The article raises the question of what to do with one of the main achievements of metal science in recent years—binary phase diagrams. These diagrams play a key role in the science of alloys and therefore their reli...The article raises the question of what to do with one of the main achievements of metal science in recent years—binary phase diagrams. These diagrams play a key role in the science of alloys and therefore their reliability must be complete. However, the discovery of the “ordering-separation” phase transition, which showed that in binary alloys at certain temperatures the sign of the chemical interatomic interaction changes (and, consequently, the microstructure changes), forces us to reconsider our ideas about those areas. Currently, these areas are designated on diagrams as areas of a “disordered solid solution.” This article proposes, using transmission electron microscopy, to study all the so-called solid solution regions, and apply the results obtained to the studied regions of the phase diagram.展开更多
The relationship between the types of binary alloy phase diagramsof VIII and Ib group elements and the Men- deleev numbers wasdiscussed for the first time using the VIII and IB group elements assolvent metals (A) and ...The relationship between the types of binary alloy phase diagramsof VIII and Ib group elements and the Men- deleev numbers wasdiscussed for the first time using the VIII and IB group elements assolvent metals (A) and the other elements as solute metals (B),basesd on their alloy phase diagram types. The Mendeleev numbers ofthe solvent metals and the solute metals were expressed as M_A andM_B, respectively. A two-dimension map of M_A/M_B was drawn. It isindi- cated that there is an oblique line in the map, which dividesthe binary alloy phase diagram types of solvent metals into twosymmetry parts, the phase diagram types of the other elements withsolvent metals located at the above or down of the line respectively,while on the line, △M = 0.展开更多
Based on the thermodynamical principle the new formula for calculation of heat of fusion and its error have been derived from binary phase diagrams which could be classified to eutectic,solid solution,degenerate eutec...Based on the thermodynamical principle the new formula for calculation of heat of fusion and its error have been derived from binary phase diagrams which could be classified to eutectic,solid solution,degenerate eutectic and involving a compound phase diagram and so on.Using these formulae heats of fusion of some rare earth ox- ides have been predicted.展开更多
The general relationship between binary phase diagrams and the thermodynamic properties was system- atically derived without any assumption.A procedure was presented to estimate the thermodynamic proper- ties from the...The general relationship between binary phase diagrams and the thermodynamic properties was system- atically derived without any assumption.A procedure was presented to estimate the thermodynamic proper- ties from the binary phase diagrams.展开更多
In this paper a critical assessment and optimization of the phase diagrams and thermodynamic properties of the PrCl_3-MCl(M=Li,Na)and PrCl_3-MCl_2(M=Mg,Ca,Sr,Ba) binary systems have been per- formed.The assessed and o...In this paper a critical assessment and optimization of the phase diagrams and thermodynamic properties of the PrCl_3-MCl(M=Li,Na)and PrCl_3-MCl_2(M=Mg,Ca,Sr,Ba) binary systems have been per- formed.The assessed and optimized binary phase diagrams and thermodynamic data with self consistency are a better basis for constructing multicomponent phase diagrams.展开更多
From the Gibbs free energy and the equations of two-phase equilibrium curves of the two-dimensionalbinary system which has the Lennard-Jones potential, using the Collins model, the eutectic-type phase diagram and thep...From the Gibbs free energy and the equations of two-phase equilibrium curves of the two-dimensionalbinary system which has the Lennard-Jones potential, using the Collins model, the eutectic-type phase diagram and theperitectic-type phase diagram of the binary system are obtained, whose results are quite similar to the behavior of thethree-dimensional (3D) substances.展开更多
The paper presents the calculation results on the construction of solidus lines of phase diagrams for some binary metal systems based on cadmium, zinc and tellurium. The investigations have been carried out using the ...The paper presents the calculation results on the construction of solidus lines of phase diagrams for some binary metal systems based on cadmium, zinc and tellurium. The investigations have been carried out using the phase equilibrium thermodynamics and known liquidus lines. By the calculation method the solidus lines of phase diagrams of the Cd-Na, Cd-Tl, Te-Ga, Te-As, Te-Cu and Zn-Sn systems were constructed in the temperature range from the base component melting point to the eutectic transformation temperature. In the Cd-Tl, Te-As, Te-Cu and Zn-Sn systems a retrograde solubility of the second component in the solid phase was observed. The temperature and maximum solubility values at the retrograde behavior of solidus lines, as well as, the limiting solubility values of components at eutectic transformation in the systems based on Cd, Zn and Te were determined.展开更多
