Towards high strength cast Mg-RE based alloys:Phase diagrams and strengthening mechanisms

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.

Optimization and Calculation of TbCl_3-ACl (A=Li, Na, K, Rb, Cs) Phase Diagrams

By using CALPHAD (Calculation of Phase Diagram) technique the optimization and calculation of the binary systems of TbCl_3-ACl (A= Li, Na, K, Rb, Cs) were carried out. For describing the Gibbs free energy of liquid phase in these systems the new modified quasichemical model in the pair-approximation for short-range ordering was used. From measured phase equilibria data and experimental integral properties the TbCl_3-ACl phase diagrams were optimized and calculated. A set of thermodynamic functions was optimized based on an interactive computer-assisted analysis. The calculated phase diagrams and thermodynamic data are self-consistent.

Magnetization and magnetic phase diagrams of a spin-1/2 ferrimagnetic diamond chain at low temperature

We used the Jordan-Wigner transform and the invariant eigenoperator method to study the magnetic phase diagram and the magnetization curve of the spin-1/2 alternating ferrimagnetic diamond chain in an external magnetic field at finite temperature.The magnetization versus external magnetic field curve exhibits a 1/3 magnetization plateau at absolute zero and finite temperatures,and the width of the 1/3 magnetization plateau was modulated by tuning the temperature and the exchange interactions.Three critical magnetic field intensities H_(CB),H_(CE)and H_(CS) were obtained,in which the H_(CB) and H_(CE)correspond to the appearance and disappearance of the 1/3 magnetization plateau,respectively,and the higher H_(CS) correspond to the appearance of fully polarized magnetization plateau of the system.The energies of elementary excitation hω_(σ,k)(σ=1,2,3)present the extrema of zero at the three critical magnetic fields at 0 K,i.e.,[hω_(3,k)(H_(CB)]_(min)=0,[hω_(2,k)(H_(CE)]_(max)=0 and[hω_(2,k)(H_(CS)]_(min)=0,and the magnetic phase diagram of magnetic field versus different exchange interactions at 0 K was established by the above relationships.According to the relationships between the system’s magnetization curve at finite temperatures and the critical magnetic field intensities,the magnetic field-temperature phase diagram was drawn.It was observed that if the magnetic phase diagram shows a three-phase critical point,which is intersected by the ferrimagnetic phase,the ferrimagnetic plateau phase,and the Luttinger liquid phase,the disappearance of the 1/3 magnetization plateau would inevitably occur.However,the 1/3 magnetization plateau would not disappear without the three-phase critical point.The appearance of the 1/3 magnetization plateau in the low temperature region is the macroscopic manifestations of quantum effect.

Phase diagrams in mixed spin-3/2 and spin-2 Ising system with two alternative layers within the effective-field theory

The phase diagrams in the mixed spin-3/2 and spin-2 Ising system with two alternative layers on a honeycomb lattice are investigated and discussed by the use of the effective-field theory with correlations. The interaction of the nearest-neighbour spins of each layer is taken to be positive （ferromagnetic interaction） and the interaction of the adjacent spins of the nearest-neighbour layers is considered to be either positive or negative （ferromagnetic or antiferromagnetic interaction）. The temperature dependence of the layer magnetizations of the system is examined to characterize the nature （continuous or discontinuous） of the phase transitions and obtain the phase transition temperatures. The system exhibits both second- and first-order phase transitions besides triple point （TP）, critical end point （E）, multicritical point （A）, isolated critical point （C） and reentrant behaviour depending on the interaction parameters. We have also studied the temperature dependence of the total magnetization to find the compensation points, as well as to determine the type of behaviour, and N-type behaviour in Neel classification nomenclature existing in the system. The phase diagrams are constructed in eight different planes and it is found that the system also presents the compensation phenomena depending on the sign of the bilinear exchange interactions.

Determination of High Pressure Phase Diagrams of the Ternary Alloy System

everal vertical sections of the phase diagram of Cd-Sn-Zn system with a constant mole fraction X_(cd)=0.2 were determined by means of differential thermal anal- ysis(DTA)at high pres:ures 0.0,0.5,1.5,and 2. 0 GPa respectively. The eutectic temperature of the system increases by about 50K from atmospheric pressure to the high pressure 2.0 GPa,but the ternary eutectic composition changes slightly with the pressure chnge.

ASSESSMENT AND OPTIMIZATION OF THE PHASE DIAGRAMS AND THERMODYNAMIC DATA OF SOME BINARY SYSTEMS CONTAINING PRASEODYMIUM CHLORIDES

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.

