This paper presents the catalytic effects of Cu-Co~* catalyst on the decomposition of AN and AN/KDN based oxidizer and propellant samples. Ozawa-Flynn-Wall(OFW) iso-conversional method was used for the kinetic studies...This paper presents the catalytic effects of Cu-Co~* catalyst on the decomposition of AN and AN/KDN based oxidizer and propellant samples. Ozawa-Flynn-Wall(OFW) iso-conversional method was used for the kinetic studies and to compute the activation energy(Ea) values for various decomposition steps of the prepared oxidizer and propellant samples in the temperature range of 50 e500C. TG-DTG experiments were carried out for both oxidizer and propellant samples at the heating rates of 3, 5, and 10C/min. AN/KDN based oxidizer samples were prepared by an evaporative co-crystallization method. Citric acid sol-gel method was used for the synthesis of Cu-Co~* catalyst. The propellant sample contains HTPB as the fuel binder along with other ingredients such as TDI, DOA, and Glycerol. The Cu-Co~* catalyst was used as 2% by weight to the total weight of catalyzed oxidizer and propellant samples. It was observed from the present study that, Cu-Co~* catalyst helps in reducing the Ea values for AN and AN based propellant samples. However, with the percentage increment of KDN in the AN crystals, Ea value increases.Further, it was observed that Cu-Co~* catalyst stabilizes the initial partial decomposition of KDN.展开更多
The doping dependence of dry thermal oxidation rates in n-type 6H-SiC was studied. The oxidation temperature ranged from 1050 to 1150℃ and the nitrogen doping concentration ranged from 9.53× 10^16, 1.44× 10...The doping dependence of dry thermal oxidation rates in n-type 6H-SiC was studied. The oxidation temperature ranged from 1050 to 1150℃ and the nitrogen doping concentration ranged from 9.53× 10^16, 1.44× 10^17, to 2.68×10^18 cm ^3. By combining the modified deal-grove model and Arrhenius equation, the linear and parabolic rate constants, and their corresponding activation energies were extracted. The results show that: higher temperature corresponded to thicker oxides; dry thermal oxidation rate in n-type 6H-SiC depended on the doping concentration; both linear-rate-constant and parabolic-rate-constant increased with the doping concentration; the parabolic activation energy increased from 0.082 to 0.104 e V, both linear and parabolic activation energies increasing with the doping concentration; and, the parabolic pre-exponential factor increased from 2.6 ×10^4 to 2.7 ×10^5nm^2/s, both linear and parabolic pre-exponential factor increasing with doping concentration. Moreover, the experiment also illustrated that it is unreasonable to use a variation of the Arrhenius activation energy to explain the doping dependence of thermal oxidation on SiC.展开更多
Ammonium perchlorate(AP)includes oxidizing and reducing elements on the same molecule.AP can act as an efficient oxidizer and mono-propellant as well.In this study,AP experienced crystallographic phase change from ort...Ammonium perchlorate(AP)includes oxidizing and reducing elements on the same molecule.AP can act as an efficient oxidizer and mono-propellant as well.In this study,AP experienced crystallographic phase change from orthorhombic centrosymmetric to non-centrosymmetric under controlled isothermal heat treatment.XRD diffractograms confirmed this crystallographic phase change.The thermal behaviour of activated AP had been investigated using DSC.Activated AP demonstrated high chemical stability with an increase in endothermic phase transition enthalpy by 170%.The enthalpy of the subsequent two main exothermic decomposition reactions was increased by 250%.Whereas AP demonstrated total decomposition enthalpy of 733 J/g,activated AP showed 2614 J/g.Activated AP can secure self-sustained response at a high rate.Propagation index(combustion enthalpy/ignition temperature)was employed to assess self-sustained reaction propagation.Activated AP demonstrated high propagation index of 8.7 compared with 2.5 for un-activated AP.Primary decomposition kinetic parameters had investigated using Kissinger and KAS methods.Activated AP showed an increase in activation energy by 89%using the Kissinger method;kinetic parameters using the KAS method were in good agreement with the Kissinger method.It can have concluded that AP with novel kinetic decomposition parameters for enhanced safety storage and high combustion characteristics has evolved.展开更多
