Yan-Li Zhu

Thermal decomposition of RDX/AP by TG–DSC–MS–FTIR

The method of TG–DSC–MS–FTIR simultaneous analysis has been used to study the thermal decomposition mechanism of the RDX/AP (1/2) mixture. TG–DSC showed that there were two mass loss processes for thermal decomposition of RDX/AP. The first one was mainly ascribed to the thermal decomposition of RDX. Addition of AP to RDX causes decomposition to take place abruptly, after melting, resulting in a very sharp and strong peak at lower temperature. The apparent activation energies, calculated by model-free Friedman method, of this process were negative. The second mass loss process of RDX/AP was confirmed to be the thermal decomposition of AP, catalyzed by RDX. This process can be divided into three stages, which were an nth-order autocatalytic and two one-dimensional diffusion stages, respectively. There was a competition among the formation reactions of N2O, HNCO, and HCl for the first stage and between NO2 and N2O for the later two stages. The production of N2O dominated in the second stage, while NO2 did in the third stage.

Kinetics of Thermal Decomposition of Ammonium Perchlorate by TG/DSC-MS-FTIR

The method of thermogravimetry/differential scanning calorimetry–mass spectrometry–Fourier transform infrared (TG/DSC-MS-FTIR) simultaneous analysis has been used to study thermal decomposition of ammonium perchlorate (AP). The processing of nonisothermal data at various heating rates was performed using NETZSCH Thermokinetics. The MS-FTIR spectra showed that N2O and NO2 were the main gaseous products of the thermal decomposition of AP, and there was a competition between the formation reaction of N2O and that of NO2 during the process with an iso-concentration point of N2O and NO2. The dependence of the activation energy calculated by Friedmans iso-conversional method on the degree of conversion indicated that the AP decomposition process can be divided into three stages, which are autocatalytic, low-temperature diffusion and high-temperature, stable-phase reaction. The corresponding kinetic parameters were determined by multivariate nonlinear regression and the mechanism of the AP decomposition process was proposed.

Influence of Aluminum Particle Size on Thermal Decomposition of RDX

The effect of aluminum particle size (10.7 µm, 2.6 µm, and 40 nm) on the thermal decomposition of 1,3,5-trimethylene trinitramine (RDX) was investigated using differential scanning calorimetry (DSC), thermogravimetry–derivative thermogravimetry (TG-DTG), and DSC-TG–mass spectrometry (MS)–Fourier transform infrared (FTIR) spectroscopy, respectively. The results showed that the first exothermic peak (512 K) of RDX diminishes gradually with an increase in the nanosize aluminum content and is overcome by the second exothermic peak when the content of nano-Al reaches 30 wt%. The reaction mechanisms demonstrated by the nonisothermal kinetics of RDX in the absence and presence of 30 wt% Al were conformed to the Avrami-Erofeev equations for all of the RDX compositions. The nucleus growth factor for the RDX/40 nm Al mixture was found to be n = 2/3 compared to n = 3/4 for RDX with and without the microsized Al. The MS and FTIR analyses indicated that the thermal decomposition of RDX in the presence of Al nanopowders favors C-N bond cleavage over N-N bond cleavage as the rate determining step.

Kinetics of thermal decomposition of ε-hexanitrohexaazaisowurtzitane by TG-DSC-MS-FTIR

Thermal decomposition of ε-hexanitrohexaazaisowurtzitane (HNIW) was studied by thermogravimetry-differential scanning calorimetry-mass spectrometry-Fourier transform infrared spectroscopy (TG-DSC-MS-FTIR) simultaneous analysis. It has been shown that there is a crystal transition point for ε-HNIW, and only a single decomposition process has been observed for HNIW. The kinetic parameters of thermal decomposition of HNIW were obtained by Kissinger and Flynn-Wall-Ozawa methods, indicating that HNIW has the higher reactivity compared to the other nitramines. The HNIW decomposition mechanism demonstrated by the non-isothermal kinetics conformed to Avrami-Erofeev equation with the factor of nucleus growth of n=1/3 and the conversion degree of α from 0.1 to 0.7. The MS and FTIR analyses indicated that the thermal decomposition of HNIW favors N-N bond cleavage over C-N bond cleavage as the rate determining step.

Effects of Aluminum on Thermal Decomposition of Hexogen/Ammonium Perchlorate

Thermogravimetry-differential scanning calorimetry-mass spectrometry-Fourier transform infrared spectrometry(TG-DSC-MS-FTIR) simultaneous analysis was used to study the effects of 10.7 μm and 40 nm Al on the thermal decomposition of the Hexogen/ammonium perchlorate(RDX/AP, 1/2, mass ratio) mixture. TG-DSC results show that there are two mass loss processes for the thermal decomposition of RDX/AP/Al. The first one is mainly ascribed to the thermal decomposition of RDX. The reaction rate of RDX/AP/10.7 μm Al is so fast that the apparent activation energy, calculated by model-free Friedman method, is negative, which is the same as that of RDX/AP. 30%(mass fraction) 40 nm Al added in RDX/AP change the activation energy from negative to positive value. The second mass loss process of the RDX/AP/Al mixture is ascribed to the thermal decomposition of AP. This process can be divided into three stages for RDX/AP with and without Al. The kinetics model is not changed in the presence of micro-sized Al, while it is changed from CnB/D1/D1 to CnB/D1/D4 after the addition of 40 nm Al to RDX/AP. The reaction rate constant of the first stage and the end temperature of the second stage decrease, while the end temperatures of the third stage increase in the presence of 40 nm Al. The MS-FTIR results show there is a competition between the formation reactions of HNCO, N2O and NO2 during the second mass loss process.