MY RESEARCH ACHIEVEMENTS IN POWDER X-RAY DIFFRACTION & PHASE DIAGRAMS

I graduated from the Department of Chemistry, Xiamen University in 1955, majoring in physical chemistry. I went to the Institute of Metallurgy under the Soviet Academy of Sciences in 1956 as a Ph.D.candidate in thermochemistry and crystal chemistry of metal alloys,and got my Ph.D.degree in 1960.In the following 30 years, I did basic and applied research in interdisciplines,including crystal chemistry,materials science and solid state physics.My main achievements can be listed in two aspects as follows:

New formulae for calculating activities from binary system phase diagrams containing solid solution by introducing the parameterθ

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.

Thermodynamic database of the phase diagrams in the Mg-Al-Zn-Y-Ce system

The Mg-Al-Zn-Y-Ce system is one of the key systems for designing high-strength Mg alloys. The purpose of the present article is to develop a thermodynamic database for the Mg-Al-Zn-Y-Ce multicomponent system to design Mg alloys using the calculation of phase diagrams （CALPHAD） method, where the Gibbs energies of solution phases such as liquid, fcc, bcc, and hcp phases were described by the subregular solution model, whereas those of all the compounds were described by the sublattice model. The thermodynamic parameters describing Gibbs energies of the different phases in this database were evaluated by fitting the experimental data for phase equilibria and thermodynamic properties. On the basis of this database, a lot of information concerning stable and metastable phase equilibria of isothermal and vertical sections, molar fractions of constituent phases, the liquidus projection, etc., can be predicted. This database is expected to play an important role in the design of Mg alloys.

Thermodynamic Optimization of TmCl_3-ACl (A=Na, K, Rb, Cs) Phase Diagrams

From the measured phase equilibria data and experimental thermochemical properties, the TmCl_3-ACl (A=Na, K, Rb, Cs) phase diagrams were optimized and calculated using the CALPHAD technique. For describing the Gibbs energies of the liquid phase in these systems, the new modified quasichemical model in the pair-approximation for short-range ordering was used. A set of thermodynamic functions was optimized and gotten based on an interactive computer-assisted analysis. The calculated phase diagrams and thermodynamic data are self-consistent.

Thermodynamic optimization and calculation of phase diagrams of YbCl_3-MCl (M=Na, K, Rb, Cs)

YbCl3-MCl （M = Na, K, Rb, Cs） systems were optimized and calculated using the CALPHAD （CALculation of PHAse Diagram） technique. The modified quasi-chemical model in the pair-approximation for short-range ordering was used to describe the Gibbs energies of liquid phase in the systems. On the basis of the measured phase diagram data and experimental thermodynamic properties, a series of thermodynamic functions were optimized and calculated through an interactive computer-assisted analysis. Furthermore, some reasonable discussions on the thermodynamic parameters for these strong interaction binary systems were carded out. The results showed that the optimized parameters and experimental data are thermodynamically self-consistent.

θ Correction to the Analytical Expressions for Calculating Activities from Phase Diagrams Involving Intermediate Compounds

A set of correct expressions for calculating activities and activity coefficients from binary phase diagrams involving intermediate compounds are presented in this paper by the introduction of a correct parameter θ. The application of these expressions to system Mg-Sn shows that they are quite feasible.

Production of Potash and N-Mg Compound Fertilizer via Mineral Shoenite from Kunteyi Salt Lake:Phase Diagrams of Quaternary System(NH_(4))_(2)SO_(4)-MgSO_(4)-K_(2)SO_(4)-H_(2)O in the Isothermal Evaporation and Crystallization Process

Based on the requirement of the new technology for producing potassium sulfate and N-Mg compound fertilizer,boussingaultite,by the reaction of the mineral shoenite from Kunteyi Salt Lake,Qinghai province,and the industrial by-product ammonium sulfate,the solubilities of the quaternary system(NH_(4))_(2)SO_(4)-MgSO_(4)-K_(2)SO_(4)-H_(2)O at 25.0℃in the isothermal evaporation and crystallization process were measured using the isothermal evaporation method,and the corresponding phase diagrams were plotted.According to the diagram,this system contains six saturation points and six solid phase fields of crystallization,which correspond to(K1-m,(NH_(4))m)_(2)SO_(4),(NH_(4))_(2)SO_(4)·MgSO_(4)·6H_(2)O,K_(2)SO_(4)·MgSO_(4)·6H_(2)O,MgSO_(4)·6H_(2)O,(K1-n,(NH_(4))n)_(2)SO_(4)·MgSO_(4)·6H_(2)O and MgSO_(4)·7H_(2)O,respectively.By analyzing and calculating the isothermal evaporation and dissolution phase diagram of this quaternary system at 25.0℃,K_(2)SO_(4)and(NH_(4))_(2)SO_(4)·MgSO_(4)·6H_(2)O can be separated via K_(2)SO_(4)·MgSO_(4)·6H_(2)O and(NH_(4))_(2)SO_(4)as raw materials.Theoretical calculations about the proposed process were carried out and verified by experiment,which indicated that the yield of potassium sulfate was improved and the magnesium resources were fully utilized.

