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High temperature thermal-mechanical stability of tribological thin coatings is extremely important to a large number of applications in modern industries. DC magnetron sputtering of single metallic element (Cr, Si) and alloy (Ni:Cr) targets formed transition metal nitrides film coatings, CrSiN and CrNiN onto M2 steel. High temperature in-situ synchrotron X-ray diffraction, in the range 25 °C–700 °C, obtained experimental data for a range of structural and mechanical properties. Furthermore, experimental room temperature Nanoindentation measurements, made before and after the in-situ heating cycle, provided corresponding hardness and shear modulus results. The structural results identified microstructure and phase transformation changes, while the mechanical results identified microstrain, hardness, elastic modulus and deformation resistance properties of the coatings. Density functional theory (DFT) and quasi-harmonic approximation (QHA) modelled the high temperature thermal and mechanical properties such as: Young's modulus, shear modulus and thermal expansion coefficients (populated up to 1200 °C). Estimates of hardness are made by correlating the bulk phase hardness and shear modulus, of the CrN and Ni phases, as a function of temperature. Results indicate that Si doping enhances the hardness of the CrN framework, increasing from 29 to 36 GPa and improves the coatings elastic modulus, and resistance to deformation. However the addition of Ni reduced these properties. Furthermore, formation of (Cr,Si)N and Ni(Cr) solid solutions is inferred from DFT, Rietveld and lattice constant analysis.

© 2020 Elsevier Ltd Graphene fragments spanning a wide range of size and shape were studied computationally using the Debye scattering equation. The calculated diffraction patterns were analysed using the Scherrer equation to infer the fragment size, La. Comparison with the known fragment sizes reveals a strong affine relationship between La and the Scherrer quantity λ/(Bcosθ). To preserve this relationship, we propose modifying the Scherrer equation to include an empirical additive constant. Our approach solves the well-known problem of size-dependence in the shape factor and yields a universal expression by defining La as the square-root of the fragment area. The relationship between observed diffraction peak positions and unit cell parameters is also discussed.

A simple modification to an existing powder diffraction specimen holder is given to allow for the presentation of filter papers for analysis. A mild steel annulus holds the filter paper in place using magnets added to the rear of the specimen holder.

Copyright © 2020 American Chemical Society. Fluorine-substituted sodium hydride is investigated for application as a thermal energy storage material inside thermal batteries. A range of compositions of NaHxF1-x (x = 0, 0.5, 0.7, 0.85, 0.95, 1) have been studied using synchrotron radiation powder X-ray diffraction (SR-XRD), near-edge X-ray absorption fine structure spectroscopy (NEXAFS), and nuclear magnetic resonance spectroscopy (NMR), with the thermal conductivity and melting points also being determined. SR-XRD and NMR spectroscopy studies identified that the solid solutions formed during synthesis contain multiple phases rather than a single stoichiometric compound, despite the materials exhibiting a single melting point. As the fluorine content of the materials increases, the Na-H(F) bond length decreases, increasing the stability of the compound. This trend is also observed during melting point analysis where increasing the fluorine content increases the melting point of the material; that is, x < 0.3 (i.e., F- > 0.7) enables melting at temperatures above 750 °C.

© 2020 American Chemical Society. Metal hydrides continue to vie for attention as materials in multiple technological applications including hydrogen storage media, thermal energy storage (TES) materials, and hydrogen compressors. These applications depend on the temperature at which the materials desorb and reabsorb hydrogen. Magnesium hydride is ideal as a TES material, although its practical operating temperature is capped at ∼450 °C because of material degradation and high operating pressure. Fluorine substitution for hydrogen in magnesium hydride has previously been shown to increase the operating temperature of the metal hydride while limiting degradation, although full characterization is required before technological application can be ensured. The present study characterizes Mg(HxF1-x)2 solid solutions (x = 1, 0.95, 0.70, 0.85, 0.50, and 0) by inelastic neutron spectroscopy, powder X-ray diffraction, and thermal conductivity measurements, with the results being verified by density functional theory. For each experiment, a clear trend is observed throughout a series of solid solutions, showing the possibility of tuning the properties of MgH2. As F- substitution increases, the average Mg-H(F) bond distance elongates along the axial positions of the Mg-H(F) octahedra. Overall, this leads to an increase in Mg-H bond strength and thermal stability, improving the viability of Mg-H-F as potential TES materials.

