Determination of the Al sub( 2)O sub( 3) Content in NaF-AlF sub( 3)-CaF sub( 2)-Al sub( 2)O sub( 3) Melts at 950 degree C by Raman Spectroscopy

The in situ control of the chemical composition of industrial aluminum smelter is a challenge mainly for physicochemical reasons: high temperature, high surrounding electromagnetic field, and the highly corrosive molten salt electrolyte to deal with. In previous works, we proposed that Raman spectroscopy is a method of choice that could be adapted to real smelters. The laboratory study presented here relies on reproducible Raman spectra recorded on molten mixtures whose compositions are identical to those used during the production of aluminum. A normalization procedure for the Raman spectra is proposed based on the equilibria taking place in the bath. In addition, we discuss two quantitative models to determine the alumina content from the Raman spectra of the molten NaF-AlF3-CaF2-Al2O3 electrolytes. Univariate and multivariate approaches are applied to determine both the COx (alumina content) and the CR (NaF/AlF3 molar ratio) by Raman spectroscopy without referring to an additional internal reference of intensity. The procedure was successfully tested and validated on industrial samples.