The direct reduction process can reduce carbon emissions by over 50%compared to traditional blast furnace ironmaking.Carbon deposition and carburization are critical for ensuring process stability and economic viabili...The direct reduction process can reduce carbon emissions by over 50%compared to traditional blast furnace ironmaking.Carbon deposition and carburization are critical for ensuring process stability and economic viability.Thermodynamic phase diagrams were developed to intuitively represent carbon deposition and carburization preferences in CH4-CO-H_(2) ternary atmospheres.High carbon potential and low oxygen potential significantly enhance carbon deposition and carburization.Increasing temperature from 500 to 1000℃ shifts the dominant reactions from CO-based to CH_(4)-based,increasing maximum carbon deposition from 0.55 to 0.80 mol and carburization from 0.25 to 0.80 mol per mole of reducing gas.Increasing pressure suppresses CH4-based reactions while promoting CO-based reactions,reducing maximum carbon deposition from 0.8 to~0.7 mol and increasing maximum carburization from 0.80 to 0.85 mol per mole of reducing gas.Equilibrium phase diagrams for various carbides were also developed,revealing preferences for Fe_(3)C_(2),Fe_(7)C_(3),Fe_(5)C_(2),and Fe_(3)C as the Fe/C ratio increases.Higher temperatures and CH_(4) concentrations favor the formation of carbides with higher carbon content.Carburization preferences under typical Energiron ZR and Midrex atmospheres were highlighted,and the higher carbon content in direct reduction iron produced by the Energiron ZR process was thermodynamically confirmed.展开更多
High cost of raw materials and the insufficient research on alloy systems severely constrained the development of Cu-Be alloys.The complex coupling relationship between composition and preparation process poses challe...High cost of raw materials and the insufficient research on alloy systems severely constrained the development of Cu-Be alloys.The complex coupling relationship between composition and preparation process poses challenges to the use of machine learning methods for the precise design of Cu-Be alloy.This study develops a novel method for integrated design of copper alloy composition and processing based on a Long Short-Term Memory model followed by an Encoder model(LSTM-Encoder)and enriches the framework by integrating phase diagram information.This approach not only capitalizes on the patterns of microstructural evolution during heat treatment as indicated in phase diagrams to reveal their intrinsic links with alloy performance but also eliminates cross-interference within sample data,thus significantly enhancing the model's generalization and predictive accuracy,which achieves high efficient and precise design of low-cost(low Be content) and high-performance Cu-Be alloys.Compared with other models,the LSTM-Encoder model incorporating phase diagram information(LSTM-Encoder-Ⅱ) showed significant superiority in prediction accuracy.After two rounds of experimental verification and iteration,the LSTM-Encoder-Ⅱ model attained prediction accuracies of 96% for hardness and 93% for electrical conductivity.Various Cu-Be-X alloys with excellent comprehensive performance and low cost have been designed,and Cu-1.5Be-0.1Ni-0.3Co alloy achieves a tensile strength of 1211 MPa and an electrical conductivity of 30.3% IACS,and Cu-1.5Be-0.6Ni alloy attains a tensile strength of1290 MPa and an electrical conductivity of 29.3% IACS,both of which are comparable to the C17200 alloy,with raw material cost reduced by more than 14%.展开更多
The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block ...The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.展开更多
Thermodynamic optimization of the AF-BeF_(2)(A=K,Rb,and Cs),KF-CsF,and RbF-CsF systems was performed within the framework of phase diagrams calculation.The model parameters were optimized based on experimental data an...Thermodynamic optimization of the AF-BeF_(2)(A=K,Rb,and Cs),KF-CsF,and RbF-CsF systems was performed within the framework of phase diagrams calculation.The model parameters were optimized based on experimental data and theoretically calculated values.The results show that the thermodynamically calculated values for the AF-BeF_(2)(A=K,Rb,and Cs),KF-CsF,and RbF-CsF systems agree well with the experimental data.Next,a set of reliable and self-consistent thermodynamic databases was built,and the liquidus projections and invariant points of the sub-ternary systems of the KF-RbF-CsF-BeF_(2)system were calculated.Furthermore,the melting temperature with the corresponding composition was predicted using the phase diagrams calculation technique,and the radial distribution functions,coordination numbers,angular distribution functions,and diffusion coefficients of the quaternary KF-RbF-CsF-BeF_(2)system were calculated using ab initio molecular dynamics.The results show that the quaternary KF-RbF-CsF-BeF_(2)system with the proportion 3.50-28.92-21.78-45.80 mol%or 1.80-35.42-52.40-10.38 mol%is one of the most promising candidate coolants for molten salt reactors in terms of thermodynamics and kinetics.This work provides direct guidelines for the screening and optimization of molten salts in the nuclear energy field.展开更多
Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulf...Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulfur(S_(8))[1].However,the electrochemical conversion reaction of S_(8) is an exceedingly complex process that involves the generation of multiple intermediates(e.g.,lithium polysulfides(LiPSs))and multiphase transitions[1,2].Currently,the mechanistic investigations of the electrochemical conversion reaction of S_(8) upon discharging a LSB cell heavily rely on electrochemical titration and spectroscopic techniques[3].Nevertheless,the considerable complexity and intrinsic instability of the LSB system present substantial obstacles to obtaining accurate information for all sulfur-containing species,which significantly obstructs in-depth elucidation of the fundamental discharge mechanism of LSB[3,4].展开更多
Taking Au?Cu system as an example, three discoveries and two methods were presented. First, a new way for boosting sustainable progress of systematic metal materials science (SMMS) and alloy gene engineering (AGE) is ...Taking Au?Cu system as an example, three discoveries and two methods were presented. First, a new way for boosting sustainable progress of systematic metal materials science (SMMS) and alloy gene engineering (AGE) is to establish holographic alloy positioning design (HAPD) system, of which the base consists of measurement and calculation center, SMMS center, AGE center, HAPD information center and HAPD cybernation center; Second, the resonance activating-sychro alternating mechanism of atom movement may be divided into the located and oriented diffuse modes; Third, the equilibrium and subequilibrium holographic network phase diagrams are blueprints and operable platform for researchers to discover, design, manufacture and deploy advanced alloys, which are obtained respectively by the equilibrium lever numerical method and cross point numerical method of isothermal Gibbs energy curves. As clicking each network point, the holographic information of three structure levels for the designed alloy may be readily obtained: the phase constitution and fraction, phase arranging structure and properties of organization; the composition, alloy gene arranging structure and properties of each phase and the electronic structures and properties of alloy genes. It will create a new era for network designing advanced alloys.展开更多
Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing exp...Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing experimental phenomena of alloy phase transitions during extremely slow variation in temperature by equilibrium thinking mode and then taking erroneous knowledge of experimental phenomena as selected information for establishing Gibbs energy function and so-called equilibrium phase diagram. Second, the equilibrium holographic network phase diagrams of AuCu3-type sublattice system may be used to describe systematic correlativity of the composition?temperature-dependent alloy gene arranging structures and complete thermodynamic properties, and to be a standard for studying experimental subequilibrium order-disorder transition. Third, the equilibrium transition of each alloy is a homogeneous single-phase rather than a heterogeneous two-phase, and there exists a single-phase boundary curve without two-phase region of the ordered and disordered phases; the composition and temperature of the top point on the phase-boundary curve are far away from the ones of the critical point of the AuCu3 compound.展开更多
Taking Au3Cu-type sublattice system as an example, three discoveries have been presented. First, the fourth barrier to hinder the progress of metal materials science is that today’s researchers do not understand that...Taking Au3Cu-type sublattice system as an example, three discoveries have been presented. First, the fourth barrier to hinder the progress of metal materials science is that today’s researchers do not understand that the Gibbs energy function of an alloy phase should be derived from Gibbs energy partition function constructed of alloy gene sequence and their Gibbs energy sequence. Second, the six rules for establishing alloy gene Gibbs energy partition function have been discovered, and it has been specially proved that the probabilities of structure units occupied at the Gibbs energy levels in the degeneracy factor for calculating configuration entropy should be degenerated as ones of component atoms occupied at the lattice points. Third, the main characteristics unexpected by today’s researchers are as follows. There exists a single-phase boundary curve without two-phase region coexisting by the ordered and disordered phases. The composition and temperature of the top point on the phase-boundary curve are far away from those of the critical point of the Au3Cu compound; At 0 K, the composition of the lowest point on the composition-dependent Gibbs energy curve is notably deviated from that of the Au3Cu compounds. The theoretical limit composition range of long range ordered Au3Cu-type alloys is determined by the first jumping order degree.展开更多
In the course of the basic research on the ammonia-evaporation reaction of manganese monoxide （MnO）, hydroxyl manganese chloride （Mn2（OH）3Cl） was found. The solubility and phase diagrams of the hydroxyl manganes...In the course of the basic research on the ammonia-evaporation reaction of manganese monoxide （MnO）, hydroxyl manganese chloride （Mn2（OH）3Cl） was found. The solubility and phase diagrams of the hydroxyl manganese chloride were investigated. The aqueous thermostat and vibrating bed were used to determine the solubility of hydroxyl manganese chloride in water, ammonium chloride and manganese chloride system, and the phase diagrams of multicomponent system were drawn. The research results indicate that hydroxyl manganese chloride has been produced in laboratory and is in favor of the solid-liquid separation at high temperature.展开更多
