Vincent van Gogh (1853−1890), one of the founding fathers of modern painting, is best known for his vivid colors, his vibrant painting style, and his short but highly productive career. His productivity is even higher than generally realized, as many of his known paintings cover a previous composition. This is thought to be the case in one-third of his early period paintings. Van Gogh would often reuse the canvas of an abandoned painting and paint a new or modified composition on top. These hidden paintings offer a unique and intimate insight into the genesis of his works. Yet, current museum-based imaging tools are unable to properly visualize many of these hidden images. We present the first-time use of synchrotron radiation based X-ray fluorescence mapping, applied to visualize a woman’s head hidden under the work Patch of Grass by Van Gogh. We recorded decimeter-scale, X-ray fluorescence intensity maps, reflecting the distribution of specific elements in the paint layers. In doing so we succeeded in v...

http://rutchem.rutgers.edu/~kyc/pdf/491/patel%20mayank/patel2.pdf

Visualization of a lost painting by Vincent van Gogh using synchrotron radiation based X-ray fluorescence elemental mapping.

Driven by the need to study precious and irreplaceable artworks without compromising their integrity, researchers have undertaken numerous efforts to develop noninvasive analytical tools and methodologies that can provide a chemical description of cultural heritage materials without any contact with the object. The challenge is that artworks are made of complex mixtures, often with heterogeneous and unknown layered materials. Their components must be identified over a range of size scales, from the molecular identification of constituent compounds to the mapping of alteration phases. In this Account, we review recent research in spectroscopic techniques accessible from the mobile laboratory (MOLAB). The lab is equipped with an array of state-of-the-art, portable, and noninvasive instruments specifically tailored to tackle the different issues confronted by archaeologists, curators, and conservators. The MOLAB approach is suitable for studying a variety of objects, from ceramics to manuscripts or from hist...

In situ noninvasive study of artworks: the MOLAB multitechnique approach.

Fourier transform infrared (FTIR) spectroscopy is one of the most widely applied techniques for the investigation of cultural heritage materials. FTIR microscopy is well established as an essential tool in the microdestructive analysis of small samples, and the recent introduction of mapping and imaging equipment allows the collection of a large number of FTIR spectra on a surface, providing a distribution map of identified compounds. In this Account, we report recent advances in FTIR spectroscopy and microscopy in our research group. Our laboratory develops, tests, and refines new and less-studied IR spectroscopy and microscopy methods, with the goal of their adoption as routine analytical techniques in conservation laboratories. We discuss (i) the analysis of inorganic materials inactive in the mid-IR region by means of far-IR spectroscopy, (ii) the development of new methods for preparing cross sections, (iii) the characterization and spatial location of thin layers and small particles, and (iv) the ev...

New Advances in the Application of FTIR Microscopy and Spectroscopy for the Characterization of Artistic Materials

Elemental distribution maps are of great interest in the study of historical paintings, as they allow to investigate the pigment use of the artist, to image changes made in the painting during or after its creation and in some cases to reveal discarded paintings that were later over painted. Yet a method that allows to record such maps of a broad range of elements in a fast, non-destructive and in situ manner is not yet commonly available; a dedicated mobile scanning XRF instrument might fill this gap. In this paper we present three self-built scanning macro-XRF instruments, each based on the experience gained with its precursor. These instruments are compared in terms of sensitivity and limits of detection, which includes a discussion of the use of polycapillary optics and pinhole collimators as beam defining devices. Furthermore, the imaging capabilities of the instruments are demonstrated in three exemplary cases: (parts of) historical paintings from the 15th to the 19th century are examined. These cases illustrate the value of element specific distribution maps in the study of historical paintings and allow in the case of Vincent van Gogh's “Patch of Grass” a direct comparison between in situ and synchrotron based scanning macro-XRF.

