The phase equilibria relationship of the system RbCl-PEG6000-H2O were investigated at temperatures of 288.2,298.2,and 308.2 K,the compositions of solid-liquid equilibria(SLE)and liquid-liquid equilibria(LLE)were deter...The phase equilibria relationship of the system RbCl-PEG6000-H2O were investigated at temperatures of 288.2,298.2,and 308.2 K,the compositions of solid-liquid equilibria(SLE)and liquid-liquid equilibria(LLE)were determined.The complete phase diagrams,binodal curve diagrams,and tie-line diagrams were all plotted.Results show that both solid-liquid equilibria and liquid-liquid equilibria relationships at each studied temperature.The complete phase diagrams at 288.2 K,298.2 K and 308.2 K consist of six phase regions:unsaturated liquid region(L),two saturated solutions with one solid phase of RbCl(L_S),one saturated liquid phase with two solid phases of PEG6000 and RbCl(2S+L),an aqueous two-phase region(2L),and a region with two liquids and one solid phase of RbCl(2L_S).With the increase in temperature,the layering ability of the aqueous two-phase system increases,and both regions(2L)and(2L_S)increase.The binodal curves were fitted using the nonlinear equations proposed by Mistry,Hu,and Jayapal.Additionally,the tie-line data were correlated with the Othmer-Tobias,Bancroft,Hand,and Bachman equations.The liquid-liquid equilibria at 288.2 K,298.2 K and 308.2 K were calculated using the NRTL model.The findings confirm that the experimental and calculated values are in close agreement,demonstrating the model’s effectiveness in representing the system’s behavior.展开更多
Mg-Zn-Mn alloys have the advantages of low cost,excellent mechanical properties,and high corrosion resistance.To clarify the phase equilibria of Mg-Zn-Mn alloy in the Mg-rich corners,the present work experimentally in...Mg-Zn-Mn alloys have the advantages of low cost,excellent mechanical properties,and high corrosion resistance.To clarify the phase equilibria of Mg-Zn-Mn alloy in the Mg-rich corners,the present work experimentally investigated the phase equilibria in the Mg-rich corner at 300-400°C with equilibrated alloy method using electron probe micro analyzer(EPMA),X-ray diffractometer(XRD),transmission electron microscopy(TEM),and differential scanning calorimeter(DSC).Mn atoms were found to dissolve into MgZn_(2) to form a ternary solid-solution type compound,in which Mn content can be up to 15.1at%at 400°C.Three-phase equilibrium ofα-Mg+MgZn_(2)+α-Mn and liquid+α-Mg+MgZn_(2) were confirmed at 400°C.Subsequently,thermodynamic modeling of the Mg-Zn-Mn system was carried out using the CALPHAD method based on the experimental data of this work and literature data.The calculated invariant reaction Liquid+α-Mn→α-Mg+MgZn_(2) at 430°C shows good agreement with the DSC results.In addition,the results of solidification path calculations explain the microstructure in the ascast and annealed alloys well.The agreement between the calculated results and experimental data proves the self-consistency of the thermodynamic database,which can provide guidance for the compositional design of Mg-Zn-Mn alloys.展开更多
Understanding the phase equilibria of the Fe_(3)O_(4)-Cr_(2)O_(3)-CaO system is essential for the efficient recycling of stainless steel pickling sludge.The isothermal section of this system at 1473 K under oxygen par...Understanding the phase equilibria of the Fe_(3)O_(4)-Cr_(2)O_(3)-CaO system is essential for the efficient recycling of stainless steel pickling sludge.The isothermal section of this system at 1473 K under oxygen partial pressure of 0.15 Pa was investigated.Key experiments on the relevant binary systems were conducted using a combination of equilibrium-quenching techniques,X-ray diffraction,high-resolution transmission electron microscope,and electron probe microanalysis.These systems were rigorously assessed using the CALPHAD(CALculation of Phase Diagram)method,incorporating the present experimental data.The liquid phase was modeled using the ionic two-sublattice model,represented as(Ca^(2+),Cr^(3+),Fe^(2+))P(O_(2)^(-),Va,FeO_(1.5))Q,where Va represents vacancy,and P and Q denote the number of sites on the cation and anion sublattices,respectively.To ensure electroneutrality,the values of P and Q adjust according to the composition of the mixture.From this,the isothermal section of the Fe_(3)O_(4)-Cr_(2)O_(3)-CaO system at 1473 K under the specified oxygen partial pressure was obtained based on the thermodynamic parameters of the binary systems.The present experimental data and calculation results hold significant implications for the comprehensive recycling of stainless steel pickling sludge.展开更多
The efficient recycling of vanadium from converter vanadium-bearing slag is highly significant for sustainable development and circular economy.The key to developing novel processes and improving traditional routes li...The efficient recycling of vanadium from converter vanadium-bearing slag is highly significant for sustainable development and circular economy.The key to developing novel processes and improving traditional routes lies in the thermodynamic data.In this study,the equilibrium phase relations for the Fe_(2)O_(3)-TiO_(2)-V_(2)O_(5)system at 1200℃in air were investigated using a high-temperature equilibrium-quenching technique,followed by analysis using scanning electron microscopy-energy dispersive X-ray spectrometer and X-ray photoelectron spectroscopy.One liquid-phase region,two two-phase regions(liquid-rutile and liquid-ferropseudobrookite),and one three-phase region(liquid-rutile-ferropseudobrookite)were determined.The variation in the TiO_(2)and V_(2)O_(5)contents with the Fe_(2)O_(3)content was examined for rutile and ferropseudobrookite solid solutions.However,on further comparison with the predictions of FactSage 8.1,significant discrepancies were identified,highlighting that greater attention must be paid to updating the current thermodynamic database related to vanadium-bearing slag systems.展开更多
