Improvement in the Hydrogenation and Dehydrogenation Features of Mg by Milling in Hydrogen with Vanadium Chloride

VCl3 (vanadium (III) chloride) was selected as an additive to Mg to increase the hydrogenation and dehydrogenation rates and the hydrogen storage capacity of Mg. Instead of MgH2, Mg was used as a starting material since Mg is cheaper than MgH2. Samples with a composition of 95 wt% Mg + 5 wt% VCl3 (named Mg-5VCl3) were prepared by milling in hydrogen atmosphere (reactive milling). In the first cycle (n=1), Mg-5VCl3 absorbed 5.38 wt% H for 5 min and 5.95 wt% H for 60 min at 573 K in 12 bar hydrogen. The activation of Mg-5VCl3 was completed after three hydrogenation-dehydrogenation cycles. During milling in hydrogen, β-MgH2 and γ-MgH2 were produced. The formed β-MgH2 and γ-MgH2 are considered to have made the effects of reactive milling stronger as β-MgH2 and γ-MgH2 themselves were being pulverized. The introduced defects and the interfaces between the Mg and the phases formed during the reactive milling and during hydrogenation-dehydrogenation cycling are believed to serve as heterogeneous active nucleation sites for MgH2 and Mg-H solid solution. The phases generated during hydrogenation-dehydrognation cycling are also believed to prevent the particles from coalescing during hydrogenation-dehydrognation cycling.

Improvement in the Hydrogenation and Dehydrogenation Features of Mg by Milling in Hydrogen with Vanadium Chloride

VCl3 (vanadium (III) chloride) was selected as an additive to Mg to increase the hydrogenation and dehydrogenation rates and the hydrogen storage capacity of Mg. Instead of MgH2, Mg was used as a starting material since Mg is cheaper than MgH2. Samples with a composition of 95 wt% Mg + 5 wt% VCl3 (named Mg-5VCl3) were prepared by milling in hydrogen atmosphere (reactive milling). In the first cycle (n=1), Mg-5VCl3 absorbed 5.38 wt% H for 5 min and 5.95 wt% H for 60 min at 573 K in 12 bar hydrogen. The activation of Mg-5VCl3 was completed after three hydrogenation-dehydrogenation cycles. During milling in hydrogen, β-MgH2 and γ-MgH2 were produced. The formed β-MgH2 and γ-MgH2 are considered to have made the effects of reactive milling stronger as β-MgH2 and γ-MgH2 themselves were being pulverized. The introduced defects and the interfaces between the Mg and the phases formed during the reactive milling and during hydrogenation-dehydrogenation cycling are believed to serve as heterogeneous active nucleation sites for MgH2 and Mg-H solid solution. The phases generated during hydrogenation-dehydrognation cycling are also believed to prevent the particles from coalescing during hydrogenation-dehydrognation cycling.

Enhancement of the Hydrogenation and Dehydrogenation Characteristics of Mg by Adding Small Amounts of Nickel and Titanium

We compared the hydrogenation and dehydrogenation properties of Mg-based alloys to which small amounts of transition elements (Ni and Ti), halides (TaF5 and VCl3), and complex hydrides (LiBH4 and NaAlH4) were added through grinding in a hydrogen atmosphere (reactive milling). Mg-1.25Ni-1.25Ti is one of the samples compared, having a composition of 97.5 wt.% Mg + 1.25 wt.% Ni and 1.25 wt.% Ti. Even though Mg-1.25Ni-1.25Ti did not have the highest initial hydrogenation rate, it had the largest quantities of hydrogen absorbed and released for 60 min and the highest initial dehydrogenation rate. In addition, Mg-1.25Ni-1.25Ti did not show the incubation period in the dehydrogenation. We thus investigated the hydrogenation and dehydrogenation properties of Mg-1.25Ni-1.25Ti in more detail. Activated Mg-1.25Ni-1.25Ti absorbed 5.91 wt.% H in 12 bar H2 and released 5.80 wt.% H in 1.0 bar H2 at 593 K for 60 min at n = 3. For 5 wt.% hydrogen absorption by Mg-1.25Ni-1.25Ti, 18.7 min was required at 593 K in 12 bar H2 at n = 3. Although only small amounts of Ni and Ti were added, the hydrogenation and dehydrogenation properties of Mg were greatly improved. Ni and Ti-added Mg had a higher initial dehydrogenation rate and a larger Hd (60 min) than only Ni-added Mg, suggesting that the TiH1.924 and NiTi formed in Mg-1.25Ni-1.25Ti play roles in the increases in the initial dehydrogenation rate and Hd (60 min), probably acting as active sites for the nucleation of the Mg-H solid solution phase.

Preparation and Characterization of Silicon-Metal Fluoride Reactive Composites

Fuel-rich composite powders combining elemental Si with the metal fluoride oxidizers BiF3 and CoF2 were prepared by arrested reactive milling. Reactivity of the composite powders was assessed using thermoanalytical measurements in both inert (Ar) and oxidizing (Ar/O2) environments. Powders were ignited using an electrically heated filament; particle combustion experiments were performed in room air using a CO2 laser as an ignition source. Both composites showed accelerated oxidation of Si when heated in oxidizing environments and ignited readily using the heated filament. Elemental Si, used as a reference, did not exhibit appreciable oxidation when heated under the same conditions and could not be ignited using either a heated filament or laser. Lower-temperature Si fluoride formation and oxidation were observed for the composites with BiF3; respectively, the ignition temperature for these composite powders was also lower. Particle combustion experiments were successful with the Si/BiF3 composite. The statistical distribution of the measured particle burn times was correlated with the measured particle size distribution to establish the effect of particle sizes on their burn times. The measured burn times were close to those measured for similar composites with Al and B serving as fuels.