Composition–thermal expandability relations and oxidation processes in tourmaline studied by in situ Raman spectroscopy

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Marco E. Ciriotti
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Iscritto il: ven 25 giu, 2004 11:31
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Composition–thermal expandability relations and oxidation processes in tourmaline studied by in situ Raman spectroscopy

Messaggio da Marco E. Ciriotti » lun 15 mag, 2017 12:17

Prossima pubblicazione.

Referenza:
▪ Watenphul, A., Malcherek, T., Wilke, F.D.H., Schlüter, J., Mihailova, B. (2017): Composition–thermal expandability relations and oxidation processes in tourmaline studied by in situ Raman spectroscopy. Physics and Chemistry of Minerals, 44, (in press).

Abstract:
The crystal chemistry of tourmaline, XY3Z6(T6O18)(BO3)3V3W, has a strong influence on the structure and physical properties. Since tourmalines occur in a wide range of geological settings and have large temperature and pressure stability fields, the understanding of the relation between the tourmaline chemistry and thermal expansion allows for better thermodynamic modeling of geological processes. Here, we report dynamic and static thermal expansions as well as mode Grüneisen parameters studied by Raman spectroscopy and single-crystal X-ray diffraction data on several tourmaline species. In addition, oxidation processes in fluor-schorl and Fe2+-bearing elbaite were followed by Raman spectroscopy. Our results emphasize the role of Y-/Z-site occupancy disorder to reduce the local strains and demonstrate that small-size octahedrally coordinated cations perturb the topology of the SiO4 rings, which in turn seems to enhance the anisotropic thermal-expansion response. In addition, it is shown that the temperature-dependent behavior of the VOH modes primarily depends on the occupancy of the Y site, whereas that of the WOH modes depends on the occupancy of the X site. High-temperature Raman experiments in air allowed to follow the oxidation of Fe2+ to Fe3+ in fluor-schorl by analyzing both the framework and OH-stretching phonon modes. It is further demonstrated that under the same conditions, no oxidation of iron is observed for Fe2+-bearing elbaite, which implies that at high oxygen fugacity, iron is only oxidized in tourmaline species with prevalent divalent cations at the Y site.
Marco E. Ciriotti

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