In order to obtain the crystalline forms of the salts of the potassium,ammonium,calcium coexisting chloride system,the phase equilibria relationship of quaternary system K^(+),NH_(4)^(+),Ca^(2+)//Cl^(-)-H_(2)O at 298....In order to obtain the crystalline forms of the salts of the potassium,ammonium,calcium coexisting chloride system,the phase equilibria relationship of quaternary system K^(+),NH_(4)^(+),Ca^(2+)//Cl^(-)-H_(2)O at 298.2,323.2,and 348.2 K was studied by isothermal dissolution equilibrium method.The solubility and density of equilibrium liquid phases of the system were experimentally determined;X-ray powder diffractometer was used to determine the compositions of the equilibrium solid phase at the quaternary invariant point.It is found that the quaternary system is a complex system at these three temperatures.The phase diagram at 298.2 K consists of three invariant points,seven univariate curves and five crystalline phase regions,forming the solid solutions(NH_(4)Cl)_(x)(KCl)_(1-x) and(KCl)_(x)(NH_(4)Cl)_(1-x);while at 323.2 and 348.2 K the phase diagram consists of five invariant points,eleven univariate curves and seven crystalline phase regions,the double salts(KClCaCl_(2))and(2NH_(4)Cl·CaCl_(2)·3H_(2)O),solid solutions(KCl)_(x)(NH_(4)Cl)_(1-x) and(NH_(4)Cl)_(x)(KCl)_(1-x) were formed.Among them,the crystalline phase region of solid solution(KCl)_(x)(NH_(4)Cl)_(1-x) is the largest at three temperatures,indicating that it is the easiest to crystallize in this system.Comparing the phase diagrams of the quaternary system at 298.2,323.2,and 348.2 K,it can be seen that the crystalline form of CaCl_(2) changes with the increase of temperature:CaCl_(2)·6H_(2)O at 298.2 K,CaCl_(2)·2H_(2)O at 323.2 and 348.2 K.From 323.2 to 348.2 K,the crystalline phase regions of(KCl·CaCl_(2))and(2NH_(4)Cl·CaCl_(2)·3H_(2)O)increased gradually.展开更多
Erratum to:RareMet.D0I 10.1007/s12598-015-0590-6 Unfortunately,in the original publication of the article the author name and the mol value present in Sect.2.2 have appeared incorrectly as below.
We construct new HLL-type moving-water equilibria preserving upwind schemes for the one-dimensional Saint-Venant system of shallow water equations with nonflat bottom topography.The designed first-and secondorder sche...We construct new HLL-type moving-water equilibria preserving upwind schemes for the one-dimensional Saint-Venant system of shallow water equations with nonflat bottom topography.The designed first-and secondorder schemes are tested on a number of numerical examples,in which we verify the well-balanced property as well as the ability of the proposed schemes to accurately capture small perturbations of moving-water steady states.展开更多
In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and wer...In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and were correlated by using Peng-Robinson model. The average relative error ofpropylene concentration in liquid phase is 1. 46 %. The results indicate that the models are very suitablefor the ternary system and the data are reliable.展开更多
The pseudo-ternary system(Na Cl + Na_2SO_4+ H_2O) of coal gasification wastewater was studied at T =(268.15 to 373.15) K. The solubility and density of the equilibrium liquid phase were determined by the isothermal so...The pseudo-ternary system(Na Cl + Na_2SO_4+ H_2O) of coal gasification wastewater was studied at T =(268.15 to 373.15) K. The solubility and density of the equilibrium liquid phase were determined by the isothermal solution saturation method. The equilibrium solids were also investigated by the Schreinemaker's method of wet residues and X-ray powder diffraction(XRD). According to the experimental data, the phase diagrams were determined. It was found that there was no significant solubility difference on the Na Cl-rich side between the ternary system(Na Cl + Na_2SO_4+ H_2O) in coal gasification wastewater and in pure water. However, the solubility on the Na_2SO_4-rich side of coal gasification wastewater was apparently higher than that of pure water. The increase in the solubility of Na_2SO_4 was most likely caused by the effects of other impurities apart from Na Cl and Na_2SO_4 in coal gasification wastewater. The measured data and phase equilibrium diagrams can provide fundamental basis for salt recovery in coal gasification wastewater.展开更多
To determine the liquid-solid phase equilibria of the Nb-Si-Ti ternary system, Nb-Si-Ti alloys of different compositions are prepared. By means of scanning electron microscopy （SEM）, X-ray diffraction （XRD） and el...To determine the liquid-solid phase equilibria of the Nb-Si-Ti ternary system, Nb-Si-Ti alloys of different compositions are prepared. By means of scanning electron microscopy （SEM）, X-ray diffraction （XRD） and electron probe microanalysis （EPMA）, the phases in the alloys, such as Si-based solutions, Ti（Nb）Si, Ti（Nb）Si2, Nb（Ti）Si2, Ti（Nb）5Si4, Nb（Ti）5Si3, Ti（Nb）5Si3, Nb（Ti）3Si and Nb-based solutions are identified, and the phase evolution is analyzed. As a result, the microstmctural and microchemical evidence provides a clear definition of the Nb-Si-Ti liquidus surface projection and indicates that the ternary phase diagram has seven transition reactions.展开更多
