T. Czujko

Particle size, grain size and γ-MgH2 effects on the desorption properties of nanocrystalline commercial magnesium hydride processed by controlled mechanical milling

The hydrogen desorption properties of commercial nanocrystalline magnesium hydride (Tego Magnan® from Degussa–Goldschmidt) processed by controlled mechanical milling (CMM) are investigated. A profound effect of the powder particle size on the hydrogen desorption characteristics has been observed. The onset (TON) and peak hydrogen desorption temperatures measured by differential scanning calorimetry (DSC) decrease initially slowly with decreasing mean particle size of hydride, and when the particle size reaches a certain critical threshold value, the desorption temperatures start decreasing more rapidly with further decrease of particle size. The total drop of desorption temperature from its initial value for the as-received MgH2 to the value attained for the milled MgH2 having a particle size of ~500–600 nm is within the range 40–60 °C. The metastable γ-MgH2 hydride coexists with the stable nanocrystalline β-MgH2 in the microstructure of the MgH2 powders ball milled for 10 h and longer. Quantitative evidence shows that two factors, namely the refined powder particle size and the γ-MgH2 phase residing within the powder particles, acting additively, are responsible for a substantial reduction of the hydrogen desorption temperature of MgH2 hydride.

Feasibility study of the direct mechano-chemical synthesis of nanostructured magnesium tetrahydroaluminate (alanate) [Mg(AlH4)2] complex hydride

The present work reports a feasibility study of the direct mechano-chemical synthesis by controlled reactive mechanical alloying (CRMA) in a magneto-ball mill of the nanostructured magnesium tetrahydroaluminate (magnesium alanate) Mg(AlH(4))(2) complex hydride. Three stoichiometric Mg-2Al mixtures, (a) elemental Mg and Al powders, (b) elemental Al powder and commercial AZ91 alloy (Mg-Al-Zn alloy) and (c) powder of as-cast Mg-2Al alloy, have been used. No successful synthesis of Mg(AlH(4))(2) has been achieved. The only nanocrystalline hydride formed up to 270 h of CRMA is beta-MgH(2), and it does not react with Al and H(2) to form Mg(AlH(4))(2). It has been found that there is strong competition between formation of Al(Mg) solid solution and the beta-MgH(2) hydride occurring to a various extent up to approximately 10 h of CRMA in all three Mg-2Al mixtures. It is hypothesized that the presence of Al(Mg) solid solution inhibits the reaction of beta-MgH(2), Al and H(2) to form Mg(AlH(4))(2). Furthermore, despite the fact that after prolonged milling the Al(Mg) solution eventually decomposes into secondary Al(s) (derived from solid solution), the latter retains its physico-chemical characteristics of the former solid solution which still inhibits the reaction to form Mg(AlH(4))(2). Experimental evidence from DSC measurements shows increasing ranges of the melting enthalpy with increasing amounts of Al(Mg) solid solution and consequently the secondary Al(s) for all the three Mg-2Al mixtures. This strongly supports the hypothesis about the different nature of Al(Mg) and the secondary Al(s) as compared to the primary elemental Al powder.

The effect of atomic volume on the hydrogen storage capacity of hexagonal metals/intermetallics

Abstract A detailed analysis of a large number of data on the gravimetric hydrogen (H) capacity of hexagonal metals and intermetallic alloys shows that their maximum gravimetric hydrogen capacity increases linearly with increasing atomic volume, starting from some threshold value of about 120×10 −4 nm 3 /atom.

Mechanosynthesis of Nanocrystalline MgB2 Ceramic Powders in Hydrogen Alloying Mills via Amorphous Hydride Intermediate

In the present work we report on the synthesis of nanocrystalline MgB2 by mechanochemical reaction (mechanosynthesis) conducted in a high-energy mechanical alloying mill filled with hydrogen. The solid-state reaction of mechanochemical alloying between Mg and B with H (hydrogen alloying) leads to formation of an intermediate amorphous (Mg,B)Hx hydride. This amorphous intermediate is subsequently annealed (devitrified) to nucleate and grow nanocrystalline boride. The first stage of synthesis was carried out at room temperature from elemental Mg and B powders in a high-energy ball mill under sequential supply of hydrogen. The subsequent annealing of the amorphous product led to nearly single-phase MgB2, with only small fraction of MgO impurity. The easy room-temperature synthesis renders the method promising for production of MgB2, which recently gained attention as a new 39K ceramic superconductor. The amorphous intermediate itself can be studied further for its capacity to store ca. 2 wt% H in a metastable hydride phase. The effort was undertaken to predict formation of amorphous hydride phase through analysis of atomic volume mismatch between atoms of Mg, B, and H.