The Ce-La-O system was investigated via experiments and thermodynamic modeling. A series of CeO2-LaO1.5 mixtures were prepared by co-precipitation technique and examined by X-ray diffraction. Mutual solubilities betwe...The Ce-La-O system was investigated via experiments and thermodynamic modeling. A series of CeO2-LaO1.5 mixtures were prepared by co-precipitation technique and examined by X-ray diffraction. Mutual solubilities between LaO1.5 and CeO2 at 1273 K were determined. Using the new experimental data together with literature information, a set of self-consistent thermodynamic parameters for the CeO2-LaO1.5 system were optimized. Combined with thermodynamic descriptions of Ce-O and La-O systems from literature, several property diagrams of Ce-La-O system were calculated and used to explain oxidation process of the Ce-La alloys. The fluorite phase is the unique oxidation products for most of the Ce-La alloys.展开更多
Based on thermodynamic equilibrium theory,a chemical equilibrium model for GaN g rowth is given in electron cyclotron resonance plasma enhanced metalorganic chem ical vapor deposition (ECR-PEMOCVD) system.Calculation ...Based on thermodynamic equilibrium theory,a chemical equilibrium model for GaN g rowth is given in electron cyclotron resonance plasma enhanced metalorganic chem ical vapor deposition (ECR-PEMOCVD) system.Calculation indicates that the growt h driving force are functions of growth conditions:group Ⅲ input partial press ure,input Ⅴ/Ⅲ ratio,and growth temperature.Furthermore,the growth phase diag rams of hexagonal and cubic GaN film growth are obtained,which are consistent wi th our experimental conditions to some extent.Through analysis,it is explained t he reason that high temperature and high input Ⅴ/Ⅲ ratio are favorable for he xagonal GaN film growth.This model can be extended to the similar systems used f or GaN single-crystal film growth.展开更多
Recent progress on research activities of phase diagrams in our laboratory has been presented. Experimental studies and thermodynamic calculations based on CALPHAD (Calculation of Phase Diagrams) method have been cond...Recent progress on research activities of phase diagrams in our laboratory has been presented. Experimental studies and thermodynamic calculations based on CALPHAD (Calculation of Phase Diagrams) method have been conducted in the following alloy systems.1.Database on microalloying steels including carbide, nitride and sulfide is now being constructed.2.ADAMIS (Alloy Database for Micro-Solders) containing 8 elements of Ag, Bi, Cu,In, Sb, Sn, Zn and Pb has been constructed, which can handle all combinations of these elements and all composition ranges.3.A thermodynamic database of Cu-base alloys including Cu-X binary system and Cu-Fe, Cu-Ni, Cu-Cr base ternary systems has been constructed.4.Experimental and thermodynamic calculations on Fe, Ni, Co and Ti aluminides have been conducted.5.Experimental and thermodynamic calculations on Co base magnetic recording media have been conducted.6.Thermodynamic analysis of interaction between magnetic and chemical orderings has been performed.By utilizing the information on phase diagrams, the following advanced materials have been developed. (A)New type of high speed steel with high hardness about Hv≈1000 by carbide dispersion carburizing method. (B)New Pb-free machinable stainless steel using titanium carbosulphide. (C)New Pb-free solder for Die-attaching use. (D)Shape memory alloys; Cu-base, Ferromagnetic Ni-base and Fe-base. (E)Invar alloys. (F)Egg-type powder.Typical examples of phase diagrams, phase stability, database and its application for the development of advanced materials will be presented.展开更多
The databases of the FactSage thermodynamic computer system have been under development for 30 years. These databases contain critically evaluated and opthnized data for thousands of compounds and hundreds of multicom...The databases of the FactSage thermodynamic computer system have been under development for 30 years. These databases contain critically evaluated and opthnized data for thousands of compounds and hundreds of multicomponent solutions of solid and liquid metals, oxides, salts, sulfides, etc. The databases are automatically accessed by user-friendly software that calculates complex multiphase equilibria in large multicomponent systems for a wide variety of possible input/output constraints. The databases for solutions have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for different types of solutions involving sublattices, ordering, etc. Through the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits and permit extrapolation into regions of tempea＇ature and composition where data are unavailable. The present article focuses on the databases for solid and liquid oxide phases involving 25 elements. A short review of the available databases is presented along with the models used for the molten slag and the solid solutions such as spinel, pyroxene, olivine, monoxide, corundum, etc. The critical evaluation/optimization procedure is outlined using examples from the Al203-SiO2-CaO-FeO-Fe2O3 system. Sample calculations are presented in which the oxide databases are used in conjunction with the FactSage databases for metallic and other phases. In particular, the use of the FactSage module for the calculation of multicomponent phase diagrams is illustrated.展开更多