Based on the available experimental data,the Bi-Ni binary system was optimized thermodynamically by the CALPHAD method.The solution phases,including liquid,fcc_A1（Ni） and rhombohedral_A7（Bi）,were described as subs...Based on the available experimental data,the Bi-Ni binary system was optimized thermodynamically by the CALPHAD method.The solution phases,including liquid,fcc_A1（Ni） and rhombohedral_A7（Bi）,were described as substitutional solution phases,of which the excess Gibbs energies were expressed with the Redlich-Kister polynomial.The intermetallic compound,BiNi,was modeled using three sublattices（Bi）（Ni,Va）（Ni,Va） considering its crystal structure（NiAs-type） and the compatibility of thermodynamic database in the multi-component systems,while Bi3Ni was treated as a stoichiometric compound.Finally,a set of self-consistent thermodynamic parameters formulating the Gibbs energies of various phases in this binary system were obtained.The calculated results are in reasonable agreement with the reported experimental data.展开更多
The universal cluster expansion technique was used in this study to determine the binary phase diagrams for the transition metal carbonate precursors MCO3(M:Mn,Ni,Co).The use of mixed cathode materials in lithium-ion ...The universal cluster expansion technique was used in this study to determine the binary phase diagrams for the transition metal carbonate precursors MCO3(M:Mn,Ni,Co).The use of mixed cathode materials in lithium-ion batteries such as NMC(Ni,Mn and Co)formulations,is a strategic approach to optimize performance,enhance safety and address cost and environmental considerations in the rapidly evolving field of energy storage.This study focuses on the cost issue related to lithium ion batteries by investigating the manganese rich NMC since manganese is more abundant and cost-effective.We doped MnCO3 with nickel and doped MnCO3 with cobalt then ran cluster expansion calculations to generate binary phases.The binary phase diagrams generated indicated that doping MnCO3 with nickel favours the Mn-rich side,while doping MnCO3 with cobalt favours 50%Mn-rich and 50%Co-rich.We further extracted the most stable structures from both binary diagrams and determined their electronic,mechanical and vibrational stabilities using DFT(density functional theory)calculations within the LDA(local gradient approximation)with Hubbard parameter(U).The electronic properties revealed that both materials are semiconductors due to their narrow energy band gap obtained while the mechanical properties showed that structures are mechanically stable since their necessary conditions for trigonal and triclinic systems were satisfied.展开更多
Nanoparticles with competitive interactions in solution can aggregate into complex structures. In this work, the synergistic self-assembles of binary particles with electrostatic and van der Waals interactions are stu...Nanoparticles with competitive interactions in solution can aggregate into complex structures. In this work, the synergistic self-assembles of binary particles with electrostatic and van der Waals interactions are studied with the particle Langevin dynamics simulation using a simple coarse-grained particle model. Various aggregations such as spherical, stacking-disk and tube structures are observed by varying the particles size and the interaction strength. The aggregation structures are explained with the packing theories of amphiphilic molecules in solution and dibolck copolymers in bulk. When the opposite ions are introduced into solution, the distribution of structures in the phase diagram appears an obvious offset. The simulation result is helpful to deeply understand the formation mechanism of complex nanostructures of multicomponent particles in solution.展开更多
A new series of binary mixture ionic liquids comprising 1-ethyl-3-methylimidozalium bromide (EMIMBr) and imidazole (IM) have been synthesized. The melting points of the ionic liquids vary with the different content o...A new series of binary mixture ionic liquids comprising 1-ethyl-3-methylimidozalium bromide (EMIMBr) and imidazole (IM) have been synthesized. The melting points of the ionic liquids vary with the different content of IM while they still keep satisfactory conductivity and viscosity. According to the analysis of its phase diagram, the eutectic point is about 16.5C with the mass percentage of IM 29%.展开更多
The Ni-Sb binary alloy system was thermodynamically assessed using CALPHAD approach in this article. Excess Gibbs energies of solution phases, liquid and fcc phases, were formulated using the Redlich-Kister expression...The Ni-Sb binary alloy system was thermodynamically assessed using CALPHAD approach in this article. Excess Gibbs energies of solution phases, liquid and fcc phases, were formulated using the Redlich-Kister expression. The intermediate phases were modeled by the sublattice model with （Ni,Va）0.5（Ni,Sb）0.25（Ni）0.25 for Ni3Sb_HT phase and （Ni,Va）0.3333（Sb）0.3333（Ni,Va）0.3333 for NiSb phase. The other phases including Ni3Sb, Ni7Sb3, and NiSb2 were treated as stoichiometric compound owing to their narrow composition ranges. Based on the reported thermodynamic properties and phase diagram data, the thermodynamic parameters of these phases were optimized, and the obtained values can reproduce the available experimental data well.展开更多
