The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this wo...The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.展开更多
The commercial ZK 60 magnesium alloy with extruded state experienced aging heat treatment(T 6)was dynamically loaded at strain rate of 3000 s−1 by means of the split Hopkinson pressure bar(SHPB)in this paper.Transmiss...The commercial ZK 60 magnesium alloy with extruded state experienced aging heat treatment(T 6)was dynamically loaded at strain rate of 3000 s−1 by means of the split Hopkinson pressure bar(SHPB)in this paper.Transmission electron microscopy(TEM)observations showed that the precipitatedβ′_(1) phases partially dissolved(spheroidized)with blurred interfaces within 160μs at 3000 s^(−1).The average length and diameter of the rod-shapedβ′_(1) phase particles were 48.5 and 9.8 nm after the T 6 heat treatment;while the average diameter of the sphericalβ′_(1) phases changed to 8.8 nm after loading.The deformedβ′_(1) phase generated larger lattice distortion energy than Mg matrix under high strain rate loading.Therefore,the difference of free energy(the driving force of dissolution)between theβ′_(1) phase and the matrix increased,making the instantaneous dissolution of theβ′_(1) phase thermodynamically feasible.The dissolution(spheroidization)of theβ′_(1) phase particles was kinetically promoted because the diffusion rate of the solute Zn atoms was accelerated by combined actions of adiabatic temperature rise,high density of dislocations(vacancies)and high deviatoric stresses during high strain rate loading.The increase in hardness of ZK 60-T 6 alloy could be attributed to solid solution strengthening,dislocation strengthening and second phase particle strengthening.展开更多
In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the re...In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the relationship between the experimental and simulation results were explored.Our computational findings on the secondary structure of SEB showed that at room temperature,the CD spectroscopic results were highly consistent with the MD results.Moreover,under heating conditions,the changing trends of helix,sheet and random coil obtained by CD spectral fitting were highly consistent with those obtained by MD.In order to gain a deeper understanding of the thermal stability mechanism of SEB,the MD trajectories were analyzed in terms of root mean square deviation(RMSD),secondary structure assignment(SSA),radius of gyration(R_(g)),free energy surfaces(FES),solvent-accessible surface area(SASA),hydrogen bonds and salt bridges.The results showed that at low heating temperature,domain Ⅰ without loops(omitting the mobile loop region)mainly relied on hydrophobic interaction to maintain its thermal stability,whereas the thermal stability of domain Ⅱ was mainly controlled by salt bridges and hydrogen bonds.Under high heating temperature conditions,the hydrophobic interactions in domain Ⅰ without loops were destroyed and the secondary structure was almost completely lost,while domain Ⅱ could still rely on salt bridges as molecular staples to barely maintain the stability of the secondary structure.These results help us to understand the thermodynamic and kinetic mechanisms that maintain the thermal stability of SEB at the molecular level,and provide a direction for establishing safer and more effective food sterilization processes.展开更多
The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly effi...The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.展开更多
Three-dimensional ordered macro/mesoporous carbon(3DOM/m-C)with high specific surface area was synthesized by colloid crystal template method with chemical activation by KOH and used as the adsorbent for removing mala...Three-dimensional ordered macro/mesoporous carbon(3DOM/m-C)with high specific surface area was synthesized by colloid crystal template method with chemical activation by KOH and used as the adsorbent for removing malachite green(MG)in aqueous solution.The microstructures of the adsorbents were characterized by FESEM,TEM and BET,and the effects of initial dye concentration,contact time,solution pH,and temperature on adsorption performance were investigated.The results show that the 3DOM/m-C exhibits extremely high adsorption capacity of 3541.1 mg/g within 2 h,which could be attributed to the novel ordered hierarchical structure with mesopores on three-dimensional ordered macroporous carbon walls.And the adsorption behavior conforms to the pseudo-second-order kinetic and Langmuir adsorption isotherm.3DOM/m-C can be recycled after being desorbed by absolute ethanol,and still maintains a high capacity of 2762.06 mg/g after 5 cycles.展开更多
Wollastonite glass ceramics were prepared using the reactive crystallization sintering method by mixing waste glass powders with gehlenite.The crystallization property,thermodynamics,and kinetics of the prepared wolla...Wollastonite glass ceramics were prepared using the reactive crystallization sintering method by mixing waste glass powders with gehlenite.The crystallization property,thermodynamics,and kinetics of the prepared wollastonite glass ceramics were determined by X-ray diffraction analysis,scanning electron microscopy,energy-dispersive spectroscopy,high-resolution transmission electron microscopy,and differential thermal analysis.Results showed that crystals of wollastonite and alumina could be found in the gehlenite through its reaction with silicon dioxide.The wollastonite crystals showed a lath shape with a certain length-to-diameter ratio.The crystals exhibited excellent bridging and reinforcing effects.In the crystallization process,the aluminum ions in gehlenite diffused into the glass and the silicon ions in the glass diffused into gehlenite.Consequently,the three-dimensional frame structure of gehlenite was partially damaged to form a chain-like wollastonite.The results of crystallization thermodynamics and kinetics indicated that crystallization reaction could occur spontaneously under a low temperature(1173 K),with 20 wt%gehlenite added as the reactive crystallization promoter.The crystallization activation energy was evaluated as 261.99 kJ/mol by using the Kissinger method.The compression strength of the wollastonite glass ceramic samples(7.5 cm×7.5 cm)reached 251 MPa.展开更多
Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency ...Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency of Mg,Fe,Al,Ni,and Co reaches 93.98%,60.09%,82.08%,90.58%,and 94.06%,respectively,under the leaching conditions of 5 mol/L H_(2)SO_(4),liquid/solid ratio of 4 mL/g,and leaching temperature 100℃.Hence,the valuable metals in serpentine were effectively recovered by sulfuric acid leaching.The leaching behaviors of Mg,Fe,and a small amount of Al were analyzed using X-ray diffraction.The results show that the unreacted Mg and Fe remained as MgFe_(2)O_(4),and Al formed Al_(2)Si_(2)O_(5)(OH)_(4) in the leaching residue.The kinetics of Mg and Ni in the leaching process was studied respectively.The leaching kinetics of Mg conformed to the shrinking core model with an activation energy of 16.95 kJ/mol,which was controlled by the combination of the diffusion and chemical reaction.The leaching kinetics of Ni accorded with the Avrami equation with an activation energy of 11.57 kJ/mol,which was controlled by diffusion.In the study,the valuable metal elements were extracted from serpentine minerals with high efficiency and low cost,which possessed important practical values.展开更多
The ilvaite-bearing skarn associations in the Galinge skarn deposit were studied to determine their physicochemical formation conditions.A thermodynamic model setting pressure of 50 MPa(Pf=Ps=50 MPa)was set up to trac...The ilvaite-bearing skarn associations in the Galinge skarn deposit were studied to determine their physicochemical formation conditions.A thermodynamic model setting pressure of 50 MPa(Pf=Ps=50 MPa)was set up to trace the skarn evolution.Petrographic evidence for replacement of garnet and magnetite by ilvaite in the early retrograde stage(Stage I)combined with thermodynamic modeling suggests that the alteration may have occurred at 400470°C under moderately high fO withΔlgfO(HM)ranges from 4 to 4.2.The model is based on a maximum 22 pressure of 50 MPa calculated from magmatic amphibole geobarometer.The continuous breakdown of ilvaite with quartz to form ferro-actinolite and magnetite occur in the late retrograde stage(Stage II).The reactions occurred at 400440°C under moderate fO(ΔlgfO(HM):4 to 4.4).In Stage III,the breakdown of ilvaite to form calcite,pyrite 22 and ferroactinolite depends on XCO which can be estimated to be in a range of 0.005 to 0.05,and the reaction would 2 occur at higher temperatures with increasing XCO.Under these conditions,the breakdown occurs at 270350°C and 2 low fO(ΔlgfO(HM):up to 5.2).The thermodynamic model for continuous evolution from Stage I to Stage III 22 completely records the conditions of the retrograde alteration,which is inconsistent with the thermobarometry imprints of fluid inclusions.Therefore,the petrography and phase relations of ilvaite are useful indicators of reaction conditions in various skarn deposit types.展开更多
Thermal decomposition of waste epoxy PCBs was performed in different atmospheres （nitrogen, argon, air and vacuum） at a heating rate of 10 ℃/rain by DSC-TGA, and the pyrolysis characteristic was analyzed. The gases...Thermal decomposition of waste epoxy PCBs was performed in different atmospheres （nitrogen, argon, air and vacuum） at a heating rate of 10 ℃/rain by DSC-TGA, and the pyrolysis characteristic was analyzed. The gases volatilized from the experiment were qualitatively analyzed by TG-FTIR. Kinetics study shows that pyrolysis reaction takes place between 300 and 400℃, and the activation energies are 256, 212 and 186.2 kJ/mol in nitrogen, argon and vacuum, respectively. There are two mass-loss processes in the decomposition under air atmosphere. In the first mass-loss process, the decomposition is the main reaction, and in the second process, the oxidation is the main reaction. The activation energy of the second mass-loss process is 99.6 kJ/mol by isothermal heat-treatments. TG-FTIR analysis shows carbon dioxide, carbon monoxide, hydrogen bromide, phenol and substituent phenol are given off during the pyrolysis of waste epoxy PCBs.展开更多
Thermogravimetric study of medical transfusion tube （MTT） waste containing polyvinyl chloride （PVC） was carried out using the thermogravimetric analyser （TGA） with N2, at different heating rates of 5, 10, 20, 30...Thermogravimetric study of medical transfusion tube （MTT） waste containing polyvinyl chloride （PVC） was carried out using the thermogravimetric analyser （TGA） with N2, at different heating rates of 5, 10, 20, 30, 50 ℃/min. The purpose is to obtain pyrolysis characteristics and kinetic parameters of medical waste. The experimental results indicate that the pyrolysis behavior of the MTT sample is in agreement with its main ingredient of PVC, appearing two stair stepping stages. The influence of the additives in MTT on pyrolysis behavior was also revealed, which could improve MTT pyrolysis at lower temperature in the first stage, and cause obvious unsmoothness and asymmetry of the second DTG peak. Four n-order kinetic models of Coats-Redfern, Ozawa, Kissinger and Freeman-carroll were used to get the kinetic parameters. Furthermore, a novel ＂two-step four-reaction model＂ was established to simulate the whole continuous process. The different methods and the kinetic parameters thus obtained were discussed and compared with each other in literatures. The reasons of deviation among kinetic values were tried to be elucidated. The new established model could more satisfactorily describe the pyrolysis process of MTT, being more mechanistic and conveniently serving for the engineering.展开更多
