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Activity Measurement of the CaS-MnS Sulfide Solid Solution and Thermodynamic Modeling of the CaO-MnO-Al2O3-CaS-MnS-Al2S3 System

Title
Activity Measurement of the CaS-MnS Sulfide Solid Solution and Thermodynamic Modeling of the CaO-MnO-Al2O3-CaS-MnS-Al2S3 System
Authors
Rongxun PiaoHae-Geon LeeKang, YB
POSTECH Authors
Kang, YB
Date Issued
Dec-2013
Publisher
ISIJ
Abstract
In order to provide a prediction tool for sulfide/oxide/oxysulfide inclusion evolution in Mn-Al steel with a Ca addition/CaO-based flux, a comprehensive thermodynamic database for the inclusion system composed of CaO-MnO-Al2O3-CaS-MnS-Al2S3 was developed in the present study. Activity of MnS in a CaS-MnS sulfide solid solution was experimentally determined by employing a chemical equilibrium technique at 1 400 degrees C and 1 500 degrees C. The measured activity exhibits a positive deviation from an ideal behavior, which is in consistent with the known two-phase separation of the sulfide solid solution at lower temperature (T-cr = similar to 1 200 degrees C). Based on the activity and the phase diagram data available in literature, a thermodynamic modeling of the CaS-MnS system was carried out. The following excess Gibbs free energy of the CaS-MnS sulfide solid solution was obtained: g(ex) = XCaSXMnS (24476.4 - 0.4184T + 2928.8 (X-CaS - X-MnS)) [J/mol] Furthermore, using available thermodynamic modeling results for other constituent sub-systems, a larger thermodynamic database of the CaO-MnO-Al2O3-CaS-MnS-Al2S3 system was developed. A Modified Quasichemical Model in the quadruplet approximation was used to model the Gibbs free energy of the oxysulfide liquid solution. Comparisons between the model calculation and available experimental data show good agreement. The developed thermodynamic model and the database were used to predict unexplored phase diagrams with various n(Mn)/(n(Ca) + n(Mn)) ratio, and sulfide capacity of the CaO-MnO-Al2O3 oxide liquid phase. The database can be used along with software for Gibbs free energy minimization in order to calculate any phase diagram section or thermodynamic property.
Keywords
CaS-MnS system; CaO-MnO-Al2O3-CaS-MnS-Al2S3 system; activity; thermodynamic modeling; inclusion; PHASE-EQUILIBRIA; MNO-SIO2-AL2O3-MNS SYSTEM; OPTIMIZATION; INCLUSIONS; SLAG; DATABASES; DIAGRAMS; STEELS; OXIDE
URI
http://oasis.postech.ac.kr/handle/2014.oak/14761
DOI
10.2355/ISIJINTERNATIONAL.53.2132
ISSN
0915-1559
Article Type
Article
Citation
ISIJ INTERNATIONAL, vol. 53, no. 12, page. 2132 - 2141, 2013-12
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강윤배KANG, YOUN-BAE
Ferrous & Energy materials Technology
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