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Graphene Activated Magnesium Diboride for Moderate Pressure and Temperature Hydrogenation to Magnesium Borohydride
The hydrogenation conditions of magnesium diboride (MgB2) to magnesium borohydride (Mg(BH4)2) can be significantly enhanced through the discovery of improved modifiers. This study demonstrates that the modification of MgB2 by mechanical milling with graphene nanoplatelets significantly reduces the hydrogenation conditions of MgB2 from 900 bar and 400 degrees C for pure MgB2 to 400 bar and 300 degrees C while achieving 77% conversion to Mg(BH4)2. The introduction of the graphene additives coupled with milling leads to a reduction of the temperature and pressure required for bulk hydrogenation by 100 degrees C and 500 bar, respectively, from that of pure MgB2. The identification of graphene additives that drastically improve the hydrogenation conditions of MgB2 represents an important step toward improving hydrogen uptake kinetics to Mg(BH4)2.
Direct Hydrogenation Magnesium Boride to Magnesium Borohydride: Demonstration of >11 Weight Percent Reversible Hydrogen Storage
We here for the first time demonstrate direct hydrogenation of magnesium boride, MgB2, to magnesium borohydride, Mg(BH4)2 at 900 bar H2-pressures and 400°C. Upon 14.8wt% hydrogen release, the end-decomposition product of Mg(BH4)2 is MgB2, thus, this is a unique reversible path here obtaining >11wt% H2 which implies promise for a fully reversible hydrogen storage material.
Magnesium behavior and structural defects in Mg+ ion implanted silicon carbide
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Deformation and spallation of a magnesium alloy under high strain rate loading
We investigate deformation and damage of a magnesium alloy, AZ91, under high strain rate (similar to 10(5) s(-1)) loading via planar impact. The soft-recovered specimens are examined with electron back-scatter diffraction (EBSD). EBSD analysis reveals three types of twinning: {1012} extension, {10 (1) over bar1} contraction, and {10 (1) over bar1}-{10 (1) over bar2) double twinning, and their number density increases with increasing impact velocity. The extension twins dominate contraction and double twins in size and number. Dislocation densities of the recovered specimens are evaluated with x-ray diffraction, and increase with increasing impact velocity. X-ray tomography is used to resolve three-dimensional microstructure of shock-recovered samples. The EBSD and tomography results demonstrate that the second phase, Mg17Al12, plays an important role in both deformation twinning and tensile cracking. Deformation twinning appears to be a common mechanism in deformation of magnesium alloys at low, medium and high strain rates, in addition to dislocation motion. (C) 2016 Elsevier B.V. All rights reserved.
Magnesium Alloy ZK60 Tubing made by Shear Assisted Processing and Extrusion (ShAPE)
ZK60 Magnesium tubing has been friction extruded from as-cast billets and T5 conditioned bars using Shear Assisted Processing and Extrusion (ShAPE). Tubes having an outer diameter of 50.8 mm and wall thickness of 1.9 mm were extruded with >20 times less ram force compared to conventional extrusion due to the unique shearing conditions and tooling inherent to ShAPE. Microstructures of the as-cast billet and T5 bar feedstock materials were significantly different from each other in terms of grain size, texture, and second phase distribution; yet the resulting microstructures after ShAPE were remarkably similar. An average grain size of 4-5 microns, 20o tilt of basal texture away from the extrusion axis, and refined second phases having a uniform distribution were achieved independent of the feedstock material. Hardness for as-extruded and artificially aged tubes are presented with isotropic behavior explained by detailed microstructural analysis. This work suggests that bulk ZK60 magnesium alloys extrusions may be fabricated in a single step, with microstructures that are unobtainable with conventional extrusion.
Atomic layer deposition of magnesium fluoride via bis(ethylcyclopentadienyl)magnesium and anhydrous hydrogen fluoride
A new process has been developed to deposit magnesium fluoride (MgF{sub 2}) thin films via atomic layer deposition (ALD) for use as optical coatings in the ultraviolet. MgF{sub 2} was deposited in a showerhead style ALD reactor using bis(ethylcyclopentadienyl)magnesium and anhydrous hydrogen fluoride (HF) as precursors at substrate temperatures from 100 to 250 °C. The use of HF was observed to result in improved morphology and reduced impurity content compared to other reported MgF{sub 2} ALD approaches that use metal fluoride precursors as the fluorine-containing chemistry. Characterization of these films has been performed using spectroscopic ellipsometry, atomic force microscopy, and x-ray photoelectron spectroscopy for material deposited on silicon substrates. Films at all substrate temperatures were transparent at wavelengths down to 190 nm and the low deposition temperature combined with low surface roughness makes these coatings good candidates for a variety of optical applications in the far ultraviolet.
Magnesium antimonide and magnesium bismuthide as potential materials for power generating thermocouples.