The feasibility study of the AlCl(g) generated by Al_2O-AlCl_2-C system under vacuum was carried out by thermodynamic analysis and CASTEP package of the Material Studio program which was based on density functional th...The feasibility study of the AlCl(g) generated by Al_2O-AlCl_2-C system under vacuum was carried out by thermodynamic analysis and CASTEP package of the Material Studio program which was based on density functional theory(DFT) formalism. Thermodynamic calculations indicate that Al Cl and CO molecules can be formed under conditions of temperature 1760 K and the pressure of 60 Pa. The interaction of Al_2O and AlCl_2 with C shows that the chemical adsorption of Al_2O and AlCl_2 does take place on C(001) crystal plane, and at the same time, new chemical bond is formed between Al atom in Al_2O and Cl atoms from one of the Al—Cl bonds in AlCl_2. The results, after 1.25 ps dynamics simulation, indicate that adsorbed Al Cl molecules are generated and CO molecule will be formed in this system, and they will escape from C(001) surface after a longer period of dynamic simulation time. It means that the reaction of Al_2O and AlCl_2 with C can be carried out under given constraint condition.展开更多
The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffracti...The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.展开更多
In this paper,the effect of sodium butyl xanthate(NaBX)adsorption on the surface of bornite at different pH on flotation was studied by adsorption kinetic and thermodynamic.The flotation results demonstrated that the ...In this paper,the effect of sodium butyl xanthate(NaBX)adsorption on the surface of bornite at different pH on flotation was studied by adsorption kinetic and thermodynamic.The flotation results demonstrated that the recovery was the highest when pH was 9 in NaBX solution(4×10^?5 mol/L).The adsorption kinetics showed the reaction of NaBX on the bornite conformed to the second order kinetic equation;it belonged to the multimolecular layer adsorption of Freundlich model;the maximum adsorption rate constant was 0.30 g/(10^?6 mol·min),and the equilibrium adsorption capacity was 2.70×10^?6 mol/g.Thermodynamic calculation results indicated that the adsorption process was spontaneous chemisorption,and the adsorption products of NaBX on bornite surface were cupric butyl xanthate,ferric butyl xanthate and dixanthogen,which were confirmed by infrared spectrum measurements.展开更多
Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion propertie...Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion properties, of which microscopic images show that these particles have spherical shapes with identical diameters of 31 μm. The measured density of these particles is 1.0779 g/cm2. Lycopodium particles contain 64.06% carbon, 25.56% oxygen, 8.55% hydrogen and 1.83% nitrogen, and no sulfur. Thermogravimetric analysis in the nitrogen environment indicates that the maximum of particle mass reduction occurs in the temperature range of 250-550 ℃ where the maximum mass reduction in the DTG diagrams also occurs in. In the oxygen environment, an additional peak can also be observed in the temperature range of 500-600 ℃, which points to solid phase combustion and ignition temperature of lycopodium particles. The kinetics of reactions is determined by curve fitting and minimization of error.展开更多
The dynamic mechanical properties of rock specimens after thermal treatment in the air-filled environment(AE:i.e.,at the free surface)have been extensively investigated,yet they are rarely estimated in the quasi-vacuu...The dynamic mechanical properties of rock specimens after thermal treatment in the air-filled environment(AE:i.e.,at the free surface)have been extensively investigated,yet they are rarely estimated in the quasi-vacuum environment(VE:i.e.,far from free surface),which is of special importance in engineering practice.Several precise laboratory tests(i.e.,split Hopkinson pressure bar test)on marble samples in both AE and VE were performed to investigate physical and dynamic mechanical behaviors of marble after heat treatment(25℃ to 900℃)in AE and VE.The tests results demonstrate that related properties of marble could be divided into three different stages by corresponding critical temperatures of 300℃ and 600℃,at which heat damage factors are 0.29(0.30)and 0.88(0.92)in VE(AE),respectively.The thermal damage developes more fully in AE than in VE.The thermal environment plays an important role,especially in Stage 3.Specifically,a conspicuous difference(greater than 20%)between AE and VE occurs in corresponding dynamic strength and the anti-deformation capacities of tested marble specimen.The influence of heat damage of rock is very important and valuable in engineering practice,particularly when the temperature is very high(greater than 600℃).展开更多
The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide ...The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.展开更多
Based on the steady-state strain measured by single-pass hot compression tests,the method by a double-pass hot compression testing was developed to measure the metadynamic-recrystallization kinetics.The metadynamic re...Based on the steady-state strain measured by single-pass hot compression tests,the method by a double-pass hot compression testing was developed to measure the metadynamic-recrystallization kinetics.The metadynamic recrystallization behavior of low-alloy steel Q345B during hot compression deformation was investigated in the temperature range of 1 000-1 100℃,the strain rate range of 0.01-0.10 s -1 and the interpass time range of 0.5-50 s on a Gleeble-3500 thermo-simulation machine.The results show that metadynamic recrystallization during the interpass time can be observed.As the deformation temperature and strain rate increase,softening caused by metadynamic recrystallization is obvious.According to the data of thermo-simulation,the metadynamic recrystallization activation energy is obtained to be Qmd=100.674 kJ/mol and metadynamic recrystallization kinetics model is set up.Finally,the error analysis of metadynamic recrystallization kinetics model proves that the model has high accuracy(correlation coefficient R=0.988 6).展开更多
