Negative thermal expansion in cuprite-type compounds: A combined synchrotron XRPD, EXAFS, and computational study of Cu2O and Ag2O
Cuprite-type oxides (Cu2O and Ag2O) are framework structures composed by two interpenetrated networks of metal-sharing M4O tetrahedra (M = Cu, Ag). Both compounds exhibit a peculiar negative thermal expansion (NTE) behaviour over an extended temperature range (9 240 K for Cu2O, 30-470 K for Ag2O). High-accuracy synchrotron powder diffraction and EXAFS measurements were performed from 10 K up to the decomposition temperature to understand the nature of the NTE effects. The critical comparison of the diffraction and absorption results concerning the temperature dependence of the interatomic distances and of the atomic vibrational parameters proves to be fundamental in defining the local dynam…
The blue enamels in the baroque decorations of the churches of Palermo, Sicily: Fe2+-coloured glasses from lime kilns
Deep blue glasses coloured by octahedral Fe 2+ cations are often reported as textbook examples of blue pigmentation. However, despite the possibility of laboratory synthesis under reducing conditions, to date there are no well-reported occurrences of their production and use in the past. A thorough historical, ethnographic, mineralogical, and chemico-physical investigation of the 'smaltini di calcara' from several baroque churches in Palermo, Sicily, has revealed that the blue enamels widely used for altar decorations in the 17th and 18th centuries are actually a unique case of ancient blue glasses pigmented by divalent iron cations in distorted octahedral coordination. This mixed-alkali gl…