Investigations of effect of hydroxyl-terminated polybutadiene-based polyurethane binders containing various curatives on thermal decomposition behaviour and kinetics of energetic composites

An energetic composite of an octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine with a polymer matrix is generally developed to reduce sensitivity, improve mechanical strength and furnish engineering shape. A hydroxyl-terminated polybutadiene (HTPB) and various curatives, namely methylene diphenyl diisocyanate (MDI), isophorone diisocyanate (IPDI), toluene diisocyanate (TDI) and trimethyl-hexamethylene diisocyanate (TMDI), were mixed in 1:1 [NCO]/[OH] equivalent ratio to form polyurethane, and these samples were designated by HTPB/MDI, HTPB/IPDI, HTPB/TDI and HTPB/TMDI, respectively. The four kinds of energetic composites were prepared by mixing of an energetic HMX with various HTPB/MDI, HTPB/IPDI, HTPB/TDI and HTPB/TMDI matrices. These composites were studied for the thermal stability by employing thermogravitry analysis (TGA) and found to be almost similar. The kinetic parameters of all kinds of composites were investigated through the isoconversional Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunose (KAS) methods for the first and second stages of the thermal decomposition using TGA data. The results of the activation energy obtained from the FWO method were analogous to those values obtained from the isoconversional KAS method. In addition, the kinetic parameters were also investigated through isoconversional KAS method using DSC data. The overall values of the activation energy of the HMX/HTPB/MDI, HMX/HTPB/IPDI, HMX/HTPB/TDI and HMX/HTPB/TMDI samples were varied in a range of 168–263, 277–409, 210–421 and 206–324 kJ mol⁻¹ at a constant value of conversion (α = 0.1–0.9), respectively. The results indicated that there was significant variation in the activation energy with varying curative groups in the HTPB-based PU matrices. The compensation effect method was used to calculate the pre-exponential factor. The energetic composites were also investigated for the thermodynamic parameters for formation of the activated complexes and are discussed.