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Since their development in the 1950s, poly(vinyl acetate) [PVAc] paints (also known as vinyl) have been used by many artists, most notably in countries such as Spain, Portugal, and the United Kingdom; they are also used globally as a common binder for house paints. However, only a relatively limited number of heritage scientific studies have focused on vinyl paints. Consequently, many critical aspects of this material, such as the degradation processes, variations in paint formulations, and responses to conservation treatments, remain largely understudied. This article aims to summarise the available relevant information on poly(vinyl acetate) paints from both the scientific and the conservation practice perspectives. The article provides a brief overview of the development of poly(vinyl acetate) paints as artist-grade and household products and the known differences in their formulations. It also focuses on poly(vinyl acetate) ageing behaviour, the physicochemical properties, the recent scientific research on poly(vinyl acetate) material characterisation and degradation, and the main conservation issues regarding these paints, such as those relating to cleaning treatments.

Systematic condition and analytical surveys were carried out on Zoe Leonard's (b. 1961) Mouth Open, Teeth Showing 2000, an installation artwork in Tate's collection consisting of 162 children's dolls. The dolls were manufactured at various points within the 20th century and encompass several potentially problematic synthetic polymers found in modern and contemporary museum collections. To explore the doll materials and conservation condition, a multi-analytical approach was used to identify key synthetic polymer types and additives present, including portable and bench analytical techniques. Challenging degradation phenomena associated with different types of doll have been discussed and related to their material composition, which has helped our understanding of the conservation challenges inherent to this contemporary artwork.

A molecular-level understanding of the structure of the polymeric network formed upon the curing of air-drying artists' oil paints still represents a challenge. In this study we used a set of analytical methodologies classically employed for the characterisation of a paint film-based on infrared spectroscopy and mass spectrometry-in combination with solid state NMR (SSNMR), to characterise model paint layers which present different behaviours towards surface cleaning with water, a commonly applied procedure in art conservation. The study demonstrates, with the fundamental contribution of SSNMR, a relationship between the painting stability and the chemical structure of the polymeric network. In particular, it is demonstrated for the first time that a low degree of cross-linking in combination with a high degree of oxidation of the polymeric network render the oil paint layer sensitive to water., (© 2021. The Author(s).)

The 20th and 21st century oil paintings are presenting a range of challenging conservation problems that can be distinctly different from those noted in paintings from previous centuries. These include the formation of vulnerable surface "skins" of medium and exudates on paint surfaces, efflorescence, unpredictable water and solvent sensitivity, and incidence of paint dripping which can occur within a few years after the paintings were completed. Physicochemical studies of modern oil paints and paintings in recent years have identified a range of possible causal factors for the noted sensitivity of painting surfaces to water and protic solvents, including the formation of water-soluble inorganic salts and/or the accumulation of diacids at the paint surface, which are oxidation products of the oil binder. Other studies have investigated the relationship between water sensitivity and the degree of hydrolysis of the binder, the proportions of free fatty and dicarboxylic acids formed, as well as the relative content of free metal soaps. Thus far, data indicate that the qualitative and quantitative composition of the nonpolymerized fractions of the oil binder cannot be solely or directly related to the solvent sensitivity of the paint film. Conclusions therefore indicate that the polymeric network, formed upon the curing of the oil, plays a fundamental role, suggesting that water sensitivity, at least in some cases, may be related to the poor development and/or polar nature of the formed polymeric network rather than the composition of the nonpolymerized fractions. Poorly developed polymeric networks, in combination with the migration of polar fractions, i.e., dicarboxylic and hydroxylated fatty acids toward the paint surface, can be related to other degradation phenomena, including the separation and migration of the paint binder which can lead to the presence of observable skins of medium as well as the more alarming phenomenon of liquefying or dripping oil paints. It is thus crucial to understand the molecular composition of these paints and their physicochemical behavior to aid the further development of appropriate conservation and preservation strategies, as the risks currently associated with surface cleaning treatments and other conservation procedures can be unacceptably high. This Account reviews the relationships between the degradation phenomena associated with modern oil paintings and the chemical composition of the oil binder and proposes a molecular model for the development of water sensitivity and other noted degradation phenomena. It is suggested that water sensitivity (and possibly other degradation phenomena) is a consequence of processes that take place upon curing, and in particular to the rate of formation and decomposition of alkoxyl and peroxyl radicals. These reactions are strongly dependent on the type of oil present, the ambient environmental conditions, and the chemical and physical nature of the pigments and additives present in the paint formulation. When the curing environment is oxidizing, the chemistry of peroxyl radicals dominates the reaction pathways, and oxidative decomposition of the paint film overwhelms cross-linking reactions.

Spectroscopic and mass spectrometric analytical techniques were used to characterise two naturally aged Winsor & Newton (W&N) Winsor Green (phthalocyanine green, PG7) artists' oil colour paint swatches dating to 1993 and 2003. Infrared and Energy Dispersive X-ray (EDX) analysis indicated that the swatches were of closely similar composition, yet the swatch from 2003 was water-sensitive whilst the swatch from 1993 was not. Water-sensitivity is a conservation challenge associated with significant numbers of modern oil paintings and this study aimed to further develop our understanding of the molecular causes of water sensitivity. SEM elemental mapping of samples taken from both swatches provided no indication for the formation of epsomite - a known cause of water sensitivity in some modern oil paintings. Liquid chromatography coupled with mass spectrometry (HPLC-MS) and gas chromatography coupled with mass spectrometry (GC-MS) also revealed very similar qualitative-quantitative composition in terms of unbound and esterified medium fractions. The polymeric network was investigated using analytical pyrolysis. A combination of flash pyrolysis coupled with gas chromatography mass spectrometry (Py-GC-MS) together with evolved gas analysis mass spectrometry (EGA-MS) revealed that the polymeric material was relatively more abundant in the non-water-sensitive paint. This is the first multi-analytical study that has demonstrated a correlation between water-sensitivity and the degree of polymerisation of the oil medium; independent of other known causes of water-sensitivity.

The 20th century has seen a significant evolution in artists' paint formulation and technology which is likely to relate to the new conservation challenges frequently presented by modern oil paintings, including unpredictable water- and solvent-sensitivity. This study examined the molecular causes and mechanisms behind these types of modern oil paint vulnerability. Research performed up to now has suggested a correlation between the occurrence of water sensitivity and the presence of relatively high amounts of extractable free dicarboxylic acids. To explore this further, as well as the influence of paint formulation, a set of model paint samples, produced in 2006 using commercial tube paints to which known amounts of additives were added, were analysed. The samples were tested for water sensitivity by aqueous swabbing and characterised using transmission Fourier Transform-Infra Red spectroscopy (FTIR) to determine the molecular composition of the main paint constituents, High Performance Liquid Chromatography-Mass Spectrometry (HPLC-MS), to identify the type(s) of drying oils used as binders, and Gas Chromatography-Mass Spectrometry (GC-MS) using a recently developed analytical procedure that can discriminate and quantify free fatty and dicarboxylic acids, as well as their corresponding metal soaps (carboxylates of fatty and dicarboxylic acids). The results indicated that the addition of small amounts of additives can influence the water sensitivity of an oil paint, as well as its molecular composition. Additionally the nature of the ionomeric/polymeric network appears to be a significant determining factor in the development of water sensitivity., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)