Semiclathrate hydrates of tetra-n-butyl ammonium bromide （TBAB） offer potential solution for gas storage, transportation, separation of flue gases and CO2 sequestration. Models for phase equilibria for these systems...Semiclathrate hydrates of tetra-n-butyl ammonium bromide （TBAB） offer potential solution for gas storage, transportation, separation of flue gases and CO2 sequestration. Models for phase equilibria for these systems have not yet been developed in open literatures and thus require urgent attention. In this work, the first attempt has been made to model phase equilibria of semiclathrate hydrates of CH4, CO2 and N2 in aqueous solution of TBAB. A thermodynamic model for gas hydrate system as proposed by Chen and Guo has been extended for semiclathrate hydrates of gases in aqueous solution of TBAB. A correlation for the activity of water relating to the system temperature, concentration of TBAB in the system and the nature of vip gas molecule has been proposed. The model results have been validated against available experimental data on phase equilibria of semiclathrate hydrate systems of aqueous TBAB with different gases as vip molecule. The extended Chen and Guo＇s model is found to be suitable to explain the promotion effect of TBAB for the studied gaseous system such as, methane, carbon dioxide and nitrogen as a vip molecule. Additionally, a correlation for the increase in equilibrium formation temperature （hydrate promotion temperature, ATp） of semiclathrate hydrate system with respect to pure gas hydrate system has been developed and applied to semiclathrate hydrate of TBAB with several gases as vip molecules. The developed correlation is found to predict the promotion effect satisfactorily for the system studied.展开更多
In this paper,a comprehensive understanding of stable and metastable phase equilibria in binary Mg-Gd system was conducted with an aid of the CALculation of PHAse Diagram(CALPHAD)modeling.Firstly,thermodynamic descrip...In this paper,a comprehensive understanding of stable and metastable phase equilibria in binary Mg-Gd system was conducted with an aid of the CALculation of PHAse Diagram(CALPHAD)modeling.Firstly,thermodynamic descriptions of all the stable phases in the Mg-Gd system were re-assessed by considering all the experimental data in the literature.The discrepancy between the phase equilibria and thermochemical properties existing in the previous assessments was eliminated,and the better agreement with the experimental data was achieved in the present assessment.Secondly,the Gibbs energies for metastable β"-Mg3Gd and β"-Mg7Gd were constructed based on the first-principles and CALPHAD computed results as well as their correlation,and then incorporated into the CALPHAD descriptions.The model-predicted solvuses of(Mg)in equilibrium with the metastable β"-Mg7Gd and β'-Mg7Gd compounds showed very good agreement with the limited experimental data.Finally,the presently obtained thermodynamic descriptions of both stable and metastable phases in the binary Mg-Gd system were further validated by realizing the quantitative Scheil-Gulliver solidification simulations of 5 as-cast Mg-Gd alloys,and the successful prediction of the precipitation sequences in Mg-15Gd and Mg-12Gd alloys during the aging process.展开更多
In this paper, a back propagation artificial neural network （BP-ANN） model is presented for the simultaneous estimation of vapour liquid equilibria （VLE） of four binary systems viz chlorodifluoromethan-carbondioxi...In this paper, a back propagation artificial neural network （BP-ANN） model is presented for the simultaneous estimation of vapour liquid equilibria （VLE） of four binary systems viz chlorodifluoromethan-carbondioxide, trifluoromethan-carbondioxide, carbondisulfied-trifluoromethan and carbondisulfied-chlorodifluoromethan. VLE data of the systems were taken from the literature for wide ranges of temperature （222.04-343.23K） and pressure （0.105 to 7.46MPa）. BP-ANN trained by the Levenberg-Marquardt algorithm in the MATLAB neural network toolbox was used for building and optimizing the model. It is shown that the established model could estimate the VLE with satisfactory precision and accuracy for the four systems with the root mean square error in the range of 0.054-0.119. Predictions using BP-ANN were compared with the conventional Redlich-Kwang-Soave （RKS） equation of state, suggesting that BP-ANN has better ability in estimation as compared with the RKS equation （the root mean square error in the range of 0.115-0.1546）.展开更多
Experimental data on the solubility of D-glucose,D-fructose and sucrose in the mixed solvents com-posed of water and ethanol from 273.2 to 293.2 K were determined.The solubility of D-glucose,D-fructose and sucrose dec...Experimental data on the solubility of D-glucose,D-fructose and sucrose in the mixed solvents com-posed of water and ethanol from 273.2 to 293.2 K were determined.The solubility of D-glucose,D-fructose and sucrose decreased as the ethanol content increased in the mixed solvent.The solubility of D-glucose,D-fructose and sucrose decreased with decreasing equilibrium temperature.The modified UNIQUAC model,S-UNIFAC model and mS-UNIFAC model were applied to predict the solid-liquid equilibria.The prediction results were compared and discussed.Better prediction accuracy was generated using the modified UNIQUAC model.展开更多
Phase equilibrium in Nb-Si-Mo ternary alloys （〈37.5 at.% Si） at 1 273 K and 2 073 K is investigated by using X-ray diffraction （XRD） analysis, scanning electron microscopy （SEM） and energy dispersive spectrosco...Phase equilibrium in Nb-Si-Mo ternary alloys （〈37.5 at.% Si） at 1 273 K and 2 073 K is investigated by using X-ray diffraction （XRD） analysis, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS）. The partial isothermal section at 1 273 K, which contains four single-phase regions, five two-phase regions and two three-phase regions, is basically the same as that at 1 973 K. However, when the temperature increases to 2 073 K, the three-phase region of Nbss＋ct-（Nb（Mo））sSi3＋13-（Nb,Mo）sSi3 obviously moves towards the Nb-rich comer. This suggests that Nb-Si-Mo ternary alloys remain stable at least up to 1 973 K.展开更多
