The conventional NaN3/oxidants gas generator pyrotechnic mixtures suffer from leaving undesirable solid residues. The presented investigation aimed to overcome this problem through mixing of NH4N3 particles with some metallic components, and to introduce some new gas generator pyrotechnic mixtures. In this work, volatile ammonium azide particles were initially stabilized via microencapsulation technique, and blended with Zr, Ti, ZrH2, and TiH2 powders to produce different gas generation mixtures. Thermal properties and kinetic parameters of these pyrotechnic mixtures were investigated by using thermal analysis (TG/DTA and DSC) techniques. The apparent activation energy (E), G(#), H-#, S-#, and critical ignition temperature (T-b) of the ignition processes of the mixtures were obtained from the DSC experiments. Among the investigated mixtures, NH4N3/ZrH2 composition was found to show desirable efficiency, and also it can be considered as a safe pyrotechnic composition for gas generation property, due to its moderate ignition temperature.