Reviving degraded colors of yellow flowers in 17th century still life paintings with macro- and microscale chemical imaging.

Over time, artist pigments are prone to degradation, which can decrease the readability of the artwork or notably change the artist's intention. In this article, the visual implication of secondary degradation products in a degraded yellow rose in a still life painting by A. Mignon is discussed as a case study. A multimodal combination of chemical and optical imaging techniques, including noninvasive macroscopic x-ray powder diffraction (MA-XRPD) and macroscopic x-ray fluorescence imaging, allowed us to gain a 3D understanding of the transformation of the original intended appearance of the rose into its current degraded state. MA-XRPD enabled us to precisely correlate in situ formed products with what is optically visible on the surface and demonstrated that the precipitated lead arsenates and arsenolite from the yellow pigment orpiment and the light-induced fading of an organic yellow lake irreversibly changed the artist's intentional light-shadow modeling.

Reflectance Imaging Spectroscopy (RIS) for Operation Night Watch: Challenges and Achievements of Imaging Rembrandt's Masterpiece in the Glass Chamber at the Rijksmuseum.

Visible and infrared reflectance imaging spectroscopy is one of the several non-invasive techniques used during Operation Night Watch for the study of Rembrandt's iconic masterpiece The Night Watch (1642). The goals of this project include the identification and mapping of the artists' materials, providing information about the painting technique used as well as documenting the painting's current state and ultimately determining the possible conservation plan. The large size of the painting (3.78 m by 4.53 m) and the diversity of the technical investigations being performed make Operation Night Watch the largest research project ever undertaken at the Rijksmuseum. To construct a complete reflectance image cube at a high spatial resolution (168 µm2) and spectral resolution (2.54 to 6 nm), the painting was imaged with two high-sensitivity line scanning hyperspectral cameras (VNIR 400 to 1000 nm, 2.54 nm, and SWIR 900 to 2500 nm, 6 nm). Given the large size of the painting, a custom computer-controlled 3-D imaging frame was constructed to move each camera, along with lights, across the painting surface. A third axis, normal to the painting, was added along with a distance-sensing system which kept the cameras in focus during the scanning. A total of 200 hyperspectral image swaths were collected, mosaicked and registered to a high-resolution color image to sub-pixel accuracy using a novel registration algorithm. The preliminary analysis of the VNIR and SWIR reflectance images has identified many of the pigments used and their distribution across the painting. The SWIR, in particular, has provided an improved visualization of the preparatory sketches and changes in the painted composition. These data sets, when combined with the results from the other spectral imaging modalities and paint sample analyses, will provide the most complete understanding of the materials and painting techniques used by Rembrandt in The Night Watch.

Standoff Mid-Infrared Emissive Imaging Spectroscopy for Identification and Mapping of Materials in Polychrome Objects.

Microscale mid-infrared (mid-IR) imaging spectroscopy is used for the mapping of chemical functional groups. The extension to macroscale imaging requires that either the mid-IR radiation reflected off or that emitted by the object be greater than the radiation from the thermal background. Reflectance spectra can be obtained using an active IR source to increase the amount of radiation reflected off the object, but rapid heating of greater than 4 °C can occur, which is a problem for paintings. Rather than using an active source, by placing a highly reflective tube between the painting and camera and introducing a low temperature source, thermal radiation from the room can be reduced, allowing the IR radiation emitted by the painting to dominate. Thus, emissivity spectra of the object can be recovered. Using this technique, mid-IR emissivity image cubes of paintings were collected at high collection rates with a low-noise, line-scanning imaging spectrometer, which allowed pigments and paint binders to be identified and mapped.

Revealing the Nature and Distribution of Metal Carboxylates in Jackson Pollock's Alchemy (1947) by Micro-Attenuated Total Reflection FT-IR Spectroscopic Imaging.

Protrusions, efflorescence, delamination, and opacity decreasing are severe degradation phenomena affecting oil paints with zinc oxide, one of the most common white pigments of the 20th century. Responsible for these dramatic alterations are the Zn carboxylates (also known as Zn soaps) originated by the interaction of the pigment and the fatty acids resulting from the hydrolysis of glycerides in the oil binding medium. Despite their widespread occurrence in paintings and the growing interest of the scientific community, the process of formation and evolution of Zn soaps is not yet fully understood. In this study micro-attenuated total reflection (ATR)-FT-IR spectroscopic imaging was required for the investigation at the microscale level of the nature and distribution of Zn soaps in the painting Alchemy by J. Pollock (1947, Peggy Guggenheim Collection, Venice) and for comparison with artificially aged model samples. For both actual samples and models, the role of AlSt(OH)2, a jellifying agent commonly added in 20th century paint tube formulations, proved decisive for the formation of zinc stearate-like (ZnSt2) soaps. It was observed that ZnSt2-like soaps first form around the added AlSt(OH)2 particles and then eventually grow within the whole painting stratigraphy as irregularly shaped particles. In some of the Alchemy samples, and diversely from the models, a peculiar distribution of ZnSt2 aggregates arranged as rounded and larger particles was also documented. Notably, in one of these samples, larger agglomerates of ZnSt2 expanding toward the support of the painting were observed and interpreted as the early stage of the formation of internal protrusions. Micro-ATR-FT-IR spectroscopic imaging, thanks to a very high chemical specificity combined with high spatial resolution, was proved to give valuable information for assessing the conservation state of irreplaceable 20th century oil paintings, revealing the chemical distribution of Zn soaps within the paint stratigraphy before their effect becomes disruptive.