The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzh...The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzhou area. Garnet amphiholites and garnet granulites are two kinds of typical lower-crustal xenoliths and were selected to reconstruct different stages of the metamorphic process. In this study, in view of multistage metamorphic evolution and reworking, phase equilibria modeling was used for the first time to better constrain peak P-T conditions of the xenoliths. Some porphyroblastic garnets have a weak zonal structure in composition with homogeneous cores and were surrounded by thin rims with an increase in XMg and a decrease in X Ca （or X Mg）- Clinopyroxene contain varying amounts of Na2O and Al2O3 as well as amphibole of TiO2, while plagioclases are different in calcium contents. Peak metamorphic P-T conditions are calculated by the smallest garnet x（g） （Fe2＋/（Fe2＋＋Mg）） contours and the smallest plagioclase ca（pl） （Ca/（Ca＋Na）） contours in NCFMASHTO （Na2O-CaO-FeO-MgO-Al2O3-SiO2- H20-TiO2-Fe2O3） system, which are consistent with those estimated by conventional geothermobarometry. The new results show that the peak and decompressional P-T conditions for the rocks are 850-900 ℃/ 1.4-1.6 GPa and 820-850 ℃/0.9-1.3 GPa, respectively, suggestive of high and middle-low pressure granulite-facies metamorphism. Combined with previous zircon U-Pb dating and conventional geothermobarometry data, it is indicated that the xenoliths experienced a clockwise P-T-t evolution with nearisothermal deeompressional process, suggestive of the Paleoproterozoic subduction-collision setting. In this regard, the studied region together with Jiao-Liao-Ji belt is further documented to make up a Paleopro- terozoic collisional orogen in the eastern block of the NCC.展开更多
Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure...Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure.It is shown that the solubilities of trans-1,2-cyclohexanediol in butyl acetate+water were affected greatly by the proportion of butyl acetate and water,and presented maximum value at given temperature.The UNIFAC model was used to correlate the experimental data.The average relative deviation(ARD)between experimental and calculated values is 3.03%.展开更多
An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering ...An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering a wide range from 2.98×10~3 to 3.84×10~6 were obtained at 35℃.The reduced pressure p/p°versus weight fraction W plot is found to be independent on the molecularweight of the polymer within the experimental error.Calculated activity coefficients are also independenton the molecular weight.However,for the Flory-Huggins interaction parameter x,not only a strongconcentration dependence is observed,but also the molecular weight of the polymer exerts definiteinfluence.Generally,the parameter x slightly increases as the molecular weight of the polymer decreasesespecially when the molecular weight is low.The dependence of the parameter x on the molecularweight can be neglected when the molecular weight of polymer is greater than 1.00×10~4.展开更多
The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems cont...The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems containing different imidazolium–based ionic liquids(ILs),i.e.MeOH+DMC+1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),and MeOH+DMC+1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])were measured at 101.3 kPa.The mole fraction of IL was varied from0.05 to 0.20.The experimental data were correlated with the NRTL and Wilson equations,respectively.The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and[Bmim][Tf2 N]showed a much more excellent performance on the activity coefficient of MeOH.The interaction energies of system components were calculated using Gaussian program,and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.展开更多
The Levenberg-Marquardt method, the best algorithm to obtain the least-square solution of nonlinear equations, is applied to calculate the stable phase equilibria. It can get the best combination between robustness an...The Levenberg-Marquardt method, the best algorithm to obtain the least-square solution of nonlinear equations, is applied to calculate the stable phase equilibria. It can get the best combination between robustness and speed of the calculations. Its application to ternary AI-Si-Mg system is executed in detail. The calculated phase equilibria agree well with the experimental results. Furthermore, the Levenberg-Marquardt method is not sensitive to the initial values.展开更多
基金supported by the National Natural Science Foundation of China(U1507111).
文摘The phase equilibria relationship of the system RbCl-PEG6000-H2O were investigated at temperatures of 288.2,298.2,and 308.2 K,the compositions of solid-liquid equilibria(SLE)and liquid-liquid equilibria(LLE)were determined.The complete phase diagrams,binodal curve diagrams,and tie-line diagrams were all plotted.Results show that both solid-liquid equilibria and liquid-liquid equilibria relationships at each studied temperature.The complete phase diagrams at 288.2 K,298.2 K and 308.2 K consist of six phase regions:unsaturated liquid region(L),two saturated solutions with one solid phase of RbCl(L_S),one saturated liquid phase with two solid phases of PEG6000 and RbCl(2S+L),an aqueous two-phase region(2L),and a region with two liquids and one solid phase of RbCl(2L_S).With the increase in temperature,the layering ability of the aqueous two-phase system increases,and both regions(2L)and(2L_S)increase.The binodal curves were fitted using the nonlinear equations proposed by Mistry,Hu,and Jayapal.Additionally,the tie-line data were correlated with the Othmer-Tobias,Bancroft,Hand,and Bachman equations.The liquid-liquid equilibria at 288.2 K,298.2 K and 308.2 K were calculated using the NRTL model.The findings confirm that the experimental and calculated values are in close agreement,demonstrating the model’s effectiveness in representing the system’s behavior.
