The works of art and artifacts that constitute our cultural heritage are subject to deterioration, both from internal and from external factors. Surfaces that interact with the environment are the most prone to aging and decay; accordingly, soiling is a prime factor in the degradation of surfaces and the attendant disfigurement of a piece. Coatings that were originally intended to protect or contribute aesthetically to an artwork should be removed if they begin to have a destructive impact on its appearance or surface chemistry. Since the mid-19th century, organic solvents have been the method of choice for cleaning painted surfaces and removing degraded coatings. Care must be taken to choose a solvent mixture that minimizes swelling of or leaching from the original paint films, which would damage and compromise the physical integrity of all the layers of paint. The use of gels and poultices, first advocated in the 1980s, helps by localizing the solvent and, in some cases, by reducing solvent permeation into underlying paint layers. Unfortunately, it is not always easy to remove gels and their residues from a paint surface. In this Account, we address the removal problem by examining the properties of three classes of innovative gels for use on artwork--rheoreversible gels, magnetic gels, and "peelable" gels. Their rheological properties and efficacies for treating the surfaces of works have been studied, demonstrating uniquely useful characteristics in each class: (1) Rheoreversible gels become free-flowing on application of a chemical or thermal "switch". For art conservation, a chemical trigger is preferred. Stable gels formed by bubbling CO(2) through solutions of polyallylamine or polyethylenimines (thereby producing ammonium carbamates, which act as chain cross-links) can be prepared with a wide range of solvent mixtures. After solubilization of varnish and dirt, addition of a weak acid (mineral or organic) displaces the CO(2), and the resulting free-flowing liquid can be removed gently. (2) Incorporation of magnetic, coated-ferrite nanoparticles into polyacrylamide gels adds functionality to a versatile system comprising oil-in-water microemulsions, aqueous micellar solutions, or xerogels that act as sponges. The ferrite particles allow the use of magnets both to place the gels precisely on a surface and to lift them from it after cleaning. (3) Novel formulations of poly(vinyl alcohol)-borate gels, which accept a range of organic cosolvents, show promise for swelling and dissolving organic coatings. This family of gels can be quite stiff but can be spread. They are non-sticky and have sufficient strength to be removed by peeling or lifting them from a sensitive surface. These three classes of gels are potentially very important soft materials to augment and improve the range of options available for conserving cultural heritage, and their interesting chemical-physical properties open a rich area for future scientific investigation.
A gel-like, high-viscosity polymeric dispersion (HVPD) based on cross-linked borate, partially hydrolyzed poly(vinyl acetate) (xPVAc, where x is the percent hydrolysis) is described. Unlike hydro-HVPDs prepared from poly(vinyl alcohol) (PVA) and borate, the liquid portion of these materials can be composed of up to 75% of an organic cosolvent because of the influence of residual acetate groups on the polymer backbone. The effects of the degree of hydrolysis, molecular weight, polymer and cross-linker concentrations, and type and amount of organic cosolvent on the rheological and structural properties of the materials are investigated. The stability of the systems is explored through rheological and melting-range studies. (11)B NMR and small-angle neutron scattering (SANS) are used to probe the structure of the dispersions. The addition of an organic liquid to the xPVAc-borate HVPDs results in a drastic increase in the number of cross-linked borate species as well as the agglomeration of the polymer into bundles. These effects result in an increase in the relaxation time and thermal stability of the networks. The ability to make xPVAc-borate HVPDs with very large amounts of and rather different organic liquids, with very different rheological properties that can be controlled easily, opens new possibilities for applications of PVAc-based dispersions.
A versatile gel-like system for the treatment of art has been prepared from partially hydrolyzed poly(vinyl acetate), borax, and large fractions of ethanol, isopropyl alcohol, n-propyl alcohol, and acetone. Variables such as the concentrations of the two gelating components, the degree of hydrolysis and molecular weight of the polymer, and the type of liquid gelated were investigated to establish formulations of gels with physical and chemical properties that are best suited for specific applications. The gels were designed to have an elastic character that allows them to conform to the topography of complex surfaces and be removed with ease by being lifted from the surface. Results from fluorescence studies demonstrated that the solvent is constrained within the area of the gel, allowing for localized treatment. Polymer and boron residues were not detected after cleaning tests on acrylic and dammar test paint-outs, and on two oil paintings with degraded surface coatings. The efficacy of the cleaning systems was determined visually. Studies of the materials removed during treatments showed that the gels appear to act by softening the coating surface while typically a pass with a solvent-dampened swab after gel treatment removes the softened coating. Two case studies and notes on other applications of the gels are described; recipes and preparation procedures are included.
