title: The mechanisms for desensitization effect of synthetic polymers on BCHMX: Physical models and decomposition pathways.
abstract: The project involves determination of the activation energies and physical models for thermolysis of BCHMX and its PBXs. The initial decomposition pathways were also proposed on the basis of molecular dynamic simulation. The goal is to find the mutual relationships among the physical models, decomposition pathways, and the impact sensitivities for BCHMX and its PBXs. It has been shown that the physical model of the first step of BCHMX thermolysis is close to first order and the second step is governed by a first order autocatalytic model, which turns to "2D or 3D Nucleation and Growth" models under the effect of polymeric binders probably due to their hindrances on topochemical reaction of BCHMX. Simulation results show that the scission of N-NO2 is the initial step for BCHMX pyrolysis, followed by HONO and HNO eliminations, where the latter is due to nitro-nitrite rearrangement. Under the effect of hydrocarbon polymers, the HONO/HON elimination and collapse of ring structure of BCHMX occur earlier without changing the time for N-NO2 scission, which might be the reason why those polymers have little effect on the thermal stability of BCHMX, while they could make it decompose almost in a single complex step.
authors: Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech Republic. Electronic address: terry.well@163.com.
authors: Qi-Long
authors: QL
authors: Yan
authors: Institute of Energetic Materials, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech Republic. Electronic address: svatopluk.zeman@upce.cz.
authors: Svatopluk
authors: S
authors: Zeman
authors: Xi'an Modern Chemistry Research Institute, 710065 Xi'an, China.
authors: Xiao-Hong
authors: XH
authors: Zhang
authors: Department of Physical Chemistry, Faculty of Chemical Technology, University of Pardubice, 53210 Pardubice, Czech Republic.
authors: Jiří
authors: J
authors: Málek
authors: Xi'an Modern Chemistry Research Institute, 710065 Xi'an, China.
authors: Wu-Xi
authors: WX
authors: Xie
mesh_terms: D007093:Imidazoles / Q000737:chemistry*; D008956:Models, Chemical; D056004:Molecular Dynamics Simulation; D011108:Polymers / Q000737:chemistry*
chemical_list: C540612:1,3,4,6-tetranitrooctahydroimidazo-(4,5-d)imidazole; D007093:Imidazoles; D011108:Polymers
keywords: Hotspots; Impact sensitivity; Molecular dynamics; Nitramine based PBXs; Reactive force field