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This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief of the 15th century entitled "Madonna with Child, Saint Catherine of Siena, and a Carthusian Prior", attributed to Giovanni Antonio Amadeo (Pavia, 1447–Milan, 1522) and owned by the Sforzesco Castle Museum of Milan. The artwork underwent a cleaning procedure whose aims were the removal of the dark coating that obscured its surface and restoration work that could bring back its original features. Before the cleaning, six microsamples were collected and analysed using optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDXS), and Fourier-transform infrared microspectroscopy in ATR mode (ATR-FTIR), providing the restorers with decisive information on the materials underlying the coating. After the cleaning, the terracotta appeared vibrantly coloured, mainly with bright red, blue, green, black, and white tones. Then, some in situ, non-destructive, spectroscopic measurements were performed by a portable Raman spectrometer on some of the areas that could not otherwise have been sampled. The analyses revealed the presence of natural pigments, including lead white, azurite, yellow ochre, carbon black, calcite, cinnabar, and gypsum. For Madonna's mantle, cobalt and Prussian blue were employed. Furthermore, the presence of barium sulphate was widely evidenced on the bas-relief. Albeit cobalt blue is of synthetic origin, its presence is compatible with the 15th-century palette, whereas Prussian blue and barium sulphate could be imputed to a previous restoration. Finally, the use of true gold for the background of the earthenware attests to the artwork's importance and value. [ABSTRACT FROM AUTHOR]

This research aimed to characterise pigments used to decorate a polychrome earthenware bas-relief of the 15th century entitled “Madonna with Child, Saint Catherine of Siena, and a Carthusian Prior”, attributed to Giovanni Antonio Amadeo (Pavia, 1447–Milan, 1522) and owned by the Sforzesco Castle Museum of Milan. The artwork underwent a cleaning procedure whose aims were the removal of the dark coating that obscured its surface and restoration work that could bring back its original features. Before the cleaning, six microsamples were collected and analysed using optical microscopy (OM), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDXS), and Fourier-transform infrared microspectroscopy in ATR mode (ATR-FTIR), providing the restorers with decisive information on the materials underlying the coating. After the cleaning, the terracotta appeared vibrantly coloured, mainly with bright red, blue, green, black, and white tones. Then, some in situ, non-destructive, spectroscopic measurements were performed by a portable Raman spectrometer on some of the areas that could not otherwise have been sampled. The analyses revealed the presence of natural pigments, including lead white, azurite, yellow ochre, carbon black, calcite, cinnabar, and gypsum. For Madonna’s mantle, cobalt and Prussian blue were employed. Furthermore, the presence of barium sulphate was widely evidenced on the bas-relief. Albeit cobalt blue is of synthetic origin, its presence is compatible with the 15th-century palette, whereas Prussian blue and barium sulphate could be imputed to a previous restoration. Finally, the use of true gold for the background of the earthenware attests to the artwork’s importance and value.