SR-FTIR imaging has been used to map the mid-IR active photo-degradation phases in two thin sections of cadmium yellow paint removed from Henri Matisse's Le Bonheur de vivre (1905-1906, The Barnes Foundation). These samples represent both the darkened cadmium yellow foliage in the upper left of the work and the lightened cadmium yellow field beneath the central reclining figures. The altered cadmium yellow paints from both regions were found to contain cadmium carbonate (CdCO3), cadmium sulphate (CdSO4), and cadmium oxalate (CdC2O4). Each of these phases was imaged to determine their positions as a function of depth, with the aim of better understanding the role of each phase in the degradation mechanism. This speciation mapping is critical because cadmium oxalate was used in this period as an additive in cadmium yellow light. In addition, cadmium carbonate and cadmium sulphate were synthesis starting materials for cadmium yellow, and so their distribution throughout the paint layer can provide an indication of their roles. It was established that cadmium oxalate is localized at the surface of the paint layer, cadmium carbonate is found deeper in the layer but still enriched at the surface, and cadmium sulphate is distributed throughout the layer. This distribution, along with the chloride content of the paint suggesting a cadmium chloride starting material, is consistent with an alteration mechanism in which the cadmium sulphide is oxidized to sulphate and this is then converted to carbonate and oxalate. The relative solubilities of the three photo-degradation products are also relevant to their locations in the paint film.

Spectral imaging modalities, including reflectance and X-ray fluorescence, play an important role in conservation science. In reflectance hyperspectral imaging, the data are classified into areas having similar spectra and turned into labeled pigment maps using spectral features and fusing with other information. Direct classification and labeling remain challenging because many paints are intimate pigment mixtures that require a non-linear unmixing model for a robust solution. Neural networks have been successful in modeling non-linear mixtures in remote sensing with large training datasets. For paintings, however, existing spectral databases are small and do not encompass the diversity encountered. Given that painting practices are relatively consistent within schools of artistic practices, we tested the suitability of using reflectance spectra from a subgroup of well-characterized paintings to build a large database to train a one-dimensional (spectral) convolutional neural network. The labeled pigment maps produced were found to be robust within similar styles of paintings.

Paints based on cadmium sulfide (CdS) were popular among artists beginning in the mid-19th century. Some paint formulations are prone to degrade, discoloring and disfiguring paintings where they have been used. Pablo Picasso's Femme (E ́poque des "Demoiselles d'Avignon") (1907) includes two commercial formulations of CdS: one is visibly degraded and now appears brownish yellow, while the other appears relatively intact and is vibrant yellow. This observation inspired the study reported here of the photoluminescence emission from trap states of the two CdS paints, complemented by data from multispectral imaging, Xray fluorescence spectroscopy, micro-FTIR, and SEM-EDS. The two paints exhibit trap state emissions that differ in terms of spectrum, intensity, and decay kinetics. In the now-brownish yellow paint, trap state emission is highly favored with respect to near band edge optical recombination. This observation suggests a higher density of surface defects in the now-brownish yellow paint that promotes the surface reactivity of CdS particles and their subsequent paint degradation. CdS is a semiconductor, and surface defects in semiconductors can trap free charge carriers; this interaction becomes stronger at reduced particle size or, equivalently, with increased surface to volume ratio. Here, we speculate that the strong trap state emission in the now-brownish cadmium yellow paint is linked to the presence of CdS particles with a nanocrystalline phase, possibly resulting from a low degree of calcination during pigment synthesis. Taken together, the results presented here demonstrate how photoluminescence studies can probe surface defects in CdS paints and lead to an improved understanding of their complex degradation mechanisms.

As one of the most desired and expensive artists’ materials throughout history, there has long been interest in studying natural lapis lazuli. The traditional method of extracting the blue component, lazurite, from lapis lazuli, as outlined in Cennini’sIl Libro dell’Arte, involves a lengthy purification process: (1) finely grind the rock; (2) mix with pine rosin, gum mastic, and beeswax; (3) massage in water to collect the lazurite. Repeating the process produces several grades of the pigment, typically referred to as ultramarine blue. Here, we investigate the sulfur environment within the aluminosilicate framework of lazurite during its extraction from lapis lazuli. The sulfur XANES fingerprint from samples taken at the different stages in Cennini’s extraction method were examined. All spectra contain a strong absorption peak at 2483 eV, attributable to sulfate present in the lazurite structure. However, intensity variations appear in the broad envelope of peaks between 2470 and 2475 eV and the pre-peak at 2469.1 eV, indicating a variation in the content of trisulfur (S3−˙) radicals. By studying the effect of each step of Cennini’s process, this study elucidates the changes occurring during the extraction and the variability within different grades of the precious coloring material. The increasing application of XANES to the study of artist’s materials and works of art motivated extending the research to assess the possibility of X-ray induced damage. Direct comparison of micro-focused and unfocused beam experiments suggests an increase of the S3−˙ radicals with prolonged exposure. Analysis indicates that induced damage follows first-order kinetics, providing a first assessment on the acceptable amount of radiation exposure to define the optimal acquisition parameters to allow safe analyses of lapis lazuli and ultramarine pigments.