Copyright © 2020 American Chemical Society. Closo-borates and derivatives thereof have shown great potential as electrolyte materials for all-solid-state batteries owing to their exceptional ionic conductivity and high thermal and chemical stability. However, because of the myriad of possible chemical modifications of the large, complex anion, only a fraction of closo-borate derivatives has so far been investigated as electrolyte materials. Here, the crystal structures, thermal properties, and ionic conductivities of M2B12(OH)12 (M = Li, Na, K, and Cs) are investigated with a focus on their possible utilization as new solid-state ion conductors for solid-state batteries. The compounds generally show rich thermal polymorphism, with eight identified polymorphs among the four dehydrated compounds. Both Li2B12(OH)12 and Na2B12(OH)12 undergo a first-order transition, in which the cation sublattices become disordered, resulting in an order of magnitude jump in ionic conductivity for Na2B12(OH)12. K2B12(OH)12 undergoes a second-order polymorphic transition driven by a change in the anion-cation interaction, with no evidence of dynamic disorder. The ionic conductivities of M2B12(OH)12 range from 1.60 × 10-8 to 5.97 × 10-5 S cm-1 at 250 °C for M = Cs and Li, respectively, showing decreasing conductivity with increasing cation size. Compared with the analogous M2B12H12 compounds, such relatively low conductivities are suggested to be a consequence of strong and directional anion-cation interactions, resulting in a more static anion framework.

© The Royal Society of Chemistry. The synthesis of a novel Rh(i)-Aryl complex is detailed and its ability to serve as an initiator in the stereospecific polymerisation of phenylacetylene evaluated. Targeting the Rh(i) species, (2-phenylnaphthalen-1-yl)rhodium(i)(2,5-norbornadiene)tris(para-fluorophenylphosphine), Rh(nbd)(P(4-FC6H4)3)(2-PhNapth), following recrystallization we obtained the isomeric (2-(naphthalen-2-yl)phenyl)rhodium(i) complex, Rh(nbd)(P(4-FC6H4)3)(2-NapthPh), as determined by X-ray single-crystal structure analysis, and confirmed by X-ray powder diffraction. The isolation of the latter species was proposed to occur from the target (2-PhNapth) derivative via an intramolecular 1,4-Rh atom migration. This supposition was supported by density functional theory (DFT) calculations that indicated the isolated (2-NapthPh) derivative has lower energy (-19 kJ mol-1) than the targeted complex. The structure of the isolated (2-NapthPh) species was confirmed by multinuclear NMR spectroscopy including 2D 31P-103Rh{1H, 103Rh}, heteronuclear multiple-quantum correlation (HMQC) experiments; however, NMR analysis indicated the presence of a second, minor species in solution in an approximate 1:4 ratio with the 2-NapthPh complex. The minor species was identified as a second structural isomer, the 3-phenylnaphthyl derivative, proposed to be formed under a dynamic equilibrium with the 2-NapthPh derivative via a second 1,4-Rh atom migration. DFT calculations indicate that this 1,4-migration proceeds through a low-energy pathway involved in the oxidative addition of a C-H bond to Rh followed by a reductive elimination with the distribution of the products being thermodynamically controlled. The recrystallized Rh(nbd)(P(4-FC6H4)3)(2-NapthPh) complex was subsequently evaluated as an initiator in the polymerisation of phenylacetylene (PA); gratifyingly, the Rh(i) species was an active initiating species with the pseudo-first-order kinetic and molecular weight evolution vs ti

Reactive silica in bauxite is a key challenge for the alumina industry due to the associated losses of sodium hydroxide and alumina associated with processing this impurity. The bauxite residue sinter leach process (BRSLP) is a potential method of recovering sodium hydroxide and alumina from bauxite residue. In this research, bauxite residue lime sinters were characterised using a combination of quantitative X-ray diffraction in conjunction with scanning electron microscopy as well as for leaching performance. It is shown that sintering reactions proceed at a significantly faster rate than previously reported which has a positive implication for industrial application. A new set of reactions and reaction pathways are proposed which describe bauxite residue lime sintering in greater detail than previously possible.

