A multi-analytical approach was used to study the pictorial layers of a set of 17th century historic glazed tiles (azulejos) of Portuguese manufacture. The pictorial layer was studied by-EDXRF,-Raman, SEM-EDS and OM. Although the established palette comprises few pigments, it was found that the tiles were enhanced by the use of pigment mixtures, which were identified by-Raman and-EDXRF. As expected, the blue colour derives from cobalt oxide, purple from manganese oxide and emerald-green from copper oxide. Regarding the yellow pigment,-Raman results show it is consistent with the composition of a ternary oxide, whereas-EDXRF shows a high intensity of Zn in this colour, indicating a composition close to a Pb-Sb-Zn ternary oxide. Some compounds from the original ores were also indentified: in two very dark blue samples, cobalt and nickel olivines (␣-Co 2 SiO 4 , ␣-Ni 2 SiO 4), and in a dark brown sample, braunite (a manganese silicate).

a b s t r a c tA group of late 15theearly 16th century Hispano-Moresque glazed tiles from the Monastery of Santa Clara-a-Velha, in Coimbra, were, for the first time, characterised chemically and morphologically. Since the prevailing idea among art historians in Portugal is to judge the Hispano-Moresque tile heritage as Spanish production, the findings concerning technological processes were compared with the Islamic technology in the Iberian Peninsula and latter Hispano-Moresque in Spain. This study is the first analytical indicator of a production technology with some differences from the Hispano-Moresque workshops (such as Seville, Toledo, etc.) and points out to a possible local production. Five different coloured glazes were identified: white, blue, green, amber and black, all displaying high-lead content, as expected for this type of ceramics. Tin oxide was identified in high contents (7e14 wt.%) in white and blue glazes, its crystals homogenously distributed in also very homogeneous glazes, showing similarities with an Islamic glazing technology. On the other hand, Ca-rich thick glazeeceramic interfaces were observed, with many mineral inclusions (wollastonite (CaSiO 3 ) and also K-feldspars (general formula KAlSi 3 O 8 ), showing a higher resemblance with a later Hispano-Moresque technology. Other compounds were also identified from reactions involving the colour compound: malayaite (CaSnOSiO 4

This work explores the combination of µ-Raman spectroscopy and scanning electron microscopy with X-ray energy dispersive spectrometry (SEM-EDS) for the study of the glazes in 15th-16th century Hispano-Moresque architectural tiles. These are high lead glazes that can be tin-opacified or transparent, and present five colors: tin-white, cobalt-blue, copper-green, iron-amber, and manganese-brown. They are generally homogenous and mineral inclusions are mostly concentrated in the glaze-ceramic interface. Through SEM-EDS, these inclusions were observed and chemically analyzed, whereas µ-Raman allowed their identification on a molecular level. K-feldspars, wollastonite and diopside were the most common compounds, as well as cassiterite agglomerates that render the glaze opaque. Malayaite was identified in green glazes, and andradite and magnesioferrite in amber glazes. Co-Ni-ferrites were identified in blue glazes, as well as Ni-Fe-olivines. Manganese-brown is the color where most compounds were identified: bustamite, jacobsite, hausmannite, braunite, and kentrolite. Through the µ-Raman analysis of different areas in large inclusions previously observed by SEM, it was possible to identify intermediate phases that illustrate the reaction process that occurs between the color-conferring compounds and the surrounding lead glaze. Furthermore, the obtained results allowed inference of the raw materials and firing temperatures used on the manufacture of these tiles.