基金financial support by the National Key Research and Development Program of China(No.2023YFB3809101)the National Natural Science Foundation of China(Nos.52371010 and 52422407)+1 种基金the Science and Technology Committee of Shanghai,China(No.21ZR1423600)the Open Project of State Key Laboratory of Baiyunobo Rare Earth Resources Researches and Comprehensive Utilization,China.
文摘Mg-Zn-Mn alloys have the advantages of low cost,excellent mechanical properties,and high corrosion resistance.To clarify the phase equilibria of Mg-Zn-Mn alloy in the Mg-rich corners,the present work experimentally investigated the phase equilibria in the Mg-rich corner at 300-400°C with equilibrated alloy method using electron probe micro analyzer(EPMA),X-ray diffractometer(XRD),transmission electron microscopy(TEM),and differential scanning calorimeter(DSC).Mn atoms were found to dissolve into MgZn_(2) to form a ternary solid-solution type compound,in which Mn content can be up to 15.1at%at 400°C.Three-phase equilibrium ofα-Mg+MgZn_(2)+α-Mn and liquid+α-Mg+MgZn_(2) were confirmed at 400°C.Subsequently,thermodynamic modeling of the Mg-Zn-Mn system was carried out using the CALPHAD method based on the experimental data of this work and literature data.The calculated invariant reaction Liquid+α-Mn→α-Mg+MgZn_(2) at 430°C shows good agreement with the DSC results.In addition,the results of solidification path calculations explain the microstructure in the ascast and annealed alloys well.The agreement between the calculated results and experimental data proves the self-consistency of the thermodynamic database,which can provide guidance for the compositional design of Mg-Zn-Mn alloys.
基金supports on the Project 52274306 from the National Natural Science Foundation of China are gratefully acknowledged.
文摘Understanding the phase equilibria of the Fe_(3)O_(4)-Cr_(2)O_(3)-CaO system is essential for the efficient recycling of stainless steel pickling sludge.The isothermal section of this system at 1473 K under oxygen partial pressure of 0.15 Pa was investigated.Key experiments on the relevant binary systems were conducted using a combination of equilibrium-quenching techniques,X-ray diffraction,high-resolution transmission electron microscope,and electron probe microanalysis.These systems were rigorously assessed using the CALPHAD(CALculation of Phase Diagram)method,incorporating the present experimental data.The liquid phase was modeled using the ionic two-sublattice model,represented as(Ca^(2+),Cr^(3+),Fe^(2+))P(O_(2)^(-),Va,FeO_(1.5))Q,where Va represents vacancy,and P and Q denote the number of sites on the cation and anion sublattices,respectively.To ensure electroneutrality,the values of P and Q adjust according to the composition of the mixture.From this,the isothermal section of the Fe_(3)O_(4)-Cr_(2)O_(3)-CaO system at 1473 K under the specified oxygen partial pressure was obtained based on the thermodynamic parameters of the binary systems.The present experimental data and calculation results hold significant implications for the comprehensive recycling of stainless steel pickling sludge.
基金financially supported by the National Natural Science Foundation of China(No.52204310)the China Postdoctoral Science Foundation(Nos.2020TQ0059 and 2020M570967)+3 种基金the Natural Science Foundation of Liaoning Province,China(No.2021-MS-083)the Fundamental Research Funds for the Central Universities(No.N2125010)the Open Project Program of Key Laboratory of Metallurgical Emission Reduction&Resources Recycling(Anhui University of Technology)of Ministry of Education(No.JKF22-02)the Key Laboratory for Anisotropy and Texture of Materials of Ministry of Education.
文摘The efficient recycling of vanadium from converter vanadium-bearing slag is highly significant for sustainable development and circular economy.The key to developing novel processes and improving traditional routes lies in the thermodynamic data.In this study,the equilibrium phase relations for the Fe_(2)O_(3)-TiO_(2)-V_(2)O_(5)system at 1200℃in air were investigated using a high-temperature equilibrium-quenching technique,followed by analysis using scanning electron microscopy-energy dispersive X-ray spectrometer and X-ray photoelectron spectroscopy.One liquid-phase region,two two-phase regions(liquid-rutile and liquid-ferropseudobrookite),and one three-phase region(liquid-rutile-ferropseudobrookite)were determined.The variation in the TiO_(2)and V_(2)O_(5)contents with the Fe_(2)O_(3)content was examined for rutile and ferropseudobrookite solid solutions.However,on further comparison with the predictions of FactSage 8.1,significant discrepancies were identified,highlighting that greater attention must be paid to updating the current thermodynamic database related to vanadium-bearing slag systems.
基金Supported by the National Key Research and Development Program of China(2023YFC2906503)Sichuan Province Science and Technology Support Program(2023ZYD0036).