Thermodynamic optimization of the binary rare earth alloy(Cee La, Cee Pr, Cee Nd and Lae Nd) systems was performed in this work through the CALPHAD method based on the critical evaluation of all available phase diagra...Thermodynamic optimization of the binary rare earth alloy(Cee La, Cee Pr, Cee Nd and Lae Nd) systems was performed in this work through the CALPHAD method based on the critical evaluation of all available phase diagram and thermodynamic data reported in the literature. During the thermodynamic modeling, the solution phases including liquid, bcc, fcc and dhcp, were treated as the substitutional solution model. Thermodynamic parameters of the stable phases in the Cee La, Cee Pr, Cee Nd and Lae Nd binary systems are obtained finally and would be used directly to develop the thermodynamic database of the multi-component Nde Fee B-based alloys, which is indispensable for designing alloy compositions and processes of Nde Fee B permanent magnets with highly abundant rare earth metals.展开更多
Mg-rare earth(RE)based systems provide several important commercial alloys and many alloy development opportunities for high strength applications,especially in aerospace and defense industries.The phase diagrams,micr...Mg-rare earth(RE)based systems provide several important commercial alloys and many alloy development opportunities for high strength applications,especially in aerospace and defense industries.The phase diagrams,microstructure,and strengthening mechanisms of these multicomponent systems are very complex and often not well understood in literature.We have calculated phase diagrams of important binary,ternary,and multicomponent RE-containing alloy systems,using CALPHAD(CALculation of PHAse Diagrams).Based on these phase diagrams,this paper offers a critical overview on phase equilibria and strengthening mechanisms in these alloy systems,including precipitation,long period stacking order(LPSO),and other intermetallic phases.This review also summarized several promising Mg-RE based cast alloys in comparison with commercial WE54 and WE43 alloys;and explored new strategies for future alloy development for high strength applications.It is pointed out that the combination of precipitation and LPSO phases can lead to superior strength and ductility in Mg-RE based cast alloys.The precipitates and LPSO phases can form a complex three-dimensional network that effectively impedes dislocation motion on the basal and non-basal planes.The LPSO phases can also prevent the coarsening of precipitates when they interact,thus providing good thermal stability at elevated temperatures.Future research is needed to determine how the combination of these two types of phases can be used in alloy design and industrial scale applications.展开更多
New formulae for calculating activities and activity coefficients from binary phase diagrams containing solidsolution are presented. In the new formulae, a parameterθ is introduced. It seems be more efficient The app...New formulae for calculating activities and activity coefficients from binary phase diagrams containing solidsolution are presented. In the new formulae, a parameterθ is introduced. It seems be more efficient The application ofthese formulae to system Ag-Pb proves its efficiency.展开更多
Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature charac...Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature characteristics and predictability are still the goals of model development.In this study,a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements:(1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range;(2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients,the liquid parameters,which associated with Gibbs energy,enthalpy,and heat capacity contribution;and(3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range.Together the activity coefficient model,property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl2-CaCl2-H2 O binary and ternary systems,and it shows excellent agreement with the literature data for the ternary and binary systems.The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-idealitv system,and the ability to extrapolate the temperature.展开更多
The three-phase behavior in the quaternary system of an alkyl (C8/10- or C12/14-) polyglucoside / 1-butanol / n-octane / water has been studied at 40 ℃ with the modified fishlike phase diagram, which is presented by ...The three-phase behavior in the quaternary system of an alkyl (C8/10- or C12/14-) polyglucoside / 1-butanol / n-octane / water has been studied at 40 ℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, AS, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed.展开更多
基金the financial support from the National Key R&D Program of China(No.2024YFC2910800)National Natural Science Foundation of China(52404336)+6 种基金China Postdoctoral Science Foundation(2024M750176)Postdoctoral Fellowship Program of CPSF(GZC20240109)the Young Elite Scientist Sponsorship Program by CAST(YESS20210090)Beijing Natural Science Foundation(J210017)the Project of SKLAM(No.KF24-14)China Baowu Low Carbon Metallurgical Technology Innovation Fund under Grant No.20210901Anhui Major Industrial Innovation Program under Contract No.AHZDCYCX-LSDT2023-01.
