The joined use of n.i. spectroscopic analyses – FTIR, Raman, visible reflectance spectrometry and EDXRF – to study drawings and illuminated manuscripts

Some art objects being small and very precious prevents conservators and conservation scientists from whatever kind of sampling, so that only completely non-invasive (n.i.) studies are permitted. Besides, also moving the object is sometimes forbidden: this happens for jewels as well as for manuscripts, illuminated codices, drawings and paintings. Some important physical n.i. analyses, such as PIXE and PIGE, therefore cannot be used in many cases. With these limitations, only imaging techniques in X, UV, Visible and IR bands, and a few spectroscopic methods that can be carried out with portable instruments can be applied, i.e. molecular spectroscopies like Fourier transform infrared (FTIR), Raman, UV visible and near IR reflectance spectrometry (UV-Vis-NIR RS) and atomic spectroscopy like energy dispersive X-ray fluorescence (EDXRF).The use of only one or two of these techniques is usually far from giving all the information required to achieve a full characterization of materials used by the artist or during restorations, and to understand some conservative problems of the object. On the contrary, a joined use of n.i. analyses can supply a larger set of data, allowing for cross checks. With this aim we show a fully integrated spectroscopic approach to polychrome objects, and, in particular, to drawings and illuminated manuscripts, using portable instruments, specifically μ-FTIR, μ-Raman, Vis-RS and EDXRF, where also the Raman signal does not suffer fluorescence caused by varnish coating and from binder.We propose the joined use of all these four physical analyses to characterize materials – support, pigments, dyes, binders, etc. – on a complex case: a painted and drawn parchment of the late 15th century, or the beginning of the 16th, partly attributed to Andrea Mantegna. The collected spectroscopic data have been compared to proper spectral databases, some of which specifically realized in our laboratories. Also, mixtures of pigments and their stratigraphical sequence have been detected, as well as important data related to the manufacturing and the type of iron-gall ink.

[1]  V. Otieno-Alego Raman Microscopy: A useful tool for the archaeometric analysis of pigments , 2000 .

[2]  F. Casadio,et al.  IDENTIFICATION OF PIGMENTS ON A XV CENTURY ILLUMINATED PARCHMENT BY RAMAN AND FTIR MICROSPECTROSCOPIES , 1999 .

[3]  Franco Lucarelli,et al.  Galileo's writings: chronology by PIXE , 1995 .

[4]  Mauro Bacci,et al.  NON-DESTRUCTIVE SPECTROSCOPIC DETECTION OF COBALT(II) IN PAINTINGS AND GLASS , 1996 .

[5]  R. Clark,et al.  Peer Reviewed: Raman Microscopy of A 13th-Century Illuminated Text , 1998 .

[6]  S. Pagés-Camagna,et al.  Study of Gustave Moreau's black drawings: identification of the graphic materials by Raman microspectrometry and PIXE , 2004 .

[7]  Emanuela Sibilia,et al.  Study of blue colour in ancient mosaic tesserae by means of thermoluminescence and reflectance measurements , 2006 .

[8]  Lucia Toniolo,et al.  Spectrochemical characterization by micro-FTIR spectroscopy of blue pigments in different polychrome works of art , 1999 .

[9]  L. Burgio,et al.  Library of FT-Raman spectra of pigments, minerals, pigment media and varnishes, and supplement to existing library of Raman spectra of pigments with visible excitation. , 2001, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[10]  P. Moioli,et al.  Analysis of art objects using a portable X-ray fluorescence spectrometer , 2000 .

[11]  P. P. Lottici,et al.  A study of medieval illuminated manuscripts by means of portable Raman equipments , 2006 .

[12]  Burkhard Beckhoff,et al.  Characterization of iron‐gall inks in historical manuscripts and music compositions using x‐ray fluorescence spectrometry , 2004 .

[13]  Manfred Schreiner,et al.  X‐ray fluorescence spectrometry in art and archaeology , 2000 .

[14]  L. Bonizzoni,et al.  In situ non‐invasive EDXRF analysis to reconstruct stratigraphy and thickness of Renaissance pictorial multilayers , 2007 .

[15]  J. L. Ferrero,et al.  Study of inks on paper engravings using portable EDXRF spectrometry , 2004 .

[16]  Aivaras Kareiva,et al.  Spectroscopic evaluation and characterization of different historical writing inks , 2005 .

[17]  G. Zerbi,et al.  Recovery of ancient parchment: characterization by vibrational spectroscopy , 2000 .

[18]  Robin J. H. Clark,et al.  Raman spectroscopic library of natural and synthetic pigments (pre- ≈ 1850 AD) , 1997 .