文摘In order to obtain the crystalline forms of the salts of the potassium,ammonium,calcium coexisting chloride system,the phase equilibria relationship of quaternary system K^(+),NH_(4)^(+),Ca^(2+)//Cl^(-)-H_(2)O at 298.2,323.2,and 348.2 K was studied by isothermal dissolution equilibrium method.The solubility and density of equilibrium liquid phases of the system were experimentally determined;X-ray powder diffractometer was used to determine the compositions of the equilibrium solid phase at the quaternary invariant point.It is found that the quaternary system is a complex system at these three temperatures.The phase diagram at 298.2 K consists of three invariant points,seven univariate curves and five crystalline phase regions,forming the solid solutions(NH_(4)Cl)_(x)(KCl)_(1-x) and(KCl)_(x)(NH_(4)Cl)_(1-x);while at 323.2 and 348.2 K the phase diagram consists of five invariant points,eleven univariate curves and seven crystalline phase regions,the double salts(KClCaCl_(2))and(2NH_(4)Cl·CaCl_(2)·3H_(2)O),solid solutions(KCl)_(x)(NH_(4)Cl)_(1-x) and(NH_(4)Cl)_(x)(KCl)_(1-x) were formed.Among them,the crystalline phase region of solid solution(KCl)_(x)(NH_(4)Cl)_(1-x) is the largest at three temperatures,indicating that it is the easiest to crystallize in this system.Comparing the phase diagrams of the quaternary system at 298.2,323.2,and 348.2 K,it can be seen that the crystalline form of CaCl_(2) changes with the increase of temperature:CaCl_(2)·6H_(2)O at 298.2 K,CaCl_(2)·2H_(2)O at 323.2 and 348.2 K.From 323.2 to 348.2 K,the crystalline phase regions of(KCl·CaCl_(2))and(2NH_(4)Cl·CaCl_(2)·3H_(2)O)increased gradually.
文摘Erratum to:RareMet.D0I 10.1007/s12598-015-0590-6 Unfortunately,in the original publication of the article the author name and the mol value present in Sect.2.2 have appeared incorrectly as below.
基金NSFC grant(No.11771201)by the fund of the Guangdong Provincial Key Laboratory of Computational Science and Material Design(No.2019B030301001)。
文摘We construct new HLL-type moving-water equilibria preserving upwind schemes for the one-dimensional Saint-Venant system of shallow water equations with nonflat bottom topography.The designed first-and secondorder schemes are tested on a number of numerical examples,in which we verify the well-balanced property as well as the ability of the proposed schemes to accurately capture small perturbations of moving-water steady states.
文摘In this article VLE data for a ternary system (propylene-methanol-water) under 30～60 C,0. 3～0. 9 MPa with a mass ratio of methanol to water of 9:1, 8: 2, 7: 3 were determined with a static equilibrium still, and were correlated by using Peng-Robinson model. The average relative error ofpropylene concentration in liquid phase is 1. 46 %. The results indicate that the models are very suitablefor the ternary system and the data are reliable.
基金Supported by the National Key Research and Development Program of China(2016YFB0600504)
文摘The pseudo-ternary system(Na Cl + Na_2SO_4+ H_2O) of coal gasification wastewater was studied at T =(268.15 to 373.15) K. The solubility and density of the equilibrium liquid phase were determined by the isothermal solution saturation method. The equilibrium solids were also investigated by the Schreinemaker's method of wet residues and X-ray powder diffraction(XRD). According to the experimental data, the phase diagrams were determined. It was found that there was no significant solubility difference on the Na Cl-rich side between the ternary system(Na Cl + Na_2SO_4+ H_2O) in coal gasification wastewater and in pure water. However, the solubility on the Na_2SO_4-rich side of coal gasification wastewater was apparently higher than that of pure water. The increase in the solubility of Na_2SO_4 was most likely caused by the effects of other impurities apart from Na Cl and Na_2SO_4 in coal gasification wastewater. The measured data and phase equilibrium diagrams can provide fundamental basis for salt recovery in coal gasification wastewater.
基金National High-tech Research and Development Pro-gram(2006AA03Z102)Aeronautical Science Foundation of China(2006ZF51069)
文摘To determine the liquid-solid phase equilibria of the Nb-Si-Ti ternary system, Nb-Si-Ti alloys of different compositions are prepared. By means of scanning electron microscopy （SEM）, X-ray diffraction （XRD） and electron probe microanalysis （EPMA）, the phases in the alloys, such as Si-based solutions, Ti（Nb）Si, Ti（Nb）Si2, Nb（Ti）Si2, Ti（Nb）5Si4, Nb（Ti）5Si3, Ti（Nb）5Si3, Nb（Ti）3Si and Nb-based solutions are identified, and the phase evolution is analyzed. As a result, the microstmctural and microchemical evidence provides a clear definition of the Nb-Si-Ti liquidus surface projection and indicates that the ternary phase diagram has seven transition reactions.
