Thermodynamic Assessment of DyCl3-MCl （M= Na, K, Rb, Cs） Systems

Using the CALPHAD （Calculation of Phase Diagram） technique, the DyCl3-MCl （M = Na, K, Rb, Cs） systems were optimized and calculated. The modified quasi-chemical model in the pair approximation for short-range ordering was used to describe the Gibbs energies of the liquid phase in these systems. From the measured phase diagram data and experimental thermodynamic properties, a series of thermodynamic functions were optimized base on an interactive computer-assisted analysis. The optimized parameters and the experimental data were thermodynamically self-consistent. The optimized results were discussed.     

Experimental Study and Thermodynamic Optimization of the FeO-V203 System

Optimization of the phase diagram of FeO-V20a system is a part of an on-going research project to develop a self-consistent multi-component thermodynamic database for vanadium slag from hot metal. Due to the lack o{ ex- perimental data for optimization, a novel experimental investigation has been carried out by thermal analysis （DSC） with a series of slags on different V2 03 contents （i. e. 3mass%- 12mass%）. All available thermodynamic and phase diagram data for the binary systems have been simultaneously optimized with CALPHAD （Calculation of Phase Dia- grams） methods to give one set of model equations for the Gibbs free energy of the liquid slag as functions of compo- sition and temperature. The modified quasi-chemical model was used to describe the binary slag system. It was dem- onstrated that the calculated phase diagram with the optimized parameters was in good agreement with the experi- mental data.     

The Thermodynamics of Cu-La,Cu-Ce Systems

The Cu-La,Cu-Ce systems have been optimized using the recommended phase diagrams and the experi-mental thermodynamic values reported in the recent years.The optimization results are in good agreement withthe experimental data.     

Co-Cr系相平衡的热力学计算和fcc相的磁性诱导相分离

Two-phase equilibria between the ferromagnetic fcc and the paramagnetic fcc phase from 800 ℃ to 900 ℃ in the Co-rich region have been detected by the diffusion couple technique. Two phase separation region of the fcc has been confirmed along the Curie temperature. The phase equilibria including the present results and the thermodynamic data of the Co-Cr system reported in the literature were analyzed on the basis of the thermodynamic evaluation. A set of thermodynarnic values for the liquid, fcc, hcp, bcc, sigma phases was obtained. The calculated phase equilibria were in good agreement with most of the experimental data.     

Mathematical Viscosity Models for Ternary Metallic and Silicate Melts

The mathematical viscosity models for metallic melts were discussed. The experimental data of Ag-Au-Cu systems were used to verify the models based on Chou‘s general geometric thermodynamic model and the calculated results are consistent with the reported experimental data. A new model predicting the viscosity of multi-component silicate melts was established. The CaO-MnO-SiO2, CaO-FeO-SiO2 and FeO-MnO-SiO2 silicate slag systems were used to verify the model.     

Computer-Aided Design of Some Advanced Steels and Cemented Carbides

Thermodynamic and kinetic study on TRIP （transformation induced plasticity） steels, cemented carbides and mold steel for plastics were carried out in order to design modern advanced materials. With the sublattice model, equilibrium compositions of ferrite and austenite phases in TRIP steels, as well as volume fraction of austenite at inter-critical temperatures for different time were calculated. Concentration profiles of carbon, manganese, aluminum and silicon in the steels were also estimated in the lattice fixed frame of reference. The effect of Si and Mn on TRIP was discussed according to thermodynamic and kinetic analyses. In order to understand and produce the graded nanophase structure of cemented carbides, miscellaneous phases in the M-Co-C （M= Ti, Ta, Nh） systems and Co-V-C system were modeled. Solution parameters and thermodynamic： properties were listed in detail. The improvement of machining behavior of prehardened mould steel for plastics was obtained by computer-aided composition design. The results showed that the matrix composition of large-section prehardened mould steel for plastic markedly influences the precipitation of non-metallic inclusion and the composition control by the aid of Thermo-Calc software package minimizes the amount of detrimental oxide inclusion. In addition, the modification of calcium was optimized in composition design.     

