To enhance the thermal decomposition properties of glycidyl azide polymer energetic thermoplastic elastomer (GAP-ETPE), the effects of nano-CuO supported on different carbon carriers (GO and CNT) were systematically investigated in this study. The structural characteristics and catalytic performances were comprehensively analyzed using XRD, Raman, XPS, UPS, BET, SEM, and TEM, coupled with thermal analysis techniques including TG-DSC and TG-MS. The results indicate that the catalytic performance follows the descending order of CuO/CNT > CuO/GO > CuO. Notably, CuO/CNT exhibits the optimal catalytic activity, advancing the exothermic peak temperature of the azide groups by approximately 33 °C and resulting in a more concentrated heat release process. The superior synergistic catalytic effect of CuO/CNT is attributed to the following: the three-dimensional network constructed by CNT effectively overcomes the agglomeration of CuO nanoparticles and the restacking defects typical of GO nanosheets, thereby significantly reducing the gas–solid mass transfer resistance. Simultaneously, the highly graphitized sp² conjugated skeleton of CNT provides an exceptional electron transport capability, facilitating rapid electron migration. These findings demonstrate that the structure of carbon supports profoundly influences the synergistic catalytic effect of CuO, offering valuable insights into the design of highly efficient catalysts for energetic binders.

Glycidyl azide polymer (GAP)-based polyurethane, a kind of energetic thermoplastic elastomer (ETPE), is a promising binder for advanced solid propellants, but its thermal decomposition involves overlapping competitive reactions that conventional single-step kinetic models cannot characterize accurately, limiting its engineering applications. To address this limitation, a constrained asymmetric Gaussian deconvolution strategy with fixed peak area ratios and shape constraints was developed in this work. This strategy was applied to resolve overlapping reaction rate curves converted from derivative thermogravimetric data of GAP-based ETPEs with 50 wt% GAP content at four heating rates of 5, 10, 15 and 20 K·min⁻¹. The complex decomposition process was successfully split into five stages, assigned to azide cleavage, polyether backbone scission, carbamate cleavage, hydrocarbon product degradation and residue decomposition, with a goodness of fit of R² > 0.998. Apparent activation energies of the five stages were determined through cross-validation by the Friedman and Flynn–Wall–Ozawa methods without prior assumption of reaction mechanisms, following the order of residue decomposition (181.4 ± 1.0 kJ·mol⁻¹) > hydrocarbon product degradation (159.9 ± 1.0 kJ·mol⁻¹) ≈ azide cleavage (156.5 ± 0.6 kJ·mol⁻¹) > backbone scission (135.1 ± 0.7 kJ·mol⁻¹) > carbamate cleavage (111.9 ± 1.1 kJ·mol⁻¹). Pre-exponential factors with lnA₀ values ranging from 22.2 to 34.0 were derived via the kinetic compensation effect. Finally, generalized master plots were employed to compare with classic solid-state reaction models for mechanistic insight, and the Šesták–Berggren model fit three major stages excellently (R² > 0.996) by accounting for synergistic nucleation-growth and phase boundary mechanisms, enabling high-precision kinetic equations. It should be noted that the constrained deconvolution method proposed in this work has general applicability for kinetic analysis of GAP-based ETPEs with different formulations and other complex energetic polymer systems, while the obtained kinetic parameters are composition-specific and only applicable to the corresponding ETPE formulation studied herein.