The combustion wave structure and thermal decomposition process of azide polymer were studied to determine the parameters which control the burning rate. The azide polymer studied was glycidyl azide polymer (GAP) which contains energetic – N3 groups. GAP was cured with hexamethylene diisocyanate (HMDI) and crosslinked with trimethylolpropane (TMP) to formulate GAP propellant. From the experiments, it was found that the burning rate of GAP propellant is significantly high even though the adiabatic flame temperature of GAP propellant is lower than that of conventional solid propellants. The energy released at the burning surface of GAP propellant is caused by the scission of NN2 bond which produces gaseous N2. The heat flux transferred back from the gas phase to the burning surface is very small compared with the heat generated at the burning surface. The activation energy of the decomposition of the burning surface of GAP propellant, Es, is determined to be 87 kJ/mol. The burning rate is represented by r = 9.16 × 103 exp(–Es/RTs) where r (m/s) is burning rate, Ts (K) is the burning surface temperature, and R is the universal gas constant. The observed high temperature sensitivity of burning rate is correlated to the relationship of (∂Ts/∂T0)p = 0.481 at 5 MPa, where T0 is the initial propellant temperature.

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3,3‐Bis(azidomethyl)oxetane (BAMO) is a typical energetic azide polymer containing two N3, bonds in the molecular structure. Since BAMO is a solidified polymer at room temperature, a liquid BAMO copolymer with tetrahydrofuran (THF) was synthesized in order to gain energetic binders for solid propellants. Various types of experiments were carried out to elucidate the decomposition and combustion processes of BAMO polymer, BAMO/THF copolymer, and crosslinked BAMO/THF copolymer. The heat produced by the decomposition is caused by the bond breakage of ‐N3 to produce N2, gas. The burning rate characteristics of crosslinked BAMO/THF copolymer depend largely on the mole fraction ratio of BAMO and THF.