If sodium azide is impinged by certain reasons, it will be produced explosives by heavy metals and toxic materials. But it is used propellent for inflating automotive safety bags and the other chemical manufacturing purpose. The investigation of thermal hazard potential of sodium azide itself and with polymers ate very important because some parts of automotives, transporting vessels of reactive chemicals and many any other constituents of structures in factories are made of polymers. The range of decomposition temperatures are about $360-380^{circ}C$, even if it depends on heating rate and sample weight. Thermal decomposition heat of sodium azide in air is higher than in nitrogen atmosphere, because the former is included oxidizing heats of sodium metal which is made by decomposition of sodium azide to end. Especially decomposition temperature of polymers are increased on the order of bonding energy between atoms in hydrocarbon moleculars.