© 2018 Hydrogen Energy Publications LLC In solid-state hydrogen storage in light metal hydrides, nanoconfinement and the use of catalysts represent promising solutions to overcoming limitations such as poor reversibility and slow kinetics. In this work, the morphology and hydrogen desorption kinetics of NaAlH4 melt-infiltrated into a previously developed Ti-based doped porous Al scaffold is analysed. Small-angle X-ray scattering and scanning electron microscopy analysis of low NaAlH4 loading in the porous Al scaffold has revealed that mesopores and small macropores are filled first, leaving the larger macropores/voids empty. Temperature-programmed desorption experiments have shown that NaAlH4-infiltrated porous Al scaffolds show a higher relative H2 release, with respect to NaAlH4 + TiCl3, in the temperature range 148–220 °C, with the temperature of H2 desorption trending to bulk NaAlH4 with increasing scaffold loading. The Ti-based catalytic effect is reproduced when the dopant is present in the scaffold. Further work is required to increase the mesoporous volume in order to enhance the nanoconfinement effect.

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. Single-atom catalysts (SACs) are the smallest entities for catalytic reactions with projected high atomic efficiency, superior activity, and selectivity; however, practical applications of SACs suffer from a very low metal loading of 1-2 wt%. Here, a class of SACs based on atomically dispersed transition metals on nitrogen-doped carbon nanotubes (MSA-N-CNTs, where M = Ni, Co, NiCo, CoFe, and NiPt) is synthesized with an extraordinarily high metal loading, e.g., 20 wt% in the case of NiSA-N-CNTs, using a new multistep pyrolysis process. Among these materials, NiSA-N-CNTs show an excellent selectivity and activity for the electrochemical reduction of CO 2 to CO, achieving a turnover frequency (TOF) of 11.7 s -1 at -0.55 V (vs reversible hydrogen electrode (RHE)), two orders of magnitude higher than Ni nanoparticles supported on CNTs.

© 2018 the Owner Societies. Magnesium hydride (MgH 2 ) is a hydrogen storage material that operates at temperatures above 300 °C. Unfortunately, magnesium sintering occurs above 420 °C, inhibiting its application as a thermal energy storage material. In this study, the substitution of fluorine for hydrogen in MgH 2 to form a range of Mg(H x F 1-x ) 2 (x = 1, 0.95, 0.85, 0.70, 0.50, 0) composites has been utilised to thermodynamically stabilise the material, so it can be used as a thermochemical energy storage material that can replace molten salts in concentrating solar thermal plants. These materials have been studied by in situ synchrotron X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis, temperature-programmed-desorption mass spectrometry and Pressure-Composition-Isothermal (PCI) analysis. Thermal analysis has determined that the thermal stability of Mg-H-F solid solutions increases proportionally with fluorine content, with Mg(H 0.85 F 0.15 ) 2 having a maximum rate of H 2 desorption at 434 °C, with a practical hydrogen capacity of 4.6 ± 0.2 wt% H 2 (theoretical 5.4 wt% H 2 ). An extremely stable Mg(H 0.43 F 0.57 ) 2 phase is formed upon the decomposition of each Mg-H-F composition of which the remaining H 2 is not released until above 505 °C. PCI measurements of Mg(H 0.85 F 0.15 ) 2 have determined the enthalpy (?H des ) to be 73.6 ± 0.2 kJ mol -1 H 2 and entropy (?S des ) to be 131.2 ± 0.2 J K -1 mol -1 H 2 , which is slightly lower than MgH 2 with ?H des of 74.06 kJ mol -1 H 2 and ?S des = 133.4 J K -1 mol -1 H 2 . Cycling studies of Mg(H 0.85 F 0.15 ) 2 over six absorption/desorption cycles between 425 and 480 °C show an increased usable cycling temperature of ~80 °C compared to bulk MgH 2 , increasing the thermal operating temperatures for technological applications.

