A critical examination was made on the reliability of kinetic parameters of nonisothermal thermoanalytical rate measurement by the widely applied Coats-Redfern(CR)equation.For this purpose,simulated TGA curves were ma...A critical examination was made on the reliability of kinetic parameters of nonisothermal thermoanalytical rate measurement by the widely applied Coats-Redfern(CR)equation.For this purpose,simulated TGA curves were made for reactions with different kinetic models,including chemical,diffusion(Janders)and mixed mechanism at different heating rates.The results show that,for reactions controlled kinetically by one mechanism,all solid state reaction models show linear trends by use of CR method and this method can not distinct the correct reaction model.For reactions with mixed mechanism,the CR method shows nonlinear trends and the reaction models and kinetic parameters can not be extracted from CR curves.The overall conclusion from this comparative appraisal of the characteristics of the CR approach to kinetic analysis of TGA data is that the CR approach is generally unsuitable for determination of kinetic parameters.展开更多
The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo...The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.展开更多
The pyrolysis and oxy-fuel combustion characteristics of Polish bituminous coal were studied using non-isothermal thermogravimetric analysis. Pyrolysis tests showed that the mass loss profiles were almost similar up t...The pyrolysis and oxy-fuel combustion characteristics of Polish bituminous coal were studied using non-isothermal thermogravimetric analysis. Pyrolysis tests showed that the mass loss profiles were almost similar up to 870℃ in both N_2 and CO_2 atmospheres, while further mass loss occurred in CO_2 atmosphere at higher temperatures due to char-CO_2 gasification. Replacement of N_2 in the combustion environment by CO_2 delayed the combustion of bituminous coal. At elevated oxygen levels, TG/DTG profiles shifted through lower temperature zone, ignition and burnout temperatures decreased and mass loss rate significantly increased and complete combustion was achieved at lower temperatures and shorter times. Kinetic analysis for the tested coal was performed using Kissinger-Akahira-Sunose(KAS) method. The activation energies of bituminous coal combustion at the similar oxygen content in oxy-fuel with that of air were higher than that in air atmosphere. The results indicated that, with O_2 concentration increasing, the activation energies decreased.展开更多
The thermal decomposition of dicumyl peroxide under the flow nitrogen atmosphere was studied by DSC-TG technique.The non-isothermal kinetics parameters were analyzed by means of the Kissinger and Flynn-Wall-Ozawa meth...The thermal decomposition of dicumyl peroxide under the flow nitrogen atmosphere was studied by DSC-TG technique.The non-isothermal kinetics parameters were analyzed by means of the Kissinger and Flynn-Wall-Ozawa methods,and the thermal decomposition mechanism of dicumyl peroxide was also studied with the Satava-Sestak method.The results showed that there was little difference between kinetic parameters calculated by DSC plot and DTG plot,the apparent activation energy and pre-exponential factor were 120.83 kJ·mol-1 and 9.12×1011s-1,respectively.The thermal decomposition mechanism of dicumyl peroxide in nitrogen was controlled by interface reaction R3.展开更多
通过对南方7种典型乔木叶片在空气气氛条件下,升温速度为10℃·min^(-1)的热重分析,研究了其热解特性和热解动力学特征,并基于热解参数对其燃烧性进行了四维评价。结果表明:(1)综纤维素开始分解的温度为140.54~158.67℃,结束温度为3...通过对南方7种典型乔木叶片在空气气氛条件下,升温速度为10℃·min^(-1)的热重分析,研究了其热解特性和热解动力学特征,并基于热解参数对其燃烧性进行了四维评价。结果表明:(1)综纤维素开始分解的温度为140.54~158.67℃,结束温度为372.01~389.91℃。木素开始分解温度为372.01~389.91℃,结束温度为538.63~581.32℃。(2)综纤维素热解的活化能为34.059~48.531 k J·mol^(-1),指前因子为72.012~1 966.463 min^(-1)。木素热解的活化能为31.264~54.091 k J·mol^(-1),指前因子为31.755~1 909.015 min^(-1)。除麻栗和毛竹外,木素热解的活化能和指前因子都高于综纤维素的活化能和指前因子。(3)7种可燃物的四维燃烧性不完全一致。华山松四维燃烧性都高,麻栗都差。其他5个树种的四维燃烧性不一致。展开更多
文摘A critical examination was made on the reliability of kinetic parameters of nonisothermal thermoanalytical rate measurement by the widely applied Coats-Redfern(CR)equation.For this purpose,simulated TGA curves were made for reactions with different kinetic models,including chemical,diffusion(Janders)and mixed mechanism at different heating rates.The results show that,for reactions controlled kinetically by one mechanism,all solid state reaction models show linear trends by use of CR method and this method can not distinct the correct reaction model.For reactions with mixed mechanism,the CR method shows nonlinear trends and the reaction models and kinetic parameters can not be extracted from CR curves.The overall conclusion from this comparative appraisal of the characteristics of the CR approach to kinetic analysis of TGA data is that the CR approach is generally unsuitable for determination of kinetic parameters.
