Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application ...Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.展开更多
In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt...In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt%) was obtained by magnetic separation under the optimum SMR conditions:siderite dosage 40wt%,roasting temperature 700℃,roasting time 10 min.According to the magnetic analysis,SMR achieved the conversion of weak magnetic minerals to strong magnetic minerals,thus enabling the recovery of iron via magnetic separation.Based on the phase transformation analysis,during the SMR process,limonite was first dehydrated and converted to hematite,and then siderite decomposed to generate magnetite and CO,where CO reduced the freshly formed hematite to magnetite.The microstructure evolution analysis indicated that the magnetite particles were loose and porous with a destroyed structure,making them easier to be ground.The non-isothermal kinetic results show that the main reaction between limonite and siderite conformed to the two-dimension diffusion mechanism,suggesting that the diffusion of CO controlled the reaction.These results encourage the application of siderite as a reductant in SMR.展开更多
The retrogression kinetics for grain boundary precipitate （GBP） of 7A55 aluminum alloy was investigated by transmission electron microscopy （TEM） observation. The results reveal that the coarsening behavior of GBP...The retrogression kinetics for grain boundary precipitate （GBP） of 7A55 aluminum alloy was investigated by transmission electron microscopy （TEM） observation. The results reveal that the coarsening behavior of GBP obeys “LSW” theory, namely, the cube of GBP average size has a linear dependence relation to retrogression time, and the coarsening rate accelerates at the elevated retrogression temperature. The GBP coarsening activation energy Qo of （115.2±1.3） kJ/mol is obtained subsequently. Taking the retrogression treatment schedule of 190℃, 45 min derived from AA7055 thin plate as reference, the non-isothermal retrogression model for GBP coarsening behavior is established based on “LSW”theory and “iso-kinetics” solution, which includes an Arrhenius form equation. After that, the average size of GBP r（t） is predicted successfully at any non-isothermal process T（t） when the initial size of GBP r0 is given. Finally, the universal characterization method for the microstructure homogeneity along the thickness direction of TA55 aluminum alloy thick plate is also set up.展开更多
The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was appli...The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was applied to analyzing the kinetics behavior of Mg-Ni hydride. The calculation results show that the theoretical value and the experimental data can reach a good agreement, especially in the case of non-isothermal dehydriding. The rate-controlling step is the diffusion of hydrogen atoms in the solid solution. The sample prepared under magnetic field of 6 T under the isothermal condition can reach the best performance. The similar tendency was observed under the non-isothermal condition and the reason was discussed.展开更多
The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characteri...The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.展开更多
Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cool...Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.展开更多
The fundamental research on thermo-mechanical conditions provides an experimental basis for high-performance Mg-Al-Ca-Mn alloys.However, there is a lack of systematical investigation for this series alloys on the hot-...The fundamental research on thermo-mechanical conditions provides an experimental basis for high-performance Mg-Al-Ca-Mn alloys.However, there is a lack of systematical investigation for this series alloys on the hot-deformation kinetics and extrusion parameter optimization. Here, the flow behavior, constitutive model, dynamic recrystallization(DRX) kinetic model and processing map of a dilute rare-earth free Mg-1.3Al-0.4Ca-0.4Mn(AXM100, wt.%) alloy were studied under different hot-compressive conditions. In addition, the extrusion parameter optimization of this alloy was performed based on the hot-processing map. The results showed that the conventional Arrhenius-type strain-related constitutive model only worked well for the flow curves at high temperatures and low strain rates. In comparison, using the machine learning assisted model(support vector regression, SVR) could effectively improve the accuracy between the predicted and experimental values. The DRX kinetic model was established, and a typical necklace-shaped structure preferentially occurred at the original grain boundaries and the second phases. The DRX nucleation weakened the texture intensity, and the further growth caused the more scattered basal texture. The hot-processing maps at different strains were also measured and the optimal hot-processing range could be confirmed at the deformation temperatures of 600~723 K and the strain rates of 0.018~0.563 s^(-1). Based on the optimum hot-processing range, a suitable extrusion parameter was considered as 603 K and 0.1 mm/s and the as-extruded alloy in this parameter exhibited a good strength-ductility synergy(yield strength of ~ 232.1 MPa, ultimate strength of ~ 278.2 MPa and elongation-to-failure of ~ 20.1%). Finally, the strengthening-plasticizing mechanisms and the relationships between the DRXed grain size, yield strength and extrusion parameters were analyzed.展开更多
Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH ...Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.展开更多
The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calori...The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calorimetry （DSC） at various heating rates. The results were compared with the corresponding results by using 1,3-dihydroxybenzene（DHB） as a model compound. The results show that HHPP can enhance the cure reaction of DGEBA, resulting in the decrease of the peak temperature of the curing curve as well as the decrease of the activation energy because of the flexible --P--O-- groups in the backbone of HHPP. However, both the activation energy of the cured polymer and the peak temperature of the curing curve are increased with DHB as a curing agent. The cure kinetics of the DGEBA/HHPP system was calculated by using the isoconversional method given by Malek. It was found that the two-parameter autocatalytic model（Sestak-Berggren equation） is the most adequate one to describe the cure kinetics of the studied System at various heating rates. The obtained non-isothermal DSC curves from the experimental data show the results being accordant with those theoretically calculated.展开更多
Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Red...Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.展开更多
The combustion characteristics of styrene-butadiene-styrene （SBS） asphalt are studied by thermogravimetric analysis （TG/DTG） at four different heating rates. According to the saturates/aromatics/resins/asphaltenes...The combustion characteristics of styrene-butadiene-styrene （SBS） asphalt are studied by thermogravimetric analysis （TG/DTG） at four different heating rates. According to the saturates/aromatics/resins/asphaltenes （SARA） fractionation method, the combustion process of SBS asphalt can be divided by Gaussian peak fitting into three main stages： oil content release, resin pyrolysis, and asphaltene and char combustion. When the heating rate increases, the mass losses of the oil content and resin pyrolysis increase, and less asphaltenes are formed at a higher temperature. The activation energy values are calculated by the Coats-Redfern method to be in the range 61.6 kJ/mol-142.9 kJ/mol. The Popescu method is used for the kinetic analysis, and the result shows that the three stages of asphalt combustion can be explained by the sphere phase boundary reaction model, the second order chemical reaction model, nucleation, and its subsequent growth model, respectively.展开更多
The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.T...The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.The results show that through the surface dissolution the adsorption rate constant for ilmenite increases from 5.272 to 8.441 mol/(g·min)while it decreases for Ol-Px,Tr-Cch and quartz from 6.332,7.309 and 7.774 mol/(g·min)to 5.034,6.223 and 7.371 mol/(g·min),respectively.Also,the flotation experiments on a binary mixture of minerals indicate that after surface dissolution the values of modified rate constant for ilmenite flotation from Ol-Px,Tr-Cch and quartz are enhanced from 36.15,36.52 and 47.86 min-1 to 41.72,45.78 and 56.24 min-1,respectively.This results in the improvement of kinetic selectivity index(SI)in the separation of treated ilmenite from gangue minerals.As evidenced by ICP-MS analysis,the decrease of kinetic parameters for gangue minerals can be due to the removal of Fe^2+,Ca^2+and Mg^2+ions from their surfaces,which results in the lack of enough active sites to interact with collector species.As confirmed by contact angle measurements,this prevents the formation of a stable hydrophobic layer on the minerals surfaces for creating stable attachments between minerals and bubbles.Generally,the improvement of ilmenite flotation kinetics has a negative correlation with the iron content in its accompanied gangue minerals.展开更多
The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic para...The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic parameters of the pyrolysis process were calculated using the method of Ozawa-Flynn-Wall and the mechanism of reactions were investi- gated using the method of Popescu. It was found that the values of activation energy varied in different temperature ranges. The pyrolysis processes are well described by the models of Zhuravlev (Zh) and valid for diffusion-controlled between 200 ℃ and 280 ℃, by Ginstling-Brounshtein (G-B), valid for diffusion-control between 280 ℃ and 310 ℃, for first-order chemical reaction between 310℃ and 350 ℃, by Zhuravlev (Zh) valid for diffusion-control between 350 ℃ and 430 ℃ and by the one-way transport model when temperatures are over 430 ℃.展开更多
Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning cal...Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.展开更多