The preparation and structural characterization of a family of viscoelastic dispersions of borate cross-linked, 80% hydrolyzed poly(vinyl acetate) (80PVAc) in aqueous-organic liquids are presented. Correlations between mechanical properties (from rheological measurements) and the degree and nature of cross-linking (from (11)B NMR spectroscopy) are reported, and the results are used to assess their potential as low-impact cleaning agents for the surfaces of paintings. Because the dispersions can be prepared at room temperature by simple procedures from readily available materials and can contain up to 50% (w/w) of an organic liquid, they offer important advantages over previously described cleaning agents that are based on fully hydrolyzed PVAc (i.e., poly(vinyl alcohol). The mechanical properties of the various aqueous-organic dispersions, as determined quantitatively by rheological investigations and qualitatively by their ease of removal from a solid surface (i.e., the so-called "peel-off" ability) have been tuned systematically by varying the amount of organic liquid, its structure, and the concentrations of borax and 80PVAc. The (11)B NMR studies demonstrate that the concentration of borate ions actively participating in cross-linking increases significantly with the amount of organic liquid in the mixture. The degree of cross-linking remains constant when the 80PVAc and borax concentrations are varied, as long as their ratios are kept constant. Some of the 80PVAc-borax dispersions have been tested successfully as cleaning agents on the surface of a 16th-17th century oil-on-wood painting by Lodovico Cardi, "Il Cigoli", that was covered by a brown patina and on the surface of a Renaissance wall painting by Vecchietta in Santa Maria della Scala, Siena, Italy, that had a degraded polyacrylate coating from a previous conservation treatment.
Roy Lichtenstein's Whaam! (1963) is an iconic artwork in Tate's collection (T00897). Over the past 50 years, the painting has been on almost continuous display and had accrued a layer of deposited soiling, which resulted in the dampening of Lichtenstein's vibrant colours and the masking of numerous subtleties across the painting surface. This paper outlines the design and execution of an optimal soiling removal strategy for this challenging work; utilising collaborative, practice-based research. The conservation treatment employed was derived through an iterative process that reflected and supported the conservation decision-making process. The research strands included: technical and art historical investigations to determine the materials and construction of Whaam! and to define the aims of the conservation treatment; preparation of accelerated aged and artificially soiled test (mock-up) paint samples based on contemporary equivalent materials and a comparative evaluation of a range of established and novel soil-removal systems, followed by further tailoring for use on the work of art. The range of cleaning systems evaluated included free-solvents, gels and emulsifiers; which were documented using star diagrams, digital microscopy and infrared spectroscopy. After a rigorous process of assessment and refinement, the strategy taken forward to Whaam! included the use of a polyvinyl alcohol-based polymeric hydrogel (Nanorestore Gel ® Peggy 6), uploaded with tailored aqueous solutions. This process facilitated a low risk, controlled and even-removal of the soiling layer, enabling the successful treatment of this sensitive painting for the first time in the painting's history.
The dynamic and structural properties of Highly Viscous Polymeric Dispersions (HVPDs), constituted of polyvinyl alcohol obtained from the 75% hydrolysis (75PVA) of polyvinlyl acetate (PVAc) cross-linked with borate ions, were studied as a function of the 75PVA concentration at a constant ratio between the OH groups and the borate ions (OH/B(OH) 4 À). The threshold 75PVA concentration C* necessary for the formation of the three-dimensional network was determined by flow rheology. The oscillating rheology measurements were performed in the linear viscoelastic region; the relaxation spectra calculated from the frequency sweep curves showed only one peak whose width increased upon increasing the 75PVA concentration due to the broadening of the relaxation modes. The dependence of the mean relaxation time s H upon the concentration of 75PVA followed a power law expression (s H $ C x with x ¼ 1.9) indicating that s H referred to a sticky reptation mechanism and that water was a good solvent for 75PVA as confirmed also by small angle X-rays scattering (SAXS) investigation. The HVPDs were used for the removal of grime layers from the surface of Carlo Carrà (1881-1966) paints decorating the walls of the Palazzo di Giustizia in Milan, Italy.
Viscoelastic, gel-like, polymeric dispersions (HVPDs) can be prepared by crosslinking polyols with borax or boric acid in water under alkaline conditions. Rheologically similar HVPDs have been prepared in organic liquids containing no water or hydroxylic groups through crosslinking partially or fully hydrolysed poly(vinyl acetate)s with trimethyl borate, boric acid, or borax. The organo-HVPDs are water-sensitive and rheoreversible on exposure to water. They were characterised rheologically and by solution and solid-state (11)B NMR spectroscopy. Spectroscopic analyses show the presence of mono- and di-diol crosslinks, as well as non-crosslinked boron species in HVPDs prepared with trimethyl borate or boric acid. The number of crosslinks in organo-HVPDs prepared with borax increased over the course of several days. Results from solution and solid-state (11)B NMR spectroscopy are comparable; no solid-like component was detectable. We demonstrate that hydro, organo, or organo-aqueous HVPDs can be obtained from partially hydrolysed poly(vinyl acetate)s by 'tuning' the structure of the boron-based crosslinker.
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