ISIJ International
Online ISSN : 1347-5460
Print ISSN : 0915-1559
ISSN-L : 0915-1559
Fundamentals of High Temperature Processes
Viscosity of Na–Si–O–N–F Melts: Mixing Effect of Oxygen, Nitrogen, and Fluorine
Sohei SukenagaMasayuki OgawaYutaka YanabaMariko AndoHiroyuki Shibata
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2020 Volume 60 Issue 12 Pages 2794-2806

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Abstract

Fluorine and nitrogen are important elements of metallurgical slags and fluxes. Studies on their viscosity have often focused on the additive effect of fluoride and nitride compounds (e.g., CaF2 and Si3N4), whereas the influence of anionic composition (i.e., oxygen, fluorine, and nitrogen concentrations) with a fixed cationic composition remains unclear. The present study reports the scarcely quantified viscosity variations due to changes in the anionic composition of a simple sodium silicate system by rotating crucible method under a controlled atmosphere. 29Si magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to characterize the structural changes against varying nitrogen and fluorine concentrations in the quenched glassy sample. The observed change in the local silicon structure was consistent with the expected variation from the conventional structural roles of nitrogen and fluorine in silicate glasses: nitrogen atoms tend to bond with silicon atoms, whereas fluorine atoms prefer to exist in surrounding sodium cations. Moreover, nitrogen tends to increase the viscosity, whereas fluorine strongly decreases the viscosity of the sodium silicate melts even with the enhancing effect of the latter on the polymerization of silicate anions. The viscosity of silicate melts has been commonly related to the overall polymerization degree of the liquid. However, the viscosity of fluorine-containing silicates cannot be explained by this conventional scenario. Fluorine ions tend to loosely bond with sodium cations. These sodium–fluorine complexes played a strong lubricant role in the network liquids.

Schematic illustrations of the possible structural variations under different anionic compositions of (a) oxide, (b) oxynitride, (c) oxyfluoride, and (d) fluoroxynitride glasses in a plane. For simplicity, the coordination number of each atoms and Qn distribution of silicon atoms were not considered. (Online version in color.) Fullsize Image
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© 2020 The Iron and Steel Institute of Japan.

This is an open access article under the terms of the Creative Commons Attribution-NonCommercial-NoDerivs license.
https://creativecommons.org/licenses/by-nc-nd/4.0/
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