The thermal decomposition of Tb_2(O-MBA)_6(PHEN)_2 (O-MBA: o-methylbenzoate;PHEN: 1,10-phenanthroline) and its kinetics were studied under the non-isothermal condition bythermogravimetry-derivative thermogravimetry (T...The thermal decomposition of Tb_2(O-MBA)_6(PHEN)_2 (O-MBA: o-methylbenzoate;PHEN: 1,10-phenanthroline) and its kinetics were studied under the non-isothermal condition bythermogravimetry-derivative thermogravimetry (TG-DTG) techniques. Kinetic parameters were obtainedfrom analysis of TG-DTG curves by the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method.The most probable mechanism function was suggested by comparing the kinetic parameters. The kineticequation for the first stage can be expressed as dα/dt = Aexp(-E/RT)·3(1 - α)^(2/3). Thelifetime equation at mass loss of 10% was deduced as lnτ= -28.7429 + 19797.795/T by isothermalthermogravimetric analysis.展开更多
The non-isothermal leaching kinetics of primary titanium-rich material by microwave heating was investigated,and the temperature-pressure curves of leaching system and microwave absorption characteristics of mixture s...The non-isothermal leaching kinetics of primary titanium-rich material by microwave heating was investigated,and the temperature-pressure curves of leaching system and microwave absorption characteristics of mixture solutions before and after leaching were measured.The research of non-isothermal kinetics was evaluated by the leaching rate of Fe and the total apparent velocity equation of the non-isothermal kinetics of leaching for primary titanium-rich material by microwave heating was obtained.It is shown from the temperature-pressure curves that the high temperature and high pressure of closed leaching system are favorable to the enhancement of the leaching rate of Fe.Microwave absorption characteristics of mixture solutions before and after leaching show that there are abrupt changes of microwave absorption characteristics for 15%HCl solution and the mixture solution after leaching by 20%HCl.展开更多
The non-isothermal decomposition kinetics of LiClO4 in flow N2 atmosphere was studied. TG-DTA curves show that the decomposition proceeded through two well-defined steps below 900℃, and the mass loss was in agreement...The non-isothermal decomposition kinetics of LiClO4 in flow N2 atmosphere was studied. TG-DTA curves show that the decomposition proceeded through two well-defined steps below 900℃, and the mass loss was in agreement with the theoretical value. XRD profile demonstrates that the product of the thermal decomposition at 500℃ is LiCI. For the decomposition kinetics study, the activation energies calculated with the Friedman method were considered as the initial values for non-linear regression and were used for verifying the correctness of the fired models. The decomposition process was fitted by a two-step consecutive reaction： extended Prout-Tompkins equation[Bna, f（α） is （1-α）^nα^α] followed by a lth order reaction（F1）. The activation energies were （215.6±0.2） and （251.6±3.6） kJ/mol, respectively. The exponentials n and a for Bna reaction were （0.25±0.05） and （0.795±0.005）, respectively. The reaction types and activation energies were in agreement with those obtained from the isothermal method, but the exponentials were optimized for better firing and prediction.展开更多
The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami ...The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.展开更多
The thermal decomposition reaction of Eu-2(p-MBA)(6)(PHEN)(2) (p-MBA=CH3C6H4COO, methylbenzoate; PHEN=C12H8N2, 1,10-phenanthroline) was studied in a static atmosphere using TG-DTG method. The thermal decomposition pro...The thermal decomposition reaction of Eu-2(p-MBA)(6)(PHEN)(2) (p-MBA=CH3C6H4COO, methylbenzoate; PHEN=C12H8N2, 1,10-phenanthroline) was studied in a static atmosphere using TG-DTG method. The thermal decomposition process of the complex was determined and its kinetics was investigated. Kinetic parameters were obtained from the analysis of TG-DTG curves by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: f(alpha) =(1-alpha)(2), g(alpha) = (1-alpha)(-1)-1. The activation energy for the first stage is 255.18 kJ/mol, the entropy of activation DeltaS is 227.32 J/mol and the Gibbs free energy of activation DeltaG is 128.04 W/mol.展开更多
Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, o...Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm^-1 by means of electro-ultrafiltration （EUF） and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield （yield of the NP treatment/yield of the NPK treatment）, relative dry matter yield （dry matter of the NP treatment/dry matter of the NPK treatment）, quantity of K uptake in the NP treatment （no K application）, soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax （the maximum desorbable quantity of K） in the second-order equation and the constant b in the first-order and Elovich equations to all five reference standards were highly significant （P ≤ 0.01）. The constant a in the power function equation was highly significant （P 〈 0.01） for four of the five reference standards with the fifth being significant （P ≤ 0.05）. The constant b in the parabolic equation was also significantly correlated （P ≤ 0.05） to the relative grain yield and soil HNO3-soluble K. These suggested that all of these parameters could be used to estimate the soil K supplying capacity and the crop response to K fertilizer.展开更多
基金supported by National Natural Science Foundation of China(51974166).
