Search

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.

The origin(s) and role(s) of metal soaps in paints are a worldwide concern today. These hybrid compounds, containing both fatty acid chains and metals associated with a carboxylate function, are increasingly identified in paints. As reviewed in the first part of this work, the presence of metal soaps in paints is differently interpreted in scientific publications: metal soaps are sometimes considered to play a positive role as anchor points, during paint drying processes; they can also be considered as responsible for many degradation processes (protrusions, efflorescences, darkening, etc.). Their origins are also interpreted in various ways. In some paintings (in particular from the twentieth century), they have sometimes introduced on purpose, as additives, to modify the physical properties of the painting materials. In older paintings, metal soaps are usually thought to result from an uncontrolled reaction of oil with lead-based pigments, in particular lead white, red lead, and lead tin yellow. In the second part of this work, the review of historical recipes of lead-based paint shows an important number of recipes based on controlled mixing of oil with lead driers. In the third part, the experimental reproduction of such traditional recipes using walnut oil and litharge (PbO) shows that lead soaps can be formed, both in about one hour at ∼100°C, or in about one month at room temperature. It shows as well that after a few years, litharge is no longer detected in the paint medium, while different lead carbonates are. Finally, the micro-infrared spectroscopy and micro-X-ray diffraction re-analysis of protrusions from a nine-year model painting shows together with lead soaps, the presence of Pb5(CO3)3(OH)2O (‘synthetic plumbonacrite’), an unusual phase recently observed in a protrusion from a painting by Vincent Van Gogh. This work highlights (i) the multiple origins and roles of metal soaps in paints and (ii) the importance of combining the analysis of fragments from historical paintings with the analysis and reproduction of historical recipes. In particular, we show that the components detected today in historical paintings may severely differ from those originally used or prepared by the painter, complicating the assessment of the painter's intentions. More than the presence of metal soaps, the key questions to be tackled should be about their origins and (re)mobilization. [ABSTRACT FROM PUBLISHER]

The interaction of pigments and binding media may result in the production of metal soaps on the surface of paintings which modifies their visible appearance and state of conservation. To characterise more fully the metal soaps found on paintings, several historically accurate oil and egg yolk tempera paint reconstructions made with different pigments and naturally aged for 10 years were submitted to attenuated total reflectance Fourier transform infrared (ATR FTIR) microspectroscopic analyses. Standard metal palmitates were synthesised and their ATR spectra recorded in order to help the identification of metal soaps. Among the different lead-based pigments, red lead and litharge seemed to produce a larger amount of carboxylates compared with lead white, Naples yellow and lead tin yellow paints. Oil and egg tempera litharge and red lead paints appeared to be degraded into lead carbonate, a phenomenon which has been observed for the first time. The formation of metal soaps was confirmed on both oil and egg tempera paints based on zinc, manganese and copper and in particular on azurite paints. ATR mapping analyses showed how the areas where copper carboxylates were present coincided with those in which azurite was converted into malachite. Furthermore, the key role played by manganese in the production of metals soaps on burnt and raw sienna and burnt and raw umber paints has been observed for the first time. The formation of copper, lead, manganese, cadmium and zinc metal soaps was also identified on egg tempera paint reconstructions even though, in this case, the overlapping of the spectral region of the amide II band with that of metal carboxylates made their identification difficult. [Figure not available: see fulltext.] [ABSTRACT FROM AUTHOR]

Metal soaps formation is a well-known issue in oil paintings. Along the lifetime of the painting, carboxylic acids coming from drying oil (free fatty acids, acids from hydrolysis of triglycerides and from oxidation processes) can react with cations of some pigments (in particular, smalt, lead white and zinc white) forming the related carboxylic salts. As observed by many authors, the formation of these carboxylates, with the tendency to migrate and to aggregate, not only modifies the behavior and the aspect of the paint film but also complicates the cleaning approach. In previous works we have demonstrated that a similar pigment reactivity is possible even in presence of natural resins (such as colophony, dammar, mastic, etc) historically used as final varnishes on paintings. In this case, in the reactions the terpenic acids, among the main components of the resins, are involved. In this work, the carboxylates formation kinetics has been studied starting from two representative acids (palmitic and abietic) of painting oils and natural varnishes. Successively, the reactivity of the palmitic acid with the potassium abietate and of the abietic acid with the potassium palmitate has been verified. This investigation aims at clarifying in which way terpenic acids can be involved in the metal soaps reactivity confirming that also surface varnishes may play a significant role in the carboxylates formation and reactivity. It is important to keep in mind that a finishing varnish can be removed and reapplied many times during the lifetime of a painting, thus renewing the provision of reactive terpenic acids at the interface of the painted layers. [ABSTRACT FROM AUTHOR]