The glass formation was intensively studied for Fe-based alloys. Parameters defining kinetics and thermodynamic behavior of crystallization were calculated using calorimetric measurements and physical properties of co...The glass formation was intensively studied for Fe-based alloys. Parameters defining kinetics and thermodynamic behavior of crystallization were calculated using calorimetric measurements and physical properties of constituent elements. It is found that the critical cooling rate Rc estimated by combining kinetic and thermodynamic parameters highly correlates with measured Rc found in literatures with correlation coefficient R2=0.944, and alloy compositions with high melting enthalpy AHm can easily form glass even without high undercooling and high value of the ,β-parameter of Tumbull＇s theory, revealing that the glass formation in this group of alloys is mostly controlled by growth limitation. This combination of kinetic and thermodynamic parameters can be used to determine alloy composition with good glass forming ability in Fe-based alloys just using physical properties of alloying elements and calorimetric measurements.展开更多
In order to study the major performance indicators of the twin-rotor piston engine(TRPE), Matlab/simulink was used to simulate the mathematical models of its thermodynamic processes. With consideration of the characte...In order to study the major performance indicators of the twin-rotor piston engine(TRPE), Matlab/simulink was used to simulate the mathematical models of its thermodynamic processes. With consideration of the characteristics of the working processes in the TRPE, corresponding differential equations were established and then simplified by period features of the TRPE. Finally, the major boundary conditions were figured out. The changing trends of mass, pressure and temperature of working fuel in the working chamber during a complete engine cycle were presented. The simulation results are consistent with the trends of an actual working cycle in the TRPE, which indicates that the method of simulation is feasible. As the pressure in the working chamber is calculated, all the performance parameters of the TRPE can be obtained. The major performance indicators, such as the indicated mean effective pressure, power to weight ratio and the volume power, are also acquired. Compared with three different types of conventional engines, the TRPE has a bigger utilization ratio of cylinder volume, a higher power to weight ratio and a more compact structure. This indicates that TRPE is superior to conventional engines.展开更多
文摘The microstructures and thermodynamic properties of mixed systems comprising pyridinium ionic liquid[HPy][BF_(4)]and acetonitrile at different mole fractions were studied using molecular dynamics simulation in this work.The following properties were determined:density,self-diffusion coefficient,excess molar volume,and radial distribution function.The results show that with an increase in the mole fraction of[HPy][BF_(4)],the self-diffusion coefficient decreases.Additionally,the excess molar volume initially decreases,reaches a minimum,and then increases.The rules of radial distribution functions(RDFs)of characteristic atoms are different.With increasing the mole fraction of[HPy][BF_(4)],the first peak of the RDFs of HA1-F decreases,while that of CT6-CT6 rises at first and then decreases.This indicates that the solvent molecules affect the polar and non-polar regions of[HPy][BF_(4)]differently.
基金Projects(51871243,51574290)supported by the National Natural Science Foundation of ChinaProject(ASSIKFJJ202304001)supported by the Open Fund of the National Key Laboratory of Strength and Structural Integrity,China+3 种基金Project(HT-CSNS-DG-CD-0092/2021)supported by the Guangdong-Hong Kong-Macao Joint Laboratory for Neutron Scattering Science and Technology,ChinaProject(2022KF-08)supported by the Hubei Longzhong Laboratory,ChinaProject(22kfgk06)supported by the Shock and Vibration of Engineering Materials and Structures Key Laboratory of Sichuan Province,ChinaProject(PBSKL2022C01)supported by the State Key Laboratory of Precision Blasting and Hubei Key Laboratory of Blasting Engineering,China。
文摘The commercial ZK 60 magnesium alloy with extruded state experienced aging heat treatment(T 6)was dynamically loaded at strain rate of 3000 s−1 by means of the split Hopkinson pressure bar(SHPB)in this paper.Transmission electron microscopy(TEM)observations showed that the precipitatedβ′_(1) phases partially dissolved(spheroidized)with blurred interfaces within 160μs at 3000 s^(−1).The average length and diameter of the rod-shapedβ′_(1) phase particles were 48.5 and 9.8 nm after the T 6 heat treatment;while the average diameter of the sphericalβ′_(1) phases changed to 8.8 nm after loading.The deformedβ′_(1) phase generated larger lattice distortion energy than Mg matrix under high strain rate loading.Therefore,the difference of free energy(the driving force of dissolution)between theβ′_(1) phase and the matrix increased,making the instantaneous dissolution of theβ′_(1) phase thermodynamically feasible.The dissolution(spheroidization)of theβ′_(1) phase particles was kinetically promoted because the diffusion rate of the solute Zn atoms was accelerated by combined actions of adiabatic temperature rise,high density of dislocations(vacancies)and high deviatoric stresses during high strain rate loading.The increase in hardness of ZK 60-T 6 alloy could be attributed to solid solution strengthening,dislocation strengthening and second phase particle strengthening.
