The microstructure and the thermoelectric properties were systematically determined in the Fe2V1+xAl1-x, Fe2+xVAl1-x, Fe2-xV1+xAl series to investigate the influence of self-substitution on the ...Fe2VAl Heusler alloy. In the explored range of compositions (−0.1 < x < 0.1), all these series are solid solutions, which form anti-site defects to accommodate the off stoichiometry. They all crystallize in the cubic L21 structure, but their lattice parameter unusually increases with |x|. A Bader analysis based on Density Functional Theory calculations indicates that these uncommon lattice parameter changes arise from variations in the interatomic electron transfer. The antisite defects behave like dopants that control the conduction type and charge carrier concentration. This leads to large thermoelectric power factor (PF) in the Fe2V1+xAl1-x series, which displays the largest electronic mobility. PF = 6.7 mW m−1 K−2 at 250 K and PF = 3.2 mW m−1 K−2 at 325 K are reached in n-type Fe2V1.03Al0.97 and p-type Fe2V0.985Al1.015 respectively. The lattice thermal conductivity systematically decreases upon self-substitution, but with differences among the series which can be traced back to the interatomic electron transfer unveiled by the Bader analysis. Finally, the figure of merit is improved to ZT = 0.06 at 500 K in p-type Fe2V0.93Al1.07 and ZT = 0.15 at 420 K in n-type Fe2V1.08Al0.92.
A Rietveld analysis of neutron powder diffraction patterns obtained in situ during temperature scans shows that Fe2VAl crystallizes at room temperature in the fully ordered L21 structure and ...transforms at 1080 °C and at 1190 °C into partially disordered B2 and fully disordered A2 variants respectively. The low temperature stability of the L21 structure as well as the two high temperature L21 → B2 → A2 transitions are theoretically predicted by a combination of ab-initio (electronic structure and phonons) and thermodynamic calculations performed on special quasi-random structures. Pronounced cold work effects and the pre-transitional antisite defects which are observed respectively at 25 °C under mechanical stress and at high temperature (above 800 °C), appear to be generic effects in the family of Heusler alloys.
Display omitted
•Y0.9Gd0.1Fe2Hx (3 < x < 4) are ferrimagnetic with TC near 310 K.•Y0.9Gd0.1Fe2H4.2 displays a FM-AFM transition around 144 K.•Y0.9Gd0.1Fe2Hx (x > 4.2) are weak ferrimagnets with Gd order below ...15 K.•Magnetovolumic effects are observed for the two monoclinic phases M1 and M2.•Magnetic entropy variations are observed near Tc, TFM-AFM and TO-D.
At 300 K, Y0.9Gd0.1Fe2Hx hydrides crystallize sequentially with increasing H concentration in various structures related to a lowering of the cubic MgCu2 type structure of the parent alloy: cubic C1, monoclinic M1, cubic C2, monoclinic M2, cubic C3, orthorhombic O. Above 300 K, they undergo a first-order transition at a TO-D temperature driven by order-disorder of hydrogen atoms into interstitial sites. Their magnetic, structural and magnetocaloric properties have been investigated through magnetic measurements, and high-resolution synchrotron diffraction experiments. The magnetization at 5 K decreases slightly from 4 to 3.8 µB for x = 3–3.9 H/f.u., then with a larger slope for higher H content. A discontinuous decrease of the magnetic transition temperature is observed: M1 and C2 hydrides are ferrimagnetic with TC near 300 K, M2 hydride displays a sharp ferromagnetic-antiferromagnetic transition at TFM-AFM = 144 K, whereas C3 and O hydrides present only a sharp increase of the magnetization below 15 K and a weak magnetization up to room temperature. Negative magnetic entropy variations (ΔSM) are measured near TC for the M1 and C2 phases, near TFM-AFM for the M2 phase, whereas positive ΔSM peaks due to inverse MCE effect are found near TO-D. A structural and magnetic phase diagram is proposed.
•Y0.9Gd0.1Fe2-H2 system displays a multiplateau Pressure-Composition Isotherm.•Y0.9Gd0.1Fe2Hx (x = 2.9–5) hydrides crystallize in six different structures at RT.•They form three cubic, two monoclinic ...and one orthorhombic phases.•One intermediate cubic phase (C2) presents superstructures indexed in a double cell.•The two monoclinic and the C2 phases undergo order-disorder structural transitions.
Display omitted
Y0.9Gd0.1Fe2, which crystallize in a C15 cubic structure, can absorb up to 5 H/f.u. and its pressure-composition isotherm displays a multiplateau behavior related to the existence of several hydrides with different crystal structures. At room temperature Y0.9Gd0.1Fe2Hx hydrides (2.9 ≤ x ≤ 5) crystallize in three phases with cubic structure (C1, C2 and C3), two phases with monoclinic structures (M1 and M2), and one phase with orthorhombic structure (O), with the following sequence for increasing H concentration: C1, M1, C2, M2, C3, O. Each phase exists as single phase within a H homogeneity range, and they are separated from each other by two-phase domains. The reductions of crystal symmetry are related to various hydrogen orders into interstitial sites. Weak superstructure peaks were indexed by doubling the cubic cell parameter of the cubic C2 phase. Upon heating, the monoclinic M1 and M2 and the cubic C2 phases undergo order-disorder (O-D) transitions toward a disordered cubic structure CDis. These O-D transitions are reversible with thermal hysteresis effects. The cubic C3 and orthorhombic O phases transform into a disordered cubic phase accompanied by H desorption.
PDF
