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20200316 H2020-NMBP‐35‐2017 CORES-PD/00253/2012 PD/BD/136678/2018 UIDB/ 50006/2020 UIDP/50006/2020 Cellulose nitrate (CN) is an intrinsically unstable material that puts at risk the preservation of a great variety of objects in heritage collections, also posing threats to human health. For this reason, a detailed investigation of its degradation mechanisms is necessary to develop sustainable conservation strategies. To investigate novel probes of degradation, we implemented deep UV photoluminescence micro spectral-imaging, for the first time, to characterize a corpus of historical systems composed of cellulose nitrate. The analysis of cinematographic films and everyday objects dated from the nineteenth c./early twentieth c. (Perlov's collection), as well as of photo-aged CN and celluloid references allowed the identification of novel markers that correlate with different stages of CN degradation in artworks, providing insight into the role played by plasticizers, fillers, and other additives in stability. By comparison with photoaged references of CN and celluloid (70% CN and 30% camphor), it was possible to correlate camphor concentration with a higher rate of degradation of the cinematographic films. Furthermore, the present study investigates, at the sub-microscale, materials heterogeneity that correlates to the artworks' history, associating the different emission profiles of zinc oxide to specific color formulations used in the late nineteenth and early twentieth centuries. publishersversion published

Cellulose nitrate (CN) is an intrinsically unstable material that puts at risk the preservation of a great variety of objects in heritage collections, also posing threats to human health. For this reason, a detailed investigation of its degradation mechanisms is necessary to develop sustainable conservation strategies. To investigate novel probes of degradation, we implemented deep UV photoluminescence micro spectral-imaging, for the first time, to characterize a corpus of historical systems composed of cellulose nitrate. The analysis of cinematographic films and everyday objects dated from the 19th c. / early 20th c. (Perlov's collection), as well as of photo-aged CN and celluloid references allowed the identification of novel markers that correlate with different phases of CN degradation in artworks, providing insight into the role played by plasticizers, fillers, and other additives instability. By comparison with photoaged references of CN and celluloid (70% CN and 30% camphor), it was possible to correlate camphor concentration with a higher rate of degradation of the cinematographic films. Furthermore, the present study investigates, at the sub-microscale, materials heterogeneity that correlates to the artworks' history, associating the different emission profiles of zinc oxide to specific color formulations used in the late 19th and early 20th centuries.

It is shown how soft X-ray nanospectroscopy maps of powders (particle size ∼200 nm) can be analyzed to quantitatively retrieve X-ray linear dichroism (XLD) parameters. A computational modeling procedure is described that can be used in conjunction with Monte Carlo simulations to prove statistical dissimilarity of XLD parameters between different samples., X-ray linear dichroism (XLD) is a fundamental property of many ordered materials that can for instance provide information on the origin of magnetic properties and the existence of differently ordered domains. Conventionally, measurements of XLD are performed on single crystals, crystalline thin films, or highly ordered nanostructure arrays. Here, it is demonstrated how quantitative measurements of XLD can be performed on powders, relying on the random orientation of many particles instead of the controlled orientation of a single ordered structure. The technique is based on a scanning X-ray transmission microscope operated in the soft X-ray regime. The use of a Fresnel zone plate allows X-ray absorption features to be probed at ∼40 nm lateral resolution – a scale small enough to probe the individual crystallites in most powders. Quantitative XLD parameters were then retrieved by determining the intensity distributions of certain diagnostic dichroic absorption features, estimating the angle between their transition dipole moments, and fitting the distributions with four-parameter dichroic models. Analysis of several differently produced ZnO powders shows that the experimentally obtained distributions indeed follow the theoretical model for XLD. Making use of Monte Carlo simulations to estimate uncertainties in the calculated dichroic model parameters, it was established that longer X-ray exposure times lead to a decrease in the amplitude of the XLD effect of ZnO.