文摘The direct reduction process can reduce carbon emissions by over 50%compared to traditional blast furnace ironmaking.Carbon deposition and carburization are critical for ensuring process stability and economic viability.Thermodynamic phase diagrams were developed to intuitively represent carbon deposition and carburization preferences in CH4-CO-H_(2) ternary atmospheres.High carbon potential and low oxygen potential significantly enhance carbon deposition and carburization.Increasing temperature from 500 to 1000℃ shifts the dominant reactions from CO-based to CH_(4)-based,increasing maximum carbon deposition from 0.55 to 0.80 mol and carburization from 0.25 to 0.80 mol per mole of reducing gas.Increasing pressure suppresses CH4-based reactions while promoting CO-based reactions,reducing maximum carbon deposition from 0.8 to~0.7 mol and increasing maximum carburization from 0.80 to 0.85 mol per mole of reducing gas.Equilibrium phase diagrams for various carbides were also developed,revealing preferences for Fe_(3)C_(2),Fe_(7)C_(3),Fe_(5)C_(2),and Fe_(3)C as the Fe/C ratio increases.Higher temperatures and CH_(4) concentrations favor the formation of carbides with higher carbon content.Carburization preferences under typical Energiron ZR and Midrex atmospheres were highlighted,and the higher carbon content in direct reduction iron produced by the Energiron ZR process was thermodynamically confirmed.
基金financial supplies supported by the National Natural Science Foundation of China(Nos.52371038 and U2202255)the Science and Technology Innovation Program of Hunan Province(No.2023RC1019)
文摘High cost of raw materials and the insufficient research on alloy systems severely constrained the development of Cu-Be alloys.The complex coupling relationship between composition and preparation process poses challenges to the use of machine learning methods for the precise design of Cu-Be alloy.This study develops a novel method for integrated design of copper alloy composition and processing based on a Long Short-Term Memory model followed by an Encoder model(LSTM-Encoder)and enriches the framework by integrating phase diagram information.This approach not only capitalizes on the patterns of microstructural evolution during heat treatment as indicated in phase diagrams to reveal their intrinsic links with alloy performance but also eliminates cross-interference within sample data,thus significantly enhancing the model's generalization and predictive accuracy,which achieves high efficient and precise design of low-cost(low Be content) and high-performance Cu-Be alloys.Compared with other models,the LSTM-Encoder model incorporating phase diagram information(LSTM-Encoder-Ⅱ) showed significant superiority in prediction accuracy.After two rounds of experimental verification and iteration,the LSTM-Encoder-Ⅱ model attained prediction accuracies of 96% for hardness and 93% for electrical conductivity.Various Cu-Be-X alloys with excellent comprehensive performance and low cost have been designed,and Cu-1.5Be-0.1Ni-0.3Co alloy achieves a tensile strength of 1211 MPa and an electrical conductivity of 30.3% IACS,and Cu-1.5Be-0.6Ni alloy attains a tensile strength of1290 MPa and an electrical conductivity of 29.3% IACS,both of which are comparable to the C17200 alloy,with raw material cost reduced by more than 14%.
基金supported by the National Natural Science Foundation of China(Nos.52394272,22333002,22203018,22303017).
文摘The self-assembly of block copolymers serves as an effective approach for fabricating various periodic ordered nanostructures. By employing self-consistent field theory (SCFT) to calculate the phase diagrams of block copolymers, one can accurately predict their self-assembly behaviors, thus providing guidance for the fabrication of various novel structures. However, SCFT is highly sensitive to initial conditions because it finds the free energy minima through an iterative process. Consequently, constructing phase diagrams using SCFT typically requires predefined candidate structures based on the experience of researchers. Such experience-dependent strategies often miss some structures and thus result in inaccurate phase diagrams. Recently, artificial intelligence (AI) techniques have demonstrated significant potential across diverse fields of science and technology. By leveraging AI methods, it is possible to reduce reliance on human experience, thereby constructing more robust and reliable phase diagrams. In this work, we demonstrate how to combine AI with SCFT to automatically search for self-assembled structures of block copolymers and construct phase diagrams. Our aim is to realize automatic construction of block copolymer phase diagrams while minimizing reliance on human prior knowledge.
基金supported by the National Natural Science Foundation of China(Nos.12205364 and 12375282)Guangdong Provincial Natural Science Foundation(Nos.2024A1515012570 and 2024A1515010885)the Fundamental Research funds for the Central Universities,Sun Yat sen University。
文摘Thermodynamic optimization of the AF-BeF_(2)(A=K,Rb,and Cs),KF-CsF,and RbF-CsF systems was performed within the framework of phase diagrams calculation.The model parameters were optimized based on experimental data and theoretically calculated values.The results show that the thermodynamically calculated values for the AF-BeF_(2)(A=K,Rb,and Cs),KF-CsF,and RbF-CsF systems agree well with the experimental data.Next,a set of reliable and self-consistent thermodynamic databases was built,and the liquidus projections and invariant points of the sub-ternary systems of the KF-RbF-CsF-BeF_(2)system were calculated.Furthermore,the melting temperature with the corresponding composition was predicted using the phase diagrams calculation technique,and the radial distribution functions,coordination numbers,angular distribution functions,and diffusion coefficients of the quaternary KF-RbF-CsF-BeF_(2)system were calculated using ab initio molecular dynamics.The results show that the quaternary KF-RbF-CsF-BeF_(2)system with the proportion 3.50-28.92-21.78-45.80 mol%or 1.80-35.42-52.40-10.38 mol%is one of the most promising candidate coolants for molten salt reactors in terms of thermodynamics and kinetics.This work provides direct guidelines for the screening and optimization of molten salts in the nuclear energy field.
