Method of production of pure hydrogen near room temperature from aluminum-based hydride materials

The present invention provides a cost-effective method of producing pure hydrogen gas from hydride-based solid materials. The hydride-based solid material is mechanically processed in the presence of a catalyst to obtain pure gaseous hydrogen. Unlike previous methods, hydrogen may be obtained from the solid material without heating, and without the addition of a solvent during processing. The described method of hydrogen production is useful for energy conversion and production technologies that consume pure gaseous hydrogen as a fuel

Erbium-based magnetic refrigerant (regenerator) for passive cryocooler

A two stage Gifford-McMahon cryocooler having a low temperature stage for reaching approximately 10K, wherein the low temperature stage includes a passive magnetic heat regenerator selected from the group consisting of Er.sub.6 Ni.sub.2 Sn, Er.sub.6 Ni.sub.2 Pb, Er.sub.6 Ni.sub.2 (Sn.sub.0.75 Ga.sub.0.25), and Er.sub.9 Ni.sub.3 Sn comprising a mixture of Er.sub.3 Ni and Er.sub.6 Ni.sub.2 Sn in the microstructure

On the edge of periodicity: Unconventional magnetism of Gd117Co56.4Sn114.3

Magnetization measurements reveal the onset of magnetic ordering at TC = 65 K followed by three additional magnetic anomalies at T1 = 47 K, T2 = 28 K, and T3 = 11 K in Gd117Co56.4Sn114.3 – a compound with a giant cubic unit cell that crystallizes in the Dy117Co56Sn112 structure type with space group Fm3¯m and lattice parameter a = 30.186 Å. The magnetic ordering temperature increases with applied magnetic field; however, the analysis of magnetic data indicates that antiferromagnetic interactions also play a role in the ground state. AC magnetic susceptibility confirms multiple magnetic anomalies and shows minor frequency dependence. The local magnetic ordering below 60 K is supported by the Mössbauer spectroscopy. A single broad anomaly is detected at T3 in the heat capacity; we suggest that magnetic domains form below this temperature. These data highlight unique features of magnetism in this and, potentially, other rare-earth intermetallics crystallizing with giant unit-cells where the exchange correlation lengths are much shorter when compared to the periodicity of the crystal lattice

Controlling Magnetism via Transition Metal Exchange in the Series of Intermetallics Eu(T1,T2)5In (T = Cu, Ag, Au)

Three series of intermetallic compounds Eu(T1,T2)5In (T = Cu, Ag, Au) have been investigated in full compositional ranges. Single crystals of all compounds have been obtained by self-flux and were analyzed by single X-ray diffraction revealing the representatives to fall into two structure types: CeCu6 (oP28, Pnma, a = 8.832(3)–9.121(2) Å, b = 5.306(2)–5.645(1) Å, c = 11.059(4)–11.437(3) Å, V = 518.3(3)–588.9(2) Å3) and YbMo2Al4 (tI14, I4/mmm, a = 5.417(3)–5.508(1) Å, c = 7.139(2)– 7.199(2) Å, V = 276.1(2)–285.8(1) Å3). The structural preference was found to depend on the cation/anion size ratio, while the positional preference within the CeCu6 type structure shows an apparent correlation with the anion size. Chemical compression, hence, a change in cell volume, which occurs upon anion substitution appears to be the main driving force for the change of magnetic ordering. While EuAg5In shows antiferromagnetic behavior at low temperatures, mixing Cu and Au within the same type of structure results in considerable changes in the magnetism. The Eu(Cu,Au)5In alloys with CeCu6 structure show complex magnetic behaviors and strong magnetic field-induced spin-reorientation transition with the critical field of the transition being dependent on Cu/Au ratio. The alloys adopting the YbMo2Al4 type structure are ferromagnets exhibiting unusually high magnetic moments. The heat capacity of EuAu2.66Cu2.34In reveals a double-peak structure evolving with the magnetic field. However, low-temperature X-ray powder diffraction does not show a structural transition

Mechanochemistry of the LiBH4–AlCl3 System: Structural Characterization of the Products by Solid-State NMR

