Abstract Phase transitions and crystal structure modifications were observed during the thermal-desorption decomposition of the alanate NaAlH 4 . This was accomplished through the use of in-situ X-ray powder diffraction. A sequence of θ –2 θ scans were collected while heating the sample under a vacuum. The resulting diffraction patterns were assembled to provide a real-time representation of the decomposition reactions. It was found that upon heating, NaAlH 4 initially experienced a lattice expansion principally in the c -axis direction. This was followed by continuous structural distortions observed as erratic variations in the Bragg intensities. Melting of NaAlH 4 was observed at 180°C followed by the rapid precipitation of a cubic Na 3 AlH X phase. This phase then underwent a slow transformation into a Na-rich cubic phase. The decomposition of NaAlH 4 doped with a double catalyst (Ti+Zr) was also investigated. The uncatalyzed sample showed no decomposition when held under a vacuum at 150°C for several hours. The catalyzed sample, on the other hand, began to decompose readily into the monoclinic (α)-Na 3 AlH 6 phase when heated to 100°C in vacuum. At 150°C the (α)-Na 3 AlH 6 phase decomposed in a second reaction according to α-Na 3 AlH 6 →3 NaH+Al+3/2 H 2 . The two decomposition reactions appear to be interdependent as the second transformation commenced only after the first reaction neared completion. The observed growth of a narrow Al (111) diffraction peak indicates the formation of aluminum crystallites (>100 nm) as a part of the decomposition reactions. This, and the fact that this solid state process is assisted through the interaction of a surface catalyst suggests long-range transport of a metal species. Some mechanisms are proposed to explain the catalytically enhanced kinetics of these materials.
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