Conservation of our cultural heritage is fundamental for conveying to future generations our culture, traditions, and ways of thinking and behaving. Cleaning art, in particular modern/contemporary paintings, with traditional tools could be risky and impractical, particularly on large collections of important works to be transferred to future generations. We report on advanced cleaning systems, based on twin-chain polymer networks made of poly(vinyl alcohol) (PVA) chains, semiinterpenetrated (semi-IPN) with PVA of lower molecular weight (L-PVA). Interpenetrating L-PVA causes a change from gels with oriented channels to sponge-like semi-IPNs with disordered interconnected pores, conferring different gel (and solvent) dynamics. These features grant residue-free, time efficient cleaning capacity and effective dirt capture, defeating risks for the artifact, making possible a safer treatment of important collections, unconceivable with conventional methods. We report as an example the conservation of Jackson Pollock’s masterpieces, cleaned in a controlled way, safety and selectivity with unprecedented performance.

Protrusions, efflorescence, delamination, and opacity decreasing are severe degradation phenomena affecting oil paints with zinc oxide, one of the most common white pigments of the 20th century. Responsible for these dramatic alterations are the Zn carboxylates (also known as Zn soaps) originated by the interaction of the pigment and the fatty acids resulting from the hydrolysis of glycerides in the oil binding medium. Despite their widespread occurrence in paintings and the growing interest of the scientific community, the process of formation and evolution of Zn soaps is not yet fully understood. In this study micro-attenuated total reflection (ATR)-FT-IR spectroscopic imaging was required for the investigation at the microscale level of the nature and distribution of Zn soaps in the painting Alchemy by J. Pollock (1947, Peggy Guggenheim Collection, Venice) and for comparison with artificially aged model samples. For both actual samples and models, the role of AlSt(OH), a jellifying agent commonly added in 20th century paint tube formulations, proved decisive for the formation of zinc stearate-like (ZnSt) soaps. It was observed that ZnSt-like soaps first form around the added AlSt(OH) particles and then eventually grow within the whole painting stratigraphy as irregularly shaped particles. In some of the Alchemy samples, and diversely from the models, a peculiar distribution of ZnSt aggregates arranged as rounded and larger particles was also documented. Notably, in one of these samples, larger agglomerates of ZnSt expanding toward the support of the painting were observed and interpreted as the early stage of the formation of internal protrusions. Micro-ATR-FT-IR spectroscopic imaging, thanks to a very high chemical specificity combined with high spatial resolution, was proved to give valuable information for assessing the conservation state of irreplaceable 20th century oil paintings, revealing the chemical distribution of Zn soaps within the paint stratigraphy before their effect becomes disruptive.

Alchemy (1947, Peggy Guggenheim Collection, Venice) is one of the most materic works by J. Pollock, whose palette is extensive, ranging from white to yellow, red, green, violet, blue, black, and silver. Each layer of color was laid on top of a previously dried one and effectively separated from the lower one forming a quite complex stratigraphy with colors intersecting each other. In this study, a non-invasive multi-technique method combining point analysis with Vis-NIR multispectral imaging has been exploited to give insights on the painting technique of the American abstract expressionist. The molecular identification of pigments, colorants and extenders contained in fifteen different paints has been achieved combining key spectral markers from elemental, electronic and vibrational spectroscopies. For those colors exhibiting similar hues but different chemical compositions, a mapping procedure based on false color rendering, obtained by properly mixing three spectral planes from the Vis-NIR multispectral imaging set, has been successfully applied. Relevant for the understanding of the evolution of Pollock's drip technique is the identification of both traditional oil-based paints and oil-modified alkyd media. Point analysis by reflection FTIR scattered throughout the painting enabled mapping the distinct use of traditional and new binding media among painted, squeezed and dripped paints.

This paper reports on the evaluation of a polyvinyl alcohol (PVA) "twin-chain" polymer network (TC-PN) combined with an oil-in-water nanostructured fluid (NSF) for the removal of a polyvinyl acetate (PVAc) varnish. Small Angle X-ray Scattering, Confocal Laser Scanning Microscopy, and Fluorescence Correlation Spectroscopy showed that the structure of the gel and the NSF are only minimally altered by loading the fluid into the gel. The NSF is partially free to diffuse through the network, but also interacts with the gel walls. During the cleaning, the dynamics of the fluid at the gel-substrate interface are controlled by the osmotic balance taking place among the interconnected pores. These features grant effective and controlled cleaning performances. The case study identified for this research is Pablo Picasso's The Studio (L'Atelier, 1928), one of the masterpieces in the Peggy Guggenheim Collection, Venice (PGC). In 1969 the oil painting, originally unprotected, was wax-lined and then varnished using a PVAc varnish. Over the years, the white shades of the painting have been compromised by the yellowing of the varnish and soiling of deposits. On painting mock-ups, the NSF-loaded hydrogels allowed the swelling and softening of PVAc varnish and wax layers, which were then removed with gentle mechanical action. Effective varnish and wax removal at the micron scale, and the absence of residues from the cleaning system (gel and NSF), were confirmed by Fourier Transform Infrared Spectroscopy (FTIR) 2D imaging. The effective and safe removal of the aged PVAc varnish and wax layer from the surface of the painting was then carried out using the same cleaning protocol successfully tested on the mock-ups, setting the NSF-loaded PVA TC-PNs as robust and reliable tools for the cleaning of sensitive works of art.

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