A multimodal spectral imaging technique is demonstrated that allows simultaneous acquisition of soft X-ray transmission and X-ray excited optical luminescence. The use of a Fresnel zone plate ensures a lateral resolution of the correlative spectral images of approximately 40 nm., X-ray absorption and optical luminescence can both provide valuable but very different information on the chemical and physical properties of materials. Although it is known that the spectral characteristics of many materials are highly heterogeneous on the micro- and/or nanoscale, no methodology has so far been shown to be capable of spatially resolving both full X-ray absorption and X-ray excited optical luminescence (XEOL) spectra on the nanoscale in a correlative manner. For this purpose, the scanning transmission X-ray microscope at the HERMES beamline of the SOLEIL synchrotron was equipped with an optical detection system capable of recording high-resolution XEOL spectra using a 40 nm soft X-ray probe. The functionality of the system was demonstrated by analyzing ZnO powder dispersions — showing simultaneously the X-ray linear dichroism and XEOL behavior of individual submicrometric ZnO crystallites.

International audience; X-ray analytical techniques are increasingly being used to study manuscripts and works of art on paper, whether with laboratory equipment or synchrotron sources. However, it is difficult to anticipate the impact of X-ray photons on paper- and cellulose-based artifacts, particularly due to the large variety of their constituents and degradation levels, and the subsequent material multiscale heterogeneity. In this context, this work aims at developing an analytical approach to study the modifications in paper upon synchrotron radiation (SR) X-ray radiation using analytical techniques, which are fully complementary and highly sensitive, yet not frequently used together. At the molecular scale, cellulose chain scissions and hydroxyl free radicals were measured using chromatographic separation techniques (size-exclusion chromatography-multiangle laser light scattering-differential refractive index (SEC-MALS-DRI) and reversed-phase high-performance liquid chromatography-fluorescence detector-diode array detector (RP-HPLC-FLD-DAD)), while the optical properties of paper were characterized using spectroscopy (UV luminescence and diffuse reflectance). These techniques showed different sensitivities toward the detection of changes. The modifications in the cellulosic material were monitored in real time, within a few days, and up to 2 years following the irradiation to define a lowest observed adverse effect dose (LOAED). As paper is a hygroscopic material, the impact of the humidity in the environment was studied using this approach. Three levels of moisture content in the paper, achieved by conditioning the samples and irradiating them at different relative humidities (RHs), were studied (0, 50, 80% RH). It was shown that very low moisture content accelerated molecular and optical modification

Zinc oxide (ZnO) is a II-VI semiconductor that has been used for the last 150 years as an artists' pigment under the name of zinc white. Oil paints containing zinc white are known to be prone to the formation of zinc carboxylates, which can cause protrusions and mechanical failure. In this article, it is demonstrated how a multispectral synchrotron-based deep-UV photoluminescence microimaging technique can be used to show the distribution of zinc soaps on the submicrometer scale and how this information is used to further the understanding of zinc white degradation processes in oil paint. The technique is based on the luminescence of zinc soaps in the near-UV (∼3.65 eV) upon excitation in the deep-UV (4.51 eV), involving transitions that are argued to subsequently involve ligand-to-metal and metal-to-ligand charge transfer with intermediate structural reconfiguration. Because the primary emission peak lies at a higher energy than the band gap of ZnO (3.3 eV), the signal can easily be isolated from the pigment's very intense band gap and trap state emission by employing a multispectral acquisition approach. Moreover, analysis at such short wavelengths, in combination with a UV-transparent optical setup, allows for lateral resolution on the order of 200 nm to be obtained. The unprecedented capabilities of the microimaging technique are illustrated by showing its application to the study of a historical cross section from an early 20th century painting by Piet Mondrian. Revealing the submicrometer distribution of crystalline zinc soaps in this cross section provides new insights that suggest that microfissures, the starting points of paint delamination, are the result of an overall expansion of a heavily saponified zinc white layer.