基金supported by the the Industrial Consultancy and Sponsored Research (ICSR),Indian Institute of Technology Madras,Chennai (Project Number OEC/10 11/530/NFSC/JITE)the National Institute of Ocean Technology (NIOT),Chennai,India (Project Number OEC/10-11/105/NIOT/JITE)
文摘Semiclathrate hydrates of tetra-n-butyl ammonium bromide （TBAB） offer potential solution for gas storage, transportation, separation of flue gases and CO2 sequestration. Models for phase equilibria for these systems have not yet been developed in open literatures and thus require urgent attention. In this work, the first attempt has been made to model phase equilibria of semiclathrate hydrates of CH4, CO2 and N2 in aqueous solution of TBAB. A thermodynamic model for gas hydrate system as proposed by Chen and Guo has been extended for semiclathrate hydrates of gases in aqueous solution of TBAB. A correlation for the activity of water relating to the system temperature, concentration of TBAB in the system and the nature of vip gas molecule has been proposed. The model results have been validated against available experimental data on phase equilibria of semiclathrate hydrate systems of aqueous TBAB with different gases as vip molecule. The extended Chen and Guo＇s model is found to be suitable to explain the promotion effect of TBAB for the studied gaseous system such as, methane, carbon dioxide and nitrogen as a vip molecule. Additionally, a correlation for the increase in equilibrium formation temperature （hydrate promotion temperature, ATp） of semiclathrate hydrate system with respect to pure gas hydrate system has been developed and applied to semiclathrate hydrate of TBAB with several gases as vip molecules. The developed correlation is found to predict the promotion effect satisfactorily for the system studied.
基金The financial support from the National Key Research and Development Program of China(Grant no.2016YFB0301101)the Hunan Provincial Science and Technology Program of China(Grant no.2017RS3002)-Huxiang Youth Talent Plan+2 种基金the Youth Talent Project of Innovation-driven Plan at Central South University(Grant no.2019XZ027)the Hebei Provincial Science and Technology Program of China(Grant no.BJ2018026)-Outstanding Young Talents Plan is acknowledgedYing Tang acknowledges the financial support from the Yuanguang fellowship released by Hebei University of Technology.
文摘In this paper,a comprehensive understanding of stable and metastable phase equilibria in binary Mg-Gd system was conducted with an aid of the CALculation of PHAse Diagram(CALPHAD)modeling.Firstly,thermodynamic descriptions of all the stable phases in the Mg-Gd system were re-assessed by considering all the experimental data in the literature.The discrepancy between the phase equilibria and thermochemical properties existing in the previous assessments was eliminated,and the better agreement with the experimental data was achieved in the present assessment.Secondly,the Gibbs energies for metastable β"-Mg3Gd and β"-Mg7Gd were constructed based on the first-principles and CALPHAD computed results as well as their correlation,and then incorporated into the CALPHAD descriptions.The model-predicted solvuses of(Mg)in equilibrium with the metastable β"-Mg7Gd and β'-Mg7Gd compounds showed very good agreement with the limited experimental data.Finally,the presently obtained thermodynamic descriptions of both stable and metastable phases in the binary Mg-Gd system were further validated by realizing the quantitative Scheil-Gulliver solidification simulations of 5 as-cast Mg-Gd alloys,and the successful prediction of the precipitation sequences in Mg-15Gd and Mg-12Gd alloys during the aging process.
文摘In this paper, a back propagation artificial neural network （BP-ANN） model is presented for the simultaneous estimation of vapour liquid equilibria （VLE） of four binary systems viz chlorodifluoromethan-carbondioxide, trifluoromethan-carbondioxide, carbondisulfied-trifluoromethan and carbondisulfied-chlorodifluoromethan. VLE data of the systems were taken from the literature for wide ranges of temperature （222.04-343.23K） and pressure （0.105 to 7.46MPa）. BP-ANN trained by the Levenberg-Marquardt algorithm in the MATLAB neural network toolbox was used for building and optimizing the model. It is shown that the established model could estimate the VLE with satisfactory precision and accuracy for the four systems with the root mean square error in the range of 0.054-0.119. Predictions using BP-ANN were compared with the conventional Redlich-Kwang-Soave （RKS） equation of state, suggesting that BP-ANN has better ability in estimation as compared with the RKS equation （the root mean square error in the range of 0.115-0.1546）.
基金Supported by the National Science and Technology Major Project （2009ZX09313-036） the China Postdoctoral Science Foundation （20090461360） the Zhejiang Provincial Education Department Projects （Y200907556）
文摘Experimental data on the solubility of D-glucose,D-fructose and sucrose in the mixed solvents com-posed of water and ethanol from 273.2 to 293.2 K were determined.The solubility of D-glucose,D-fructose and sucrose decreased as the ethanol content increased in the mixed solvent.The solubility of D-glucose,D-fructose and sucrose decreased with decreasing equilibrium temperature.The modified UNIQUAC model,S-UNIFAC model and mS-UNIFAC model were applied to predict the solid-liquid equilibria.The prediction results were compared and discussed.Better prediction accuracy was generated using the modified UNIQUAC model.
基金National High-tech Research and Development Pro-gram (2006AA03Z102)Aeronautical Science Foundation of China (2006ZF51069)
文摘Phase equilibrium in Nb-Si-Mo ternary alloys （〈37.5 at.% Si） at 1 273 K and 2 073 K is investigated by using X-ray diffraction （XRD） analysis, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS）. The partial isothermal section at 1 273 K, which contains four single-phase regions, five two-phase regions and two three-phase regions, is basically the same as that at 1 973 K. However, when the temperature increases to 2 073 K, the three-phase region of Nbss＋ct-（Nb（Mo））sSi3＋13-（Nb,Mo）sSi3 obviously moves towards the Nb-rich comer. This suggests that Nb-Si-Mo ternary alloys remain stable at least up to 1 973 K.