文摘In this study,circular dichroism(CD)and molecular dynamics(MD)simulation were used to investigate the thermal unfolding pathway of staphylococcal enterotoxin B(SEB)at temperatures of 298–371 and 298–500 K,and the relationship between the experimental and simulation results were explored.Our computational findings on the secondary structure of SEB showed that at room temperature,the CD spectroscopic results were highly consistent with the MD results.Moreover,under heating conditions,the changing trends of helix,sheet and random coil obtained by CD spectral fitting were highly consistent with those obtained by MD.In order to gain a deeper understanding of the thermal stability mechanism of SEB,the MD trajectories were analyzed in terms of root mean square deviation(RMSD),secondary structure assignment(SSA),radius of gyration(R_(g)),free energy surfaces(FES),solvent-accessible surface area(SASA),hydrogen bonds and salt bridges.The results showed that at low heating temperature,domain Ⅰ without loops(omitting the mobile loop region)mainly relied on hydrophobic interaction to maintain its thermal stability,whereas the thermal stability of domain Ⅱ was mainly controlled by salt bridges and hydrogen bonds.Under high heating temperature conditions,the hydrophobic interactions in domain Ⅰ without loops were destroyed and the secondary structure was almost completely lost,while domain Ⅱ could still rely on salt bridges as molecular staples to barely maintain the stability of the secondary structure.These results help us to understand the thermodynamic and kinetic mechanisms that maintain the thermal stability of SEB at the molecular level,and provide a direction for establishing safer and more effective food sterilization processes.
基金supported by the National Natural Science Foundation of China(22171001,22305001,51972001,52372073)the Natural Science Foundation of Anhui Province of China(2108085MB49).
文摘The realization of real-time thermal feedback for monitoring photothermal therapy(PTT)under near-infrared(NIR)light irradiation is of great interest and challenge for antitumor therapy.Herein,by assembling highly efficient photothermal conversion gold nanorods and a temperature-responsive probe((E)-4-(4-(diethylamino)styryl)-1-methylpyridin-1-ium,PyS)within MOF-199,an intelligent nanoplatform(AMPP)was fabricated for simultaneous chemodynamic therapy and NIR light-induced temperature-feedback PTT.The fluorescence intensity and temperature of the PyS probe are linearly related due to the restriction of the rotation of the characteristic monomethine bridge.Moreover,the copper ions resulting from the degradation of MOF-199 in an acidic microenvironment can convert H_(2)O_(2)into•OH,resulting in tumor ablation through a Fenton-like reaction,and this process can be accelerated by increasing the temperature.This study establishes a feasible platform for fabricating highly sensitive temperature sensors for efficient temperature-feedback PTT.
基金Projects(U1802254,51871201)supported by the National Natural Science Foundation of ChinaProject(LY18E040003)supported by the Zhejiang Provincial Natural Science Foundation,China
文摘Three-dimensional ordered macro/mesoporous carbon(3DOM/m-C)with high specific surface area was synthesized by colloid crystal template method with chemical activation by KOH and used as the adsorbent for removing malachite green(MG)in aqueous solution.The microstructures of the adsorbents were characterized by FESEM,TEM and BET,and the effects of initial dye concentration,contact time,solution pH,and temperature on adsorption performance were investigated.The results show that the 3DOM/m-C exhibits extremely high adsorption capacity of 3541.1 mg/g within 2 h,which could be attributed to the novel ordered hierarchical structure with mesopores on three-dimensional ordered macroporous carbon walls.And the adsorption behavior conforms to the pseudo-second-order kinetic and Langmuir adsorption isotherm.3DOM/m-C can be recycled after being desorbed by absolute ethanol,and still maintains a high capacity of 2762.06 mg/g after 5 cycles.
基金Project(51308086)supported by the National Natural Science Foundation of ChinaProject(LJQ2015020)supported by the Program for Liaoning Excellent Talents in University,ChinaProject(2016RQ051)supported by the Program of Science-Technology Star for Young Scholars by the Dalian Municipality,China
文摘Wollastonite glass ceramics were prepared using the reactive crystallization sintering method by mixing waste glass powders with gehlenite.The crystallization property,thermodynamics,and kinetics of the prepared wollastonite glass ceramics were determined by X-ray diffraction analysis,scanning electron microscopy,energy-dispersive spectroscopy,high-resolution transmission electron microscopy,and differential thermal analysis.Results showed that crystals of wollastonite and alumina could be found in the gehlenite through its reaction with silicon dioxide.The wollastonite crystals showed a lath shape with a certain length-to-diameter ratio.The crystals exhibited excellent bridging and reinforcing effects.In the crystallization process,the aluminum ions in gehlenite diffused into the glass and the silicon ions in the glass diffused into gehlenite.Consequently,the three-dimensional frame structure of gehlenite was partially damaged to form a chain-like wollastonite.The results of crystallization thermodynamics and kinetics indicated that crystallization reaction could occur spontaneously under a low temperature(1173 K),with 20 wt%gehlenite added as the reactive crystallization promoter.The crystallization activation energy was evaluated as 261.99 kJ/mol by using the Kissinger method.The compression strength of the wollastonite glass ceramic samples(7.5 cm×7.5 cm)reached 251 MPa.
