Study on the Application of Fluorinated Polyimide in the Acidic Corrosion Protection of 3-nitro-1,2,4-trizole-5-one (NTO)-Based Explosive Formulations.

3-nitro-1,2,4-triazol-5-one (NTO) has been widely used as a kind of insensitive single-compound explosive owing to its excellent balance between safety and explosive energy. To reduce its possible acid corrosion and extend its application to insensitive ammunition, acid protection research on NTO-based explosives is significant. Traditionally, the acid protection effect was evaluated by metal corrosion, which is time-consuming and qualitative. An efficient and quantitative method is desirable for evaluating the acid protection effect and exploring novel protection materials. Herein, a polyimide of 4,4'-(hexafluoroisopropene)diphthalic anhydride (6FDA)/2,2-bis(trifluoromethyl)-4,4-diaminobiphenyl (TFMB) was synthesized by replacing the 4,4'-diaminodiphenyl ether (ODA) monomer with a TFMB monomer to act as an acid-protective coating material for NTO-based explosives. Compared with three other coating materials, polyvinylidene fluoride (PVDF), polyetherimide (PEI), and copolyimide (P84), the fluorinated polyimide exhibits the best acid protection effect. Moreover, a new method was constructed to obtain the pH time-dependent curve in order to evaluate efficiently the acid protection effect of the polymer materials. By the virtue of molecular dynamic simulation (Materials Studio 2023), the interfacial effects of the coating materials with NTO-based explosives were obtained. The study provides an interpretation of the acid protection effect on the molecular level, suggesting that the higher content of fluorine atoms is beneficial for stabilizing the active hydrogen atom of the NTO by forming intermolecular hydrogen bonds.

Coupling Effect of Non-Ignition Impact and Heat on the Decay of FOX-7.

Non-ignition impact and heat stimuli are the most common external stimuli loaded on energetic materials. Nevertheless, there is thereby an urgent need, but it is still a significant challenge to comprehend their coupling effects on the decay and safety mechanisms of energetic materials. Then, reactive molecular dynamics simulation was employed to mimic practical situations and reveal the impact heat coupling effect on the decay mechanism of FOX-7. The temperature and the degree of compression of the crystal caused by the impact are considered variables in the simulation. Both increasing the degree of compression and elevating the temperature promotes the decay of FOX-7. However, their underlying response mechanism is not the same. The acceleration of decomposition is due to the elevated potential energy of the FOX-7 molecules because of elevating the temperature. In addition to the elevated potential energy of the molecule, the main contribution to the decomposition from the compression is to change the decomposition path. The results of the analysis show that compression reduces the stability of the C=C bond, so that chemical reactions related to the double bond occur. In addition, interestingly, the compression along the c direction has an almost equal effect on the final product as the compression along the b direction. Finally, the decay reaction networks are proposed to provide insights into the decomposition mechanism on atomic level. All these findings are expected to pave a way to understand the underlying response mechanism for the FOX-7 against external stimuli.

Initial Decomposition Mechanism of 3-Nitro-1,2,4-triazol-5-one (NTO) under Shock Loading: ReaxFF Parameterization and Molecular Dynamic Study.

We report a reactive molecular dynamic (ReaxFF-MD) study using the newly parameterized ReaxFF-lg reactive force field to explore the initial decomposition mechanism of 3-Nitro-1,2,4-triazol-5-one (NTO) under shock loading (shock velocity >6 km/s). The new ReaxFF-lg parameters were trained from massive quantum mechanics data and experimental values, especially including the bond dissociation curves, valence angle bending curves, dihedral angle torsion curves, and unimolecular decomposition paths of 3-Nitro-1,2,4-triazol-5-one (NTO), 1,3,5-Trinitro-1,3,5-triazine (RDX), and 1,1-Diamino-2,2-dinitroethylene (FOX-7). The simulation results were obtained by analyzing the ReaxFF dynamic trajectories, which predicted the most frequent chain reactions that occurred before NTO decomposition was the unimolecular NTO merged into clusters ((C2H2O3N4)n). Then, the NTO dissociated from (C2H2O3N4)n and started to decompose. In addition, the paths of NO2 elimination and skeleton heterocycle cleavage were considered as the dominant initial decomposition mechanisms of NTO. A small amount of NTO dissociation was triggered by the intermolecular hydrogen transfer, instead of the intramolecular one. For α-NTO, the calculated equation of state was in excellent agreement with the experimental data. Moreover, the discontinuity slope of the shock-particle velocity equation was presented at a shock velocity of 4 km/s. However, the slope of the shock-particle velocity equation for ß-NTO showed no discontinuity in the shock wave velocity range of 3-11 km/s. These studies showed that MD by using a suitable ReaxFF-lg parameter set, could provided detailed atomistic information to explain the shock-induced complex reaction mechanisms of energetic materials. With the ReaxFF-MD coupling MSST method and a cheap computational cost, one could also obtain the deformation behaviors and equation of states for energetic materials under conditions of extreme pressure.

Density Functional Theory (DFT) Study on the Structures and Energetic Properties of Isomers of Tetranitro-bis-1,2,4-triazoles.

A series of isomers of tetranitro-bis-1,2,4-triazoles were designed, and their electronic structures, heats of formation, densities, detonation performances, thermal stabilities, and impact sensitivities were investigated by density functional theory (DFT). The structure and energetic properties of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) were also calculated at the same level. On comparing with the detonation velocity and pressure and bond dissociation energy (BDE) of HMX, it was found that four isomers (BT2, BT5, BT6, BT7) have higher detonation performances than HMX and three isomers (BT5, BT6, BT7) have better thermal stabilities than HMX. The calculated results of impact sensitivities indicated that all of the designed isomers have more sensitivity than HMX. The calculated results of energy gaps between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) indicated that all of the designed isomers were more easily excited than HMX in the chemical reaction process. In particular, 3,3',5,5'-tetranitro-1,1'-bis-1,2,4-triazoles (BT5) exhibited excellent detonation performances (9464 m s-1, 39.44 GPa) and good thermal stability (BDE 256.81 kJ mol-1). The results indicated that the isomerization of tetranitro-bis-1,2,4-triazoles could improve their detonation performance or thermal stability and might lead to a promising isomer possessing both good performance and high thermal stability.