Solvent Azeotropes in Art Conservation

Solvent mixtures are often fine-tuned by art conservators for the difficult tasks of safely removing yellowed varnishes and obfuscating dirt from oil paintings. These two goals are often loosely termed “picture cleaning.” Concern has been raised over the impact of differential evaporation rates for solvents in the cleaning mixture. Differential evaporation can lead to changes in the mixture’s potency over time and potentially lead to solvent mixtures on the surface of the artwork having solubility characteristics deleterious to artists’ oil paints. Azeotropic mixtures of solvents have been proposed as an alternative for maintaining consistent solvent composition. Azeotropes are specific mixtures of two or more solvents that behave as a single solvent and maintain a constant composition at their boiling point. The azeotropes that have appeared in the art conservation literature are taken from tables of azeotropic compositions in the CRC Handbook given at their boiling point. This research examines whether these solvent blends, in particular a hexane/isopropanol combination found to be an effective cleaner in the treatment of painted royal sleighs at the Palace of Versailles, in fact behave azeotropically under room temperature evaporation conditions. For the first time, the actual evaporation behavior of this purported azeotropic mixture will be explored in depth. A range of hexane/isopropanol mixtures around the boiling point azeotrope composition have been assessed for their room temperature vapor pressure and evaporation weight loss kinetics. Aliquots of the evaporating solutions are also being analyzed chemically using gas chromatography of both the liquid phase and the vapor phase in the headspace. This research aims to provide conservators information on the evaporation of purportedly azeotropic solvent blends and to suggest new approaches to the cleaning of oil paintings

The room temperature evaporation behavior of purported azeotropes used as cleaning solutions in art conservation

Finely-tuned solvent mixtures are used by art conservators for the difficult task of safely and selectively removing yellowed varnish, disfiguring grime, and discolored overpaint from the surface of oil paintings. This process is often referred to as picture cleaning and depends on the different solubilities of the obfuscating surface materials and the underlying paint medium. However, differential evaporation rates for the solvents used in these carefully formulated cleaning mixtures can change the potency of the mixture over time, which could potentially lead to solutions having solubility characteristics that are ineffective at cleaning, or worse yet, are deleterious to artists\u27 oil paints. Azeotropic blends of solvents have been proposed as an alternative for maintaining consistent solvent composition throughout the evaporation process while benefiting from their high vapor pressure relative to the pure solvents. Azeotropes are specific combinations of two or more solvents at a precise concentration that behave as a single solvent, maintaining a constant composition in both the liquid and vapor phases. The use of purportedly azeotropic solvent blends has appeared in the art conservation literature for the cleaning of historic objects and paintings. However, these solvent mixtures are taken from tables of azeotropic compositions given at their boiling point. We have studied one of these solutions, a 19:81 vol% mixture of isopropanol and n-hexane. For the first time, the actual evaporation behavior of this purported azeotropic mixture was followed in detail at room temperature conditions. Through the use of rudimentary vapor pressure measurements, gravimetric analysis, as well as sophisticated compositional determinations of both the liquid phase and headspace of evaporating mixtures by gas chromatography, this particular cleaning solution has been shown to be zeotropic (i.e. NOT an azeotrope) under the conditions typical of conservation studios. The true room temperature azeotropic composition was found instead to contain half as much isopropanol at 9.5 vol%. Art conservators should therefore be dubious of purportedly azeotropic mixtures reported at boiling points well above room temperature. Individual azeotropic cleaning blends are best determined chemically prior to their use in art restoration. Furthermore, the introduction of a model paint film to the evaporating room temperature azeotrope was shown to further confound its behavior, calling into question whether solvent systems can be configured to evaporate with constant composition from the surface of an artwork