文摘Recently,azobenzene-4,4'-dicarboxylic acid(ADCA)has been produced gradually for use as an organic synthesis or pharmaceutical intermediate due to its eminent performance.With large quantities put into application in the future,the thermal stability of this substance during storage,transportation,and use will become quite important.Thus,in this work,the thermal decomposition behavior,thermal decomposition kinetics,and thermal hazard of ADCA were investigated.Experiments were conducted by using a SENSYS evo DSC device.A combination of differential iso-conversion method,compensation parameter method,and nonlinear fitting evaluation were also used to analyze thermal kinetics and mechanism of ADCA decomposition.The results show that when conversion rate α increases,the activation energies of ADCA's first and main decomposition peaks fall.The amount of heat released during decomposition varies between 182.46 and 231.16 J·g^(-1).The proposed kinetic equation is based on the Avrami-Erofeev model,which is consistent with the decomposition progress.Applying the Frank-Kamenetskii model,a calculated self-accelerating decomposition temperature of 287.0℃is obtained.
基金financially supported by the National Natural Science Foundation of China(Nos.51874071 and 52022019)。
文摘In order to develop limonite and decrease CO_(2) emissions,siderite is proposed as a clean reductant for suspension magnetization roasting(SMR) of limonite.An iron concentrate(iron grade:65.92wt%,iron recovery:98.54wt%) was obtained by magnetic separation under the optimum SMR conditions:siderite dosage 40wt%,roasting temperature 700℃,roasting time 10 min.According to the magnetic analysis,SMR achieved the conversion of weak magnetic minerals to strong magnetic minerals,thus enabling the recovery of iron via magnetic separation.Based on the phase transformation analysis,during the SMR process,limonite was first dehydrated and converted to hematite,and then siderite decomposed to generate magnetite and CO,where CO reduced the freshly formed hematite to magnetite.The microstructure evolution analysis indicated that the magnetite particles were loose and porous with a destroyed structure,making them easier to be ground.The non-isothermal kinetic results show that the main reaction between limonite and siderite conformed to the two-dimension diffusion mechanism,suggesting that the diffusion of CO controlled the reaction.These results encourage the application of siderite as a reductant in SMR.
基金Project(2012CB619505)supported by the National Basic Research Program of China
文摘The retrogression kinetics for grain boundary precipitate （GBP） of 7A55 aluminum alloy was investigated by transmission electron microscopy （TEM） observation. The results reveal that the coarsening behavior of GBP obeys “LSW” theory, namely, the cube of GBP average size has a linear dependence relation to retrogression time, and the coarsening rate accelerates at the elevated retrogression temperature. The GBP coarsening activation energy Qo of （115.2±1.3） kJ/mol is obtained subsequently. Taking the retrogression treatment schedule of 190℃, 45 min derived from AA7055 thin plate as reference, the non-isothermal retrogression model for GBP coarsening behavior is established based on “LSW”theory and “iso-kinetics” solution, which includes an Arrhenius form equation. After that, the average size of GBP r（t） is predicted successfully at any non-isothermal process T（t） when the initial size of GBP r0 is given. Finally, the universal characterization method for the microstructure homogeneity along the thickness direction of TA55 aluminum alloy thick plate is also set up.
基金Project(51464008) supported by the National Natural Science Foundation of ChinaProject(KY[2012]004) supported by the Key Laboratory Item of Education Office in Guizhou Province,China
文摘The Mg-Ni hydride was prepared by hydriding combustion synthesis under a high magnetic field. The dehydriding kinetics of the hydrides was measured under the isothermal and non-isothermal conditions. A model was applied to analyzing the kinetics behavior of Mg-Ni hydride. The calculation results show that the theoretical value and the experimental data can reach a good agreement, especially in the case of non-isothermal dehydriding. The rate-controlling step is the diffusion of hydrogen atoms in the solid solution. The sample prepared under magnetic field of 6 T under the isothermal condition can reach the best performance. The similar tendency was observed under the non-isothermal condition and the reason was discussed.