International audience; The detailed description of corrosion processes in ancient and historical metal artifacts currently relies on the in-depth study of prepared cross sections. The in-plane elemental and phase distributions can be established from a combination of light and electron microscopy characterization. Here, we show that high-resolution virtual sectioning through synchrotron X-ray microcomputed tomography allows a precise noninvasive 3D description of the distribution of both internal and external mineral phases in whole objects. In fragments of early copper artifacts (third–second millennium BC) from Southern Mesopotamia and the Indus valley, this approach provided essential clues on long-term corrosion processes. Major and minor phases were identified through semiquantitative evaluation of attenuation coefficients using polychromatic X-ray illumination. We found evidence for initially unidentified phases through statistical processing of images. We discuss interpretation of the distribution of these phases. A good correlation between the corrosion phases identified by CT and by invasive BSE-SEM is demonstrated. In addition to the stratigraphy of the copper corrosion compounds, we examine and discuss the variations observed in the attenuation coefficients of Cu(I) phases. Semiquantitative synchrotron X-ray microtomography phase mapping requires no specific sample preparation, in particular polishing or surface finishing, and any material tearing or displacement is avoided. We also provide evidence for the noninvasive observation of phases rapidly altered upon preparation of real cross sections. The method can be applied when cross-sectioning even of minute fragments is impossible.

Bart van der Leck, as a member and co-founder of the artistic movement De Stijl, is well-known for his abstract color plane compositions, set on extensive white backgrounds. The white background in The Woodcutters (1928, oil on canvas), which comprises the brightly luminescing semiconductor pigment zinc white, was noticed to exhibit unusual luminescence behavior under UV light. Based on the observation of three distinctly different intensities of green luminescence, it was possible to differentiate between regions within the white background. This observation raised the question whether photoluminescence could be used as a tool to gain insight into different stages of the paint process and the condition of the different paint layers. This study was conducted on the microscale, on three paint cross-sections taken in the differently luminescing regions of the zinc white background. Optical microscopy and scanning electron microscopy – energy dispersive X-ray spectrometry (SEM-EDX) were used in combination with a synchrotron-based multispectral photoluminescence micro-imaging technique to examine the stratigraphy of each cross-section and reveal the photoluminescence behavior of each layer. The submicron spatial resolution and deep-UV excitation energy allowed resolution of individual zinc white particles, as well as thin surface layers which are thought to be caused by the reaction of zinc white with atmospheric contaminants. The results demonstrate how photoluminescence micro-imaging can be used to differentiate between zinc whites from different sources in the multi-layer build-up of a paint cross-section, and explain the origin of the luminescence behavior of The Woodcutters at the macroscale.

This paper describes a photoluminescence imaging approach coupled to a synchrotron source (SR-PL imaging) that provides a new, powerful way to probe the processes involved in metal soap formation in paint films, processes that play an important role in the deterioration of paint films in traditional and modern oil paintings.

Luminescence multispectral imaging is a developing and promising technique in the fields of conservation science and cultural heritage studies. In this article, we present a new methodology for recording the spatially resolved luminescence properties of objects. This methodology relies on the development of a lab-made multispectral camera setup optimized to collect low-yield luminescence images. In addition to a classic data preprocessing procedure to reduce noise on the data, we present an innovative method, based on a neural network algorithm, that allows us to obtain radiometrically calibrated luminescence spectra with increased spectral resolution from the low-spectral resolution acquisitions. After preliminary corrections, a neural network is trained using the 15-band multispectral luminescence acquisitions and corresponding spot spectroscopy luminescence data. This neural network is then used to retrieve a megapixel multispectral cube between 460 and 710 nm with a 5 nm resolution from a low-spectral-resolution multispectral acquisition. The resulting data are independent from the detection chain of the imaging system (filter transmittance, spectral sensitivity of the lens and optics, etc.). As a result, the image cube provides radiometrically calibrated emission spectra with increased spectral resolution. For each pixel, we can thus retrieve a spectrum comparable to those obtained with conventional luminescence spectroscopy. We apply this method to a panel of lake pigment paints and discuss the pertinence and perspectives of this new approach.