文摘This paper presents the catalytic effects of Cu-Co~* catalyst on the decomposition of AN and AN/KDN based oxidizer and propellant samples. Ozawa-Flynn-Wall(OFW) iso-conversional method was used for the kinetic studies and to compute the activation energy(Ea) values for various decomposition steps of the prepared oxidizer and propellant samples in the temperature range of 50 e500C. TG-DTG experiments were carried out for both oxidizer and propellant samples at the heating rates of 3, 5, and 10C/min. AN/KDN based oxidizer samples were prepared by an evaporative co-crystallization method. Citric acid sol-gel method was used for the synthesis of Cu-Co~* catalyst. The propellant sample contains HTPB as the fuel binder along with other ingredients such as TDI, DOA, and Glycerol. The Cu-Co~* catalyst was used as 2% by weight to the total weight of catalyzed oxidizer and propellant samples. It was observed from the present study that, Cu-Co~* catalyst helps in reducing the Ea values for AN and AN based propellant samples. However, with the percentage increment of KDN in the AN crystals, Ea value increases.Further, it was observed that Cu-Co~* catalyst stabilizes the initial partial decomposition of KDN.
基金Project supported by the National Natural Science Foundation of China(No.F040405)
文摘The doping dependence of dry thermal oxidation rates in n-type 6H-SiC was studied. The oxidation temperature ranged from 1050 to 1150℃ and the nitrogen doping concentration ranged from 9.53× 10^16, 1.44× 10^17, to 2.68×10^18 cm ^3. By combining the modified deal-grove model and Arrhenius equation, the linear and parabolic rate constants, and their corresponding activation energies were extracted. The results show that: higher temperature corresponded to thicker oxides; dry thermal oxidation rate in n-type 6H-SiC depended on the doping concentration; both linear-rate-constant and parabolic-rate-constant increased with the doping concentration; the parabolic activation energy increased from 0.082 to 0.104 e V, both linear and parabolic activation energies increasing with the doping concentration; and, the parabolic pre-exponential factor increased from 2.6 ×10^4 to 2.7 ×10^5nm^2/s, both linear and parabolic pre-exponential factor increasing with doping concentration. Moreover, the experiment also illustrated that it is unreasonable to use a variation of the Arrhenius activation energy to explain the doping dependence of thermal oxidation on SiC.
文摘Ammonium perchlorate(AP)includes oxidizing and reducing elements on the same molecule.AP can act as an efficient oxidizer and mono-propellant as well.In this study,AP experienced crystallographic phase change from orthorhombic centrosymmetric to non-centrosymmetric under controlled isothermal heat treatment.XRD diffractograms confirmed this crystallographic phase change.The thermal behaviour of activated AP had been investigated using DSC.Activated AP demonstrated high chemical stability with an increase in endothermic phase transition enthalpy by 170%.The enthalpy of the subsequent two main exothermic decomposition reactions was increased by 250%.Whereas AP demonstrated total decomposition enthalpy of 733 J/g,activated AP showed 2614 J/g.Activated AP can secure self-sustained response at a high rate.Propagation index(combustion enthalpy/ignition temperature)was employed to assess self-sustained reaction propagation.Activated AP demonstrated high propagation index of 8.7 compared with 2.5 for un-activated AP.Primary decomposition kinetic parameters had investigated using Kissinger and KAS methods.Activated AP showed an increase in activation energy by 89%using the Kissinger method;kinetic parameters using the KAS method were in good agreement with the Kissinger method.It can have concluded that AP with novel kinetic decomposition parameters for enhanced safety storage and high combustion characteristics has evolved.