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In situ pair distribution function analysis of crystallizing Fe-silicate melts

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Abstract

The structures of a series of Na2O–FeO–Fe2O3–SiO2 melts with Si/Fe = 1, 2, or 3 have been characterized via synchrotron X-ray total scattering using aerodynamic levitation, a containerless technique, paired with laser heating. The melt structure has been simulated using empirical potential structure refinement (EPSR) based on X-ray scattering data and molecular dynamics (MD) simulations with effective partial charge potentials. Pair distribution functions and coordination numbers of cations in the melt were obtained from the data refinement and from the MD simulations. Iron redox and accompanying density were modeled for each composition assuming either (1) oxidized (all Fe3+) or (2) reduced (some Fe2+) to the level predicted for the Ar levitator environment from a literature model. The actual redox of the melts appears to be intermediate, with some Fe2+ but not as much as assumed from the literature model of redox. Comparison of EPSR and MD models at the same redox conditions indicates generally good agreement, and precise values of coordination numbers depend sensitively on the assumptions for cutoff lengths. Stepwise cooling of each melt in the series resulted in formation of magnetite on the free surface of the sample, but no silica-containing crystalline phases were observed. This study provides a comprehensive assessment of coupled factors (composition, redox, density) needed to assess high-temperature in situ structural measurements of simplified iron silicates.

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Acknowledgements

Levitation experiments were conducted at the Advanced Photon Source, Argonne National Laboratory, Argonne, IL, on beamline 6-ID-D on GUP-60502. The authors would like to thank Chris Benmore of the Advanced Photon Source and Martin Wilding of Manchester University Harwell for the assistance with the total scattering experiments, and Richard Weber of Materials Development Inc. for use of the laser hearth for sample preparation. The authors thank Scott Boroughs for help with the electron microprobe measurements. The authors also thank José Marcial for assistance with processing the total scattering data. This manuscript benefited greatly from the careful reading and comments of several reviewers.

Funding

The research was funded by the Department of Energy, Office of Environmental Management, through the Office of River Protection, Waste Treatment and Immobilization Plant Federal Project Office, contract numbers DE-EM002904 and 89304017CEM000001, under the direction of Dr. Albert A. Kruger. JD acknowledges National Science Foundation (NSF) support with the DMR Ceramics program under grant 1508001 and UNT HPC for providing computing resources.

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Authors and Affiliations

  1. Materials Science and Engineering Program, Washington State University, Pullman, WA, USA

    Emily T. Nienhuis & John S. McCloy

  2. Department of Materials Science and Engineering, University North Texas, Denton, TX, USA

    Manzila Tuheen & Jincheng Du

  3. School of Mechanical and Materials Engineering, Washington State University, Pullman, WA, USA

    John S. McCloy

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  1. Emily T. Nienhuis
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  2. Manzila Tuheen
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Correspondence to John S. McCloy.

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Nienhuis, E.T., Tuheen, M., Du, J. et al. In situ pair distribution function analysis of crystallizing Fe-silicate melts. J Mater Sci 56, 5637–5657 (2021). https://doi.org/10.1007/s10853-020-05643-x

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