Abstract
Synchrotron radiation X-ray micro-analytical techniques and vibrational micro-spectroscopy methods were used to establish the factors and mechanism of darkening of “fake-gilded” decorations in theMaestàby Cimabue and aged paint mock-ups.
Highlights
In chemical sciences the study of the causes triggering the color change of paintings is a grand challenge
We propose a comprehensive multi-material and multi-method approach based on the combination of synchrotron radiation X-ray micro-analytical techniques (i.e., X-ray diffraction, X-ray fluorescence and X-ray absorption near edge structure spectroscopy at S K-/Ag L3-/As K-edges) and vibrational micro-spectroscopy methods to unveil the causes and mechanism of darkening of “fake-gilded” decorations in tempera paintings, originally consisting of an unusual mixture of As2S3 and metallic silver (Ag0)
We propose the use of a comprehensive multimaterial and multi-method approach, based on the combination of synchrotron radiation (SR) X-ray micro-analytical techniques and vibrational micro-spectroscopy methods, to study the darkening issue affecting As2S3-based areas of the painting Maestaof Santa Maria dei Servi attributed to Cimabue (1240–1302) (Fig. 1a) and of tempera paint mock-ups aged with either light or moisture
Summary
In chemical sciences the study of the causes triggering the color change of paintings is a grand challenge. In the context of orpiment-based paints, despite a large quantity of data on the general characterization and distribution of degraded compounds has been recently acquired,[19,20,21,22,23,24,25,26,27] very little is still known about the interactions that take place among As2S3 and other paint components (e.g., other pigments, additives, binder) and their reactivity with the surrounding environment Such data, being in most of the cases limited to the study of historical paintings, do not prove directly how and why such alterations activate. In order to elucidate which of the above mechanisms may have taken place, on the one hand, SR-based m-XRD and m-XRF mapping along with Ag L3-/As K-edges m-XANES and m-Raman spectroscopy analyses at selected spots of two darkened paint micro-fragments taken from the Maestaby Cimabue and arti cially aged tempera paint mock-ups permitted to gain complementary insights into the chemical nature, stratigraphic distribution and relative-abundances of Ag- and As-based compounds. XANES analysis and attenuated total re ection (ATR) mode mFTIR mapping allowed characterizing and semi-quantifying Sbased compounds and other secondary products formed as a consequence of the chemical alteration of pigments and the pigment–binder interactions
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