基金Project(201011005-5)supported by the National Land and Resources Public Welfare Scientific Research Project of ChinaProject(41030426)supported by the National Natural Science Foundation of China+1 种基金Project(20095122110015)supported by Specialized Research Fund for the Doctoral Program of Higher Education of ChinaProject(2010-32)supported by Scientific Research Foundation of the Education Ministry for Returned Chinese Scholars,China
文摘The single phase La2（CO3）3·3.4H2 O was synthesized by hydrothermal method. The thermal decomposition and intermediates and final solid products of La2（CO3）3·3.4H2O from 30 to 1000 °C were characterized by XRD, FTIR and DTA-TG. The kinetics of dehydration of La2（CO3）3·3.4H2O in the temperature range of 30-366 °C was investigated under non-isothermal conditions. Flynn-Wall-Ozawa and Friedman isoconversion methods were used to calculate the activation energy and analyze the reaction steps; multivariate non-linear regression program was applied to determine the most probable mechanism and the kinetic parameters. The results show that the thermal dehydration of La2（CO3）3·3.4H2O is a kind of three-step competitive reaction, and controlled by an n-order initial reaction followed by n-order competitive reaction（FnFnFn model）. The activation energy matching with the most probable model is close to value obtained by Friedman method. The fitting curves match the original TG-DTG curves very well.
基金financially supported by a grant provided by Mitsubishi Heavy Industries。
文摘Polypropylene is commonly used as a binder for ceramic injection molding,and rapid cooling is often encountered during processing.However,the crystallization behavior of polypropylene shows a strong dependence on cooling rate due to its semi-crystalline characteristics.Therefore,the influence of cooling rate on the quality of final product cannot be ignored.In this study,the fast differential scanning calorimetry(FSC)test was performed to study the influence of cooling rate on the non-isothermal crystallization behavior and non-isothermal crystallization kinetics of a copolymer polypropylene(PP BC03B).The results show that the crystallization temperatures and crystallinity decrease as the cooling rate increases.In addition,two exothermic peaks occur when cooling rate ranges from 30 to 300 K·s^(-1),indicating the formation of another crystal phase.Avrami,Ozawa and Mo equations were used to explore the non-isothermal crystallization kinetics,and it can be concluded that the Mo method is suitable for this study.
基金funded by the Postgraduate Research & Practice Innovation Program of Jiangsu Province (No.SJCX22_1720)the National Natural Science Foundation of China (No.51901204)+1 种基金the Chongqing Science and Technology Commission (Nos.cstc2020jcyj-msxmX0184 and cstc2019jscx-mbdxX0031)the University Innovation Research Group of Chongqing (No.CXQT20023)。
文摘The fundamental research on thermo-mechanical conditions provides an experimental basis for high-performance Mg-Al-Ca-Mn alloys.However, there is a lack of systematical investigation for this series alloys on the hot-deformation kinetics and extrusion parameter optimization. Here, the flow behavior, constitutive model, dynamic recrystallization(DRX) kinetic model and processing map of a dilute rare-earth free Mg-1.3Al-0.4Ca-0.4Mn(AXM100, wt.%) alloy were studied under different hot-compressive conditions. In addition, the extrusion parameter optimization of this alloy was performed based on the hot-processing map. The results showed that the conventional Arrhenius-type strain-related constitutive model only worked well for the flow curves at high temperatures and low strain rates. In comparison, using the machine learning assisted model(support vector regression, SVR) could effectively improve the accuracy between the predicted and experimental values. The DRX kinetic model was established, and a typical necklace-shaped structure preferentially occurred at the original grain boundaries and the second phases. The DRX nucleation weakened the texture intensity, and the further growth caused the more scattered basal texture. The hot-processing maps at different strains were also measured and the optimal hot-processing range could be confirmed at the deformation temperatures of 600~723 K and the strain rates of 0.018~0.563 s^(-1). Based on the optimum hot-processing range, a suitable extrusion parameter was considered as 603 K and 0.1 mm/s and the as-extruded alloy in this parameter exhibited a good strength-ductility synergy(yield strength of ~ 232.1 MPa, ultimate strength of ~ 278.2 MPa and elongation-to-failure of ~ 20.1%). Finally, the strengthening-plasticizing mechanisms and the relationships between the DRXed grain size, yield strength and extrusion parameters were analyzed.
基金Supported by the Research Fund for the Doctoral Program of Higher Education(20050145029)the Science and Technology Talents Fund for Excellent Youth of Liaoning Province(2005221012)
文摘Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.