In order to obtain the thermodynamic description of the Mg-Ga binary system,the thermodynamic assessment of the system was carried out using the CALPHAD method through Thermo-calc software package based on the evaluat...In order to obtain the thermodynamic description of the Mg-Ga binary system,the thermodynamic assessment of the system was carried out using the CALPHAD method through Thermo-calc software package based on the evaluation of all available experimental data from the published literature.The solution phases,including liquid,hcp(Mg) and orthorhombic(Ga),were described by the substitutional solution model,of which the excess Gibbs energies were expressed with the Redlich-Kister polynomial.Meanwhile,all intermetallic compounds,Mg5Ga2,Mg2Ga,MgGa,MgGa2 and Mg2Ga5,were modeled as stoichiometric compounds.A set of self-consistent thermodynamic parameters formulating the Gibbs energies of various phases in the Mg-Ga binary system were obtained finally.The much better agreement is achieved between the calculated results and the reported experimental data.展开更多
The Ge-La binary system was critically assessed by means of the calculation of phase diagram （CALPHAD） technique. The asso- ciate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5...The Ge-La binary system was critically assessed by means of the calculation of phase diagram （CALPHAD） technique. The asso- ciate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5, and Ge1.7La. The terminal solid solution diamond-（Ge） with a small solubility of La was described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, μ（Gel.7La）, β（Ge1.7La）, and （GeLa）, were modeled using two sublatrices asα（Ge,La）l.7La, β（Ge,La）l.7La, and （Ge,La）（Ge,La）, respectively. The intermediate phases with no solubility ranges, Ge4Las, GeaLa4, Ge3Las, and GeLa3, were treated as stoichiometric compounds. The three allotropic modifications of La, dhcp-La, fcc-La, and bcc-La, were kept as pure element phases since no solubility of Ge in La was reported. A set of self-consistent thermodynamic parameters of the Ge-La binary system was obtained. The calculation results agree well with the available experimental data from literatures.展开更多
Accounting for static phased-mission systems (PMS) and imperfect coverage (IPC), generalized and integrated algorithm (GPMS-CPR) implemented a synthesis of several approaches into a single methodology whose advantages...Accounting for static phased-mission systems (PMS) and imperfect coverage (IPC), generalized and integrated algorithm (GPMS-CPR) implemented a synthesis of several approaches into a single methodology whose advantages were in the low computational complexity, broad applicability, and easy implementation. The approach is extended into analysis of each phase in the whole mission. Based on Fussell-Vesely importance measure, a simple and efficient importance measure is presented to analyze component’s importance of phased-mission systems considering imperfect coverage.展开更多
文摘The article raises the question of what to do with one of the main achievements of metal science in recent years—binary phase diagrams. These diagrams play a key role in the science of alloys and therefore their reliability must be complete. However, the discovery of the “ordering-separation” phase transition, which showed that in binary alloys at certain temperatures the sign of the chemical interatomic interaction changes (and, consequently, the microstructure changes), forces us to reconsider our ideas about those areas. Currently, these areas are designated on diagrams as areas of a “disordered solid solution.” This article proposes, using transmission electron microscopy, to study all the so-called solid solution regions, and apply the results obtained to the studied regions of the phase diagram.
文摘The relationship between the types of binary alloy phase diagramsof VIII and Ib group elements and the Men- deleev numbers wasdiscussed for the first time using the VIII and IB group elements assolvent metals (A) and the other elements as solute metals (B),basesd on their alloy phase diagram types. The Mendeleev numbers ofthe solvent metals and the solute metals were expressed as M_A andM_B, respectively. A two-dimension map of M_A/M_B was drawn. It isindi- cated that there is an oblique line in the map, which dividesthe binary alloy phase diagram types of solvent metals into twosymmetry parts, the phase diagram types of the other elements withsolvent metals located at the above or down of the line respectively,while on the line, △M = 0.
文摘Based on the thermodynamical principle the new formula for calculation of heat of fusion and its error have been derived from binary phase diagrams which could be classified to eutectic,solid solution,degenerate eutectic and involving a compound phase diagram and so on.Using these formulae heats of fusion of some rare earth ox- ides have been predicted.
文摘The general relationship between binary phase diagrams and the thermodynamic properties was system- atically derived without any assumption.A procedure was presented to estimate the thermodynamic proper- ties from the binary phase diagrams.