New Methodological Approach to Investigation of Kinetics of REE Extraction in Nonstationary Conditions

The influence of periodical oscillations of the temperature on extraction and stripping processes in the extraction systems was studied. Two extraction systems were investigated： （1） 6 mol · L^-1 NaNO3-Nd（NO3）3-Pr（NO3）3-TBP kerosene and （2） [Nd（NO3）3 · 3TBP] -[ Pr（NO3）3 · 3TBP] -kerosene - 0.1 mol · L^-1 HNO3. Mathematical modeling of the nonstationary membrane extraction has been enhanced by including the dependence of the extraction rate constants on temperature. The values of activation energy for direct and reverse extraction and stripping reactions of Pr and Nd were calculated from experimental temporal dependencies of metal concentration and temperature by solving the reverse kinetics problem using the proposed mathematical model, A series of experiments with periodical oscillations of the temperature on the extraction system for the separation of rare earth elements （REE） using bulk liquid membrane between two extractors were performed. The mathematical model adequately describes the experimental data. The optimization of the extraction process for separation of REE by liquid membrane, under the influence of periodical oscillation of the temperature, was made based on the extraction rate constants and activation energies. The optimal conditions of separation by liquid membrane were found： frequency and amplitude of thermal oscillations, liquid membrane flow rate, and optimal ratio between organic and aqueous phase in extractors.     

Calculation of thermodynamic parameters of 75 gaseous PCDDs using the density functional theory

In this paper, the thermodynamic parameters are calculated for all gaseous Poly Chlorinat Dibenzo-p-dioxins （PCDDs） using the Density Functional Theory （DFF） method and both the enthalpy of formation （ΔfH^0） and Gibbs free energy of formation （Δf G^0） are derived, from which the order of stability of individual congeners is then predicted. All these properties, together with the calculated entropies （ S^0） and heat capacities （ Cp）, are presented as a function of the number of chlorine atoms in the various PCDD molecules. The accuracy of the method used here, is evaluated by comparing the thermodynamic parameters of gaseous chlorobenzenes with experimental values collected from literature.     

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 propertiesof 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 area better basis for constructing multicomponent phase diagrams.     

THERMODYNAMIC OPTIMIZATION AND CALCULATION OF THE Fe-Pr SYSTEM

Based on the phase diagram of the Fe-Pr system available,the thermodynamic optimization and calcula-tion of the system have been carried out by the least square method.The lattice stabilities of Fe and Pr aredescribed by the expression recommended by SGTE organization.The liquid phase is described by thesubregular solution model.The intermetallic compounds,Fe_(17)Pr_2 and Fe_2Pr,are treated as stoichiometriccompounds.The optimized parameters describing phases in the system are presented.The comparision be-tween the calculated and experimentally determined phase diagram shows that the agreement is generally verygood except for the liquid δ-Fe equilibrium.It is suggested to measure this part of phase diagram again.     

Experimental and thermodynamic study of the equilibria between ferrite,austenite and intermediate phases in the fe-mo,fe-w,and fe-mo-w systems

The phase equilibria between ferrite and austenite and between ferrite and the intermediateR- andμ-phases have been studied by subjecting high purity alloys of Fe-Mo, Fe-W, and Fe-Mo-W to well controlled heat treatments. The equilibrium compositions at the two-phase interfaces were measured with an electron microprobe. Some of the experimental results show reasonable agreement with previously reported values, but are believed to be of higher accuracy. The new experimental data were, together with available relevant thermodynamic information, evaluated in terms of mathematical models for the individual phases and the parameters thus obtained were then used to calculate the two-phase boundaries in the binary Fe-Mo, Fe-W, and ternary Fe-Mo-W systems. In the course of this study the free energy of formation of theR andμ phases was also evaluated. Formerly Assistant Professor, the Division of Physical Metallurgy, Royal Institute of Technology, Stockholm, Sweden.     