THREE-DIMENSIONAL TOPOLOGICAL ANALYSIS OF Nd-Fe-B AND Pr-Fe-B PHASE DIAGRAMS

With the aid of 3-dimensional topological analysis methodology,relationships among phage regions on the isothermal section of the Nd-Fe-B phase diagram at 1000℃ and those on vertical sections of the Pr-Fe-B phase diagram passing through Pr_2 Fe_(14)B point have been re-discussed and modified.

PHASE DIAGRAMS OF KF-LiCI-BaCl_2 AND LiF-LiCI-BaCl_2 SYSTEMS

The phase diagrams of molten salt systems KF-LiCI-BaCl_2 and LiCI-LiF-BaCl_2 have been determined by visual polythermal method.The relationship between the change of cation radius of monovalent fluoride and the areas of primary crystal region in the phase diagrams is discussed.

Relationship between the types of binary alloy phase diagrams of Ⅷ and IB group elements and the Mendeleev numbers

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.

Preparation of Y-Zr-Hf,Y-Zr-Nb Ternary Diffusion Couples and Phase Diagrams Determination

Work has been done in preparing ternary diffusion couple containing one rare earth element.Though rare earth is highly reactive,we have successfully prepared two ternary diffusion couples containing yttrium by means of special technique.By using electron microprobe analysis(EMPA),the two isothermal sections of Y-Zr-Hf and Y-Zr-Nb ternary systems at 1273K have been determined.The section of Y-Zr-Hf system consists of three one-phase regions,three two-phase regions and one three-phase region.And that of Y-Zr-Nb system consists of two one-phase regions and one two-phase region.The effeet of some factors on EMP measuring ac- curacy was also discussed.

Magnetic hysteresis, compensation behaviors, and phase diagrams of bilayer honeycomb lattices

Magnetic behaviors of the Ising system with bilayer honeycomb lattice（BHL） structure are studied by using the effective-field theory（EFT） with correlations. The effects of the interaction parameters on the magnetic properties of the system such as the hysteresis and compensation behaviors as well as phase diagrams are investigated. Moreover, when the hysteresis behaviors of the system are examined, single and double hysteresis loops are observed for various values of the interaction parameters. We obtain the L-, Q-, P-, and S-type compensation behaviors in the system. We also observe that the phase diagrams only exhibit the second-order phase transition. Hence, the system does not show the tricritical point（TCP）.

Phase diagrams of Li_2MoO_4-Na_2MoO_4 and Na_2MoO_4-K_2MoO_4 systems

The phase diagrams of the Li2MoO4-Na2MoO4 and Na2MoO4-K2MoO4 systems have been reassessed using differential thermal analysis together with high-temperature and room-temperature X-ray diffraction analysis. The results showed that the compound Li2MoO4.6Na2MoO4 did not exist; however, it confirmed the existence of the compound Li2MoO4.3Na2MoO4 in the Li2MoO4-Na2MoO4 systen＇ls. With regard to the system of Na2MoO4-K2MoO4, we could not confirm the results reported by Bukhanova who claimed that the system was eutectic type with 1：1 and 1：2 intermediate compounds, refuting the statement of Amadori who thought there was an apparent phase boundary at high temperature in α-solid solution region of the Na2MoO4-K2MoO4 binary system. The revised phase diagrams of these systems are illustrated in this article. These experimental results are in agreement with the computerized prediction using the support vector machine-atomic parameter method for the assessment of phase diagrams.

A Powerful Optimization Technique for the Calculation of Binary Phase Diagrams Using Partial Phase Diagram Data

The interaction parameters for various phases in the Ti-W and Pd-W systems were calcula- ted using phase diagram information by means of a numerical procedure.The approach differs significantly from the trial and error method and has the advantage of being very robust in the sense that one can make full use of the accurate experimental phase diagram data and deal with situations which are difficult or even impossible for the trial and error method. Using calculated parameters and lattice stability values for Ti,W and Pd given in literature, the diagrams of the above systems were recalcula- ted.The results are in good agreement with experimental information.