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Primary phases in aluminous slags produced by the aluminothermic reduction of pyrochlore

Published online by Cambridge University Press:  02 January 2018

Roger H. Mitchell  and
Anthony N. Mariano
Roger H. Mitchell*
Affiliation:
Department of Geology, Lakehead University, Thunder Bay, Ontario Canada P7B 5E1
Anthony N. Mariano
Affiliation:
48 Page Brook Road, Carlisle, Massachusetts 01741, USA
*
*E-mail: rmitchel@lakeheadu.ca
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Abstract

Phases present in slags from Araxá (Brazil), Oka (Quebec) and Fen (Norway) resulting from the production of ferroniobium by the aluminothermic reduction of pyrochlore-group minerals are a function of composition of the pyrochlore feed and the diverse fluxes (CaO, CaF2) added to the alumina and iron oxide used in the reduction process. Absent from all slags investigated are Fe-bearing compounds. All of the slags are modally-dominated by prismatic crystals of β-alumina or hibonite, with a wide variety of Th-Ba-Ti-Nb-Al-oxide compounds and silico-aluminate glasses occurring in the interstices between these crystals. Slag from Fen consists of a framework of β-alumina (Ba and/or CaTi varieties) with a barian titanian niobate, considered to be an highly reduced Nb3+- and Ti3+-bearing anion deficient perovskite, as the first oxide phase to crystallize. This was followed by a Zr-Ti-Th-niobate (21.7–24.1 wt.% ThO2), a Nb-rich, Thbearing zirconolite-like phase (17.7–21.2 wt.%; Nb2O5; 6.8–9.5 wt.% ThO2) and diverse Th-Nb-rich, Alpoor (< 1 wt.% Al2O3) perovskites (29.4–40.5 wt.% Nb2O5; 3.3–11.4 wt.% ThO2). The latter represents a NaNbO3–CaTiO3–Na2/3Th1/3TiO3–ThTi2O6 solid solution. Late Na-rich silicate glass contains celsian. Slag from Araxá also consists of a framework of β-alumina (Ti-poor). Interstitial compounds differ from Fen in being predominantly rare-earth element (REE)-Nb-Al-Th-perovskites belonging to a REEAlO3–Ca2AlNbO6–CaTiO3–ThTi2O6 solid solution with minor NaNbO3 and CaZrO3, and compositionally diverse barium calcium aluminates [(Ba, Ca)Al2O4] set in a F-bearing (6–7 wt.%) Na-Ba-Si-aluminate glass with minor Ba4Nb2O9, CaF2, BaF2 and NaF. Slag from Oka consists of a framework of hibonite [(Ca, REE) (Al, Ti, Mg)12O19] zoned with respect to the REE content. Interstitial compounds are CaZr4O9, Nb-Th-poor perovskites belonging to the REEAlO3–CaTiO3 series with minor CaZrO3 set in a F-bearing (5–6 wt.%) calcium aluminate glass. These data demonstrate that during ferroniobium production REE, Zr, Th, U and significant amounts of Nb are sequestered in the oxide phases in accord with their lithophile geochemical character. None of these elements are present as compounds in the siderophillic ferroniobium alloys. These data demonstrate that the aluminothermic reduction process results in the loss of significant amounts of Nb to the slag. Perovskite-group compounds are present in all of the slags but differ widely in their composition as a result of compositional differences in the feed pyrochlores and fluxes added to the smelting process. Slags originating from ferroniobium production are enriched in Th and U and could be considered as an environmental hazard if these elements are mobilized during chemical weathering of slag.

Keywords

SlagPerovskiteZirconolitePyrochloreβ-AluminaHiboniteAluminothermic ReductionOkaFenAraxá
Type
Research Article
Information
Mineralogical Magazine , Volume 80 , Issue 2 , April 2016 , pp. 383 - 397
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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