Thermochemistry on Coordination Behavior of Neodymium Chloride Hydrate with Diethylammonium Diethyldithiocarbamate

The complex of neodymium chloride lower hydrate with diethylammonium diethyldithiocarbamate (D-DDC) was synthesized conveniently in absolute alcohol and dry N2 atmosphere. The title complex was identified as Et2NH2 [ Nd(S2CNEt2)4] by chemical and elemental analyses and the bonding characteristics of which was characterized by IR. The enthalpies of solution of neodymium chloride hydrate and D-DDC in absolute alcohol at 298.15 K and the enthalpies change of liquid-phase reaction of formation for Et2NH2[ Nd (S2CNEt2)4] at different temperatures were determined by microealorimetry. On the basis of experimental and calculated results, three thermodynamic parameters (the activation enthalpy, the activation entropy and the activation free energy), the rate constant and three kinetic parameters (the apparent activation energy, the pre-exponential constant and the reaction order) of liquid-phase reaction of formation were obtained.The enthalpy change of the solid-phase title reaction at 298.15 K was calculated by a thermochemical cycle.     

Structure modeling of terbium doped strontium-lanthanum borate

Terbium doped strontium-lanthanum borate, Sr3La2（BO3）4：Tb （SLB）, was studied by semi-empirical computational ap- proaches using PM6 parametrization and the SPARKLE model for lanthanide（Ⅲ） （Ln（Ⅲ）） cations. The focus of interest was on structural aspects, e.g. the cell parameters and distribution of dopant ions between various sites as a function of dopant concentration. The cell linear dimensions were calculated to decrease linearly with increasing dopant molar concentration. SLB offered two sites for the dopant. Calculations predicted that one of these sites should be preferred by the Tb（Ⅲ） dopant. The optimized cell dimensions as well as the total energies differed for structures with dopant exclusively in site 1 or site 2. Computational predictions were tested against experimental results obtained for SLB synthesized by sol-gel method varying the dopant concentration. The agreement be- tween experimental and computational results was found sufficiently promising to continue the computational studies.     

First principles study of structural,electronic, elastic and magnetic properties of cerium and praseodymium hydrogen system REH_x(RE:Ce,Pr and x=2, 3)

The structural, electronic, elastic and magnetic properties of cerium, praseodymium and their hydrides REH x(RE=Ce, Pr and x=2, 3) were investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation package. At zero pressure all the hydrides were stable in the ferromagnetic state. The calculated lattice parameters were in good agreement with the experimental results. The bulk modulus decreased with the increase in the hydrogen content for these hydrides. The electronic structure revealed that di-hydrides were metallic whereas trihydrides were half metallic at zero pressure. A pressure-induced structural phase transition from cubic to hexagonal phase was predicted in these hydrides. The computed elastic constants indicated that these hydrides were mechanically stable at zero pressure. The calculated Debye temperature values were in good agreement with experimental and other theoretical results. A half metallic to metallic transition was also observed in REH3 under high pressure. Ferromagnetism was quenched in these hydrides at high pressures.     

Synthesis,spectral characterization,thermal and biological studies of lanthanide（III） complexes of oxyphenbutazone

Lanthanide（III） complexes of 4-butyl-1-（4-hydroxyphenyl）-2-phenyl-3,5-pyrazolidinedione （OPB） were prepared by ho-mogeneous precipitation. The solid complexes were characterized by elemental analysis, magnetic susceptibility data, molar conduc-tivity measurements and IR, UV-Vis, mass, 1H NMR and 13C NMR spectral methods. The thermal decomposition of the complexes under static air atmosphere was investigated by simultaneous TG/DTG at a heating rate of 10 °C/min. The final decomposition prod-ucts were found to be metal oxides. The spectroscopic data suggested that OPB acted as a bidentate, mono-ionic ligand coordinating through two carbonyl oxygens of the pyrazolidinedione ring. The kinetic and thermodynamic parameters such as activation energy, pre-exponential factor and entropy of activation for each step of the decomposition reactions were evaluated using Coats-Redfern and MacCallum-Tanner equations. The negative entropy values of the complexes indicated that the activated complexes had a more or-dered structure than the reactant and that the reactions were slower than normal. Investigations of antimicrobial activity of the com-pounds were carried out by the disk diffusion technique.     