文摘Lithium-sulfur battery(LSB)has attracted worldwide attention owing to its overwhelmingly high theoretical energy density of 2600Wh/kg due to the unique 16-electron electrochemical conversion reaction of elemental sulfur(S_(8))[1].However,the electrochemical conversion reaction of S_(8) is an exceedingly complex process that involves the generation of multiple intermediates(e.g.,lithium polysulfides(LiPSs))and multiphase transitions[1,2].Currently,the mechanistic investigations of the electrochemical conversion reaction of S_(8) upon discharging a LSB cell heavily rely on electrochemical titration and spectroscopic techniques[3].Nevertheless,the considerable complexity and intrinsic instability of the LSB system present substantial obstacles to obtaining accurate information for all sulfur-containing species,which significantly obstructs in-depth elucidation of the fundamental discharge mechanism of LSB[3,4].
基金Project(51071181)supported by the National Natural Science Foundation of ChinaProject(2013FJ4043)supported by the Natural Science Foundation of Hunan Province,China
文摘Taking Au?Cu system as an example, three discoveries and two methods were presented. First, a new way for boosting sustainable progress of systematic metal materials science (SMMS) and alloy gene engineering (AGE) is to establish holographic alloy positioning design (HAPD) system, of which the base consists of measurement and calculation center, SMMS center, AGE center, HAPD information center and HAPD cybernation center; Second, the resonance activating-sychro alternating mechanism of atom movement may be divided into the located and oriented diffuse modes; Third, the equilibrium and subequilibrium holographic network phase diagrams are blueprints and operable platform for researchers to discover, design, manufacture and deploy advanced alloys, which are obtained respectively by the equilibrium lever numerical method and cross point numerical method of isothermal Gibbs energy curves. As clicking each network point, the holographic information of three structure levels for the designed alloy may be readily obtained: the phase constitution and fraction, phase arranging structure and properties of organization; the composition, alloy gene arranging structure and properties of each phase and the electronic structures and properties of alloy genes. It will create a new era for network designing advanced alloys.
基金Project(51071181)supported by the National Natural Science Foundation of ChinaProject(2013FJ4043)supported by the Natural Science Foundation of Hunan Province,China
文摘Taking AuCu3-type sublattice system as an example, three discoveries have been presented: First, the third barrier hindering the progress in metal materials science is that researchers have got used to recognizing experimental phenomena of alloy phase transitions during extremely slow variation in temperature by equilibrium thinking mode and then taking erroneous knowledge of experimental phenomena as selected information for establishing Gibbs energy function and so-called equilibrium phase diagram. Second, the equilibrium holographic network phase diagrams of AuCu3-type sublattice system may be used to describe systematic correlativity of the composition?temperature-dependent alloy gene arranging structures and complete thermodynamic properties, and to be a standard for studying experimental subequilibrium order-disorder transition. Third, the equilibrium transition of each alloy is a homogeneous single-phase rather than a heterogeneous two-phase, and there exists a single-phase boundary curve without two-phase region of the ordered and disordered phases; the composition and temperature of the top point on the phase-boundary curve are far away from the ones of the critical point of the AuCu3 compound.
基金Project(51071181)supported by the National Natural Science Foundation of ChinaProject(2013FJ4043)supported by the Natural Science Foundation of Hunan Province,China
文摘Taking Au3Cu-type sublattice system as an example, three discoveries have been presented. First, the fourth barrier to hinder the progress of metal materials science is that today’s researchers do not understand that the Gibbs energy function of an alloy phase should be derived from Gibbs energy partition function constructed of alloy gene sequence and their Gibbs energy sequence. Second, the six rules for establishing alloy gene Gibbs energy partition function have been discovered, and it has been specially proved that the probabilities of structure units occupied at the Gibbs energy levels in the degeneracy factor for calculating configuration entropy should be degenerated as ones of component atoms occupied at the lattice points. Third, the main characteristics unexpected by today’s researchers are as follows. There exists a single-phase boundary curve without two-phase region coexisting by the ordered and disordered phases. The composition and temperature of the top point on the phase-boundary curve are far away from those of the critical point of the Au3Cu compound; At 0 K, the composition of the lowest point on the composition-dependent Gibbs energy curve is notably deviated from that of the Au3Cu compounds. The theoretical limit composition range of long range ordered Au3Cu-type alloys is determined by the first jumping order degree.