文摘The cure kinetics of diglycidyl ether of bisphenol A （DGEBA） with hyperbranched poly （3-hydroxyphenyl） phosphate（HHPP） as the curing agent was investigated by means of non-isothermal differential scanning calorimetry （DSC） at various heating rates. The results were compared with the corresponding results by using 1,3-dihydroxybenzene（DHB） as a model compound. The results show that HHPP can enhance the cure reaction of DGEBA, resulting in the decrease of the peak temperature of the curing curve as well as the decrease of the activation energy because of the flexible --P--O-- groups in the backbone of HHPP. However, both the activation energy of the cured polymer and the peak temperature of the curing curve are increased with DHB as a curing agent. The cure kinetics of the DGEBA/HHPP system was calculated by using the isoconversional method given by Malek. It was found that the two-parameter autocatalytic model（Sestak-Berggren equation） is the most adequate one to describe the cure kinetics of the studied System at various heating rates. The obtained non-isothermal DSC curves from the experimental data show the results being accordant with those theoretically calculated.
基金Supported by the Key Research of Science & Technology of Education(No.0202)and the Fundamental Research Plan of HuoYingdong(No.81063).
文摘Experiments on thermal decomposition of nano-sized calcium carbonate were carried out in a thermo-gravimetric analyzer under non-isothermal condition of different heating rates (5 to 20K·min-1). The Coats and Redfern's equation was used to determine the apparent activation energy and the pre-exponential factors. The mechanism of thermal decomposition was evaluated using the master plots, Coats and Redfern's equation and the kinetic compensation law. It was found that the thermal decomposition property of nano-sized calcium carbonate was different from that of bulk calcite. Nano-sized calcium carbonate began to decompose at 640℃, which was 180℃lower than the reported value for calcite. The experimental results of kinetics were compatible with the mechanism of one-dimensional phase boundary movement. The apparent activation energy of nano-sized calcium carbonate was estimated to be 151kJ·mol-1 while the literature value for normal calcite was approximately 200kJ·mol-1. The order of magnitude of pre-exponential factors was estimated to be 10~9 s-1.
基金supported by the National Natural Science Foundation of China (Grant Nos. 61154002 and 51078331)the China Postdoctoral Science Foundation(Grant No. 20090451471)the Natural Science Foundation of Zhejiang Province,China (Grant No. Z1110222)
文摘The combustion characteristics of styrene-butadiene-styrene （SBS） asphalt are studied by thermogravimetric analysis （TG/DTG） at four different heating rates. According to the saturates/aromatics/resins/asphaltenes （SARA） fractionation method, the combustion process of SBS asphalt can be divided by Gaussian peak fitting into three main stages： oil content release, resin pyrolysis, and asphaltene and char combustion. When the heating rate increases, the mass losses of the oil content and resin pyrolysis increase, and less asphaltenes are formed at a higher temperature. The activation energy values are calculated by the Coats-Redfern method to be in the range 61.6 kJ/mol-142.9 kJ/mol. The Popescu method is used for the kinetic analysis, and the result shows that the three stages of asphalt combustion can be explained by the sphere phase boundary reaction model, the second order chemical reaction model, nucleation, and its subsequent growth model, respectively.
文摘The effects of acid surface dissolution on the flotation kinetics of ilmenite(IL)and its common accompanied gangue minerals including olivine-pyroxene(Ol-Px),tremolite-clinochlore(Tr-Cch)and quartz were investigated.The results show that through the surface dissolution the adsorption rate constant for ilmenite increases from 5.272 to 8.441 mol/(g·min)while it decreases for Ol-Px,Tr-Cch and quartz from 6.332,7.309 and 7.774 mol/(g·min)to 5.034,6.223 and 7.371 mol/(g·min),respectively.Also,the flotation experiments on a binary mixture of minerals indicate that after surface dissolution the values of modified rate constant for ilmenite flotation from Ol-Px,Tr-Cch and quartz are enhanced from 36.15,36.52 and 47.86 min-1 to 41.72,45.78 and 56.24 min-1,respectively.This results in the improvement of kinetic selectivity index(SI)in the separation of treated ilmenite from gangue minerals.As evidenced by ICP-MS analysis,the decrease of kinetic parameters for gangue minerals can be due to the removal of Fe^2+,Ca^2+and Mg^2+ions from their surfaces,which results in the lack of enough active sites to interact with collector species.As confirmed by contact angle measurements,this prevents the formation of a stable hydrophobic layer on the minerals surfaces for creating stable attachments between minerals and bubbles.Generally,the improvement of ilmenite flotation kinetics has a negative correlation with the iron content in its accompanied gangue minerals.
