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In situ voltammetric observation of transitions above the liquidus in silicate melts

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Abstract

Reduction potentials (E 0) and diffusion rates (D) for divalent nickel in a variety of silicate melts and as a function of temperature have been measured in situ using voltammetric methods. These measurements provide an indirect window into structural changes in melts at temperatures above the liquidus. Slope of the reduction potential versus temperature (related to entropy) and slope of the diffusion rate versus 1/T (related to diffusional activation energy) remain roughly constant or change only gradually above the liquidus, with the exception of a sharp break in slope typically observed about 60–160°C above the liquidus. This sharp break is consistent with a structural transition in the melt rather than with a gradual change in melt structure. A correlation between the transition temperature and the liquidus temperature, combined with the qualitative effect of prior crystallization, suggests that the transition may be related to the melt “preparing” for crystallization roughly 100°C above the liquidus. These observations may have implications for understanding melt activities, partitioning between melt and crystalline phases, and liquid immiscibility.

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Notes

  1. The focus of this study is on changes above the liquidus, and therefore possible formation of non-visible "microcrystals" below the liquidus temperature was not examined in detail. However, voltammetric scans made after the sample was cooled below the liquidus (but without visible crystallization) show no significant change from measurements made prior to cooling, arguing that microcrystals, even if present below the liquidus, do not affect our results. Also, no sharp change in either the diffusion rate or reduction potential was observed in crossing the liquidus temperature, and thus there is no reason to suspect micro-crystallization. In contrast, very obvious changes in electrochemical properties were observed in experiments with confirmed crystallization.

  2. The absence of an observed slope shift in ggAl4-B and ggAl2-B may be a consequence of lower Al2O3 concentrations in those compositions. ggAl4-B and ggAl2-B have the lowest Al2O3 concentrations of the compositions studied, whereas the largest change in slope (e.g., change in B/nF) is observed in the highest-Al2O3 composition (P3AN1300), as seen in Table 3.

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Acknowledgments

This work was supported in part by the NASA Grant NAG5-7366. Our thanks are due to P. Richet, J. K. Russell, B. Mysen, and an anonymous reviewer for comments and suggestions that led to improvements in this manuscript. We also thank Tim Grove for the editorial handling.

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  1. Department of Anthropology and Earth Science, Minnesota State University Moorhead, Moorhead, MN, USA

    Russell O. Colson

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Correspondence to Russell O. Colson.

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Communicated by T.L. Grove.

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Colson, R.O. In situ voltammetric observation of transitions above the liquidus in silicate melts. Contrib Mineral Petrol 159, 703–717 (2010). https://doi.org/10.1007/s00410-009-0449-7

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