Experimental Validation is Always Required for Molten Oxide Electrolysis Laboratory Crucibles

Abstract

Molten oxide electrolysis (MOE) is a promising electrochemical route to de-carbonize primary and secondary metal production. Developing MOE processes starts with laboratory experiments at temperatures > 1000∘C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1000\\,^\\circ{\\rm C}$$\\end{document} lasting ~10 hours and requiring long heating/cooling times to protect furnace hardware. Before investigating MOE processes, crucibles must be selected that tolerate the required temperatures while minimizing chemical interactions with the oxide to control melt contamination and contain the melt. Unfortunately no general procedure guiding MOE crucible selection is documented. Here we focus on laboratory crucibles in air for two MOE melts: titania-sodia at 1100∘C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1100\\,^\\circ{\\rm C}$$\\end{document} and neodymia-boria at 1300∘C\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1300\\,^\\circ{\\rm C}$$\\end{document}. After shortlisting generic crucible materials using Ashby’s method, thermodynamic predictions were made for all-oxide titania-sodia charges using FactSage and cup test experiments were conducted on (i) all-oxide and carbonate charges for titania-sodia and (ii) neodymia-boria charges. While magnesia was predicted to be the best crucible for the titania-sodia melt, alumina was the best choice for both oxide and carbonate charges. The grain boundary networks of both magnesia and YSZ were infiltrated by the oxide and carbonate charges. Platinum was the best crucible for neodymia-boria melts. We show that compositional control during long, high-temperature MOE experiments requires experimental validation for specific chemistries every time.