© 2018 The Royal Society of Chemistry. Complex transition metal hydrides have been identified as being materials for multi-functional applications holding potential as thermal energy storage materials, hydrogen storage materials and optical sensors. Na2Mg2NiH6(2Na+·2Mg2+·2H-·[NiH4]4-) is one such material. In this study, the decomposition pathway and thermodynamics have been explored for the first time, revealing that at 225 °C, hydrogen desorption commences with two major decomposition steps, with maximum H2desorption rates at 278 and 350 °C as measured by differential scanning calorimetry. The first step of decomposition results in the formation of Mg2NiHx(x < 0.3) and NaH, before these compounds decompose into Mg2Ni and Na, respectively. PCI analysis of Na2Mg2NiH6has determined the thermodynamics of decomposition for the first step to have a ?Hdesand ?Sdesof 83 kJ mol-1H2and 140 J K-1mol-1H2, respectively. Hydrogen cycling of the first step has been achieved for 10 cycles without any significant reduction in hydrogen capacity, with complete hydrogen desorption within 20 min at 395 °C. Despite the relatively high cost of Ni, the ability to effectively store hydrogen reversibly at operational temperatures of 318-568 °C should allow this material to be considered as a thermal energy storage material.

© 2017, Springer Science+Business Media, LLC, part of Springer Nature. Purpose: This study aims to investigate the influence of different storage humidity conditions on crystallization and aerosol performance of inhalable spray dried amorphous powder formulations (Ciprofloxacin hydrochloride as the model drug). Methods: The spray dried samples were stored at 20%, 55% and 75% relative humidity (RH). Crystallinity was monitored by Powder X-ray diffraction (PXRD), and particle morphology was measured by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Aerosol performance was evaluated using a multi-stage liquid impinger (MSLI). Results: PXRD diffractograms showed the spray dried Ciprofloxacin stored at 20% RH for three weeks were amorphous; whereas those stored at 55% RH and 75% RH started crystallizing after one hour. Fine particle fraction (FPF) of the particles was improved from 28% to 42% after storage at 55% RH for three days. Such improvement was attributed to the crystallization of amorphous powders, which led to increased particle roughness and reduced particulate contact area, as visualized by SEM and quantified by AFM. A linear relationship was observed between degree of crystallinity/crystallite size and FPF (R 2 = 0.94 and R 2 = 0.96, respectively). However, deterioration in aerosol performance was observed after storage at 75% RH due to formation of inter-particulate liquid/solid bridges, as confirmed by SEM. Conclusions: This study provides a fundamental understanding in moisture-induced physical and aerosol instability of the spray dried powder formulations.

Page 4, right column, under section heading “In-Vitro Aerosol Performance”, line 11. “ < 4 kPa (approximately 3.2 kPa at 100 L/min)” should be changed to “approximately 4 kPa at 100 L/min”.

© 2017 Acta Materialia Inc. Interactions between neighboring grains influence the macroscale behavior of polycrystalline materials, particularly their deformation behavior, damage initiation and propagation mechanisms. However, mapping all of the critical material properties normally requires that several independent measurements are performed. Here we report the first grain mapping of a polycrystalline foil using a pixelated energy-dispersive X-ray area detector, simultaneously measuring X-ray fluorescence and diffraction with the Maia detector in order to determine grain orientation and estimate lattice strain. These results demonstrate the potential of the next generation of X-ray area detectors for materials characterization. By scanning the incident X-ray energy we investigate these detectors as a complete solution for simultaneously mapping the crystallographic and chemical properties of the sample. The extension of these techniques to broadband X-ray sources is also discussed.

An atomic absorption spectrometer unit fitted with a graphite furnace module is used to perform high temperature treatment on three carbonized polymers: polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and polyacrylonitrile (PAN). Using short pulses up to 45 s, we heat small samples to a maximum of 3000 °C. High-resolution transmission electron microscopy and X-ray diffractometry are used to track the growth of crystallites in the materials as a function of the heating temperature. We observe the well-known behaviour of large crystalline graphite growth in PVC-derived samples and the formation of curved graphitic layers in PVDC- and PAN-derived samples. This graphite furnace atomic absorption spectrometer approach is an attractive alternative to conventional laboratory-scale graphite furnaces in research of high temperature treatment of carbon and other refractory materials.