Optimization of mobile scanning macro-XRF systems for the in situ investigation of historical paintings

The darkening of the original yellow areas painted with the chrome yellow pigment (PbCrO4, PbCrO4·xPbSO4, or PbCrO4·xPbO) is a phenomenon widely observed on several paintings by Vincent van Gogh, such as the famous different versions of Sunflowers. During our previous investigations on artificially aged model samples of lead chromate, we established for the first time that darkening of chrome yellow is caused by reduction of PbCrO4 to Cr2O3·2H2O (viridian green), likely accompanied by the presence of another Cr(III) compound, such as either Cr2(SO4)3·H2O or (CH3CO2)7Cr3(OH)2 [chromium(III) acetate hydroxide]. In the second part of this work, in order to demonstrate that this reduction phenomenon effectively takes place in real paintings, we study original paint samples from two paintings of V. van Gogh. As with the model samples, in view of the thin superficial alteration layers that are present, high lateral resolution spectroscopic methods that make use of synchrotron radiation (SR), such as microscopic...

http://ematweb.cmi.ua.ac.be/emat/pdf/1918.pdf

Degradation Process of Lead Chromate in Paintings by Vincent van Gogh Studied by Means of Synchrotron X-ray Spectromicroscopy and Related Methods. 1. Artificially Aged Model Samples

Ancient paintings are complex materials in terms of chemical analysis because they are usually made of organic/mineral, amorphous/crystallized, major/minor mixtures, evolving with time, and organized in micrometric multi-layered arrangements. In this context, synchrotron micro-imaging techniques offer a powerful analytical platform to reveal the two dimensional atomic, molecular and structural compositions of such complex systems, at a micrometre resolution. The two selected examples illustrate the two main concerns of restorers and conservators: looking backwards, to get insight into ancient artistic practices (in particular through the identification of pigments and binders in Bamiyan Buddhist mural paintings); and looking forward, to preserve works of art as long as possible (through a better understanding of cinnabar blackening in Medieval Spanish paintings). From the analytical chemistry point of view, they also illustrate the relevance of combining micro X-ray fluorescence, micro X-ray absorption spectroscopy, micro X-ray diffraction, and micro-FTIR for the complete analysis of painting cross-sections (binders and pigments).

Applications of synchrotron-based micro-imaging techniques to the chemical analysis of ancient paintings

The perfection of Leonardo da Vincis painting technique hasalwaysbeenfascinating.Thegradationoftonesorcolorsfromlight to dark is barely perceptible. Neither brushstroke norcontourisvisible:lightsandshadesareblendedinthemannerof smoke. Understanding this technique, usually calledsfumato, remains one of the challenges still unaddressed inart history. Herein we show that quantitative X-ray fluores-cence spectroscopy performed directly on the works of artmakes it possible to access the description of the paint layersused in the flesh tones. We determined the composition andthe thickness of the paint layers of nine faces, painted byLeonardo (or attributed to him) over 40 years of his activity.Theresultsshednewlightonhisconstantresearchtoimprovethe visual aspects of his works of art. In his later paintings, hewas able to apply translucent layers (glazes), which weremainly composed of an organic medium in very thin films,down to a micrometer scale.How did Leonardo da Vinci obtain such impressivenaturalistic effects in his paintings? The description of themasters sfumato technique is the subject of active discussionin arthistory.

Revealing the sfumato Technique of Leonardo da Vinci by X-Ray Fluorescence Spectroscopy

X-ray fluorescence spectrometry (XRF) allows a rapid and simple determination of the elemental composition of a material. As a non-destructive tool, it has been extensively used for analysis in art and archaeology since the early 1970s. Whereas it is commonly used for qualitative analysis, recent efforts have been made to develop quantitative treatment even with portable systems. However, the interpretation of the results obtained with this technique can turn out to be problematic in the case of layered structures such as easel paintings. The use of differential X-ray attenuation enables modelling of the various layers: indeed, the absorption of X-rays through different layers will result in modification of intensity ratio between the different characteristic lines. This work focuses on the possibility to use XRF with the fundamental parameters method to reconstruct the composition and thickness of the layers. This method was tested on several multilayers standards and gives a maximum error of 15% for thicknesses and errors of 10% for concentrations. On a painting test sample that was rather inhomogeneous, the XRF analysis provides an average value. This method was applied in situ to estimate the thickness of the layers a painting from Marco d’Oggiono, pupil of Leonardo da Vinci.

Multilayers quantitative X-ray fluorescence analysis applied to easel paintings

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Applications of synchrotron-based micro-imaging techniques to the chemical analysis of ancient paintings

Revealing the sfumato Technique of Leonardo da Vinci by X-Ray Fluorescence Spectroscopy

Multilayers quantitative X-ray fluorescence analysis applied to easel paintings