文摘The degradation of the epoxy system was studied for the prepared six blend samples with the incorporation of 0 wt% - 25 wt% carboxyl terminated butadiene acrylonitrile (CTBN) copolymer, on a dynamic basis using Thermo gravimetric analysis (TGA) technique under a nitrogen atmosphere. The blends were prepared by physical mixing and were cured with diamine. The degradation of each sample followed second-order degradation kinetics, which was calculated by Coats-Redfern equation using best-fit analysis. This was further confirmed by linear regression analysis. The validity of data was checked by t-test statistical analysis. From this value of reaction order, activation energy (E), and pre-exponential factor (Z) were calculated. It was found that the activation energy increased with the addition of liquid elastomer.
基金financially supported by the National Science Centre(Poland)under grant No.N N512 457940the Ministry of Science and Higher Education(Poland)under the statutory funds(BS-1-103-3020/2016)
文摘The pyrolysis and oxy-fuel combustion characteristics of Polish bituminous coal were studied using non-isothermal thermogravimetric analysis. Pyrolysis tests showed that the mass loss profiles were almost similar up to 870℃ in both N_2 and CO_2 atmospheres, while further mass loss occurred in CO_2 atmosphere at higher temperatures due to char-CO_2 gasification. Replacement of N_2 in the combustion environment by CO_2 delayed the combustion of bituminous coal. At elevated oxygen levels, TG/DTG profiles shifted through lower temperature zone, ignition and burnout temperatures decreased and mass loss rate significantly increased and complete combustion was achieved at lower temperatures and shorter times. Kinetic analysis for the tested coal was performed using Kissinger-Akahira-Sunose(KAS) method. The activation energies of bituminous coal combustion at the similar oxygen content in oxy-fuel with that of air were higher than that in air atmosphere. The results indicated that, with O_2 concentration increasing, the activation energies decreased.
文摘The thermal decomposition of dicumyl peroxide under the flow nitrogen atmosphere was studied by DSC-TG technique.The non-isothermal kinetics parameters were analyzed by means of the Kissinger and Flynn-Wall-Ozawa methods,and the thermal decomposition mechanism of dicumyl peroxide was also studied with the Satava-Sestak method.The results showed that there was little difference between kinetic parameters calculated by DSC plot and DTG plot,the apparent activation energy and pre-exponential factor were 120.83 kJ·mol-1 and 9.12×1011s-1,respectively.The thermal decomposition mechanism of dicumyl peroxide in nitrogen was controlled by interface reaction R3.
文摘通过对南方7种典型乔木叶片在空气气氛条件下,升温速度为10℃·min^(-1)的热重分析,研究了其热解特性和热解动力学特征,并基于热解参数对其燃烧性进行了四维评价。结果表明:(1)综纤维素开始分解的温度为140.54~158.67℃,结束温度为372.01~389.91℃。木素开始分解温度为372.01~389.91℃,结束温度为538.63~581.32℃。(2)综纤维素热解的活化能为34.059~48.531 k J·mol^(-1),指前因子为72.012~1 966.463 min^(-1)。木素热解的活化能为31.264~54.091 k J·mol^(-1),指前因子为31.755~1 909.015 min^(-1)。除麻栗和毛竹外,木素热解的活化能和指前因子都高于综纤维素的活化能和指前因子。(3)7种可燃物的四维燃烧性不完全一致。华山松四维燃烧性都高,麻栗都差。其他5个树种的四维燃烧性不一致。