The double-cation metal borohydride, Li4Al3(BH4)(13), mechanochemically produced from a 13:3 mixture of lithium borohydride (LiBH4) and aluminum chloride (AlCl3), has a low hydrogen desorption temperature; however, the material\u27s decomposition is accompanied by a large emission of toxic diborane (B2H6). We found that a decrease of the LiBH4:AICl(3) ratio in the starting mixture yields increased amounts of partially chlorinated products that also dehydrogenate at low temperature, but release negligibly small amounts of diborane. Extensive characterization by solid-state NMR spectroscopy (SSNMR) and powder X-ray diffraction (XRD) found that the 11:3 ratio product maintains the Li(4)A(13)(BH4)(13)-like structure, with additional anions substituting for [BH4](-) compared to the 13:3 mixture. Further decrease of relative LiBH4 concentration in the starting mixture to 9:3 results in a different product composed of tetrahedral [Al(BH4)(4)](-) and [Al(BH4)(2)Cl-2](-) complexes, in which two hydrogen atoms of each borohydride group are bridged to aluminum sites. Additionally, SSNMR revealed the covalent character of the Al-H bonds, which is not observed in Li(4)A(13)(BH4)(13). These findings suggest that the Al-Cl bonding present in the chlorinated complexes prevents the formation of Al(BH4)(3), which is a known intermediate leading to the formation of diborane during thermal dehydrogenation of the nearly chlorine-free Li(4)A(13)(BH4)(13)

Anomalous effects of Sc substitution and processing on magnetism and structure of (Gd1−xScx)5Ge4

The kinetic arrest observed in the parent Gd5Ge4 gradually vanishes when a small fraction (x = 0.025, 0.05 and 0.10) of Gd is replaced by Sc in (Gd1−xScx)5Ge4, and the magnetic ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM). A first order phase transition coupled with the FM-AFM transition occurs at TC = 41 K for x = 0.05 and at TC = 53 K for x = 0.10 during heating in applied magnetic field of 1 kOe, and the thermal hysteresis is near 10 K. The first-order magnetic transition is coupled with the structural Sm5Ge4-type to Gd5Si4-type transformation. The magnetization measured as a function of applied magnetic field shows sharp metamagnetic-like behavior. At the same time, the AFM to paramagnetic transition in (Gd1−xScx)5Ge4 with x = 0.10, is uncharacteristically broad indicating development of strong short-range AFM correlations above the Néel temperature. Comparison of the magnetization data of bulk, powdered, and metal-varnish composite samples of (Gd0.95Sc0.05)5Ge4 shows that mechanical grinding and fabrication of a composite have little effect on the temperature of the first-order transformation, but short-range ordering and AFM/FM ratio below TC are surprisingly strongly affected

Anomalous specific heat and magnetic properties of TmxDy1-xAl2 (0 ≤ x ≤ 1)

We study crystal structure, phase transitions and magnetism of pseudo-binary TmxDy1-xAl2 (0 ≤ x ≤ 1) compounds using temperature dependent X-ray powder diffraction, specific heat and magnetization measurements, first principles, and model calculations. In low external magnetic fields, Dy-rich compounds undergo continuous, second-order phase transitions at the respective Curie temperatures, TC. In contrast, the Tm-rich compounds exhibit discontinuous, first-order anomalies in the magnetically ordered states. These sharp transitions correlate with a substantial energy difference between the room temperature cubic and ground state rhombohedral structures of TmAl2. A clear anomaly in the lattice parameter is observed at ∼30 K for x = 0.5, which nearly coincides with TC = 31.2 K. The effective quadrupolar moment of the lanthanides changes sign around x = 0.5, which leads to a nearly zero anisotropy constant and approximately spherical effective 4f charge densities, providing an explanation for the lack of structural distortions below TC for x = 0.5. The calculations confirm [001] as the easy magnetization axis in the ground state tetragonal structure of DyAl2, and reveal collapse of the orbital magnetic moment when the easy magnetization direction changes to [111]. Within the rhombohedral ground state of TmAl2 [111] is the easy magnetization direction

Best practices in evaluation of the magnetocaloric effect from bulk magnetization measurements

