Kinetics and mechanism of (re)hydroxylation in fired clay minerals

Abstract

AbstractThree types of smectite with various crystallochemical compositions and interlayer cations as well as kaolinite and illite were fired at 800°C and 650°C and tested for their rehydroxylation's (RHX) potential and kinetics in the presence of water vapor at 200°C–350°C. A dehydroxylated structure of 2:1 Al‐rich mineral with the interlayer pillared by a large cation (like K+ or Cs+) is wide enough to allow H2O diffusion which results in advanced RHX, that is, restoring up to several tens of percent of the original OH content. Such 2:1 layer structures (beidellite, illite) do not follow the time‐to‐the‐quarter (TTTQ) kinetics during RHX and show a non‐Arrhenius behavior for isothermal RHX. Because TTTQ kinetics is assumed in an RHX dating of ceramic artifacts in archaeometry, fired‐clay ceramics prepared from material dominated by Al‐rich 2:1 minerals was found unfeasible for RHX dating.Kaolinite and Mg2+‐ or Ca2+‐exchanged smectites show the Arrhenius behavior and follow the TTTQ kinetics of RHX, resulting in apparent Ea increase with the progress of reaction (up to α ∼0.2) of ∼20–50 kJ/mol in beidellite and 15–35 kJ/mol in montmorillonite. We suggest using ‘hydroxylation’ rather than ‘rehydroxylation’ for structurally‐disordered fired clays gaining OH groups in an unknown position.