Poly(vinyl alcohol)/poly(vinyl pyrrolidone) hydrogels for the cleaning of art.

The cleaning of modern and contemporary paintings is a delicate and challenging operation. Many contemporary paintings exhibit rough, clotted and pitted surfaces, where the removal of soil is difficult. Gels are among the most efficient tools to achieve controlled and efficient cleaning of works of art. However, most gels used in the conservation practice are too rigid to adapt rough surfaces, or too mechanically weak to be removed without leaving polymer residues. Several formulations of physically cross-linked poly(vinyl alcohol) (PVA)-based hydrogels, obtained by cast-drying or freeze-thawing of aqueous polymeric solutions, were formulated and characterized. The viscoelastic properties, porosity, and crystallinity of the gels were studied, along with the behavior of water inside the polymeric network. It was shown that the properties of the gels were improved through blending with poly(vinyl pyrrolidone) (PVP). The most promising gel formulation, in terms of mechanical properties and water retentiveness, was assessed for the removal of soil from an alkyd painting mock-up. A traditional gel, gellan gum, was also tested as a reference system. The effectiveness of soil removal was investigated by 2D Fourier transform infrared (FTIR) microscopy, using a Focal Plane Array (FPA) detector. In conclusion, it was shown that the newly developed formulation grants the residue-free removal of soil from rough and irregular artistic surfaces, overcoming the limits of traditional cleaning methods.

Restoration of paper artworks with microemulsions confined in hydrogels for safe and efficient removal of adhesive tapes.

The presence of pressure-sensitive tapes (PSTs) on paper artworks, either fortuitous or specifically applied for conservation purposes, is one of the most frequent and difficult issues encountered during restoration. Aged PSTs can damage or disfigure artworks, compromising structural integrity, readability, and enjoyment. Current procedures are often inherently hazardous for artistic media and paper support. Challenged by the necessity to remove PSTs from a contemporary and an ancient drawing (20th century, by artists da Silva and Hayter, and a 16th-century drawing of one figure from the Sistine Chapel by Michelangelo), we addressed this issue from a physicochemical perspective, leveraging colloid and interface science. After a characterization of the specific PSTs present on the artifact, we selected a highly water-retentive hydrogel as the host of 23% wt/wt of "green" organic solvents uniformly dispersed within the gel in the form of nanosized droplets. The double confinement of the organic solvent in the nanodroplets and into the gel network promotes a tailored, controlled removal of PSTs of different natures, with virtually no interaction with the solvent-sensitive artwork. This noninvasive procedure allows complete retrieval of artwork readability. For instance, in the ancient drawing, the PST totally concealed the inscription, "di mano di Michelangelo" ("from Michelangelo's hand"), a possibly false attribution hidden by a collector, which is now perfectly visible and whose origin is currently under investigation. Remarkably, the same methodology was successful for the removal of aged PST adhesive penetrated inside paper fibers of a drawing from the celebrated artist Lucio Fontana.

Surface cleaning of artworks: structure and dynamics of nanostructured fluids confined in polymeric hydrogel networks.

Nanosystems and confinement tools for the controlled release of a cleaning agent, e.g., hydrogels and microemulsions, have been used for several years for the treatment of delicate surfaces in art restoration interventions. However, notwithstanding the unprecedented achievements from an application point of view, a fundamental comprehension of their interaction mechanism is still lacking. In this study PVA hydrogels, obtained via freeze-thaw processes, are prepared as scaffolds for water-based nanostructured fluids for application in the cleaning of artworks: rheological, thermal, microscopic and scattering techniques showed that, depending on the number of freeze-thaw cycles, the hydrogels exhibit different physicochemical and viscoelastic properties, making them suitable for application in a broad range of cleaning issues. The gels have been loaded with an oil-in-water microemulsion and the diffusion of the microemulsion droplets inside the polymeric network has been investigated through Fluorescence Correlation Spectroscopy (FCS), demonstrating that the microemulsion is permanently kept inside the matrix and can freely diffuse in the network. In addition, we show that when the gel-microemulsion system is put in contact with a layer of hydrophobic grime, a dynamic interaction between the microemulsion droplets and the underlying layer is established, leading to the solubilization of the hydrophobic molecules inside the droplets in the gel matrix. Thus, for the first time, through FCS, insights into the removal mechanism of hydrophobic grime upon interaction with a cleaning agent embedded in the polymeric matrix are obtained.

Innovative chemical gels meet enzymes: A smart combination for cleaning paper artworks.

HYPOTHESIS: Due to their highly retentive properties, innovative recently developed, semi-interpenetrated hydrogels made up of poly(vinyl pyrrolidone) (PVP) chains embedded in a poly(2-hydroxyethyl methacrylate) (p(HEMA)) network should be efficiently used as cleaning material for fragile and degraded paper artworks. In restoration practice, indeed the wet cleaning of these artworks is usually performed by immersion of paper in water, a procedure which may lead to several drawbacks, including paper fibers swelling and dissolution of water-soluble original components. EXPERIMENTS: This class of gels were yet presented in literature, but their interactions with paper materials and ability to be spiked with active enzymes (as cleaning agents), have not been analyzed. To establish the suitability of these hydrogels as paper cleaning materials, first, a rheological and microstructural characterization of the gels was performed. Moreover, diffusion of macromolecules inside gels was studied using fluorescence microscopy, to check if these innovative hydrogels can be used as carriers for hydrolytic enzymes. Indeed, pastes and glues are usually found in old paper artworks, and their removal is a very delicate operation that requires a selective action, which is granted by specific hydrolytic enzymes. At the same time, spectroscopic analyses on paper samples under investigation before and after cleaning treatment has been performed, thus assessing the capabilty of these gels as cleaning materials. FINDINGS: With the aim of demonstrating the versatility of these hydrogels, several case studies, i.e., the removal of grime and water-soluble cellulose degradation byproducts, the removal of animal glue and the removal of starch paste from real samples, are presented. Results obtained with these gels have been compared to those obtained by using another gel used for paper artworks cleaning, i.e., Gellan gel.

Innovative hydrogels based on semi-interpenetrating p(HEMA)/PVP networks for the cleaning of water-sensitive cultural heritage artifacts.

Water-based detergent systems offer several advantages, over organic solvents, for the cleaning of cultural heritage artifacts in terms of selectivity and gentle removal of grime materials or aged varnish, which are known to alter the readability of the painting. Unfortunately, easel paintings present specific characteristics that make the usage of water-based systems invasive. The interaction of water with wood or canvas support favors mechanical stresses between the substrate and the paint layers leading to the detachment of the pictorial layer. In order to avoid painting loss and to ensure a fine control (layer by layer) of grime removal, water-based cleaning systems have been confined into innovative chemical hydrogels, specifically designed for cleaning water-sensitive cultural heritage artifacts. The synthesized hydrogels are based on semi-interpenetrating chemical poly(2-hydroxyethyl methacrylate)/poly(vinylpyrrolidone) networks with suitable hydrophilicity, water retention properties, and required mechanical strength to avoid residues after the cleaning treatment. Three different compositions were selected. Water retention and release properties have been studied by quantifying the amount of free and bound water (from differential scanning calorimetry); mesoporosity was obtained from scanning electron microscopy; microstructure from small angle X-ray scattering. To demonstrate both the efficiency and versatility of the selected hydrogels in confining and modulating the properties of cleaning systems, a representative case study is presented.