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The preservation of paper-based archival documents is crucial for safeguarding historical and cultural heritage. Some records possess visually inaccessible text or images because of previous conservation measures, their method of construction, or historic damage. Micro-spatially Offset Raman Spectroscopy (micro-SORS) has emerged as a promising method for probing below or through opaque material substrates non-invasively. This study explores the potential of micro-SORS to image hidden text and figures in paper-based archival documents, utilizing Raman signals, fluorescence emissions, and overall spectral intensity reflecting also sample absorption. We present case studies involving sealed letters and playing cards from historical collections, demonstrating the efficacy of micro-SORS in identifying pigments and deciphering hidden ink writings. Results show the successful mapping of vermilion pigment in playing cards and reconstruction of hidden iron gall ink text in sealed letters. Chemometric analysis further enhances the visualization of hidden text. Despite challenges such as the absence of Raman signal of the target materials, micro-SORS proves to be a valuable tool for accessing hidden information in paper-based artifacts, aiding in preservation efforts and historical research., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2024. Published by Elsevier B.V. All rights reserved.)

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.

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., (© 2011 American Chemical Society)

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.