Doped alkaline earth (nitride) hydrides
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The work in this thesis relates to the preparation and structural and electrical characterisation of calcium and strontium hydrides, imides and nitride hydrides. Conventional solid state methods in controlled atmospheres were used to synthesise these materials. High temperature neutron diffraction, thermal analysis and conductivity studies performed on calcium and strontium hydride suggest an order – disorder transition in these materials at 350 – 450°C. Disordering is believed to involve rapid exchange of hydride ions across two crystallographic sites. This manifests itself in a lowering of the activation energy for bulk hydride ion conduction. The hydride ion conduction is good in these undoped materials: σ[total]subscript = 0.01 S/cm for CaH₂ at 1000K; for SrH₂, σ[total]subscript = 0.01 S/cm at 830K. Doping of SrH₂ with NaH causes a significant increase in the low temperature conductivity, due to presence of extrinsic defects. The high temperature conductivity is negatively affected by NaH doping. Calcium nitride hydride (Ca₂NH) was obtained as a single phase material by reacting either calcium metal or calcium hydride (CaH₂) in an argon atmosphere containing 5 – 7% H₂ and 1 – 7% N₂. Imide ions substituting for hydride and nitride ions constitute a major chemical defect in this material. Long range ordering of the nitride and hydride ions occurs, giving rise to a double cubic crystal symmetry. This order breaks down at 600 – 650°C. Applying the same reaction conditions to strontium metal results in a mixed phase of strontium nitride hydride and imide. No long range order in the nitride hydride phase could be observed. Doping Ca₂NH with lithium hydride (LiH) causes the appearance of a second calcium imide phase, whereas doping with sodium hydride (NaH) increases the amount of imide ions as a defect in the nitride hydride structure, thereby decreasing the long range ordering of nitride and hydride ions.
Thesis, PhD Doctor of Philosophy
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