Magnesium antimonide and magnesium bismuthide as materials for power generating thermocouples
Research on magnesium antimonide and magnesium bismuthide as thermocouple materials for thermoelectric power generation
Magnesium antimonide and magnesium bismuthide evaluated as thermocouple material for thermoelectric power generation
An integrated two-dimensional modeling method for predicting ductility of thin-walled die cast magnesium
In this paper, a two-dimensional (2D) microstructure-based modeling method is developed in order to predict the ductility of a thin-walled high pressure die cast magnesium (Mg) by considering the three-dimensional (3D) thru-thickness pore distributions. For this purpose, a series of 3D synthetic microstructure-based finite element models and the corresponding 2D models are first generated with various pore volume fractions, pore size distributions and pore shapes. The input material properties for the 2D models are determined based on the 3D cubic model with a spherical pore and the generalized Neuber’s rule. Based on the resulting ductility of the 3D and 2D models, a 3D/2D ductility correlation curve is developed as a function of the characteristics/shape of the input fracture strain curve used in the 3D model. The validity of the ductility correlation curve is examined with casting samples with actual microstructures. Here, the results show that the suggested 2D modeling methodology can be used together with the ductility correlation curve in predicting the ductility of thin-walled Mg castings.
Investigation of crossed-twin structure formation in magnesium and magnesium alloys
In this work, the effect of alloying addition on the propensity for twin-twin interactions to transform into crossed-twin structures in magnesium alloys is investigated. A full-field elasto-viscoplastic fast Fourier transform (EVP-FFT) framework combined with a discrete twin model and dislocation density-based hardening law for slip strengths is used to calculate the micromechanical fields in the crystalline matrix around the interacting twins. AZ31 and MgLi alloys are selected along with pure Mg to study the influence of plastic anisotropy in connection with alloying elements. These alloys were selected since their plastic anisotropy measure, which is defined as the ratio between the critical resolved shear stress for pyramidal $\langle$c +a$\rangle$ and basal $\langle$a$\rangle$ slip modes, spanned a wide range. To quantify the role of twin thicknesses, we probe a range of impinging twin thicknesses while fixing the recipient twin thickness. The analysis reveals that: (i) the local driving stress for crossed twin structure formation generated from the interaction of the two twins is lower in a low plastically anisotropic material, like a MgLi alloy, than a high plastically anisotropic material like pure Mg and (ii) the critical impinging twin thickness needed to form the crossed twin structure in pure Mg, AZ31 and MgLi alloys is ~0.5, ~0.75 and ~1.5 times the recipient twin thickness. We propose a relationship between the tendency for crossed twin structure formation and the experimentally observed higher ductility in MgLi alloys compared to pure Mg. Finally, one key implication of the findings is that crossed- twin structure formation can be hindered and the ductility of magnesium alloy thereby improved by properly choosing alloying elements that lower the slip strength for pyramidal $\langle$c + a$\rangle$ slip.
A CALPHAD study on the thermodynamic stability of calcium-, zinc-, and yttrium-doped magnesium in aqueous environments
Magnesium has attracted the attention of the biomaterials community as a potential biodegradable metallic candidate for use in stents and orthopedic applications. Alloying of Mg with metals such as Ca, Y and Zn, etc., to form alloy precursors is important to optimize its corrosion rate in electrolytic and aqueous environments to understand the alloy response in body fluid environments. In the current study, the chemical reactions of Mg–Me alloys (Me = Ca, Y, and Zn) with pure water have been investigated using the CALPHAD technique. A qualitative agreement between CALPHAD and first-principles results has been obtained. The CALPHAD method has also been employed to study the reactions of Mg alloys in the human blood fluid environment. The effects of alloying elements and compositions on the reaction enthalpies, reaction products, amount of gas release and gas compositions as well as the pH of the fluids have been systematically discussed and reported.
Nanoconfinement of Molecular Magnesium Borohydride Captured in a Bipyridine-Functionalized Metal-Organic Framework
The lower limit of metal hydride nanoconfinement is demonstrated through the coordination of a molecular hydride species to binding sites inside the pores of a metal-organic framework (MOF). Magnesium borohydride, which has a high hydrogen capacity, is incorporated into the pores of UiO-67bpy (Zr6O4(OH)4(bpydc)6 with bpydc2- = 2,2'-bipyridine-5,5'- dicarboxylate) by solvent impregnation. The MOF retained its long-range order, and transmission electron microscopy and elemental mapping confirmed the retention of the crystal morphology and revealed a homogeneous distribution of the hydride within the MOF host. Notably, the B-, N-, and Mg-edge XAS data confirm the coordination of Mg(II) to the N atoms of the chelating bipyridine groups. In situ 11B MAS NMR studies helped elucidate the reaction mechanism and revealed that complete hydrogen release from Mg(BH4)2 occurs as low as 200 °C. Sieverts and thermogravimetric measurements indicate an increase in the rate of hydrogen release, with the onset of hydrogen desorption as low as 120 °C, which is approximately 150 °C lower than that of the bulk material. Furthermore, density functional theory calculations support the improved dehydrogenation properties and confirm the drastically lower activation energy for B-H bond dissociation.
