Direct identification of pigments in mediaeval illuminated manuscripts was one of the first applications of Raman spectroscopy in art and archaeology. In previous in situ analysis of handwritings, the equipment was typically provided with a single excitation source. In this work, a portable Raman spectrometer (EZRAMAN-I-DUAL Raman system) is introduced to characterise the pigments used in an important illuminated mediaeval manuscript, De Civitate Dei (Library in Bruges, Ms.106). Characteristics important for these in situ measurements were discussed. We introduce a set-up that allows stable positioning of the equipment and point out the advantage of the availability of two lasers, which are part of the instrument. Good performance of the introduced Raman spectrometer, to allow pigment identification in a short time, is proved. Finally, pigments such as lead white (2PbCO 3 · Pb(OH) 2 ), lead-tin yellow type I (Pb 2 SnO 4 ), malachite (Cu 2 CO 3 (OH) 2 ), mosaic gold (SnS 2 ), vermillion (HgS), carbon black (C), red lead (Pb 3 O 4 ) and azurite (Cu 3 (CO 3 ) 2 (OH) 2 ) could be identified. These pigments were often used in mediaeval artworks and contribute to the enrichment of information of the materials used by the illuminator.
Raman spectroscopy has grown to be one of the techniques of interest for the investigation of art objects. The approach has several advantageous properties, and the non-destructive character of the technique allowed it to be used for in situ investigations. However, compared with laboratory approaches, it would be useful to take advantage of the small spectral footprint of the technique, and use Raman spectroscopy to study the spatial distribution of different compounds. In this work, an in situ Raman mapping system is developed to be able to relate chemical information with its spatial distribution. Challenges for the development are discussed, including the need for stable positioning and proper data treatment. To avoid focusing problems, nineteenth century porcelain cards are used to test the system. This work focuses mainly on the post-processing of the large dataset which consists of four steps: (i) importing the data into the software; (ii) visualization of the dataset; (iii) extraction of the variables; and (iv) creation of a Raman image. It is shown that despite the challenging task of the development of the full in situ Raman mapping system, the first steps are very promising.This article is part of the themed issue 'Raman spectroscopy in art and archaeology'.
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