Microscopy and microanalysis of crystalline glazes

Crystalline glazes on ceramic plates produced commercially in the U.K. and on ceramic pots produced commercially in Taiwan and Spain have been examined by X‐ray diffraction, conventional and polarized light microscopy, and scanning electron microscopy in order to identify the crystalline phases present in the glazes and to ascertain through X‐ray microanalysis the partitioning behaviour of the transition metal ions used to colour the glazes and the crystals within them. In each case examined, the macroscopic two‐dimensional spherulites within the glazes clearly seen by the naked eye were found to consist of large numbers of radially orientated acicular crystals each 5 µm or less in width embedded within the silica‐rich glaze. Energy dispersive X‐ray microanalysis and X‐ray diffraction of these crystals identified these crystals as willemite, α‐Zn₂SiO₄. The strong 001] texture of these crystals within the glaze evident from the X‐ray diffraction patterns was consistent with polarized light microscopy observations of the willemite crystals. In addition to willemite, small iron‐doped gahnite (ZnAl₂O₄) crystals were found in a honey‐coloured crystalline glaze and acicular rutile (TiO₂) crystals were found in the Portmeirion Pottery plates examined. Transition metal ions with a preference for tetrahedral coordination were observed to substitute for Zn²⁺ ions in willemite and to partition preferentially to the willemite crystals, whereas ions preferring octahedral coordination preferred to remain in the glaze.