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.

Mapping of egg yolk and animal skin glue paint binders in Early Renaissance paintings using near infrared reflectance imaging spectroscopy.

In situ chemical imaging techniques are being developed to provide information on the spatial distribution of artists' pigments used in polychrome works of art such as paintings. The new methods include reflectance imaging spectroscopy and X-ray fluorescence mapping. Results from these new methods have extended the knowledge obtained from site-specific chemical analyses widely in use. While these mapping methods have aided in determining the distribution of pigments, there is a growing interest to develop methods capable of identifying and mapping organic paint binders as well. Near infrared (NIR) reflectance spectroscopy has been extensively used in the remote sensing field as well as in the chemical industry to detect organic compounds. NIR spectroscopy provides a rapid method to assay organics by utilizing vibrational overtones and combination bands of fundamental absorptions that occur in the mid-IR. Here we explore the utility of NIR reflectance imaging spectroscopy to map organic binders in situ by examining a series of panel paintings known to have been painted using distemper (animal skin glue) and tempera (egg yolk) binders as determined by amino acid analysis of samples taken from multiple sites on the panels. In this report we demonstrate the success in identifying and mapping these binders by NIR reflectance imaging spectroscopy in situ. Three of the four panel paintings from Cosimo Tura's The Annunciation with Saint Francis and Saint Louis of Toulouse (ca. 1475) are imaged using a highly sensitive, line-scanning hyperspectral imaging camera. The results show an animal skin glue binder was used for the blue skies and blue robe of the Virgin Mary, and egg yolk tempera was used for the red robes and brown landscape. The mapping results show evidence for the use of both egg yolk and animal skin glue in the faces of the figures. The strongest absorption associated with lipidic egg yolk features visually correlates with areas that appear to have white highlights. The results are in agreement with prior site-specific amino acid analysis, underscoring the synergy of both methods. The work here demonstrates that NIR reflectance imaging spectroscopy is a useful technique that can identify and map paint binding media based on differences in chemical composition.

Visible and infrared imaging spectroscopy of Picasso's Harlequin musician: mapping and identification of artist materials in situ.

Reflection imaging spectroscopy is a useful technique to remotely identify and map minerals and vegetation. Here we report on the mapping and identification of artists' materials in paintings using this method. Visible and infrared image cubes of Picasso's Harlequin Musician are collected using two hyperspectral cameras and combined into a single cube having 260 bands (441 to 1680 nm) and processed using convex geometry algorithms. The resulting 18 spectral end members are identified by comparison with library spectra, fitting by nonlinear mixing, and using results from luminescence imaging spectroscopy. The results are compared with those from X-ray fluorescence spectrometry, polarized light microscopy, and scanning electron microscopy-energy dispersive spectrometry (SEM/EDS). This work shows the potential of reflection imaging spectroscopy, in particular if the shortwave infrared region is included along with information from luminescence imaging spectroscopy.