Portuguese tin-glaze earthenware from 17th century: pigments and glazes characterization

Two sherds representative of the Portuguese faience production of the first and second halves of the 17th century were studied carefully with the use of non-invasive spectroscopies, namely: Ground State Diffuse Reflectance Absorption (GSDR), micro-Raman, Fourier-Transform Infrared (FT-IR), Laser Induced Luminescence (LIL) and Proton Induced X-ray (PIXE). These results were compared with the ones obtained for a Chinese Ming porcelain, Wanli period (16th/beginning of the 17th centuries), which served as an influence for the initial Lisbon's faience production. By combining information of the different non-destructive spectroscopic techniques used in this work, it was possible to conclude that: Co3O4 (Co II and Co III) can be found in the silicate matrix and is the blue pigment in the "Especieiro" sample (1st half of the 17th C.). Cobalt olivine silicate (Co2SiO4, Co II only) was clearly identified as the blue pigment in "Aranhões" sample (2nd half of the17th C.) - 824cm-1 band in the micro-Raman-spectrum. Cobalt aluminate (CoAl2O4, Co II only) is the blue pigment in the Wanli plate - 203 and 512cm-1 bands in the micro-Raman spectrum. The blue pigment in the 1st half 17th century of Lisbon's production was obtained by addition of a cobalt ore in low concentrations, which gives no specific Raman signature, because of complete dissolution in the glass. However, in most cases of the 2nd half 17th century, the Raman signature was quite evident, from a cobalt silicate. These findings point to the use of higher temperature kilns in the second case.