基金Project (062702) supported by Innovation Funds of Institute of Process Engineering,Chinese Academy of Sciences
文摘In the course of the basic research on the ammonia-evaporation reaction of manganese monoxide （MnO）, hydroxyl manganese chloride （Mn2（OH）3Cl） was found. The solubility and phase diagrams of the hydroxyl manganese chloride were investigated. The aqueous thermostat and vibrating bed were used to determine the solubility of hydroxyl manganese chloride in water, ammonium chloride and manganese chloride system, and the phase diagrams of multicomponent system were drawn. The research results indicate that hydroxyl manganese chloride has been produced in laboratory and is in favor of the solid-liquid separation at high temperature.
基金Project (51171069) supported by the National Natural Science Foundation of ChinaProject (S2011010004094) supported by Natural Science Foundation of Guangdong Province, ChinaProject support by the Special Talents of Higher Education Office of Guangdong Province ,China
文摘The Ce-La-O system was investigated via experiments and thermodynamic modeling. A series of CeO2-LaO1.5 mixtures were prepared by co-precipitation technique and examined by X-ray diffraction. Mutual solubilities between LaO1.5 and CeO2 at 1273 K were determined. Using the new experimental data together with literature information, a set of self-consistent thermodynamic parameters for the CeO2-LaO1.5 system were optimized. Combined with thermodynamic descriptions of Ce-O and La-O systems from literature, several property diagrams of Ce-La-O system were calculated and used to explain oxidation process of the Ce-La alloys. The fluorite phase is the unique oxidation products for most of the Ce-La alloys.
文摘Based on thermodynamic equilibrium theory,a chemical equilibrium model for GaN g rowth is given in electron cyclotron resonance plasma enhanced metalorganic chem ical vapor deposition (ECR-PEMOCVD) system.Calculation indicates that the growt h driving force are functions of growth conditions:group Ⅲ input partial press ure,input Ⅴ/Ⅲ ratio,and growth temperature.Furthermore,the growth phase diag rams of hexagonal and cubic GaN film growth are obtained,which are consistent wi th our experimental conditions to some extent.Through analysis,it is explained t he reason that high temperature and high input Ⅴ/Ⅲ ratio are favorable for he xagonal GaN film growth.This model can be extended to the similar systems used f or GaN single-crystal film growth.
文摘Recent progress on research activities of phase diagrams in our laboratory has been presented. Experimental studies and thermodynamic calculations based on CALPHAD (Calculation of Phase Diagrams) method have been conducted in the following alloy systems.1.Database on microalloying steels including carbide, nitride and sulfide is now being constructed.2.ADAMIS (Alloy Database for Micro-Solders) containing 8 elements of Ag, Bi, Cu,In, Sb, Sn, Zn and Pb has been constructed, which can handle all combinations of these elements and all composition ranges.3.A thermodynamic database of Cu-base alloys including Cu-X binary system and Cu-Fe, Cu-Ni, Cu-Cr base ternary systems has been constructed.4.Experimental and thermodynamic calculations on Fe, Ni, Co and Ti aluminides have been conducted.5.Experimental and thermodynamic calculations on Co base magnetic recording media have been conducted.6.Thermodynamic analysis of interaction between magnetic and chemical orderings has been performed.By utilizing the information on phase diagrams, the following advanced materials have been developed. (A)New type of high speed steel with high hardness about Hv≈1000 by carbide dispersion carburizing method. (B)New Pb-free machinable stainless steel using titanium carbosulphide. (C)New Pb-free solder for Die-attaching use. (D)Shape memory alloys; Cu-base, Ferromagnetic Ni-base and Fe-base. (E)Invar alloys. (F)Egg-type powder.Typical examples of phase diagrams, phase stability, database and its application for the development of advanced materials will be presented.
文摘The databases of the FactSage thermodynamic computer system have been under development for 30 years. These databases contain critically evaluated and opthnized data for thousands of compounds and hundreds of multicomponent solutions of solid and liquid metals, oxides, salts, sulfides, etc. The databases are automatically accessed by user-friendly software that calculates complex multiphase equilibria in large multicomponent systems for a wide variety of possible input/output constraints. The databases for solutions have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for different types of solutions involving sublattices, ordering, etc. Through the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits and permit extrapolation into regions of tempea＇ature and composition where data are unavailable. The present article focuses on the databases for solid and liquid oxide phases involving 25 elements. A short review of the available databases is presented along with the models used for the molten slag and the solid solutions such as spinel, pyroxene, olivine, monoxide, corundum, etc. The critical evaluation/optimization procedure is outlined using examples from the Al203-SiO2-CaO-FeO-Fe2O3 system. Sample calculations are presented in which the oxide databases are used in conjunction with the FactSage databases for metallic and other phases. In particular, the use of the FactSage module for the calculation of multicomponent phase diagrams is illustrated.