Magnesium, Iron and Aluminum in LLNL Air Particulate and Rain Samples with Reference to Magnesium in Industrial Storm Water
Storm water runoff from the Lawrence Livermore National Laboratory’s (LLNL’s) main site and Site 300 periodically exceeds the Discharge Permit Numeric Action Level (NAL) for Magnesium (Mg) under the Industrial General Permit (IGP) Order No. 2014-0057-DWQ. Of particular interest is the source of magnesium in storm water runoff from the site. This special study compares new metals data from air particulate and precipitation samples from the LLNL main site and Site 300 to previous metals data for storm water from the main site and Site 300 and alluvial sediment from the main site to investigate the potential source of elevated Mg in storm water runoff. Data for three metals (Mg, Iron {Fe}, and Aluminum {Al}) were available from all media; data for additional metals, such as Europium (Eu), were available from rain, air particulates, and alluvial sediment. To attribute source, this study compared metals concentration data (for Mg, Al, and Fe) in storm water and rain; metal-metal correlations (Mg with Fe, Mg with Al, Al with Fe, Mg with Eu, Eu with Fe, and Eu with Al) in storm water, rain, air particulates, and sediments; and metal-metal ratios ((Mg/Fe, Mg/Al, Al/Fe, Mg/Eu, Eu/Fe, and Eu/Al) in storm water, rain, air particulates and sediments. The results presented in this study are consistent with a simple conceptual model where the source of Mg in storm water runoff is air particulate matter that has dry-deposited on impervious surfaces and subsequently entrained in runoff during precipitation events. Such a conceptual model is consistent with 1) higher concentrations of metals in storm water runoff than in precipitation, 2) the strong correlation of Mg with Aluminum (Al) and Iron (Fe) in both storm water and air particulates, and 3) the similarity in metal mass ratios between storm water and air particulates in contrast to the dissimilarity of metal mass ratios between storm water and precipitation or alluvial sediment. The strong correlation of Mg with Fe and Al and of Fe with Al in storm water and air particulates and the strong association of Mg, Fe, and Al with Eu in air particulates strongly suggests that a dominant source of the Mg in storm water is associated with mineral phases of natural origin. These observations all point to Mg exceedances being associated with natural sources and processes and not with anthropogenic processes or pollutant sources.
Isotopically pure magnesium isotope-24 is prepared from magnesium-24 oxide
Apparatus is used to prepare isotopically pure magnesium isotope-24, suitable for use in neutron scattering and polarization experiments. The apparatus permits thermal reduction of magnesium-24 oxide with aluminum and calcium oxide, and subsequent vaporization of the product metal in vacuum. It uses a resistance-heated furnace tube and cap assembly.
Anolyte studies of the magnesium electrode in molten mixtures of lithium chloride, potassium chloride, and magnesium chloride
Anolyte studies of magnesium electrode in molten mixtures of lithium chloride, potassium chloride, and magnesium chloride
Alkoxide-based magnesium electrolyte compositions for magnesium batteries
Alkoxide magnesium halide compounds having the formula: RO--Mg--X (1) wherein R is a saturated or unsaturated hydrocarbon group that is unsubstituted, or alternatively, substituted with one or more heteroatom linkers and/or one or more heteroatom-containing groups comprising at least one heteroatom selected from fluorine, nitrogen, oxygen, sulfur, and silicon; and X is a halide atom. Also described are electrolyte compositions containing a compound of Formula (1) in a suitable polar aprotic or ionic solvent, as well as magnesium batteries in which such electrolytes are incorporated.
Design and Fabrication of Pellets for Magnesium Production by Carbothermal Reduction
For carbothermal reduction (CTR) to be an economic and clean process for magnesium metal production, operational challenges must be overcome. Strong and reactive precursor pellets are necessary to effectively and selectively produce Mg{sub (g)} from any feedstock. In this study, the effects of ore (magnesia and dolime), carbon (petroleum coke, charcoal, algal char, and carbon black), and binder (organic and inorganic) on pellet strength and reactivity, product yield and purity, and reduction selectivity were analyzed. Theoretically and experimentally, the CTR of dolime (MgO·CaO) favored MgO reduction over CaO reduction; however, with enough carbon and heat, both oxides could be reduced. CaO carbothermal reduction produced CaC{sub 2} and Ca{sub (g).} The selectivity to CaC{sub 2} remained constant (7 ± 4 pct) for all C/MgO·CaO ratios analyzed, while the selectivity to Ca{sub (g)} increased (5 pct → 40 pct) when C/MgO·CaO was increased from 0.5 to 2.0. As the overall metal yield decreased (77.6 pct → 59.7 pct) with increasing CaO reduction (38.2 pct → 78.1 pct), Ca{sub (g)} reverted faster than Mg{sub (g).} Heavy metal impurities primarily remained in the residue (< 30 pct volatilized) and, when volatilized, condensed at high temperatures (700 °C to 1450 °C), relative to light metal impurities (350 °C to 1000 °C, > 78 pct volatilized). Organic binders added reducing power to the pellets but produced frail pellets (radial crush strength = 9.1 ± 0.7 N) after pyrolysis, relative to pellets with inorganic binders (15.1 ± 3.2 N). Kinetic parameters were determined for extruded pellets to predict the reaction rate as a continuous function of pressure and temperature.