International audience; Synchrotrons have provided significant methods and instruments to study ancient materials from cultural and natural heritages. New ways to visualise (surfacic or volumic) morphologies are developed on the basis of elemental, density and refraction contrasts. They now apply to a wide range of materials, from historic artefacts to paleontological specimens. The tunability of synchrotron beams owing to the high flux and high spectral resolution of photon sources is at the origin of the main chemical speciation capabilities of synchrotron-based techniques. Although, until recently, photon-based speciation was mainly applicable to inorganic materials, novel developments based, for instance, on STXM and deep UV photoluminescence bring new opportunities to study speciation in organic and hybrid materials, such as soaps and organometallics, at a submicrometric spatial resolution over large fields of view. Structural methods are also continuously improved and increasingly applied to hierarchically structured materials for which organisation results either from biological or manufacturing processes. High-definition (spectral) imaging appears as the main driving force of the current trend for new synchrotron techniques for research on cultural and natural heritage materials.

High-flux synchrotron techniques allow microspectroscopic analyses of artworks that were not feasible even a few years ago, allowing for a more detailed characterization of their constituent materials and a better understanding of their chemistry. However, interaction between high-flux photons and matter at the sub-microscale can generate damages which are not visually detectable. We show here different methodologies allowing to evidence the damages induced by microscopic X-ray absorption near-edge structure spectroscopy analysis ( $$\mu$$ XANES) at the Fe and Zn K-edges of a painting dating from the turn of the twentieth century containing Prussian blue and zinc white. No significant degradation of the pigments was noticed, in agreement with the excellent condition of the painting. However, synchrotron radiation damages occurred at several levels, from chemical changes of the binder, modification of crystal defects in zinc oxide, to Prussian blue photoreduction. They could be identified by using both the $$\mu$$ XANES signal during analysis and with photoluminescence imaging in the deep ultraviolet and visible ranges after analysis. We show that recording accurately damaged areas is a key step to prevent misinterpretation of results during future re-examination of the sample. We conclude by proposing good practices that could help in integrating radiation damage avoidance into the analytical pathway.

International audience; Deep ultraviolet (DUV) photoluminescence (PL) microimaging is an emerging approach to characterise materials from historical artefacts (see M. Thoury, J.-P. Echard, M. Réfrégiers, B. H. Berrie, A. Nevin, F. Jamme and L. Bertrand, Anal. Chem., 2011, 83, 1737–1745). Here we further assess the potential of the method to access a deeper understanding of multi-layered varnishes coating wooden violins and lutes. Cross-section micro samples from important 16th- to 18th-century instruments were investigated using synchrotron PL microimaging and microspectroscopy. Excitation was performed in the DUV and the near ultraviolet (NUV) regions, and emission recorded from the DUV to the visible region, at a submicrometric spatial resolution. Intercomparison of microspectroscopy and microimaging was made possible by radiometrically correcting PL spectra both in excitation and emission. Based on an optimised selection of emission and excitation bands, the specific PL features of the organic binding materials allowed a vastly enhanced discrimination between collagen-based sizing layers and oil/resin-based layers compared to epiluminescence microscopy. PL therefore appears to be a very promising analytical tool to provide new insights into the diversity of surface coating techniques used by instrument-makers. More generally, our results demonstrate the potential of synchrotron PL for studying complex heterogeneous materials beyond the core application of the technique to life sciences.

International audience; In order to fully characterize the zinc white artists' pigment (ZnO), much used since the mid-nineteenth century, three samples collected in the early 20th century were studied using a combination of synchrotron and macroscopic photoluminescence spectroscopy and imaging. An improved microscope setup based on synchrotron microspectroscopy and microimaging was used to study the powders dispersed onto indium foil. The synchrotron setup offered a diffraction-limited resolution of 153 nm. The PL spectra of individual grains were measured and the distribution of particles' emission spectra was mapped at the nanoscale. The results revealed that while the samples have apparent homogeneous photoluminescence behavior at the macroscale (bulk), their PL signatures are inhomogeneous below 20 μm. At the nanoscale the three powder samples have quite different PL signatures. Different sources, perhaps even different batches, of zinc white might be readily differentiated using this method.

