Non-Invasive Raman and XRF Study of Mīnā’ī Decoration, the First Sophisticated Painted Enamels

Mīnā’ī wares, crafted during the 12th–13th centuries, represent some of the earliest examples of sophisticated painted enamel decoration by potters. Due to the thinness of these enamel layers, their detailed characterization remains challenging, even with the use of advanced techniques, such as Proton-Induced X-ray Emission (PIXE) analysis and Rutherford Backscattering Spectrometry (RBS). This study provides the first combined non-invasive analysis, using X-ray fluorescence (XRF) and Raman spectroscopy, of five shards attributed to mīnā’ī wares. For comparison, two İznik shards from the 17th century, which feature similarly styled but thicker enamel decorations, were also analyzed. Interestingly, the mīnā’ī paste was found to contain lead and tin, suggesting the use of a lead-rich frit in its composition. This finding was confirmed through micro-destructive analysis, using Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM–EDS). Elements, such as rubidium (Rb), strontium (Sr), yttrium (Y), and zirconium (Zr), produced significant XRF signals and effectively distinguished mīnā’ī wares from İznik wares. A uniform tin-rich glaze, measuring 300–500 µm in thickness, was used as a base layer for the much thinner painted mīnā’ī enamels. The colored areas (blue, turquoise, red, green, black, white, eggplant) revealed the presence of various coloring agents and phases, such as spinels, chromite, and ions like Cu²⁺ and Co²⁺, as well as opacifiers like cassiterite and lead–calcium/potassium arsenates. Two distinct cobalt sources were identified: one associated with arsenic and the other with manganese and nickel. These cobalt sources are comparable to those used in İznik pottery. For the first time, boron was detected in the blue enamel of mīnā’ī wares.