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Testing the (time)1/4 diffusion law of rehydroxylation in fired clays: evidence for single-file diffusion in porous media?

Fired clay minerals rehydroxylate after firing, a phenomenon that causes the long-term mass gain and expansion seen in archaeological ceramics. During rehydroxylation, fired clay minerals react with H2O to form structural hydroxyl (OH). Recent models propose that rehydroxylation is described by a quartic root (t1/4) time dependence, which has led to a dating method based on the process (RHX, rehydroxylation dating). The time dependence has been interpreted as an indication of a transport process of single-file diffusion of H2O molecules along restricted pathways in clay mineral, as theory predicts that the associated root mean
square displacement is proportional to t1/4. However, dating trials have led to alternative models, and the process is still poorly understood. Here we outline currently outstanding problems found in different experimental studies, and propose novel ways of investigating the phenomenon. These include (i) gravimetric analyses using pure clay ceramics which are free of calcite and other minerals, and reducing cooling effects by using thin samples; (ii) highresolution nuclear magnetic resonance (NMR) with aluminum and silicon as well as with protons (hydroxyls, water) for exploring structure and dynamics, and pulsed field gradient (PFG) NMR for exploring water/proton diffusivities; (iii) IR spectroscopy, and micro-IR imaging to explore the spatial-temporal dependence of rehydroxylation of fired clay and (iv) structural investigations by high-resolution electron microscopy and X-ray diffraction.

Identiferoai:union.ndltd.org:DRESDEN/oai:qucosa.de:bsz:15-qucosa-201186
Date05 April 2016
CreatorsHare, Vincent J., Kärger, Jörg, Moinester, Murray, Piasetzky, Eli
ContributorsUniversity of Oxford, Research Laboratory for Archaeology and the History of Art, Universität Leipzig, Fakultät für Physik und Geowissenschaften, Tel Aviv University, School of Physics and Astronomy, Universität Leipzig, Fakultät für Physik und Geowissenschaften
PublisherUniversitätsbibliothek Leipzig
Source SetsHochschulschriftenserver (HSSS) der SLUB Dresden
LanguageEnglish
Detected LanguageEnglish
Typedoc-type:article
Formatapplication/pdf
SourceDiffusion fundamentals 25 (2016) 5, S. 1-11

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