Abstract
The high-pressure behavior of Keokuk kaolinite has been studied to 9.5 GPa by infrared spectroscopy using synchrotron radiation. The kaolinite-I → kaolinite-II and kaolinite-II → kaolinite-III transformations have clear spectroscopic expression, with discontinuities coinciding with the transformation pressures bracketed by X-ray diffraction (Welch and Crichton in Am Mineral 95:651–654, 2010). The experimental spectra have been interpreted from band assignments derived from density functional theory for the structures of kaolinite-II and kaolinite-III, using as starting models the ab initio structures reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) and unit-cell parameters from Welch and Crichton (Am Mineral 95:651–654, 2010). The relaxed theoretical structures are very similar to those reported by Mercier and Le Page (Acta Crystallogr A B64:131–143, 2008, Mater Sci Technol 25:437–442, 2009) in their theoretical investigation of kaolinite polytypes at high pressure. The vibrational spectra calculated from the quantum-mechanical analysis allow band assignments of the IR spectra to be made and provide insights into the behavior of different OH environments in the two high-pressure polytypes. The single perpendicular-interlayer OH group of kaolinite-III has a distinctive spectroscopic signature that is diagnostic of this polytype (ν = 3,595 cm−1 at 9.5 GPa) and is sensitive to the compression/expansion of the interlayer space. This OH group also has a distinctive signature in the calculated spectra. The spectra collected on decompression are those of kaolinite-III and persist largely unchanged to 4.6 GPa, except for a continuous blue shift of the 3,595 cm−1 band to 3,613 cm−1. Finally, kaolinite-I is recovered at 0.6 GPa, confirming the kaolinite-III → kaolinite-I transformation previously observed by X-ray diffraction, and the irreversibility of the kaolinite-II → kaolinite-III transformation. The ambient spectra collected at the start and finish of the experiment are those of kaolinite-I, and start/finish band frequencies agree to within 6 cm−1.
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Acknowledgments
The Swiss Light Source is acknowledged for the provision of beam-time and Luca Quaroni for technical support. We thank Patrick Mercier and an anonymous reviewer for their perceptive and constructive reviews and Associate Editor Milan Rieder for his guidance on the preparation of the revised manuscript. This work was performed using HPC resources from GENCI-IDRIS (Grant 2011-i2011041519).
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Welch, M.D., Montgomery, W., Balan, E. et al. Insights into the high-pressure behavior of kaolinite from infrared spectroscopy and quantum-mechanical calculations. Phys Chem Minerals 39, 143–151 (2012). https://doi.org/10.1007/s00269-011-0469-5
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DOI: https://doi.org/10.1007/s00269-011-0469-5