Abstract

Paintings and painted objects are quite susceptible to degradation, as paint layers are usually composed of complex mixtures of materials that can participate in chemical degradation processes. The identification of the constituent materials in paint (including binders, pigments, and fillers) and the degradation products within paint layers is of particular importance to ensuring the conservation of paintings, by providing important information both about their material history as well as their state of conservation. Metal fatty acid salts (metal soaps) are degradation products that can form in situ from interactions between inorganic pigments and free fatty acids in oil-based binding media, and can cause significant condition issues in paintings. Fourier transform infrared (FTIR) spectroscopy is one of the leading analytical techniques for the study of metal soaps. In this article, the materials analysis of several cross-sections from paintings and painted objects from works in Canadian collections is presented. Recent results on the use of external reflection FTIR (R-FTIR) spectroscopy to identify and map the distribution of paint components and metal soap degradation products is presented. In particular, zinc, lead, calcium, and copper fatty acid salts were all readily identified in paint cross-sections by R-FTIR spectroscopy, along with several pigments and the oil binding medium. The results shown here are among the first detailed examinations of these metal soaps in paint cross-sections using R-FTIR spectroscopy. The use of highly polished samples in which specular reflection is dominant allowed for spectral transformations to be applied to generate transmission/absorption-like spectra which facilitated identification of these species. The distribution of these species across the cross-sections was mapped by integrating characteristic absorption features in the R-FTIR spectra. Attenuated total internal reflection (ATR) FTIR spectroscopy was also performed on several samples, which provided additional compositional details at the interface of paint layers and degradation products.

Highlights

  • Works of art and cultural heritage objects are continuously subjected to degradation processes that can significantly compromise their integrity, function and aesthetic quality

  • The results shown here are among the first detailed examinations of these metal soaps in paint cross-sections using R-Fourier transform infrared (FTIR) spectroscopy

  • The Kramers–Kronig transformations (KKT)-corrected reflection FTIR (R-FTIR) spectrum is very similar to the transmission/absorption FTIR spectrum obtained on an unmounted fragment of the protrusion removed from the same sample (Fig. 2b)

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Summary

Introduction

Works of art and cultural heritage objects are continuously subjected to degradation processes that can significantly compromise their integrity, function and aesthetic quality. Metal soaps are sometimes added to paints as extenders or processing aids (e.g. aluminum stearate) [4], they can form in situ from interactions between inorganic pigments and free fatty acids in oilbased binding media. Of particular concern, they have been shown to be mobile within the paint layers, and can lead to flaking, interlayer adhesion failure, and phenomena such as protrusions and surface haze. Lead and zinc-based soaps have been extensively studied [5, 6], mostly owing to the prevalence of lead and zinc-based pigments in historical works of art and their reactivity towards fatty acids in oil paints. Copper carboxylates are well-documented, in the form of green copper resinate glazes (copper salts of resin acids), and as soaps in oil paints applied to copper substrates [8]

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