Investigation of the discoloration of smalt pigment in historic paintings by micro-X-ray absorption spectroscopy at the Co K-edge.

Smalt was commonly used as a pigment by artists between the 16th and 18th centuries. It is a powdered blue potash glass colored by cobalt ions and often degrades causing dramatic changes in the appearance of paintings. The aim of the work presented in this paper was to investigate the changes in the structure and environment around the cobalt ion on deterioration, to further our understanding of the basis of the loss of color. Particles of well-preserved and altered smalt in microsamples from paintings in the National Gallery, London, and the Louvre, Paris, were analyzed using synchrotron micro-X-ray absorption spectroscopy at the Co K-edge. X-ray absorption near-edge spectroscopy (XANES) and extended X-ray absorption fine structure (EXAFS) measurements showed that in intense blue particles the cobalt is predominantly present as Co(2+) in tetrahedral coordination, whereas in colorless altered smalt the Co(2+) coordination number in the glass structure is increased and there is a shift from tetrahedral toward octahedral coordination. The extent of this shift correlates clearly with the alkali content, indicating that it is caused by leaching of potassium cations, which act as charge compensators and stabilize the tetrahedral coordination of the cobalt ions that is responsible for the blue color.

Speckle noise reduction in optical coherence tomography of paint layers.

We present and characterize a sequential angular compounding method for reducing speckle contrast in optical coherence tomography images of paint layers. The results are compared with postprocessing methods, and we show that the compounding technique can improve the speckle contrast ratio in B-scans by better than a factor of 2 in exchange for a negligible loss of resolution. As a result, image aesthetics are improved, thin layers become more distinct, and edge-detection algorithms work more efficiently. The effect of varying the angular scan size and number of averages is investigated, and it is found that a degree of statistical correlation between speckle patterns exists, even for relatively large changes in angle of incidence. Angular compounding is also performed on three-dimensional data sets and compared with a method whereby en face slices are averaged over depth.

ATR-FTIR imaging for the analysis of organic materials in paint cross sections: case studies on paint samples from the National Gallery, London.

The potential of attenuated total reflection Fourier transform infrared (ATR-FTIR) imaging for the characterisation of the chemical components of paint cross sections from old master paintings was investigated. Three cross sections were chosen to cover a variety of the analytical problems encountered in samples from paintings. The binding medium and degradation products in a green paint sample from a fifteenth-century Florentine painting were imaged, as well as a thin layer within a cross-section from a fifteenth-century German painting, and multiple thin surface coatings on a painting of the 1760s by Peter Romney. The application of chemometric methods for further analysis of the large data set generated for each sample was also explored. The study demonstrated the advantages of ATR-FTIR imaging, which allowed images to be obtained with high spatial resolution (ca. 3-4 microm) without the need to microtome the sample. The gain in sensitivity in detecting trace materials and the information derived from the location of these compounds in the sample was especially valuable, improving interpretation of the FTIR analysis and extending knowledge of the sample composition beyond that obtainable with other analytical techniques.