rates were estimated to be 27?±?2 and 16?±?8?μmol/L/d, respectively. We observed a difference in the relative importance of aerobic and anaerobic CH₄ oxidation during the rainy and the dry season, with a greater role for aerobic oxidation during the dry season. Lower anaerobic CH₄ oxidation rates were measured in presence of molybdate in half of the measurements, suggesting the occurrence of linkage between SO₄^2? reduction and anaerobic CH₄ oxidation. NO₃^? consumption and dissolved Mn production rates were never high enough to sustain the measured anaerobic CH₄ oxidation, reinforcing the idea of a coupling between SO₄^2? reduction and CH₄ oxidation in the anoxic waters of Lake Kivu. Finally, significant rates (up to 0.37?μmol/L/d) of pelagic CH₄ production were also measured in oxygenated waters.     

Synthesis and Photocatalytic Properties of Single Crystalline (Ga1-xZnx)(N1-xOx) Nanotubes

Recently, (Ga_1-xZn_x)(N_1-xO_x) has gained widespread attention as a comparatively high efficiency photocatalyst for visible-light-driven overall water splitting. Despite significant gains in efficiency over the past several years, a majority of the photogenerated carriers recombine within bulk powders. To improve the photocatalytic activity, we used an epitaxial casting method to synthesize single-crystalline, high surface area (Ga_1-xZn_x)(N_1-xO_x) nanotubes with ZnO compositions up to x=0.10. Individual nanotubes showed improved homogeneity over powder samples due to a well defined epitaxial interface for ZnO diffusion into GaN. Absorption measurements showed that the ZnO incorporation shifts the absorption into the visible region with a tail out to 500 nm. Gas chromatography (GC) was used to compare the solar water splitting activity of (Ga_1-xZn_x)(N_1-xO_x) nanotubes (x=0.05–0.10) with similar composition powders. Cocatalyst decorated samples were dispersed in aqueous solutions of CH₃OH and AgO₂CCH₃ to monitor the H⁺ reduction and H₂O oxidation half reactions, respectively. The nanotubes were found to have approximately 1.5–2 times higher photocatalytic activity than similar composition powders for the rate limiting H⁺ reduction half reaction. These results demonstrate that improvements in homogeneity and surface area using the nanotube geometry can enhance the photocatalytic activity of GaN:ZnO for solar water splitting.     

NMR imaging of low pressure,gas‐phase transport in packed beds using hyperpolarized xenon‐129

Gas‐phase magnetic resonance imaging (MRI) has been used to investigate heterogeneity in mass transport in a packed bed of commercial, alumina, catalyst supports. Hyperpolarized ¹²⁹Xe MRI enables study of transient diffusion for microscopic porous systems using xenon chemical shift to selectively image gas within the pores, and, thence, permits study of low‐density, gas‐phase mass‐transport, such that diffusion can be studied in the Knudsen regime, and not just the molecular regime, which is the limitation with other current techniques. Knudsen‐regime diffusion is common in many industrial, catalytic processes. Significantly, larger spatial variability in mass transport rates across the packed bed was found compared to techniques using only molecular diffusion. It has thus been found that that these heterogeneities arise over length‐scales much larger than ～100 µm. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4013–4019, 2015     

Helium permeability of polymer materials as liners for composite overwrapped pressure vessels

Polymers have been identified as replacement materials for metallic liners in composite overwrapped pressure vessels (COPVs) for future space launchers. PEEK, Nylon, and PVDF plastics formed from base powder grades have been permeability tested to determine their susceptibility to the diffusion of helium through flatwise panel cross sections. Permeability, diffusion, and solubility coefficients have been obtained for each material with PVDF and PA11 grades showing the lowest permeability coefficients and hence the best barrier properties to permeation. Crystallinity percentages and internal air void contents in the polymer samples have also been used to assess the differences in permeability between materials with an analysis of void dispersion effects given through X‐ray CT scanning techniques. The measured permeability coefficients have been used to assess the ability of all materials tested to act as a functional polymer liner in a standard COPV with final leak rates predicted based on liner thicknesses and weights. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43675.     

Investigation on the effect of spinning conditions on the properties of hollow fiber membrane for hemodialysis application

Polyethersulfone (PES) hollow fiber membranes were fabricated via the dry‐wet phase inversion spinning technique, aiming to produce an asymmetric, micro porous ultrafiltration hollow‐fiber specifically for hemodialysis membrane. The objective of this study is to investigate the effect of spinning conditions on the morphological and permeation properties of the fabricated membrane. Among the parameters that were studied in this work are air gap distance, dope extrusion rate, bore fluid flow rate, and the take‐up speed. The contact angle was measured to determine the hydrophilicity of the fibers. Membrane with sufficient hydrophilicity properties is desired for hemodialysis application to avoid fouling and increase its biocompatibility. The influences of the hollow fiber's morphology (i.e., diameter and wall thickness) on the performance of the membranes were evaluated by pure water flux and BSA rejection. The experimental results showed that the dope extrusion rate to bore fluid flow rate ratio should be maintained at 1:1 ratio to produce a perfectly rounded asymmetric hollow fiber membrane. Moreover, the flux of the hollow fiber spun at higher air gap distance had better flux than the one spun at lower air gap distance. Furthermore, spinning asymmetric hollow fiber membranes at high air gap distance helps to produce a thin and porous skin layer, leading to a better flux but a relatively low percentage of rejection for BSA separation. Findings from this study would serve as primary data which will be a useful guide for fabricating a high performance hemodialysis hollow fiber membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43633.     

Large Piezoelectricity and Ferroelectricity in Mn‐Doped (Bi0.5Na0.5)TiO3‐BaTiO3 Thin Film Prepared by Pulsed Laser Deposition

Mn‐doped (Bi_0.5Na_0.5)_0.94Ba_0.06TiO₃ (MnBNBT) thin films were prepared on SrRuO₃ (SRO)‐coated (001) SrTiO₃ (STO) single crystal substrates by pulsed laser deposition under different processing conditions. Structural characterization (i.e., XRD and TEM) confirms the epitaxial growth of STO/SRO/MnBNBT heterostructures. Through the judicious control of deposition temperature, the defect level within the films can be finely tuned. The MnBNBT thin film deposited at the optimized temperature exhibits superior ferroelectric and piezoelectric responses with remanent polarization P_r of 33.0 μC/cm² and piezoelectric coefficient d₃₃ of 120.0 ± 20 pm/V.