基金Project(51574286)supported by the National Natural Science Foundation of China。
文摘Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency of Mg,Fe,Al,Ni,and Co reaches 93.98%,60.09%,82.08%,90.58%,and 94.06%,respectively,under the leaching conditions of 5 mol/L H_(2)SO_(4),liquid/solid ratio of 4 mL/g,and leaching temperature 100℃.Hence,the valuable metals in serpentine were effectively recovered by sulfuric acid leaching.The leaching behaviors of Mg,Fe,and a small amount of Al were analyzed using X-ray diffraction.The results show that the unreacted Mg and Fe remained as MgFe_(2)O_(4),and Al formed Al_(2)Si_(2)O_(5)(OH)_(4) in the leaching residue.The kinetics of Mg and Ni in the leaching process was studied respectively.The leaching kinetics of Mg conformed to the shrinking core model with an activation energy of 16.95 kJ/mol,which was controlled by the combination of the diffusion and chemical reaction.The leaching kinetics of Ni accorded with the Avrami equation with an activation energy of 11.57 kJ/mol,which was controlled by diffusion.In the study,the valuable metal elements were extracted from serpentine minerals with high efficiency and low cost,which possessed important practical values.
基金Projects(41172076,41802080)supported by the National Natural Science Foundation of ChinaProject(1212011085528)supported by Geological Survey Program from the China Geological Survey+3 种基金Project(2019CX035)supported by Innovation-driven Plan of Central South University,ChinaProject(201411025)supported by the Scientific Research Fund from Ministry of Land and Re-sources,ChinaProject(201309)supported by the Program of High-level Geological Talents,ChinaProject(201112)supported by the Youth Geological Talents of the China Geological Survey
文摘The ilvaite-bearing skarn associations in the Galinge skarn deposit were studied to determine their physicochemical formation conditions.A thermodynamic model setting pressure of 50 MPa(Pf=Ps=50 MPa)was set up to trace the skarn evolution.Petrographic evidence for replacement of garnet and magnetite by ilvaite in the early retrograde stage(Stage I)combined with thermodynamic modeling suggests that the alteration may have occurred at 400470°C under moderately high fO withΔlgfO(HM)ranges from 4 to 4.2.The model is based on a maximum 22 pressure of 50 MPa calculated from magmatic amphibole geobarometer.The continuous breakdown of ilvaite with quartz to form ferro-actinolite and magnetite occur in the late retrograde stage(Stage II).The reactions occurred at 400440°C under moderate fO(ΔlgfO(HM):4 to 4.4).In Stage III,the breakdown of ilvaite to form calcite,pyrite 22 and ferroactinolite depends on XCO which can be estimated to be in a range of 0.005 to 0.05,and the reaction would 2 occur at higher temperatures with increasing XCO.Under these conditions,the breakdown occurs at 270350°C and 2 low fO(ΔlgfO(HM):up to 5.2).The thermodynamic model for continuous evolution from Stage I to Stage III 22 completely records the conditions of the retrograde alteration,which is inconsistent with the thermobarometry imprints of fluid inclusions.Therefore,the petrography and phase relations of ilvaite are useful indicators of reaction conditions in various skarn deposit types.
基金Project(2006AA06Z375) supported by the National High-tech Research and Development Program of China
文摘Thermal decomposition of waste epoxy PCBs was performed in different atmospheres （nitrogen, argon, air and vacuum） at a heating rate of 10 ℃/rain by DSC-TGA, and the pyrolysis characteristic was analyzed. The gases volatilized from the experiment were qualitatively analyzed by TG-FTIR. Kinetics study shows that pyrolysis reaction takes place between 300 and 400℃, and the activation energies are 256, 212 and 186.2 kJ/mol in nitrogen, argon and vacuum, respectively. There are two mass-loss processes in the decomposition under air atmosphere. In the first mass-loss process, the decomposition is the main reaction, and in the second process, the oxidation is the main reaction. The activation energy of the second mass-loss process is 99.6 kJ/mol by isothermal heat-treatments. TG-FTIR analysis shows carbon dioxide, carbon monoxide, hydrogen bromide, phenol and substituent phenol are given off during the pyrolysis of waste epoxy PCBs.
基金Project(50378062) supported by the National Natural Science Foundation of ChinaProject(09JCYBJC08100) supported by the Natural Science Foundation of Tianjin City,China
文摘Thermogravimetric study of medical transfusion tube （MTT） waste containing polyvinyl chloride （PVC） was carried out using the thermogravimetric analyser （TGA） with N2, at different heating rates of 5, 10, 20, 30, 50 ℃/min. The purpose is to obtain pyrolysis characteristics and kinetic parameters of medical waste. The experimental results indicate that the pyrolysis behavior of the MTT sample is in agreement with its main ingredient of PVC, appearing two stair stepping stages. The influence of the additives in MTT on pyrolysis behavior was also revealed, which could improve MTT pyrolysis at lower temperature in the first stage, and cause obvious unsmoothness and asymmetry of the second DTG peak. Four n-order kinetic models of Coats-Redfern, Ozawa, Kissinger and Freeman-carroll were used to get the kinetic parameters. Furthermore, a novel ＂two-step four-reaction model＂ was established to simulate the whole continuous process. The different methods and the kinetic parameters thus obtained were discussed and compared with each other in literatures. The reasons of deviation among kinetic values were tried to be elucidated. The new established model could more satisfactorily describe the pyrolysis process of MTT, being more mechanistic and conveniently serving for the engineering.
