Emeline Pouyet

The ID21 Scanning X-ray Microscope at ESRF

The ID21 Scanning X-ray Microscope (SXM) is optimized for micro-spectroscopy with submicron resolution in the 2 to 9.5 keV energy range. After a brief description of the microscope setup, we present here recent developments, in particular, the latest version of the compact Wavelength Dispersive Spectrometer and the refurbished cryo-stage.

Tracking the transformation and transport of arsenic sulfide pigments in paints: synchrotron-based X-ray micro-analyses

Realgar and orpiment, arsenic sulfide pigments used in historic paints, degrade under the influence of light, resulting in transparent, whitish, friable and/or crumbling paints. So far, para-realgar and arsenic trioxide have been identified as the main oxidation products of arsenic sulfide pigments. This paper shows that after photo-degradation, various oxidation and migration processes take place. Synchrotron radiation (SR) micro-X-ray fluorescence (μ-XRF) reveals arsenic to be distributed throughout the whole multi-layered paint system. Arsenic (As) K-edge micro-X-ray absorption near edge structure (μ-XANES) analyses indicate the presence of an intact AsxSy pigment, arsenite compounds (As3+; As2O3), and arsenate compounds (As5+); the latter are certainly present as calcium, lead, aluminium and iron arsenates. Sulfur (S) K-edge μ-XANES points to the conversion of the sulfide (S2−) group to a sulfate (SO42−) group, probably via an elemental sulfur (S0) or sulfoxide (S2+) compound. Principal Component Analysis (PCA) and subsequent k-means clustering of multi-energy SR μ-XRF maps and μ-XANES were performed to identify the various arsenic species and visualize their distribution. The arsenates (As5+) are spread throughout the entire paint system and dominate the photo-degraded paint and ground layers, while the arsenite compounds (As3+) are located close to the intact arsenic sulfide pigment. The oxidation of arsenic trioxide into arsenates likely takes place in aqueous solutions. The presence of As5+ compounds in the paint systems indicates that the arsenic trioxide is dissolved by ambient water present in the paint. Arsenite and arsenate compounds are water soluble and are transported by water throughout the paint system. This knowledge is crucial for the conservation field, as this is the first time that (indirect) evidence of water transport within paintings has been given.

Full-field XANES analysis of Roman ceramics to estimate firing conditions—A novel probe to study hierarchical heterogeneous materials

Roman black gloss ceramics from two different locations and separated by 50–80 years were investigated by X-ray absorption near edge structure analysis in full field hard X-ray transmission microscopes. These spectro-microscopy measurements were complemented by Raman spectroscopy, and X-ray diffraction spot analyses to gain insights into possible differences in manufacturing technology. Our results indicate that the two vessels underwent significantly different firing protocols, suggesting that there was a surprisingly quick evolution of a complex technological process in response to changing needs and tastes of a burgeoning empire. Furthermore, our results show that the ability of the full field X-ray spectro-microscope to investigate large sample areas (from hundreds of µm2 to as much as 2 mm2) with high spatial resolution (of 300 nm down to 30 nm) together with its ability to correlate sample porosity (derived from tomography) with the distribution of chemical phases makes it an invaluable tool in the investigation of nanoscale processes in hierarchically heterogeneous chemical systems—from Roman ceramics to some of the most advanced technological products of today.

Preparation of thin-sections of painting fragments: classical and innovative strategies.

For more than a century, the analyses of painting fragments have been carried out mainly through the preparation of thick resin-embedded cross-sections. Taking into account the development of innovative micro-analytical imaging techniques, alternatives to this standard preparation method are considered. Consequently, dedicated efforts are required to develop preparation protocols limiting the risks of chemical interferences (solubilisation, reduction/oxidation or other reactions) which modify the sample during its preparation, as well as the risks of analytical interferences (overlap of detected signals coming from the sample and from materials used in the preparation). This study focuses particularly on the preparation of thin-sections (1-20 μm) for single or combined fourier transform infrared (FTIR) spectroscopy and X-ray 2D micro-analysis. A few strategies specially developed for the μFTIR analysis of painting cross-sections have already been reported and their potential extrapolation to the preparation of thin-sections is discussed. In addition, we propose two new specific methods: (i) the first is based on a free-embedding approach, ensuring a complete chemical and analytical neutrality. It is illustrated through application on polymeric design objects corpus; (ii) the second is based on a barrier coating approach which strengthens the sample and avoids the penetration of the resin into the sample. The barrier coating investigated is a silver chloride salt, an infrared transparent material, which remains malleable and soft after pellet compression, enabling microtoming. This last method was successfully applied to the preparation of a fragment from a gilded Chinese sculpture (15th C.) and was used to unravel a unique complex stratigraphy when combining μFTIR and μXRF.

Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile–butadiene–styrene model samples and historical objects

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile-butadiene-styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3×3 μm(2)) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time.

The ID21 X-ray and infrared microscopy beamline at the ESRF: status and recent applications to artistic materials

The ID21 beamline (European Synchrotron Radiation facility, France) is a multi micro-analytical platform combining X-ray and infrared micro-probes, for characterization of elements, species, molecular groups and crystalline structures in complex materials. Applications are mainly in the fields of cultural heritage, life science, environmental and earth sciences, materials sciences. Here, we first present the status of instruments: (i) the scanning micro-spectroscopy end-station, operating from 2.0 to 9.2 keV, under vacuum and offering cryo conditions, for the acquisition of 2D micro X-ray fluorescence (μXRF) maps, single point micro X-ray Absorption Near Edge Structure (μXANES) spectra and speciation maps with sub-micrometric resolution; (ii) the XANES full-field end-station, operating in the same vacuum and energy conditions, for the acquisition of hyper-spectral radiographs of thin concentrated samples, resulting in speciation maps with micrometric resolution and millimetric field of view; (iii) the scanning micro-X-ray diffraction (μXRD)/μXRF end-station, operating at 8.5 keV, in air, for the acquisition of 2D crystalline phase maps, with micrometric resolution; and (iv) the scanning infrared microscope, operating in the mid-infrared range for the acquisition of molecular maps and some structural maps with micrometric resolution. Recent hardware and software developments are presented, as well as new protocols for improved sample preparation of thin sections. Secondly, a review of recent applications for the study of cultural heritage is presented, illustrated by various examples: determination of the origin of the color in blue Chinese porcelains and in brown Sevres porcelains; detection of lead in ink on Herculaneum papyri; identification and degradation of modeling materials used by Auguste Rodin and of chrome yellow pigments used by Vincent van Gogh. Cryo capabilities are illustrated by the analysis of plants exposed to chromate solutions. These examples show the variety of materials analyzed, of questions tackled, and particularly the multiple advantages of the ID21 analytical platform for the analysis of ancient and artistic materials.

Synchrotron radiation-based multi-analytical approach for studying underglaze color: The microstructure of Chinese Qinghua blue decors (Ming dynasty).

In this paper, we develop a methodological approach combining macro-X-ray fluorescence and synchrotron radiation-based techniques (μXRF, full-field XANES and μXRD) to determine the composition and microstructure of underglaze decors of Qinghua porcelains (Ming dynasty). Various transition metal elements (Fe, Mn, Co) are present in the blue decoration of these ceramics and the approach proposed allows for establishing the feature of each. Thus it shows that Fe ions are distributed homogeneously over the whole glaze without any significant difference in blue and white parts. They do not play a significant role in the color. In contrast, Co ions exhibit a heterogeneous distribution with CoAl2O4 particles close to the body/glaze interphase. These particles play a key role in the blue color and, the hue variations seem in greater part to link to their density and repartition. Co dispersed in the glassy matrix is also bivalent and mainly in tetragonal coordination, leading also to a blue color. Mn ion distribution is similar to the one of Co but without presenting local high concentrations associated to Mn based particles. Mn affects the darkness of the color and for the sample without CoAl2O4 particle; it is the main color contribution. The presence of CoAl2O4 crystals was confirmed by μXRD, which revealed, in addition, a variation of cell parameters certainly linking to a Co partial substitution.

Image stack alignment in full-field X-ray absorption spectroscopy using SIFT_PyOCL.

Full-field X-ray absorption spectroscopy experiments allow the acquisition of millions of spectra within minutes. However, the construction of the hyperspectral image requires an image alignment procedure with sub-pixel precision. While the image correlation algorithm has originally been used for image re-alignment using translations, the Scale Invariant Feature Transform (SIFT) algorithm (which is by design robust versus rotation, illumination change, translation and scaling) presents an additional advantage: the alignment can be limited to a region of interest of any arbitrary shape. In this context, a Python module, named SIFT_PyOCL, has been developed. It implements a parallel version of the SIFT algorithm in OpenCL, providing high-speed image registration and alignment both on processors and graphics cards. The performance of the algorithm allows online processing of large datasets.