Synchrotron photon-based methods are increasingly being used for the physico-chemical study of ancient and historical materials (archaeology, palaeontology, conservation sciences, palaeo-environments). In particular, parameters such as the high photon flux, the small source size and the low divergence attained at the synchrotron make it a very efficient source for a range of advanced spectroscopy and imaging techniques, adapted to the heterogeneity and great complexity of the materials under study. The continuous tunability of the source — its very extended energy distribution over wide energy domains (meV to keV) with a high intensity — is an essential parameter for techniques based on a very fine tuning of the probing energy to reach high chemical sensitivity such as XANES, EXAFS, STXM, UV/VIS spectrometry, etc . The small source size attained (a few micrometres) at least in the vertical plane leads to spatial coherence of the photon beams, giving rise in turn to a series of imaging methods already crucial to the field. This review of the existing literature shows that microfocused hard X-ray spectroscopy (absorption, fluorescence, diffraction), full-field X-ray tomography and infrared spectroscopy are the leading synchrotron techniques in the field, and presents illustrative examples of the study of ancient and historical materials for the various methods. Fast developing analytical modalities in scanning spectroscopy (STXM, macro-XRF scanning) and novel analytical strategies regarding optics, detectors and other instrumental developments are expected to provide major contributions in the years to come. Other energy domains are increasingly being used or considered such as far-infrared and ultraviolet/visible for spectroscopy and imaging. We discuss the main instrumental developments and perspectives, and their impact for the science being made on ancient materials using synchrotron techniques.

The use of synchrotron radiation techniques to study cultural heritage and archaeological materials has undergone a steep increase over the past 10-15 years. The range of materials studied is very broad and encompasses painting materials, stone, glass, ceramics, metals, cellulosic and wooden materials, and a cluster of organic-based materials, in phase with the diversity observed at archaeological sites, museums, historical buildings, etc. Main areas of investigation are: (1) the study of the alteration and corrosion processes, for which the unique non-destructive speciation capabilities of X-ray absorption have proved very beneficial, (2) the understanding of the technologies and identification of the raw materials used to produce archaeological artefacts and art objects and, to a lesser extent, (3) the investigation of current or novel stabilisation, conservation and restoration practices. In terms of the synchrotron methods used, the main focus so far has been on X-ray techniques, primarily X-ray fluorescence, absorption and diffraction, and Fourier-transform infrared spectroscopy. We review here the use of these techniques from recent works published in the field demonstrating the breadth of applications and future potential offered by third generation synchrotron techniques. New developments in imaging and advanced spectroscopy, included in the UV/visible and IR ranges, could even broaden the variety of materials studied, in particular by fostering more studies on organic and complex organic-inorganic mixtures, while new support activities at synchrotron facilities might facilitate transfer of knowledge between synchrotron specialists and users from archaeology and cultural heritage sciences.

International audience

Qualitative UV-fluorescence of varnishes is commonly used to locate repaints on paintings or to specify the homogeneousness of a varnish layer. Photographers can now use flash UV-lamps coupled with a CCD camera to obtain colour images of the fluorescence of paintings, unveiling thus both interest and difficulty to interpret these colours. Starting from this point of view, UV-fluorescence spectra appear to be a potential technique to characterize the nature of varnishes and, if possible, their state of degradation. This identification will be non-invasive, without contact, obtained in real time and workable in situ , as the identification of pigments or dyes by reflectance spectrometry which is already done in our group. The last goal will be to realize both identifications with the same device. Emission fluorescence spectra are implemented with the Jobin-Yvon Fluorolog-3, providing an incident wavelength laying between 200 and 850 nm. The emission spectra are implemented with an optical fiber linked to a Jobin-Yvon spectrometer HR460 and a multi-channel CCD detector. In a first step, popular, fresh, raw resins used between the XVI th and the XIX th century, as mastic, dammar and sandarac, have been used to prepare varnishes films with different solvents. The fluorescence spectra of these films have been carried out at different excitation wavelengths to build databases. After having tested the coherence, the limits and the accuracy of the method, we suggest different applications of our method. A synthesis of the results will be presented to characterize each varnish by their fluorescence spectra.