基金financially supported by the National Natural Science Foundation of China (No. 41773020)the National Basic Research Program of China (No. 2015CB856104)the PhD Foundation of the Ministry of Education of China (No. 20133402130008)
文摘The Precambrian lower crust rocks at the southeastern margin of the North China Craton （NCC） are mainly exposed as granulite xenoliths hosted by Mesozoic dioritic porphyry and metamorphic terrains in the Xuzhou-Suzhou area. Garnet amphiholites and garnet granulites are two kinds of typical lower-crustal xenoliths and were selected to reconstruct different stages of the metamorphic process. In this study, in view of multistage metamorphic evolution and reworking, phase equilibria modeling was used for the first time to better constrain peak P-T conditions of the xenoliths. Some porphyroblastic garnets have a weak zonal structure in composition with homogeneous cores and were surrounded by thin rims with an increase in XMg and a decrease in X Ca （or X Mg）- Clinopyroxene contain varying amounts of Na2O and Al2O3 as well as amphibole of TiO2, while plagioclases are different in calcium contents. Peak metamorphic P-T conditions are calculated by the smallest garnet x（g） （Fe2＋/（Fe2＋＋Mg）） contours and the smallest plagioclase ca（pl） （Ca/（Ca＋Na）） contours in NCFMASHTO （Na2O-CaO-FeO-MgO-Al2O3-SiO2- H20-TiO2-Fe2O3） system, which are consistent with those estimated by conventional geothermobarometry. The new results show that the peak and decompressional P-T conditions for the rocks are 850-900 ℃/ 1.4-1.6 GPa and 820-850 ℃/0.9-1.3 GPa, respectively, suggestive of high and middle-low pressure granulite-facies metamorphism. Combined with previous zircon U-Pb dating and conventional geothermobarometry data, it is indicated that the xenoliths experienced a clockwise P-T-t evolution with nearisothermal deeompressional process, suggestive of the Paleoproterozoic subduction-collision setting. In this regard, the studied region together with Jiao-Liao-Ji belt is further documented to make up a Paleopro- terozoic collisional orogen in the eastern block of the NCC.
基金Supported by the Natural Science Foundation of Henan Province （No.0211020800）.
文摘Using a laser observation technique,the solubilities of trans-1,2-cyclohexanediol in butyl acetate+wa- ter were measured at the temperature range from 298.15K to 323.15K by a synthetic method at atmospheric pres- sure.It is shown that the solubilities of trans-1,2-cyclohexanediol in butyl acetate+water were affected greatly by the proportion of butyl acetate and water,and presented maximum value at given temperature.The UNIFAC model was used to correlate the experimental data.The average relative deviation(ARD)between experimental and calculated values is 3.03%.
文摘An experimental system for measuring the VLE of polymer solutions based on the staticvapor-pressure method has been established,VLE data for mixtures of toluene and polystyrene withdifferent molecular weight covering a wide range from 2.98×10~3 to 3.84×10~6 were obtained at 35℃.The reduced pressure p/p°versus weight fraction W plot is found to be independent on the molecularweight of the polymer within the experimental error.Calculated activity coefficients are also independenton the molecular weight.However,for the Flory-Huggins interaction parameter x,not only a strongconcentration dependence is observed,but also the molecular weight of the polymer exerts definiteinfluence.Generally,the parameter x slightly increases as the molecular weight of the polymer decreasesespecially when the molecular weight is low.The dependence of the parameter x on the molecularweight can be neglected when the molecular weight of polymer is greater than 1.00×10~4.
基金supported by the National Key R&D Program of China(2018YFB0605804)the National Natural Science Foundation of China(21606237)+2 种基金the Transformational Technologies for Clean Energy and Demonstration,Strategic Priority Research Program of the Chinese Academy of Sciences(XDA 21030500)the Fund of State Key Laboratory of Multiphase Complex Systems,IPE,CAS(MPCS-2019-A-02)the DNL Cooperation Fund,CAS(DNL180202)。
文摘The separation of methanol(MeOH)and dimethyl carbonate(DMC)is important but difficult due to the formation of an azeotropic mixture.In this work,isobaric vapor–liquid equilibrium(VLE)data for the ternary systems containing different imidazolium–based ionic liquids(ILs),i.e.MeOH+DMC+1-butyl-3-methy-limidazolium bis[(trifluoromethyl)sulfonyl]imide([Bmim][Tf2N]),MeOH+DMC+1-ethyl-3-methyl-imidazolium bis[(trifluoromethyl)sulfonyl]imide([Emim][Tf2N]),and MeOH+DMC+1-ethyl-3-methylimidazolium hexafluorophosphate([Emim][PF6])were measured at 101.3 kPa.The mole fraction of IL was varied from0.05 to 0.20.The experimental data were correlated with the NRTL and Wilson equations,respectively.The results show that imidazolium-based ILs were beneficial to improve the relative volatility of MeOH to DMC,and[Bmim][Tf2 N]showed a much more excellent performance on the activity coefficient of MeOH.The interaction energies of system components were calculated using Gaussian program,and the effects of cation and anion on the separation coefficient of the azeotropic system were discussed.
基金This research is supported by the State Key Fundamental Research Project(G2000067202-1).
文摘The Levenberg-Marquardt method, the best algorithm to obtain the least-square solution of nonlinear equations, is applied to calculate the stable phase equilibria. It can get the best combination between robustness and speed of the calculations. Its application to ternary AI-Si-Mg system is executed in detail. The calculated phase equilibria agree well with the experimental results. Furthermore, the Levenberg-Marquardt method is not sensitive to the initial values.
