Thermodynamic Properties of CaCl2-CaF2-CaO System: Phase Diagram Investigation

The CaCl2-CaF2-CaO phase diagram was investigated in the CaO low region (<40 mol.%). CaCl2-CaF2 and CaCl2-CaO binary diagrams, constituting the ternary system, were first studied by Differential Scanning Calorimetry (DSC) measurements and X-Ray Diffraction (XRD) characterization; a good agreement was obtained between the phase diagram models calculated with FactSage® software (FTsalt database) and present experimental data. As the CaF2-CaO liquidus could not be measured by DSC due to the high melting temperature, this diagram was calculated using FTsalt database combined with FToxid database of FactSage® software. The ternary phase diagram was obtained by calculations and exhibits an eutectic at the composition CaCl2-CaF2-CaO (78.2-15.7-6.1 mol.%) melting at 637°C, and five peritectic points. Measurements of relevant vertical cross-sections for three CaCl2-CaF2 compositions (50-50, 40-60 and 30-70 mol.%) up to 18 mol.% CaO are in agreement with the ternary phase diagram model. For each section, the liquidus temperature is constant up to around 11 mol.% CaO and then sharply increases. Moreover, an increase of CaF2 content in CaCl2-CaF2 melt leads to a decrease of the CaO solubility in isothermal condition.

[1]  L. Rycerz Practical remarks concerning phase diagrams determination on the basis of differential scanning calorimetry measurements , 2013, Journal of Thermal Analysis and Calorimetry.

[2]  I. Jung,et al.  Phase Diagram Study of the CaO–CaF2 System , 2012 .

[3]  Marie-Aline Van Ende,et al.  A Critical Evaluation and Thermodynamic Optimization of the CaO-CaF2 System , 2012, Metallurgical and Materials Transactions B.

[4]  Stephen Shaw,et al.  Solubility of Calcium in CaCl2-CaO , 2009 .

[5]  Gunnar Eriksson,et al.  FactSage thermochemical software and databases - recent developments , 2009 .

[6]  Xuan Liu,et al.  CaO solubility and activity coefficient in molten salts CaCl2–x (x = 0, NaCl, KCl, SrCl2, BaCl2 and LiCl) , 2008 .

[7]  F. Tsukihashi,et al.  Calculation of thermodynamic properties and phase diagrams for the CaO-CaF2, BaO-CaO and BaO-CaF2 systems by molecular dynamics simulation , 2005 .

[8]  Gunnar Eriksson,et al.  FactSage thermochemical software and databases , 2002 .

[9]  P. Chartrand,et al.  Thermodynamic evaluation and optimization of the Li, Na, K, Mg, Ca//F, Cl reciprocal system using the modified quasi-chemical model , 2001 .

[10]  D. Fray,et al.  Study of the ternary system CaCl2–NaCl–CaO by DSC , 2000 .

[11]  M. E. Brown Differential scanning calorimetry — An introduction for practitioners , 1997 .

[12]  J. Guenet Contributions of phase diagrams to the understanding of organized polymer-solvent systems , 1996 .

[13]  F. Tsukihashi,et al.  THERMODYNAMICS OF PHOSPHORUS IN CAO-CAF2-SIO2 AND CAO-CAF2-CACL2 MELTS SATURATED WITH CAO , 1991 .

[14]  G. Perry,et al.  Role of CaCl2 in the reduction of PuO2 , 1985 .

[15]  K. Schwerdtfeger,et al.  Contribution to the phase diagram CaF2-CaO-Al2O3 , 1980 .

[16]  C. E. Messer Hydrides versus fluorides: Structural comparisons☆☆☆ , 1970 .

[17]  R. D. Wolson,et al.  CaCl2-rich region of the CaCl2-CaF2-CaO system , 1969 .

[18]  W. D. Threadgill The Calcium Chloride‐Calcium Oxide Fused Salt Electrolytic System: Solubilities, Metal Contents, and Freezing Points , 1965 .

[19]  Joydeb Mukerji Phase Equilibrium Diagram CaO—CaF2—2CaO.SiO2 , 1965 .

[20]  C. Kröger,et al.  Die Systeme Erdalkalichlorid-Erdalkalioxyd und die Zersetzung der Erdalkalichloride durch Wasserdampf , 1935 .

[21]  K. Arndt,et al.  Über Lösungen von Kalk und Kieselsäure in geschmolzenem Chlorcalcium) , 1909 .

[22]  G. Tammann Über die Ermittelung der Zusammensetzung chemischer Verbindungen ohne Hilfe der Analyse , 1903 .

[23]  A. Zaitsev,et al.  Thermodynamic calculation of phase equilibria in the CaF2-SiO2-CaO system , 1993 .

[24]  A. Chatterjee,et al.  The phase equilibrium diagram of the system CaO-Al2O3-CaF2 , 1972 .

[25]  W. Plato Erstarrungserscheinungen an anorganischen Salzen und Salzgemischen. II , 2022 .