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Abstract: Two new ternary intermetallic compounds, CeMgCo4 (C15b pseudo-Laves phase, MgCu4Sn type) and Ce2MgCo9 (substitution derivative of PuNi3 type) were synthesized by mechanical alloying method. The structural and hydrogenation properties of these compounds were studied by X-ray diffraction and Pressure–Composition–Temperature measurements. Both compounds absorb hydrogen at room temperature and pressures below 10MPa forming hydrides with maximum compositions CeMgCo4H6 and Ce2MgCo9H12. Single plateau behavior was observed in P–C isotherm during hydrogen absorption/desorption by Ce2MgCo9 alloy. The CeMgCo4–H2 system is characterized by the presence of two absorption/desorption plateaus corresponding to formation of β-CeMgCo4H4 and γ-CeMgCo4H6 hydride phases. The structure of β-hydride CeMgCo4H(D)4 was determined from X-ray and neutron powder diffraction data. In this structure initial cubic symmetry of CeMgCo4 is preserved and hydrogen atoms fill only one type of interstitial sites, triangular MgCo2 faces. These positions are occupied by 70% and form octahedron around Mg atom with Mg–D bond distances 1.84Å. [Copyright &y& Elsevier]

Abstract: The present work is focused on studies of the influence of magnesium on the hydrogenation behaviour of the (La,Mg)2Ni7 alloys. Substitution of La in La2Ni7 by Mg to form La1.5Mg0.5Ni7 preserves the initial Ce2Ni7 type of the hexagonal P63/mmc structure and leads to contraction of the unit cell. The system La1.5Mg0.5Ni7–H2 (D2) was studied using in situ synchrotron X-ray and neutron powder diffraction in H2/D2 gas and pressure–composition–temperature measurements. La replacement by Mg was found to proceed in an ordered way, only within the Laves-type parts of the hybrid crystal structure, yielding formation of LaMgNi4 slabs with statistic and equal occupation of one site by La and Mg atoms. Mg alters structural features of the hydrogenation process. Instead of a strong unilateral anisotropic expansion which takes place on hydrogenation of La2Ni7, the unit cell of La1.5Mg0.5Ni7D9.1 is formed by nearly equal hydrogen-induced expansions proceeding in the basal plane (Δa/a=7.37%) and along [001] (Δc/c=9.67%). In contrast with La2Ni7D6.5 where only LaNi2 layers absorb hydrogen atoms, in La1.5Mg0.5Ni7D9.1 both LaNi5 and LaMgNi4 layers become occupied. Nine types of sites were found to be filled by D in total, including tetrahedral (La,Mg)2Ni2, (La,Mg)Ni3, Ni4, tetragonal pyramidal La2Ni3 and trigonal bipyramidal (La,Mg)3Ni2 interstices. The hydrogen sublattice around the La/Mg site shows formation of two co-ordination spheres of D atoms: an octahedron MgD6 and a 16-vertex polyhedron LaD16 around La. The interatomic distances are in the following ranges: La–D (2.28–2.71), Mg–D (2.02–2.08), Ni–D (1.48–1.86Å). All D–D distances exceed 1.9Å. Thermodynamic PCT studies yielded the following values for the ΔH and ΔS of hydrogenation/decomposition; ΔH H=−15.7±0.9kJ(molH)−1 and ΔS H=−46.0±3.7J(KmolH)−1 for H2 absorption, and ΔH H=16.8±0.4kJ(molH)−1 and ΔS H=48.1±1.5J(KmolH)−1 for H2 desorption. [Copyright &y& Elsevier]

Abstract: A new intermetallic deuteride Ce2Ni7D4.7 with an anomalous volume expansion has been studied. Its structure was solved on the basis of in situ neutron diffraction data. Expansion proceeds along the c-axis and within the CeNi2 slabs only. All D atoms are located inside these slabs and on the border between CeNi2 and CeNi5. Ordering of D atoms in the bulk of CeNi2 is accompanied by substantial deformation of these slabs thus lowering the hexagonal symmetry to orthorhombic [space group Pmcn (No. 62); a=4.9251(3)Å, b=8.4933(4)Å, c=29.773(1)Å]. Inside the CeNi2 layer the hydrogen sublattice is completely ordered; all D–D distances exceed 2.0Å. Local coordination of Ni by D inside the CeNi2 blocks is of “open”, saddle-like type. Hydrogen ordering is mainly determined by Ce–H and H–H interactions. The pressure–composition–temperature measurements yielded the following thermodynamic parameters of the formation of the hydride: ΔH=−22.4kJ/molH, ΔS=−59.9J/(KmolH). [Copyright &y& Elsevier]