基金Projects(51104078,51264023)supported by the National Natural Science Foundation of ChinaProject(2010CD022)supported by Yunnan Province Applied Basic Research Fund,China+2 种基金Project(IRT1250)supported by the Program for Innovative Research Team in University of Ministry of Education of ChinaProject(U1202271)supported by the National Natural Science Foundation of China-Yunnan United FundProject(KKZ3201252020)supported by Kunming University of Science and Technology for Talent Training,China
文摘The feasibility study of the AlCl(g) generated by Al_2O-AlCl_2-C system under vacuum was carried out by thermodynamic analysis and CASTEP package of the Material Studio program which was based on density functional theory(DFT) formalism. Thermodynamic calculations indicate that Al Cl and CO molecules can be formed under conditions of temperature 1760 K and the pressure of 60 Pa. The interaction of Al_2O and AlCl_2 with C shows that the chemical adsorption of Al_2O and AlCl_2 does take place on C(001) crystal plane, and at the same time, new chemical bond is formed between Al atom in Al_2O and Cl atoms from one of the Al—Cl bonds in AlCl_2. The results, after 1.25 ps dynamics simulation, indicate that adsorbed Al Cl molecules are generated and CO molecule will be formed in this system, and they will escape from C(001) surface after a longer period of dynamic simulation time. It means that the reaction of Al_2O and AlCl_2 with C can be carried out under given constraint condition.
基金Project(20876160) supported by the National Natural Science Foundation of China
文摘The thermal decomposition process of basic magnesium carbonate was investigated. Firstly, Basic magnesium carbonate was prepared from magnesite, and the characteristics of the product were detected by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. Subsequently, the thermal decomposition process of basic magnesium carbonate in air was studied by thermogravimetry-differential thermogravimetry （TG-DTG）. The results of XRD confirm that the chemical composition of basic magnesium carbonate is 4MgCO3·Mg（OH）2·4H2O. And the SEM images show that the sample is in sheet structure, with a diameter of 0.1-1 μm. The TG-DTG results demonstrate that there are two steps in the thermal decomposition process of basic magnesium carbonate. The apparent activation energies （E） were calculated by Flyrm-Wall-Ozawa method. It is obtained from Coats-Redfem＇s equation and Malek method that the mechanism functions of the two decomposition stages are D3 and A1.5, respectively. And then, the kinetic equations of the two steps were deduced as well.
基金Projects(51504053,51374079)supported by the National Natural Science Foundation of ChinaProject(2015M571324)supported by the Postdoctoral Science Foundation of China
文摘In this paper,the effect of sodium butyl xanthate(NaBX)adsorption on the surface of bornite at different pH on flotation was studied by adsorption kinetic and thermodynamic.The flotation results demonstrated that the recovery was the highest when pH was 9 in NaBX solution(4×10^?5 mol/L).The adsorption kinetics showed the reaction of NaBX on the bornite conformed to the second order kinetic equation;it belonged to the multimolecular layer adsorption of Freundlich model;the maximum adsorption rate constant was 0.30 g/(10^?6 mol·min),and the equilibrium adsorption capacity was 2.70×10^?6 mol/g.Thermodynamic calculation results indicated that the adsorption process was spontaneous chemisorption,and the adsorption products of NaBX on bornite surface were cupric butyl xanthate,ferric butyl xanthate and dixanthogen,which were confirmed by infrared spectrum measurements.
基金supported by the Ministry of Science, Research & Technology of Iran
文摘Biomass is a kind of renewable energy which is used increasingly in different types of combustion systems or in the production of fuels like bio-oil. Lycopodium is a cellulosic particle, with good combustion properties, of which microscopic images show that these particles have spherical shapes with identical diameters of 31 μm. The measured density of these particles is 1.0779 g/cm2. Lycopodium particles contain 64.06% carbon, 25.56% oxygen, 8.55% hydrogen and 1.83% nitrogen, and no sulfur. Thermogravimetric analysis in the nitrogen environment indicates that the maximum of particle mass reduction occurs in the temperature range of 250-550 ℃ where the maximum mass reduction in the DTG diagrams also occurs in. In the oxygen environment, an additional peak can also be observed in the temperature range of 500-600 ℃, which points to solid phase combustion and ignition temperature of lycopodium particles. The kinetics of reactions is determined by curve fitting and minimization of error.