Evaluation of D113 cation exchange resin for the removal of Eu(Ⅲ) from aqueous solution

Batch adsorption experiments were conducted for the adsorption of Eu(Ⅲ) ions from aqueous solution by D113 resin. The results indicated that D113 resin could adsorb Eu(Ⅲ) ion effectively from aqueous solution. The adsorption was strongly dependent on pH of the medium with enhanced adsorption as the pH turned from 3.50 to 7.00 and the optimal adsorption condition was in HAc-NaAc medium with pH value of 6.50. The maximum uptake capacity of Eu(Ⅲ) ions was 290.9 mg/g D113 at 298 K, at an initial pH value of 6.50. The overall adsorption process was best described by Lagergren-first-order kinetics. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The thermodynamic parameters such as free energy (G) which were all negative, indicated that the adsorption of Eu(Ⅲ) ions onto D113 resin was spontaneous and the positive value of enthalpy (H) showed that the adsorption was endothermic in nature. Thomas model was applied to experimental column data to determine the characteristic parameters of column useful for process design. Furthermore, Eu(Ⅲ) could be eluted by using 3.0 mol/L HCl solution and the D113 resin could be regenerated and reused.     

Stability of phases in （Ba,Gd）MnO3 solid solution system

The existing phases in BaxGd1-xMnO3 solid solution system （0≤x≤ 1） were studied by analyzing the detailed crystal structure of each composition from the results of the Rietveld method using powder X-ray diffraction data. For a small substitution of Ba for Gd （0≤x〈0. 1）, the orthorhombic phase with a perovskite type structure （Pnma space group） was stably formed and this fact was supported by the electron diffraction data. There existed an intermediate phase of Ba0.33Gd0.67MnO3, which was characterized as the tetragonal phase with perovskite structure. The composition range of this phase was narrow and almost line compound. Between the regions of these phases, there existed two-phase region. There was also a two-phase region between the intermediate tetragonal phase and BaMnO3. Measurement of electrical conductivities of these orthorhombic solid solutions and tetragonal phases showed semiconducting behaviors for both phases and the existence of the phase transition at high temperature for the orthorhombic phase, The transition temperature decreased as the Ba content increased.     

Prediction of Activities in Fe-Based Ternary Liquid Alloys by Hoch-Arpshofen Model

 Thermodynamic properties for an alloy system play an important role in the materials science and engineering. Therefore, theoretical calculations having the flexibility to deal with complexity are very useful and have scientific meaning. The Hoch-Arpshofen model was deduced from physical principles and is applicable to binary, ternary and larger system using its binary interaction parameters only. Calculations of the activities of Fe-based liquid alloys are calculated using Hoch-Arpshofen model from data on the binary subsystems. Results for the activities for Fe-Au-Ni, Fe-Cr-Ni, Fe-Co-Cr and Fe-Co-Ni systems at required temperature are presented by Hoch-Arpshofen model. The average relative errors of prediction are 78%, 45%, 49% and 27%, respectively. It shows that the calculated results are in good agreement with the experimental data except Fe-Au-Ni system, which exhibits strong interaction between unlike atoms. The model provides a simple, reliable and general method for calculating the activities for Fe-based liquid alloys.     

Structural,electrical and magnetic studies on Y-Fe-O system

The compounds of iron substituted yttrium oxide systems have been prepared for the importance in the field of magneto electric materials.The polycrystalline samples of Y2-xFexO3-y(x=0.1,0.2) were prepared by solid-state reaction method.The single-phase formation of these compounds was confirmed by X-ray diffraction studies.It was found that the samples crystallized in tetragonal phase and the lattice parameters were calculated as a=1.0559(7) nm,c=1.0832(9) nm for Y1.9Fe0.1O3-y and a=1.0545(6) nm,c=1.0841(8)...