The pyrolysis behavior of polycarbosilane （PCS） and chemical reaction mechanism during the pyrolysis process were studied by thermogravimetric-mass spectrometry （TG-MS） combined with X-ray diffraction and infrared...The pyrolysis behavior of polycarbosilane （PCS） and chemical reaction mechanism during the pyrolysis process were studied by thermogravimetric-mass spectrometry （TG-MS） combined with X-ray diffraction and infrared spectroscopic analysis methods. The experimental results indicate that the main gas phase products generated during pyrolysis of PCS in nitrogen atmosphere include H2, -CH3 and CH4. The heating rate has a large effect on the pyrolysis process of PCS, the lower heating rate releases more small molecule gases and gets bigger rate of pyrolysis mass loss, demonstrating that the lower heating rate is beneficial to fully pyrolysis of PCS and obtain ceramics products with better microstructure.展开更多
A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energ...A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.展开更多
The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aro...The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aromatic-rich oils.Molecular dynamics simulation was used to investigate the variations in pyrolysis behavior between PAH and NC-PAH based on the composition analysis.Through adjusting the content of NC-PAH,the influence of NC-PAH on the thermal stability of slurry oils(SOs)was evaluated by thermogravimetry,viscosity,coke value,and quinoline insoluble(QI).The morphology and structure of mesocarbon microbeads(MCMBs)prepared with SOs were measured by a polarized-light microscope,SEM,XRD,and Raman.Simulation results indicate that NC-PAH possesses much higher reactivity and tends to produce highly condensed solid and coke products.It corresponds to the QI and high viscosity in thermal stability experiments.Therefore,high concentrations of NC-PAH result in nonuniform morphology and disordered structures.In a system with low viscosity and few QIs,SO,which has a low nitrogen content(475 ppm),reacts gently to produce MCMBs with a uniform particle size(10-40μm)and an excellent spherical shape.As NC-PAH content decreases,the crystalline size of graphitization elevates,as evidenced by parallel layers(10.472-11.764)and stack height(3.269-3.701 nm).The graphitization degree becomes worse and nonuniform with the increase of the content of NC-PAH,and the best is 20.58%evaluated by Raman spectra area ratio(AG/Aall).Overall,this work suggests a nitrogen content reference and a controlling technology of nitrogen for the preparation of superior MCMB.展开更多
基金Funded by the Natural Science Foundation of Hubei Province(No.2013CFB340)
文摘The pyrolysis behavior of polycarbosilane （PCS） and chemical reaction mechanism during the pyrolysis process were studied by thermogravimetric-mass spectrometry （TG-MS） combined with X-ray diffraction and infrared spectroscopic analysis methods. The experimental results indicate that the main gas phase products generated during pyrolysis of PCS in nitrogen atmosphere include H2, -CH3 and CH4. The heating rate has a large effect on the pyrolysis process of PCS, the lower heating rate releases more small molecule gases and gets bigger rate of pyrolysis mass loss, demonstrating that the lower heating rate is beneficial to fully pyrolysis of PCS and obtain ceramics products with better microstructure.
基金supported by the National Natural Science Foundation of China,China(Grant Nos.U20B2018,U21B2086,11972087)。
文摘A novel design of micro-aluminum(μAl)powder coated with bi-/tri-component alloy layer,such as:Ni-P and Ni-P-Cu(namely,Al@Ni-P,Al@Ni-P-Cu,respectively),as combustion catalysts,were introduced to release its huge energy inside Al-core and promote rapid pyrolysis of ammonium perchlorate(AP)at a lower temperature in aluminized propellants.The microstructure of Al@Ni-P-Cu demonstrates that a three-layer Ni-P-Cu shell,with the thickness of~100 nm,is uniformly supported byμAl carrier(fuel unit),which has an amorphous surface with a thickness of~2.3 nm(catalytic unit).The peak temperature of AP with the addition of Al@Ni-P-Cu(3.5%)could significantly drop to 316.2℃ at high-temperature thermal decomposition,reduced by 124.3℃,in comparison to that of pure AP with 440.5℃.It illustrated that the introduction of Al@Ni-P-Cu could weaken or even eliminate the obstacle of AP pyrolysis due to its reduction of activation energy with 118.28 kJ/mol.The laser ignition results showed that the ignition delay time of Al@Ni-P-Cu/AP mixture with 78 ms in air is shorter than that of Al@Ni-P/AP(118 ms),decreased by 33.90%.Those astonishing breakthroughs were attributed to the synergistic effects of adequate active sites on amorphous surface and oxidation exothermic reactions(7597.7 J/g)of Al@Ni-P-Cu,resulting in accelerated mass and/or heat transfer rate to catalyze AP pyrolysis and combustion.Moreover,it is believed to provide an alternative Al-based combustion catalyst for propellant designer,to promote the development the propellants toward a higher energy.
基金support of National Natural Science Foundation of P.R.China(22308104).
文摘The influence of nitrogen-containing polycyclic aromatic hydrocarbons(NC-PAH)on the formation of carbonaceous mesophase remains enigmatic,despite extensive research on the production of carbonaceous materials from aromatic-rich oils.Molecular dynamics simulation was used to investigate the variations in pyrolysis behavior between PAH and NC-PAH based on the composition analysis.Through adjusting the content of NC-PAH,the influence of NC-PAH on the thermal stability of slurry oils(SOs)was evaluated by thermogravimetry,viscosity,coke value,and quinoline insoluble(QI).The morphology and structure of mesocarbon microbeads(MCMBs)prepared with SOs were measured by a polarized-light microscope,SEM,XRD,and Raman.Simulation results indicate that NC-PAH possesses much higher reactivity and tends to produce highly condensed solid and coke products.It corresponds to the QI and high viscosity in thermal stability experiments.Therefore,high concentrations of NC-PAH result in nonuniform morphology and disordered structures.In a system with low viscosity and few QIs,SO,which has a low nitrogen content(475 ppm),reacts gently to produce MCMBs with a uniform particle size(10-40μm)and an excellent spherical shape.As NC-PAH content decreases,the crystalline size of graphitization elevates,as evidenced by parallel layers(10.472-11.764)and stack height(3.269-3.701 nm).The graphitization degree becomes worse and nonuniform with the increase of the content of NC-PAH,and the best is 20.58%evaluated by Raman spectra area ratio(AG/Aall).Overall,this work suggests a nitrogen content reference and a controlling technology of nitrogen for the preparation of superior MCMB.
