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Chinese Journal of Materials Research  2016, Vol. 30 Issue (12): 940-946    DOI: 10.11901/1005.3093.2016.152
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Thermal Decomposition Behaviour of ANPyO at High Temperature by Molecular Dynamics Simulation
Xinlong ZHOU1,Zuliang LIU1,*(),Xiaoming WANG2,Yu ZHENG2,Qunrong SHI1
1. Department of Chemistry, Nanjing University of Science and Technology, Nanjing 210094, China
2. ZNDY of Ministerial Key Laboratory, Nanjing Universityof Science and Technology, Nanjing 210094, China
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Xinlong ZHOU,Zuliang LIU,Xiaoming WANG,Yu ZHENG,Qunrong SHI. Thermal Decomposition Behaviour of ANPyO at High Temperature by Molecular Dynamics Simulation. Chinese Journal of Materials Research, 2016, 30(12): 940-946.

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The initial decomposition of the condensed phase ANPyO crystal at various temperature (T=1500 K、2000 K、2500 K、3000 K and 3500 K) were studied by using ReaxFF reactive molecular dynamics simulation. The time evolution curve of the potential energy can be described reasonably well by a single exponential function from which the initial equilibration and induction time as well as the overall characteristic time of pyrolysis were obtained. Afterward, the activation energy Ea (88.65 kJmol-1) also was obtained from these simulations. Result show when the ANPyO molecules in the unit cell almost decomposed, the potential energy of the system significantly attenuated. Meanwhile ANPyO showed different reaction mechanisms at different temperatures. At lower temperatures (1500 K≤T≤2500 K) the hydrogen from NH2 transferred to ortho—NO2 and promote C—NO2 bond fission, while the H2O and NO molecules formed. At very high temperatures 2500 K≤T≤3500 K), the C-NO2 homolytic cleavage and C—NO2→C—ONO rearrangement hemolysis are thermo dynamically favorable pathways in the early thermal decomposition of ANPyO. According to calculations using limited time steps, the main products are H2O、N2、NO2、NO、CO2、CO、OH and HONO. Secondary products are mainly NO2、NO、OH and HONO, which has strong oxidizing property, so that the distribution has a dramatic fluctuation characteristics. It is found that H2O and N2 are the main stable products of thermal decomposition. Pyridine ring fission does not take place until most of the attached groups have interacted or disconnected, and increasing temperature accelerates fission of Pyridine ring and further decomposition to generate both CO2, CO, NO, and amount of carbon-containing clusters.

Key words:  other disciplines of      the materials science      high temperature thermal decomposition      ReaxFF potencial energy      ANPyO      molecular dynamics     
Received:  20 March 2016     
Fund: *Supported by National Natural Science Foundation of China No. 11302108.

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Fig.1  Molecular and crystal structure for ANPyO (gray, carbon; blue, nitrogen; red, oxygen; white, hydrogen)
Fig.2  Time evolution of potential energy of the system (a) and total species during reaction (b)
Fig.3  Logarithm of initial decomposition rate constant of ANPyO vs inverse temperature at 2500~3500 K
Fig.4  Time evolution of main products for T=2000 K、2500 K、3000 K and 3500 K
Fig.5  Comparative distribution curve of main products per ANPyO molecule for four high temperature
Fig.6  Initial steps of ANPyO decomposition at low temperature
Fig.7  Initial steps of ANPyO decomposition at high temperature
Fig.8  Radial distribution of function g(r) of C—C bonds for T=1500 K、2500 K and 3500 K
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