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.

Experimental and Thermodynamic Analysis on Phase Equilibria of Ni-rich Region in Ni-Al-Ti System

Phase equilibria including γ,γ′,η,β and H in Ni Al Ti system were investigated by diffusion couple method and calculated with thermodynamic model.The experimental phase equilibria generally agree with ones reported till now.Regular solution and sublattice models were used in order to calculate these phase equilibria.The calculated results show agreement with experimental data.

INFLUENCE OF ALCOHOL-BASED NONSOLVENTS ON THE FORMATION AND MORPHOLOGY OF PVDF MEMBRANES IN PHASE INVERSION PROCESS

Through the preparation of PVDF membranes using various nonsolvent coagulation baths following the phase inversion process, the influence of alcohol-based nonsolvents on the formation and structure of PVDF membranes were investigated. The light scattering and light transmission measurements were used to characterize the equilibrium phase diagram and the gelation speed, respectively. The locations of the crystallization-induced gelation boundaries for various systems and precipitation processes were explained from the corresponding thermodynamic and kinetic parameters. It was found that the better affinity between alcohol-based nonsolvents and DMAc solvent caused the gelation boundaries further away from the PVDF-DMAc axis with the coagulation bath varying from water, methanol, ethanol to iso-propanol. Due to the lower exchange rate of DMAc and alcohols, the delayed demixing took place for the membrane-forming using alcohols as baths, and the delayed time became longer when the coagulation bath was changed from methanol, ethanol to iso-propanol. The characterization results of membranes indicate that the influence of nonsolvents on the phase diagram and the precipitation process are in agreement with those on the membrane morphology. The better thermodynamic stability and a low exchange diffusion rate of PVDF/DMAc/alcohols favor the liquid-solid phase separation in gelation process, and therefore yield the membranes with a porous upper surface, a particular bottom surface and symmetrical structure.

FactSage Thermodynamic Database for Steelmaking Refractory Research

Thermodynamic databases are very useful to analyze the complex chemical reactions happening in high temperature material processes. An accurate thermodynamic database based on physically sound thermodynamic models can provide thermodynamic calculations of useful phase diagrams and comprehensive chemical reactions related to refractory corrosion in steelmaking processes. In this study,the FactS age thermodynamic database,one of the most comprehensive thermodynamic databases for oxide systems among other commercial software,is reviewed in particular for the steelmaking refractory research,and several applications to refractory corrosion are presented.

Thermodynamic Analysis of Chemical Vapor Deposition of BCl_3-NH_3-SiCl_4-H_2-Ar System

The thermodynamic phase stability area diagrams of BCl3-NH3-Si Cl4-H2-Ar system were plotted via Factsage software to predict the kinetic experimental results. The effects of parameters(i e, partial pressure of reactants, deposition temperature and total pressure) on the distribution regions of solid phase products were analyzed based on the diagrams. The results show that:(a) Solid phase products are mainly affected by deposition temperature. The area of BN+Si3N4 phase increases with the temperature rising from 650 to 900 ℃, and decreases with the temperature rising from 900 to 1 200 ℃;(b) When temperature and total pressure are constants, BN+Si3N4 phase exists at a high partial pressure of NH3;(c) The effect of total system pressure is correlated to deposition temperature. The temperature ranging from 700 to 900 ℃ under low total pressure is the optimum condition for the deposition.(d) Appropriate kinetic parameters can be determined based on the results of thermodynamic calculation. Si–B–N coating is obtained via low pressure chemical vapor deposition. The analysis by X-ray photoelectron spectroscopy indicates that B–N and Si–N are the main chemical bonds of the coating.

Thermodynamic Assessments of Ternary Ga-As-P,Ga-P-Sb,In-As-P and In-P-Sb Systems

The experimental phase diagram data of the Ga-As-P,Ga-P-Sb,In-As-P and In-P-Sb ternary systems were critically assessed. A set of self-consistent thermodynamic model parameters were obtained and used to describe the phase equilibria of these systems. In most cases, the calculated values agree very well with the experimental data.

Thermodynamic and Phase Diagram Modeling of CsF-MF4（M=U, Th） Systems

Phase diagrams for the CsF-UF4 and CsF-ThF4 systems were modeled in the present work through computational thennodynamics. The associate solution model with various complex species（CsMFs, Cs2MF6 and Cs3MF7; M=Th, U） was used to thermodynamically describe the binary molten salts. A total of ten intermediate phases were treated as stoichiometric compounds with their Gibbs energies modeled according to the Neumann-Kopp rule. All these model parameters were optimized by the least squares procedure until good coincidence was achieved between the calculated results and most of the experimental data. The derived thermodynamic parameters will be merged into the multicomponent CsF-LiF-BeF2-ThF4-UF4 database for analyzing physicochemical behavior of CsF in the fuel salt of the molten salt breeder reactor.

Experimental study and thermodynamic calculation of Lu2O3-SiO2 binary system

As a binary system of BaO-Lu_2O_3-SiO_2 ternary system, Lu_2O_3-SiO_2 system was optimized and calculated by CALPHAD approach based on available phase diagram and relevant thermodynamic data of RE_2O_3-SiO_2（RE=Lu,Yb,Y） binary systems as well as our experimental data of Lu_2O_3-SiO_2 system obtained by quenching experiment. The Gibbs free energy of high temperature solution was described by an ionic two-sublattice model as（Lu^（3＋））P（O^（2-）, SiO_2~0）Q. The calculated phase diagram below 1873 K was in good agreement with experimental data at 1573, 1773 and 1873 K. The calculated Gibbs energies of two intermediate phases Lu_2SiO_5 and Lu_2Si_2O_7, the activity of Lu_2O_3 and SiO_2 and specific heat capacities of intermediate phases agreed well with experimental results of Y_2O_3-SiO_2 system. This tentative study will offer help for the research of single-phase phosphor and related metallurgical slags, refractories, high-temperature superconductivity material systems.