Abstract
Oil paint is a dynamic system that undergoes chemical alteration on several time and length scales. At the short term, curing reactions are necessary for oil to dry properly. At longer time scales, a wide variety of other chemical processes can negatively affect the visual appearance or mechanical properties of historical artistic paint systems. The development of chemical imaging methods capable of covering length scales continuously from the millimetric to micro- or even nanoscale is key in understanding the chemical composition of a painting and the historical changes thereof. Such imaging methods can help in assessing to which extent the original painting’s composition may have been modified by chemical degradation processes. Processes that occur in the highly heterogeneous mixtures of binders, pigments, additives, alteration products and possibly later repainting and restoration treatments. Establishing the precise biography of the painting contributes to evaluate its authenticity. New modalities and novel methods of microchemical imaging provide access to previously unexplored length scales, are capable of better differentiation between the various oil paint components (original composition or later addition), and allow performing faster analysis to produce higher definition images. In this review, we report on recent methodological developments and future prospects to determine oil paints composition using microchemical imaging at the micro- and nanoscale.
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Acknowledgements
The authors would like to express their gratitude to The Bennink Foundation for funding this research, to Edwin Verweij for providing the sample from the window frame of De Witte Roos in Delft, and to Dawn Rogala, Frederik Vanmeert, and Xiao Ma for providing figures for and/or proofreading the examples of SEM-EDX, XRD tomography and AFM-IR. They also warmly thank ESRF for granting in-house beamtime and Manfred Burghammer and Wout de Nolf for their support in data acquisition and data processing. SH, MT, LB and KK acknowledge support from the France–Netherlands Van Gogh program (Partenariat Hubert Curien MEAE/MESRI and NUFFIC).
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Glossary
Glossary
Concept/abbreviation | Description |
Absorption edge | Distinct step in the absorption spectrum of a compound, corresponding to element-specific electronic transitions from a core-level orbital to other core-level orbitals, valence-level orbitals, and continuum states. |
AFM | Atomic force microscopy |
Annular detector | A ring-shaped detector primarily used to collect signal from a large solid angle, while permitting transmission of an excitation beam through the center. |
ATR | Attenuated total reflectance |
Band gap | Property of a semiconductor: the gap between the highest occupied and lowest unoccupied energy levels. The bandgap strongly influences the ability of the semiconductor to absorb (or emit) ultraviolet, visible, and /or infrared light. |
CCD detector | Charge-coupled device: a 2D photodetector array used primarily for the detection of ultraviolet and visible light. See also: CMOS detector. |
Chemical contrast | Ambiguous term, here defined as: differences in the signal recorded by a measurement modality from different chemical compounds. |
Chemical specificity | Ambiguous term, here defined as: the ability of a measurement modality to distinguish different chemical compounds. A modality with a high chemical specificity is capable of recording signal from specific compounds without interference from any others. |
CMOS detector | Complementary metal oxide semiconductor: a 2D photodetector array used primarily for the detection of ultraviolet and visible light. Similar to, but operated differently than CCD detectors. |
Compton scattering | An inelastic scattering effect in which energy is transferred from an X-ray photon to an electron. |
Core-level transition | An electronic transition in which the lower energy level corresponds to a tightly bound core-orbital. Core-level transition energies are diagnostic of certain elements. |
Cross-section (of a process) | The probability that a certain process will take place. Primarily used in the context of scattering, absorption, and emission processes. |
Energy-dispersive detection | Ambiguous term. In the context of SEM-EDX: a means of detecting photon energy directly by probing the amount of ionization the photon produces in a detector material. In the context of energy-dispersive XAS: a detection method in which the energies in a polychromatic X-ray beam are spatially dispersed and detected separately on a detector array. See also: wavelength-dispersive detection. |
EXAFS | Extended X-ray absorption fine structure |
Far-field | An approach in optics in which the distance between the sample and the collection or focusing elements is far greater than the wavelength of the photons being used. |
FTIR | Fourier-transform infrared |
Full-field imaging | An approach to imaging in which a whole region-of-interest is projected onto a 2D detector array at once. |
Hyperspectral | An approach to spectral imaging in which full spectra are collected for each pixel. |
Length scale | Ambiguous term. Imaging at a certain length scale is here defined to be done with a spatial resolution and field of view that allows to resolve physical features whose dimensions lie in a certain range. |
Measurement modality | Ambiguous term, here defined as: the physical principle according to which an analytical measurement is performed. |
Metal soap | A salt consisting of metal ions and fatty acids. Often found in oil paints as a result of pigment degradation. |
Method | Ambiguous term, defined in the context of microchemical imaging as: a physical or computational tool that can be used to prepare or analyze a sample or dataset. |
Methodology | Ambiguous term, defined in the context of microchemical imaging as: the overarching approach by which analysis is performed; includes sample preparation, instrumental analysis, and data treatment. |
Multispectral | An approach to spectral imaging in which absorption, emission, or scattering is probed at a small number of energies (typically 5-15) for each pixel. |
Near-field | An approach in optics in which the distance between the sample and the collection or focusing elements is smaller than the wavelength of the photons being used. |
Numerical aperture | A metric of optical elements that measures the angular range over which light is accepted or emitted. See also: solid angle |
PL | Photoluminescence |
Polymorph | A compound that exists in a particular crystal structure, but can exist in one or more others. |
Pump-probe | An approach to spectroscopy in which one light source (the pump) promotes electrons from one energy level to another and a second light source (the probe) is used to measure the population or depopulation of certain energy levels. |
RXES | Resonant X-ray emission spectroscopy, sometimes referred to as resonant inelastic X-ray scattering (RIXS) |
Saponification | The process of fatty acids being converted into (metal) soaps. |
SEM-EDX | Scanning electron microscopy-energy-dispersive X-ray spectrometry. See also: energy-dispersive detection. |
Semiconductor pigment | An inorganic pigment that consists of crystallites that possess semiconducting properties, such as a bandgap and the ability to luminesce. Due to its bandgap structure, small changes in the composition of the pigment can strongly affect its color or luminescing properties. |
SIMS | Secondary ion mass spectrometry |
SNR | Signal-to-noise ratio |
Solid angle | The angular range over which an optical element or detector accepts incoming photons. |
STEM | Scanning transmission electron microscopy |
Synchrotron | A large cyclic particle accelerator that can be used as a source of high-intensity and tunable X-rays, infrared, visible, and ultraviolet radiation. |
TEM | Transmission electron microscopy |
Tomography | A collection of techniques that are aimed at reconstructing sections through a sample. |
Voxel | The three-dimensional equivalent of a pixel. |
Wavelength-dispersive detection | A means to detect a spectrum in which different wavelengths are separated based on some form of diffraction and directed towards a 2D detector array. |
XANES | X-ray absorption near-edge structure |
XAS | X-ray absorption spectroscopy |
XRD | X-ray diffraction |
XRF | X-ray fluorescence |
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Hageraats, S., Thoury, M., Cotte, M., Bertrand, L., Janssens, K., Keune, K. (2022). Microchemical Imaging of Oil Paint Composition and Degradation: State-of-the-Art and Future Prospects. In: Colombini, M.P., Degano, I., Nevin, A. (eds) Analytical Chemistry for the Study of Paintings and the Detection of Forgeries. Cultural Heritage Science. Springer, Cham. https://doi.org/10.1007/978-3-030-86865-9_12
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