基金Project 50474056 supported by the National Natural Science Foundation of China
文摘The pyrolysis kinetics of three different kinds of fresh biomass (grass: triple A, wheat straw, corn straw) in nitrogen flow were studied by thermogravimetric analysis at five different heating rates. The kinetic parameters of the pyrolysis process were calculated using the method of Ozawa-Flynn-Wall and the mechanism of reactions were investi- gated using the method of Popescu. It was found that the values of activation energy varied in different temperature ranges. The pyrolysis processes are well described by the models of Zhuravlev (Zh) and valid for diffusion-controlled between 200 ℃ and 280 ℃, by Ginstling-Brounshtein (G-B), valid for diffusion-control between 280 ℃ and 310 ℃, for first-order chemical reaction between 310℃ and 350 ℃, by Zhuravlev (Zh) valid for diffusion-control between 350 ℃ and 430 ℃ and by the one-way transport model when temperatures are over 430 ℃.
基金Supported by the National Science and Technology Support Program of China(No.2013BAE02B01)the Special Project on the Integration of Industry,Education and Research of Guangdong Province(No.2013B090500003)the Commissioner Workstation Project of Guangdong Province(No.2014A090906002)
文摘Nylon 10 T and Nylon 10T/1010 samples were synthesized by direct melt polymerization. The non-isothermal crystallization kinetics of Nylon 10 T and Nylon 10T/1010 was investigated by means of differential scanning calorimetry(DSC). Jeziorny equation and Mo equation were applied to describe the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. The activation energies for non-isothermal crystallization were obtained by Vyazovkin's method and Friedman's method, respectively. These results showed that Jeziorny equation and Mo equation well described the non-isothermal crystallization kinetics of the Nylon 10 T and the Nylon 10T/1010. It was found that the values of the activation energy for non-isothermal crystallization of the Nylon 10T/1010 were lower than those of the Nylon 10 T at a given temperature or relative crystallinity degree,which revealed that crystallization ability of the Nylon 10T/1010 was higher. The crystal morphology was observed by means of a polarized optical microscope(POM) and X-ray diffraction(XRD). It was found that the addition of sebacic acid comonomer not only did not change the crystal form of the Nylon 10 T, but also significantly increased the number and decreased the size of spherulites. Comparing with the Nylon 10 T, the crystallization rate was increased with the addition of the sebacic acid comonomer.
基金This project was financially supported by the Natural Science Foundation of Hebei Province (Nos. 202140 and 203148) Hebei Education Department (No. 2001121)
文摘The thermal decomposition of Tb_2(O-MBA)_6(PHEN)_2 (O-MBA: o-methylbenzoate;PHEN: 1,10-phenanthroline) and its kinetics were studied under the non-isothermal condition bythermogravimetry-derivative thermogravimetry (TG-DTG) techniques. Kinetic parameters were obtainedfrom analysis of TG-DTG curves by the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method.The most probable mechanism function was suggested by comparing the kinetic parameters. The kineticequation for the first stage can be expressed as dα/dt = Aexp(-E/RT)·3(1 - α)^(2/3). Thelifetime equation at mass loss of 10% was deduced as lnτ= -28.7429 + 19797.795/T by isothermalthermogravimetric analysis.
基金Project(2007CB613606)supported by the National Basic Research Program of China
文摘The non-isothermal leaching kinetics of primary titanium-rich material by microwave heating was investigated,and the temperature-pressure curves of leaching system and microwave absorption characteristics of mixture solutions before and after leaching were measured.The research of non-isothermal kinetics was evaluated by the leaching rate of Fe and the total apparent velocity equation of the non-isothermal kinetics of leaching for primary titanium-rich material by microwave heating was obtained.It is shown from the temperature-pressure curves that the high temperature and high pressure of closed leaching system are favorable to the enhancement of the leaching rate of Fe.Microwave absorption characteristics of mixture solutions before and after leaching show that there are abrupt changes of microwave absorption characteristics for 15%HCl solution and the mixture solution after leaching by 20%HCl.
