A computation-guided framework combining reactive molecular dynamics (MD) simulations with thermogravimetry-differential scanning calorimetry-Fourier transform infrared spectroscopy (TG-DSC-FTIR) was developed to elucidate how interfacial constraint regulates the thermolysis of 2,6-diamino-3,5-dinitropyrazine-1-oxide (LLM-105) through coupled early- and late-stage mechanisms. Using this integrated approach, we show that introducing triaminoguanidine-glyoxal energetic polymer (TAGP) sheets between LLM-105 crystallites (intergranular/interparticle regions) measurably modulates decomposition behavior. Consistent trends from MD and DSC reveal a delayed decomposition onset and suppressed early NO2 release, with the minimum NO2 evolution occurring at ∼2.24 wt % TAGP. At elevated temperatures, the TAGP-modified composite further shifts the reaction network toward a safer product profile, yielding higher N2, H2O, and CO2 while reducing CO formation. This shift is consistent with strengthened NOx reduction and CO oxidation pathways. Mechanistically, the effect originates from the earlier pyrolysis of TAGP, which supplies hydrogen-donating fragments and reactive radicals (e.g., aminyl/imidyl) that regulate interfacial chemistry and redirect dominant decomposition routes. Overall, a small TAGP loading (∼2.24 wt %) both delays decomposition initiation and improves effluent composition by promoting N2/H2O-rich decomposition, highlighting interfacial engineering as an effective strategy to enhance the safety performance of insensitive high-energy materials.
Zhang et al. (Wed,) studied this question.