The alloy TiFe has interesting hydrogen storage properties for practical applications: low cost, operation at room temperature, and good hydrogen capacity. However, the first hydrogenation is difficult and increases the cost of the alloy. In this work, we studied the effect of adding hafnium to TiFe in order to enhance the first hydrogenation process. TiFe + x Hf alloys, with x = 0, 4, 8, 12, and 16 wt.%, were synthesized by arc melting. The microstructure of the as-cast alloys was investigated by scanning electron microscopy and electron microprobe analysis. These alloys consisted of B2-TiFe, C14-Laves, and BCC (Body Centered Cubic) phases. A minimum of 8 wt.% of hafnium is required to obtain an enhancement of the first hydrogenation. In the first hydrogenation, the material reaches its maximal hydrogen capacity in less than two hours at room temperature and under 20 bars of hydrogen. Hafnium addition also had the effect of lowering the plateau pressure in the pressure-composition isotherm. It could be concluded that hafnium has a positive effect on the activation properties of TiFe.
We report here the effect on hydrogen sorption behavior of replacing vanadium by ferrovanadium (FeV) in Ti-V-Cr Body Centred Cubic (BCC) solid solution alloys. The compositions studied were Ti1.56V0.36Cr1.08 and Ti1.26V0.63Cr1.11. Both of the alloys were synthesized by melting with 4 wt % of Zr7Ni10 in order to enhance the first hydrogenation (i.e., activation) kinetics. The ferrovanadium substitution leads to the same microstructure as the vanadium pristine alloys and no significant change in the lattice parameters was found. However, a longer incubation time was observed in the activation process for the FeV substituted alloy. Finally, the replacement of vanadium by ferrovanadium did not have a noticeable impact on the hydrogen capacities, heat of formation, and entropy.
The new intermetallic NdNiMg5 was discovered during the study of the Mg-rich part of the Mg–Nd–Ni system. It was synthetized by melting of the constituent elements in a sealed tantalum tube with subsequent annealing. Its structure was determined by X-ray diffraction on a single crystal. Crystal data: orthorhombic system, Cmcm, Z = 4, a = 4.4799(2) Å, b = 9.9827(3) Å, c = 13.7854(10) Å, dcalc = 3.49 g·cm–3. Its structure is made of infinite layers of Mg atoms that form blocks stacked along the c axis. These blocks, with a close-packed array of Mg atoms, are separated by infinite NiNd layers and connected through short Mg–Mg bonds. In the NiNd layer, the Ni and Nd atoms form an ordered graphite-type network. Antiferromagnetic ordering is observed with TN = 12 K, and the effective magnetic moment μeff is equal to 3.89(1) μB.
1 October 2011 in International Journal of Hydrogen Energy
In the present work, the effects of (i) Ti replacement by Hf and (ii) the synthesis method on microstructure and crystal structure evolution in the high-entropy alloy HfxTi(1−x)NbVZr are reported. The results of scanning electron microscopy and X-ray diffraction analysis of alloys prepared by both arc-melting and induction-melting are compared with theoretical thermodynamic calculations using the CALPHAD approach. The non-equilibrium thermodynamic calculations agree well with the experimental observations for the arc-melted alloys: a mixture of body-centered cubic (BCC) and cubic C15 Laves phases occurs for low-Ti-concentration alloys and a single BCC phase is obtained for high-Ti alloys. The agreement is not as good when using the induction-melting method: equilibrium solidification calculations predict that the most stable state is a phase mixture of BCC, hexagonal close-packed, and a cubic C15 Laves phase, while experimentally only one BCC and one hexagonal C14 Laves phase were found. The estimation of the exact cooling rate and the lack of a thermodynamic database can explain the difference. In addition, for both methods, the thermodynamic calculation confirms that for a high Ti concentration, the BCC phase is stable, whereas phase separation is enhanced with a higher Hf concentration.