基金Supported by the National Natural Science Foundation of China(No.20071026)
文摘The non-isothermal decomposition kinetics of LiClO4 in flow N2 atmosphere was studied. TG-DTA curves show that the decomposition proceeded through two well-defined steps below 900℃, and the mass loss was in agreement with the theoretical value. XRD profile demonstrates that the product of the thermal decomposition at 500℃ is LiCI. For the decomposition kinetics study, the activation energies calculated with the Friedman method were considered as the initial values for non-linear regression and were used for verifying the correctness of the fired models. The decomposition process was fitted by a two-step consecutive reaction： extended Prout-Tompkins equation[Bna, f（α） is （1-α）^nα^α] followed by a lth order reaction（F1）. The activation energies were （215.6±0.2） and （251.6±3.6） kJ/mol, respectively. The exponentials n and a for Bna reaction were （0.25±0.05） and （0.795±0.005）, respectively. The reaction types and activation energies were in agreement with those obtained from the isothermal method, but the exponentials were optimized for better firing and prediction.
基金Guoxin Sui would like to acknowledge the financial supports of the Hundreds’ Talents Program of Chinese Academy of Sciences.
文摘The non-isothermal crystallization kinetics of polyamide 6/diamine-modified multi-walled carbon nanotube （PA6/D-MWNT） nanocomposite was investigated by differential scanning calorimetry （DSC）. The modified Avrami equation, the Ozawa equation and the combined Avrami/Ozawa equation were employed to analyze the non-isothermal crystallization data. The crystallization activation energies were also evaluated by the Kissinger method. It was found that the combined Avrami/Ozawa equation could successfully describe the non-isothermal crystallization process. The results showed that D-MWNTs not only acted as effective heterogeneous nucleating agents for PA6 and noticeably increased the crystallization temperature of PA6, but also influenced the mechanism of nucleation and crystal growth of PA6 and then reduced the overall crystallization rate of the neat PA6 matrix. The crystallization activation energy for the nanocomposite sample was greater than that of the neat PA6, which indicated that the addition of D-MWNTs hindered the mobility of PA6 chain segments.
基金This project was financially supported by the Education Department of Hebei Province.]
文摘The thermal decomposition reaction of Eu-2(p-MBA)(6)(PHEN)(2) (p-MBA=CH3C6H4COO, methylbenzoate; PHEN=C12H8N2, 1,10-phenanthroline) was studied in a static atmosphere using TG-DTG method. The thermal decomposition process of the complex was determined and its kinetics was investigated. Kinetic parameters were obtained from the analysis of TG-DTG curves by means of the Achar method and the Madhusudanan-Krishnan-Ninan (MKN) method. The most probable mechanism functions of the thermal decomposition reaction for the first stage are: f(alpha) =(1-alpha)(2), g(alpha) = (1-alpha)(-1)-1. The activation energy for the first stage is 255.18 kJ/mol, the entropy of activation DeltaS is 227.32 J/mol and the Gibbs free energy of activation DeltaG is 128.04 W/mol.
基金Project supported by the National Key Basic Research Support Foundation of China (No. G1999011809) the Natural Science Foundation of Zhejiang Province, China (No. RC99035).
文摘Corn field experiments with two treatments, NP and NPK, where N in the form of urea, P in the form of calcium phosphate, and K in the form of KCl were applied at rates of 187.5, 33.3, and 125 kg ha^-1, respectively, on soils derived from Quaternary red clay were conducted in the hilly red soil region of Zhejiang Province, China. Plant grains and stalks were collected for determination of K content. Seven equations were used to describe the kinetics of K release from surface soil samples taken before the corn experiments under electric field strengths of 44.4 and 88.8 V cm^-1 by means of electro-ultrafiltration （EUF） and to determine if their parameters had a practical application. The second-order and Elovich equations excellently described K release; the first-order, power function, and parabolic diffusion equations also described K release well; but the zero-order and exponential equations were not so good at reflecting K release. Five reference standards from the field experiments, including relative grain yield （yield of the NP treatment/yield of the NPK treatment）, relative dry matter yield （dry matter of the NP treatment/dry matter of the NPK treatment）, quantity of K uptake in the NP treatment （no K application）, soil exchangeable K, and soil HNO3-soluble K, were used to test the effectiveness of equation parameters obtained from the slope or intercept of these equations. Correlations of the ymax （the maximum desorbable quantity of K） in the second-order equation and the constant b in the first-order and Elovich equations to all five reference standards were highly significant （P ≤ 0.01）. The constant a in the power function equation was highly significant （P 〈 0.01） for four of the five reference standards with the fifth being significant （P ≤ 0.05）. The constant b in the parabolic equation was also significantly correlated （P ≤ 0.05） to the relative grain yield and soil HNO3-soluble K. These suggested that all of these parameters could be used to estimate the soil K supplying capacity and the crop response to K fertilizer.