Conventional magnetometry is irreplaceable in evaluating bulk magnetization of materials over broad temperature and field ranges. The technique is also effective in quantifying hysteresis that may be associated with magnetic and structural phase transitions that occur during the magnetizing/demagnetizing cycling, and the derived magnetic field-induced isothermal entropy change – one of the most important properties in the field of magnetocalorics. Both systematic and random errors present during the measurements of magnetization, however, may lead to erroneous conclusions. Using two well-known materials – elemental Gd and intermetallic Gd5Si2Ge2 as examples, we consider best practices in performing reliable and rapid magnetization measurements for proper characterization of magnetocaloric properties

Formation, Stability and Magnetism of New Gd3TAl3Ge2 Quaternary Compounds (T = Mn, Cu)

A study on the formation and stability of new quaternary compounds with the general chemical formula Gd3TAl3Ge2 (T = Mn, Cu) has been undertaken by experimental investigations (SEM-EDX, DTA and XRD) and density functional theory (DFT) calculations. These compounds crystallize in the hexagonal Y3NiAl3Ge2-type structure (hP9, P–62m, Z = 1) (an ordered, quaternary derivative of the ternary ZrNiAl or of the binary Fe2P prototypes), with lattice parameters values a = 7.0239(2) Å and c = 4.2580(1) Å for Gd3MnAl3Ge2 and a = 7.0434(1) Å and c = 4.2089(1) Å for Gd3CuAl3Ge2. DTA suggests a peritectic reaction for the formation of these compounds (at 1245°C for Gd3CuAl3Ge2). The existence and stability of these phases has been explained on the basis of DFT calculations, and a comparison of ground state properties of the studied compounds with the earlier known Gd3CoAl3Ge2 phase is outlined. The negative formation energies in all three cases govern the stability of compounds from theory as well, predicting Gd3MnAl3Ge2 as the most stable phase with highest formation energy (–13.01 eV/f.u.). The total DOS are generic in nature and suggest the robust magnetism, with the Gd-f moments of ≈7 μB. An antiparallel coupling among Gd-f and T-d states is observed for all compounds, as usually seen in rare earth (R) - transition metal (T) compounds. Preliminary magnetization measurements on Gd3MnAl3Ge2 show two ferromagnetic/ferrimagnetic (FM/FIM) like transitions at TC1 = 142 K and TC2 = 97 K, with another anomaly seen at ≈15 K. Isothermal magnetization data show no hysteresis even at 5 K, and the magnetization does not saturate up to 50 kOe, further suggesting a possible FIM behavior

Crystal, magnetic, calorimetric and electronic structure investigation of GdScGe1–x Sb x compounds

Experimental investigations of crystal structure, magnetism and heat capacity of compounds in the pseudoternary GdScGe-GdScSb system combined with density functional theory projections have been employed to clarify the interplay between the crystal structure and magnetism in this series of RTX materials (R  =  rare-earth, $T$   =  transition metal and X  =  p-block element). We demonstrate that the CeScSi-type structure adopted by GdScGe and CeFeSi-type structure adopted by GdScSb coexist over a limited range of compositions $0.65 \leqslant x \leqslant 0.9$ . Antimony for Ge substitutions in GdScGe result in an anisotropic expansion of the unit cell of the parent that is most pronounced along the c axis. We believe that such expansion acts as the driving force for the instability of the double layer CeScSi-type structure of the parent germanide. Extensive, yet limited Sb substitutions $0 \leqslant x \u3c 0.65$ lead to a strong reduction of the Curie temperature compared to the GdScGe parent, but without affecting the saturation magnetization. With a further increase in Sb content, the first compositions showing the presence of the CeFeSi-type structure of the antimonide, $x \approx 0.7$ , coincide with the appearance of an antiferromagnetic phase. The application of a finite magnetic field reveals a jump in magnetization toward a fully saturated ferromagnetic state. This antiferro–ferromagnetic transformation is not associated with a sizeable latent heat, as confirmed by heat capacity measurements. The electronic structure calculations for $x = 0.75$ indicate that the key factor in the conversion from the ferromagnetic CeScSi-type to the antiferromagnetic CeFeSi-type structure is the disappearance of the induced magnetic moments on Sc. For the parent antimonide, heat capacity measurements indicate an additional transition below the main antiferromagnetic transition