基金Projects(51579239,42077240,51979280)supported by the National Natural Science Foundation of China。
文摘The dynamic mechanical properties of rock specimens after thermal treatment in the air-filled environment(AE:i.e.,at the free surface)have been extensively investigated,yet they are rarely estimated in the quasi-vacuum environment(VE:i.e.,far from free surface),which is of special importance in engineering practice.Several precise laboratory tests(i.e.,split Hopkinson pressure bar test)on marble samples in both AE and VE were performed to investigate physical and dynamic mechanical behaviors of marble after heat treatment(25℃ to 900℃)in AE and VE.The tests results demonstrate that related properties of marble could be divided into three different stages by corresponding critical temperatures of 300℃ and 600℃,at which heat damage factors are 0.29(0.30)and 0.88(0.92)in VE(AE),respectively.The thermal damage developes more fully in AE than in VE.The thermal environment plays an important role,especially in Stage 3.Specifically,a conspicuous difference(greater than 20%)between AE and VE occurs in corresponding dynamic strength and the anti-deformation capacities of tested marble specimen.The influence of heat damage of rock is very important and valuable in engineering practice,particularly when the temperature is very high(greater than 600℃).
基金Technology fund on Applied Physical Chemistry Laboratory(9140C3703051105 and 9140C370303120C37142)State Key Laboratory of Explosion Science and Technology(QNKT12-02)
文摘The dissolving processes,thermochemical properties and thermokinetic parameters of manganese carbohydrazide styph-nate([Mn2(CHZ)2(TNR)2(H2O)4]),nickel carbohydrazide styphnate([Ni(CHZ),(TNR)],)and lead carbohydrazide styphnate([Pb_(2)(CHZ)_(2)(TNR)_(2)(H_(2)O)_(2)])in N,N-dimethylformamide(DMF)at 298,15 K were studied by a SETARAM C80 calorime-ter.The results show that the dissolving process of them in DMF are exothermic,however the exothermic peaks are different.The results are associated with the different molecular structure and polarity of solutes.The empirical formulas for the enthalpies of dis-solution(△mH),the relative apparent molar enthalpies(ΦL;),the relative partial molar enthalpies(L,),and the enthalpies of di-lution(△aHt.:)are respectively deduced by polynomial fitting of experimental data.The standard enthalpies of dissolution(Aai H)are calculated respectively as-17.75kJ·mol^(-1),-29.76kJ·mol^(-1)and-15.35 kJ·mol^(-1).The rate constant of dissolution reaction(k),and the reaction order(n)are obtained from the kinetic formulas.
基金Project(101048) supported by Fok Ying Tung Education FoundationProject(E2008000835) supported by the Natural Science Foundation of Hebei Province,China
文摘Based on the steady-state strain measured by single-pass hot compression tests,the method by a double-pass hot compression testing was developed to measure the metadynamic-recrystallization kinetics.The metadynamic recrystallization behavior of low-alloy steel Q345B during hot compression deformation was investigated in the temperature range of 1 000-1 100℃,the strain rate range of 0.01-0.10 s -1 and the interpass time range of 0.5-50 s on a Gleeble-3500 thermo-simulation machine.The results show that metadynamic recrystallization during the interpass time can be observed.As the deformation temperature and strain rate increase,softening caused by metadynamic recrystallization is obvious.According to the data of thermo-simulation,the metadynamic recrystallization activation energy is obtained to be Qmd=100.674 kJ/mol and metadynamic recrystallization kinetics model is set up.Finally,the error analysis of metadynamic recrystallization kinetics model proves that the model has high accuracy(correlation coefficient R=0.988 6).
基金Projects(51174094, 51101059) supported by the National Natural Science Foundation of China
文摘The glass formation was intensively studied for Fe-based alloys. Parameters defining kinetics and thermodynamic behavior of crystallization were calculated using calorimetric measurements and physical properties of constituent elements. It is found that the critical cooling rate Rc estimated by combining kinetic and thermodynamic parameters highly correlates with measured Rc found in literatures with correlation coefficient R2=0.944, and alloy compositions with high melting enthalpy AHm can easily form glass even without high undercooling and high value of the ,β-parameter of Tumbull＇s theory, revealing that the glass formation in this group of alloys is mostly controlled by growth limitation. This combination of kinetic and thermodynamic parameters can be used to determine alloy composition with good glass forming ability in Fe-based alloys just using physical properties of alloying elements and calorimetric measurements.
基金Project(7131109)supported by the National Defense Pre-research Foundation of ChinaProject(51175500)supported by the National Natural Science Foundation of China
文摘In order to study the major performance indicators of the twin-rotor piston engine(TRPE), Matlab/simulink was used to simulate the mathematical models of its thermodynamic processes. With consideration of the characteristics of the working processes in the TRPE, corresponding differential equations were established and then simplified by period features of the TRPE. Finally, the major boundary conditions were figured out. The changing trends of mass, pressure and temperature of working fuel in the working chamber during a complete engine cycle were presented. The simulation results are consistent with the trends of an actual working cycle in the TRPE, which indicates that the method of simulation is feasible. As the pressure in the working chamber is calculated, all the performance parameters of the TRPE can be obtained. The major performance indicators, such as the indicated mean effective pressure, power to weight ratio and the volume power, are also acquired. Compared with three different types of conventional engines, the TRPE has a bigger utilization ratio of cylinder volume, a higher power to weight ratio and a more compact structure. This indicates that TRPE is superior to conventional engines.
