Non-destructive characterization of oriental porcelain glazes and blue underglaze pigments using μ-EDXRF, μ-Raman and VP-SEM

The study of ancient materials with recognized cultural and economic value is a challenge to scientists and conservators, since it is usually necessary an approach through non-destructive techniques. Difficulties in establishing a correct analytical strategy are often significantly increased by the lack of knowledge on manufacture technologies and raw materials employed combined with the diversity of decay processes that may have acted during the lifetime of the cultural artefacts. A non-destructive characterization was performed on the glaze and underglaze pigments from a group of Chinese porcelain shards dated from the late Ming Dynasty (1368-1644) excavated at the Monastery of Santa Clara-a-Velha in Coimbra (Portugal). Chemical analysis was performed using micro-energy dispersive X-ray fluorescence spectrometry (mu-EDXRF). Mineralogical characterization was achieved by Raman microscopy (mu-Raman) and observation of small-surface crystallization dark spots with a metallic lustre in areas with high pigment concentration was done by variable pressure scanning electron microscopy (VP-SEM). Cobalt aluminate was identified as the blue underglaze pigment and a comparison of blue and dark blue pigments was performed by the ratio of Co, Mn, and Fe oxides, indicating a compositional difference between the two blue tonalities. Manganese oxide compounds were also identified as colouring agents in dark blue areas and surface migration of manganese compounds was verified.