基金Project supported by National Key Research and Development Program of China(2016YFB0700901)National Basic Foundation of China(2014CB643703)+3 种基金National Natural Science Foundation of China(51761008,51461013)Guangxi Natural Science Foundation(2016GXNSFDA380015,2016GXNSFGA380001)Guangxi Project of Science and Technology(2017AD23031)Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology,China(171005-Z)
文摘Thermodynamic optimization of the binary rare earth alloy(Cee La, Cee Pr, Cee Nd and Lae Nd) systems was performed in this work through the CALPHAD method based on the critical evaluation of all available phase diagram and thermodynamic data reported in the literature. During the thermodynamic modeling, the solution phases including liquid, bcc, fcc and dhcp, were treated as the substitutional solution model. Thermodynamic parameters of the stable phases in the Cee La, Cee Pr, Cee Nd and Lae Nd binary systems are obtained finally and would be used directly to develop the thermodynamic database of the multi-component Nde Fee B-based alloys, which is indispensable for designing alloy compositions and processes of Nde Fee B permanent magnets with highly abundant rare earth metals.
基金partially funded by the United States Army Research Laboratory (ARL)Terves LLC。
文摘Mg-rare earth(RE)based systems provide several important commercial alloys and many alloy development opportunities for high strength applications,especially in aerospace and defense industries.The phase diagrams,microstructure,and strengthening mechanisms of these multicomponent systems are very complex and often not well understood in literature.We have calculated phase diagrams of important binary,ternary,and multicomponent RE-containing alloy systems,using CALPHAD(CALculation of PHAse Diagrams).Based on these phase diagrams,this paper offers a critical overview on phase equilibria and strengthening mechanisms in these alloy systems,including precipitation,long period stacking order(LPSO),and other intermetallic phases.This review also summarized several promising Mg-RE based cast alloys in comparison with commercial WE54 and WE43 alloys;and explored new strategies for future alloy development for high strength applications.It is pointed out that the combination of precipitation and LPSO phases can lead to superior strength and ductility in Mg-RE based cast alloys.The precipitates and LPSO phases can form a complex three-dimensional network that effectively impedes dislocation motion on the basal and non-basal planes.The LPSO phases can also prevent the coarsening of precipitates when they interact,thus providing good thermal stability at elevated temperatures.Future research is needed to determine how the combination of these two types of phases can be used in alloy design and industrial scale applications.
文摘New formulae for calculating activities and activity coefficients from binary phase diagrams containing solidsolution are presented. In the new formulae, a parameterθ is introduced. It seems be more efficient The application ofthese formulae to system Ag-Pb proves its efficiency.
基金financial support of the National Natural Science Foundation of China(U1407204,U1707602)the Yangtze Scholars and Innovative Research Team in University of Education of China+1 种基金the Innovative Research Team of Tianjin Municipal Education Commission(TD12-5004)Foundation of Tianjin Key Laboratory of Marine Resources and Chemistry(201602)。
文摘Salt lake brine is a complex salt-water system under natural environment.Although many models can express the thermodynamic properties and phase equilibrium of electrolyte aqueous solution,the multi-temperature characteristics and predictability are still the goals of model development.In this study,a comprehensive thermodynamic model system is re-established based on the eNRTL model and some improvements:(1) new expression of long-range electrostatic term with symmetrical reference state is proposed to handle the electrolyte solution covering entire concentration range;(2) the temperature dependence of the binary interaction parameters is formulated with a Gibbs Helmholtz expression containing three temperature coefficients,the liquid parameters,which associated with Gibbs energy,enthalpy,and heat capacity contribution;and(3) liquid parameters and solid species data are regressed from properties and solubility data at full temperature range.Together the activity coefficient model,property models and parameters of liquid and solid offer a comprehensive thermodynamic model system for the typical bittern of MgCl2-CaCl2-H2 O binary and ternary systems,and it shows excellent agreement with the literature data for the ternary and binary systems.The successful prediction of complete phase diagram of ternary system shows that the model has the ability to deal with high concentration and high non-idealitv system,and the ability to extrapolate the temperature.
文摘The three-phase behavior in the quaternary system of an alkyl (C8/10- or C12/14-) polyglucoside / 1-butanol / n-octane / water has been studied at 40 ℃ with the modified fishlike phase diagram, which is presented by us for the first time. The mass fraction of 1-butanol in the hydrophile-lipophile balanced interfacial layer, AS, the coordinates of the start point B and the end point E of the phase diagram, and the solubilities of alkyl polyglucoside and 1-butanol in n-octane phase were calculated. The solubilization of the microemulsion was also discussed.
