Institute Royal du Patrimoine Artistique

Brussels, Belgium

Institute Royal du Patrimoine Artistique

Brussels, Belgium
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Sanyova J.,Institute Royal du Patrimoine Artistique | Cersoy S.,French National Center for Scientific Research | Richardin P.,French National Center for Scientific Research | Laprevote O.,CNRS Natural Product Chemistry Institute | And 3 more authors.
Analytical Chemistry | Year: 2011

The painting materials of the Portrait of Nicolaes van Bambeeck (Royal Museums of Fine Arts of Belgium, Brussels, inv. 155) painted by Rembrandt van Rijn in 1641 has been studied using high resolution cluster-TOF-SIMS imaging. In the first step, a moderate spatial resolution (2 μm) was used to characterize the layer structure and the chemical composition of each layer on account of a high mass resolution. Then, in the second step, and despite a low mass resolution, the cluster primary ion beam was focused well below 1 μm in order to reveal smaller structures in the painting sample. The study confirmed the presence of starch in the second ground layer, which is quite surprising and, at least for Rembrandt paintings, has never been reported before. TOF-SIMS also indicated the presence of proteins, which, added to the size and shape of lake particles, suggests that it was manufactured from shearings (waste of textile manufacturing) of dyed wool, used as the source of the dyestuff. The analyses have also shown various lead carboxylates, being the products of the interaction between lead white and the oil of the binding medium. These findings considerably contribute to the understanding of Rembrandt's studio practice and thus demonstrate the importance and potential of cluster-TOF-SIMS imaging in the characterization on a submicrometer scale of artist painting materials. © 2011 American Chemical Society.

Samain L.,University of Liège | Silversmit G.,Ghent University | Sanyova J.,Institute Royal du Patrimoine Artistique | Vekemans B.,Ghent University | And 8 more authors.
Journal of Analytical Atomic Spectrometry | Year: 2011

The fading of modern laboratory-synthesized and commercial Prussian blue, iron(iii) hexacyanoferrate(ii), based pigments in a linseed oil medium during exposure to light has been investigated. The Prussian blue pigments were painted with linseed oil, as a pure pigment and mixed with white lead, (PbCO 3)2Pb(OH)2, zinc white, ZnO, or titanium white, TiO2, pigment. The samples were subjected to accelerated ageing for 800 h and the light fastness of the Prussian blue pigment was evaluated by reference to blue wool standards. Pure Prussian blue is extremely light fast whilst it strongly fades when mixed with a white pigment, especially with lead white or zinc oxide. The painted samples were studied by UV-visible, iron K-edge X-ray absorption, iron-57 transmission Mössbauer, and attenuated total reflectance infrared spectroscopy. X-ray absorption results reveal a decrease in the iron coordination number in aged samples in the presence of white pigment. The Mössbauer spectra of the pure Prussian blue and the unaged and aged mixtures of Prussian blue and lead white or zinc oxide at 1:100 and 1:10 dilution ratios, respectively, indicate the presence of iron(ii) and iron(iii) in a ratio close to one as expected for the bulk stoichiometric KFe III[FeII(CN)6]; no change in the spectral parameters was observed upon ageing. Combined with the X-ray near edge absorption and infrared studies, these results suggest reduction of the surface iron ions in the Prussian blue with ageing upon exposure to light. © 2011 The Royal Society of Chemistry.

Samain L.,University of Liège | Samain L.,University of Stockholm | Grandjean F.,University of Liège | Grandjean F.,Missouri University of Science and Technology | And 5 more authors.
Journal of Synchrotron Radiation | Year: 2013

Prussian blue, a hydrated iron(III) hexacyanoferrate(II) complex, is a synthetic pigment discovered in Berlin in 1704. Because of both its highly intense color and its low cost, Prussian blue was widely used as a pigment in paintings until the 1970s. The early preparative methods were rapidly recognized as a contributory factor in the fading of the pigment, a fading already known by the mid-eighteenth century. Herein two typical eighteenth-century empirical recipes have been reproduced and the resulting pigment analyzed to better understand the reasons for this fading. X-ray absorption and Mössbauer spectroscopy indicated that the early syntheses lead to Prussian blue together with variable amounts of an undesirable iron(III) product. Pair distribution functional analysis confirmed the presence of nanocrystalline ferrihydrite, Fe10O14(OH)2, and also identified the presence of alumina hydrate, Al10O14(OH)2, with a particle size of ∼15 Å. Paint layers prepared from these pigments subjected to accelerated light exposure showed a tendency to turn green, a tendency that was often reported in eighteenth-and nineteenth-century books. The presence of particles of hydrous iron(III) oxides was also observed in a genuine eighteenth-century Prussian blue sample obtained from a polychrome sculpture. © 2013 International Union of Crystallography Printed in Singapore-all rights reserved.

Tuccimei P.,Third University of Rome | van Strydonck M.,Institute Royal du Patrimoine Artistique | Gines A.,University of the Balearic Islands | Gines J.,University of the Balearic Islands | And 4 more authors.
International Journal of Speleology | Year: 2011

This investigation reports on the comparison between ICP-MS U-Th and AMS 14C ages of Phreatic Overgrowths on Speleothems (POS) from two different caves on the island of Mallorca (Spain). These speleothem encrustations form at the water table of coastal caves in a low-amplitude tide-controlled microenvironment and are used to reconstruct past sea level changes. The aim of this study is to evaluate if this particular type of speleothem is datable using 14C method and to investigate possible problems connected with the incorporation of dead carbon inherited from the dissolution of 14C-free limestone. The results show that 14C ages are strongly site dependent and appear related to local residence time of water infiltration through the soil and epikarst. When short transit time and limited interaction with soil and bedrock, as in Cova de Cala Varques A, the so-called "reservoir" effect is negligible and 14C and U-Th ages corresponds within the error range. When the residence time is longer, as in Cova des Pas de Vallgornera, 14C ages are steadily 2,300-2,400 years older than the U-Th data, as shown by the mean value (25%) of estimated percent dead carbon proportions and by higher and better correlated contents of major and trace elements in the vadose support of this speleothem encrustation. The potential use of this multi-method approach to paleoenvironmental studies is also suggested.

Crabbe A.,Institute Royal du Patrimoine Artistique | Languille M.-A.,Synchrotron Soleil | Vandendael I.,Vrije Universiteit Brussel | Hammons J.,Vrije Universiteit Brussel | And 4 more authors.
Applied Physics A: Materials Science and Processing | Year: 2013

The colour of gildings can be modified by many artistic techniques. This article refers to the possibility of a specific chemical treatment to change the colour of gildings. The model samples-gilded silver plate, the mixture and the application of a medieval recipe based on ancient writings from Theophilius and Cellini have been described. We propose a strategy to identify the chemical processes involved in the change of colour of the metallic surface through the advanced study of these model samples. Synchrotron X-ray photoelectron spectroscopy and X-ray absorption spectroscopy were carried out both on the gilding with and without the application of the treatment with the aim to understand the chemical reactions occurring during the treatment. © 2013 Springer-Verlag Berlin Heidelberg.

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