文摘In this paper a critical assessment and optimization of the phase diagrams and thermodynamic properties of the PrCl_3-MCl(M=Li,Na)and PrCl_3-MCl_2(M=Mg,Ca,Sr,Ba) binary systems have been per- formed.The assessed and optimized binary phase diagrams and thermodynamic data with self consistency are a better basis for constructing multicomponent phase diagrams.
文摘From the Gibbs free energy and the equations of two-phase equilibrium curves of the two-dimensionalbinary system which has the Lennard-Jones potential, using the Collins model, the eutectic-type phase diagram and theperitectic-type phase diagram of the binary system are obtained, whose results are quite similar to the behavior of thethree-dimensional (3D) substances.
文摘The paper presents the calculation results on the construction of solidus lines of phase diagrams for some binary metal systems based on cadmium, zinc and tellurium. The investigations have been carried out using the phase equilibrium thermodynamics and known liquidus lines. By the calculation method the solidus lines of phase diagrams of the Cd-Na, Cd-Tl, Te-Ga, Te-As, Te-Cu and Zn-Sn systems were constructed in the temperature range from the base component melting point to the eutectic transformation temperature. In the Cd-Tl, Te-As, Te-Cu and Zn-Sn systems a retrograde solubility of the second component in the solid phase was observed. The temperature and maximum solubility values at the retrograde behavior of solidus lines, as well as, the limiting solubility values of components at eutectic transformation in the systems based on Cd, Zn and Te were determined.
基金Projects(50371104,50771106and50731002)supported by the National Natural Science Foundation of ChinaProject(2008K22)supported by the Scientific Research Foundation of Hunan Provincial Department of Land&Resources,ChinaProject supported by Geology Exploration Foundation of Hunan Provincial Department of Land&Resources,China
文摘Based on the available experimental data,the Bi-Ni binary system was optimized thermodynamically by the CALPHAD method.The solution phases,including liquid,fcc_A1（Ni） and rhombohedral_A7（Bi）,were described as substitutional solution phases,of which the excess Gibbs energies were expressed with the Redlich-Kister polynomial.The intermetallic compound,BiNi,was modeled using three sublattices（Bi）（Ni,Va）（Ni,Va） considering its crystal structure（NiAs-type） and the compatibility of thermodynamic database in the multi-component systems,while Bi3Ni was treated as a stoichiometric compound.Finally,a set of self-consistent thermodynamic parameters formulating the Gibbs energies of various phases in this binary system were obtained.The calculated results are in reasonable agreement with the reported experimental data.
基金This work was performed at MMC(Materials Modelling Centre)of the University of Limpopo and the CHPC(Centre for High Performance Computing)with the support of the South African Research Chair Initiative of the Department of Science and Technology is greatly appreciatedThe study was funded by the NRF(National Research Foundation)with grant number 128934,and this funding is really appreciated.
文摘The universal cluster expansion technique was used in this study to determine the binary phase diagrams for the transition metal carbonate precursors MCO3(M:Mn,Ni,Co).The use of mixed cathode materials in lithium-ion batteries such as NMC(Ni,Mn and Co)formulations,is a strategic approach to optimize performance,enhance safety and address cost and environmental considerations in the rapidly evolving field of energy storage.This study focuses on the cost issue related to lithium ion batteries by investigating the manganese rich NMC since manganese is more abundant and cost-effective.We doped MnCO3 with nickel and doped MnCO3 with cobalt then ran cluster expansion calculations to generate binary phases.The binary phase diagrams generated indicated that doping MnCO3 with nickel favours the Mn-rich side,while doping MnCO3 with cobalt favours 50%Mn-rich and 50%Co-rich.We further extracted the most stable structures from both binary diagrams and determined their electronic,mechanical and vibrational stabilities using DFT(density functional theory)calculations within the LDA(local gradient approximation)with Hubbard parameter(U).The electronic properties revealed that both materials are semiconductors due to their narrow energy band gap obtained while the mechanical properties showed that structures are mechanically stable since their necessary conditions for trigonal and triclinic systems were satisfied.
基金V. ACKNOWLEDGMENTS The computer simulation is performed on the High Performance Computing Center of Tianjin University,China. This work was supported by the National Natural Science Foundation of China （No.21274107 and No.91127046）. We thank Prof. Bin Zhang, Rui Xu, Bo Du, and Dr. Zi-lu Wang in Tianjin University for helpful discussions.
