Calcium in ancient glazes and glasses: a XAFS study

Ceramic tiles used to manufacture artistic panels during the XVI to the XVIII centuries were decorated with high-lead soda-lime glazes, incorporating a diversity of chromophore cations, as ascertained by SRXRF (synchrotron radiation X-ray fluorescence). Previous X-ray absorption spectroscopy (XAS) studies have shown that sodium and lead are hosted by the glassy matrix in those glazes. However, the possible role of calcium as a modifier of the tetrahedral silica network is not fully clarified, despite being recognized that calcium cations alter some fundamental properties of glazes, namely transparency. An X-ray absorption fine structure (XAFS) study of glazes with varied colorings was therefore undertaken at Ca K- and L-edges. Well crystallized oxide minerals were used to model distinct coordination environments by oxygen atoms – close to octahedral geometry in calcite and dodecahedral in gypsum – while fluorite was chosen to mimic ideal cubic coordination. A first XAS approach suggested a minor variation in the energy separation between L2–L3 absorption edges when comparing blue and yellow glazes, irrespective of the period of manufacture. A further study on the X-ray absorption near-edge structure (XANES) carried out at the K-edge corroborated this difference and, along with the theoretical spectra modeling performed with the FEFF code, allowed interpreting of the Ca 1s absorption spectra of glazes as arising from a non-regular high-coordination environment within the silica matrix.