ABSTRACT: The use of nanostructured fluids (NSFs), that is, micellar solutions and microemulsions, in art conservation is often associated with cleaning purposes as the removal of polymeric coatings and/or soil from artistic surfaces. In both cases, the use of NSFs grants significant improvements over the use of traditional cleaning techniques that employ neat unconfined organic solvents, water, or aqueous solutions. The study of the nature and properties of surfactants present in NSF formulations is important to boost the effectiveness of these systems in applicative contexts and in the search of innovative and highly performing amphiphiles. This work reports on the methoxy-pentadeca(oxyethylene) dodecanoate (MPD) surfactant in two different NSFs, whose utilization in conservation of cultural heritage is new. Its effectiveness is compared to the conventional nonionic amphiphiles used in conservation practice, as pentadeca(oxyethylene) dodecyl ether, for the cleaning of poly(ethyl methacrylate/methyl acrylate) 70:30, p(EMA/MA), and artificially soiled surfaces. The mechanism, through which NSFs interact with polymeric coatings or soiled surfaces, was investigated by confocal laser scanning microscopy, fluorescence correlation spectroscopy, photographic observation, contact angle, surface tension measurements, and small-angle X-ray scattering. The results highlighted the superior MPD's performance, both in inducing polymer removal and in detaching the soil from coated surfaces. At the microscale, the cleaning involves dewetting-like processes, where the polymer or the soil oily phase is detached from the surface and coalesce into separated droplets. This can be accounted by considering the different surface tensions and the different adsorption mechanisms of MPD with respect to ordinary nonionic surfactants (likely due to the methyl capping of the polar head chain and to the presence of the ester group between the hydrophilic and hydrophobic parts of the MPD surfactant molecule), showing how a tiny change in the surfactant architecture can lead to important differences in the cleaning capacity. Overall, this paper provides a detailed description of the mechanism and the kinetics involved in the NSFs cleaning process, opening new perspectives on simple formulations that are able to target at a specific substance to be removed. This is of utmost importance in the conservation of irreplaceable works of art.