文摘Nanoparticles with competitive interactions in solution can aggregate into complex structures. In this work, the synergistic self-assembles of binary particles with electrostatic and van der Waals interactions are studied with the particle Langevin dynamics simulation using a simple coarse-grained particle model. Various aggregations such as spherical, stacking-disk and tube structures are observed by varying the particles size and the interaction strength. The aggregation structures are explained with the packing theories of amphiphilic molecules in solution and dibolck copolymers in bulk. When the opposite ions are introduced into solution, the distribution of structures in the phase diagram appears an obvious offset. The simulation result is helpful to deeply understand the formation mechanism of complex nanostructures of multicomponent particles in solution.
基金Supported by the State Key Basic Program(NO.G2000048)the Foundation of Shanghai Science and Technology Development(01JC14002).
文摘A new series of binary mixture ionic liquids comprising 1-ethyl-3-methylimidozalium bromide (EMIMBr) and imidazole (IM) have been synthesized. The melting points of the ionic liquids vary with the different content of IM while they still keep satisfactory conductivity and viscosity. According to the analysis of its phase diagram, the eutectic point is about 16.5C with the mass percentage of IM 29%.
基金the National Natu-ral Science Foundation of China (Nos. 50601001 and 50771105)
文摘The Ni-Sb binary alloy system was thermodynamically assessed using CALPHAD approach in this article. Excess Gibbs energies of solution phases, liquid and fcc phases, were formulated using the Redlich-Kister expression. The intermediate phases were modeled by the sublattice model with （Ni,Va）0.5（Ni,Sb）0.25（Ni）0.25 for Ni3Sb_HT phase and （Ni,Va）0.3333（Sb）0.3333（Ni,Va）0.3333 for NiSb phase. The other phases including Ni3Sb, Ni7Sb3, and NiSb2 were treated as stoichiometric compound owing to their narrow composition ranges. Based on the reported thermodynamic properties and phase diagram data, the thermodynamic parameters of these phases were optimized, and the obtained values can reproduce the available experimental data well.
基金Project supported by Scientific Research Foundation for Advanced Talents in Central South University of Forestry and Technology,ChinaProject(50731002) supported by the National Natural Science Foundation of China
文摘In order to obtain the thermodynamic description of the Mg-Ga binary system,the thermodynamic assessment of the system was carried out using the CALPHAD method through Thermo-calc software package based on the evaluation of all available experimental data from the published literature.The solution phases,including liquid,hcp(Mg) and orthorhombic(Ga),were described by the substitutional solution model,of which the excess Gibbs energies were expressed with the Redlich-Kister polynomial.Meanwhile,all intermetallic compounds,Mg5Ga2,Mg2Ga,MgGa,MgGa2 and Mg2Ga5,were modeled as stoichiometric compounds.A set of self-consistent thermodynamic parameters formulating the Gibbs energies of various phases in the Mg-Ga binary system were obtained finally.The much better agreement is achieved between the calculated results and the reported experimental data.
基金supported by the National Natural Science Foundation of China (Nos.50731002 and 50671009)
文摘The Ge-La binary system was critically assessed by means of the calculation of phase diagram （CALPHAD） technique. The asso- ciate model was used for the liquid phase containing the constituent species Ge, La, Ge3La5, and Ge1.7La. The terminal solid solution diamond-（Ge） with a small solubility of La was described using the substitutional model, in which the excess Gibbs energy was formulated with the Redlich-Kister equation. The compounds with homogeneity ranges, μ（Gel.7La）, β（Ge1.7La）, and （GeLa）, were modeled using two sublatrices asα（Ge,La）l.7La, β（Ge,La）l.7La, and （Ge,La）（Ge,La）, respectively. The intermediate phases with no solubility ranges, Ge4Las, GeaLa4, Ge3Las, and GeLa3, were treated as stoichiometric compounds. The three allotropic modifications of La, dhcp-La, fcc-La, and bcc-La, were kept as pure element phases since no solubility of Ge in La was reported. A set of self-consistent thermodynamic parameters of the Ge-La binary system was obtained. The calculation results agree well with the available experimental data from literatures.
基金Supported by National Outstanding Youth Science Foundation of China (No.79725002)
文摘Accounting for static phased-mission systems (PMS) and imperfect coverage (IPC), generalized and integrated algorithm (GPMS-CPR) implemented a synthesis of several approaches into a single methodology whose advantages were in the low computational complexity, broad applicability, and easy implementation. The approach is extended into analysis of each phase in the whole mission. Based on Fussell-Vesely importance measure, a simple and efficient importance measure is presented to analyze component’s importance of phased-mission systems considering imperfect coverage.
