Assessing Fire-Damage in Historical Papers and Alleviating Damage with Soft Cellulose Nanofibers.

The conservation of historical paper objects with high cultural value is an important societal task. Papers that have been severely damaged by fire, heat, and extinguishing water, are a particularly challenging case, because of the complexity and severity of damage patterns. In-depth analysis of fire-damaged papers, by means of examples from the catastrophic fire in a 17th-century German library, shows the changes, which proceeded from the margin to the center, to go beyond surface charring and formation of hydrophobic carbon-rich layers. The charred paper exhibits structural changes in the nano- and micro-range, with increased porosity and water sorption. In less charred areas, cellulose is affected by both chain cleavage and cross-linking. Based on these results and conclusions with regard to adhesion of auxiliaries, a stabilization method is developed, which coats the damaged paper with a thin layer of cellulose nanofibers. It enables the reliable preservation of the paper and-most importantly-retrieval of the contained historical information: the nanofibers form a flexible, transparent film on the surface and adhere strongly to the damaged matrix, greatly reducing its fragility, giving it stability, and enabling digitization and further handling.

A Methodology for Discriminant Time Series Analysis Applied to Microclimate Monitoring of Fresco Paintings.

The famous Renaissance frescoes in Valencia's Cathedral (Spain) have been kept under confined temperature and relative humidity (RH) conditions for about 300 years, until the removal of the baroque vault covering them, carried out in 2006. In the interest of longer-term preservation and in order to maintain these frescoes in good condition, a unique monitoring system was implemented to record both air temperature and RH. Sensors were installed in different points at the vault of the apse, during the restoration process. The present study proposes a statistical methodology for analyzing a subset of RH data recorded in 2008 and 2010, from the sensors. This methodology is based on fitting different functions and models to the time series, in order to classify the sensors. The methodology proposed, computes classification variables and applies a discriminant technique to them. The classification variables correspond to estimates of parameters of the models and features such as mean and maximum, among others. These features are computed using values of the functions such as spectral density, sample autocorrelation (sample ACF), sample partial autocorrelation (sample PACF), and moving range (MR). The classification variables computed were structured as a matrix. Next, Sparse Partial Least Squares Discriminant Analysis (sPLS-DA) was applied in order to discriminate sensors according to their position in the vault. It was found that the classification of sensors derived from Seasonal ARIMA-TGARCH showed the best performance (i.e., lowest classification error rate). Based on these results, the methodology applied here can be useful for characterizing the differences in RH, measured at different positions in a historical building.

Multivariate Time Series Analysis of Temperatures in the Archaeological Museum of L'Almoina (Valencia, Spain).

An earlier study carried out in 2010 at the archaeological site of L'Almoina (Valencia, Spain) found marked daily fluctuations of temperature, especially in summer. Such pronounced gradient is due to the design of the museum, which includes a skylight as a ceiling, covering part of the remains in the museum. In this study, it was found that the thermal conditions are not homogeneous and vary at different points of the museum and along the year. According to the European Standard EN10829, it is necessary to define a plan for long-term monitoring, elaboration and study of the microclimatic data, in order to preserve the artifacts. With the aforementioned goal of extending the study and offering a tool to monitor the microclimate, a new statistical methodology is proposed. For this propose, during one year (October 2019-October 2020), a set of 27 data-loggers was installed, aimed at recording the temperature inside the museum. By applying principal component analysis and k-means, three different microclimates were established. In order to characterize the differences among the three zones, two statistical techniques were put forward. Firstly, Sparse Partial Least Squares Discriminant Analysis (sPLS-DA) was applied to a set of 671 variables extracted from the time series. The second approach consisted of using a random forest algorithm, based on the same functions and variables employed by the first methodology. Both approaches allowed the identification of the main variables that best explain the differences between zones. According to the results, it is possible to establish a representative subset of sensors recommended for the long-term monitoring of temperatures at the museum. The statistical approach proposed here is very effective for discriminant time series analysis and for explaining the differences in microclimate when a net of sensors is installed in historical buildings or museums.

Revealing the Distribution of Metal Carboxylates in Oil Paint from the Micro- to Nanoscale.

Oil paints comprise pigments, drying oils, and additives that together confer desirable properties, but can react to form metal carboxylates (soaps) that may damage artworks over time. To obtain information on soap formation and aggregation, we introduce a new tapping-mode measurement paradigm for the photothermal induced resonance (PTIR) technique that enables nanoscale IR spectroscopy and imaging on highly heterogenous and rough paint thin sections. PTIR is used in combination with µ-computed tomography and IR microscopy to determine the distribution of metal carboxylates in a 23-year old oil paint of known formulation. Results show that heterogeneous agglomerates of Al-stearate and a Zn-carboxylate complex with Zn-stearate nano-aggregates in proximity are distributed randomly in the paint. The gradients of zinc carboxylates are unrelated to the Al-stearate distribution. These measurements open a new chemically sensitive nanoscale observation window on the distribution of metal soaps that can bring insights for understanding soap formation in oil paint.

Polymer Film Dewetting by Water/Surfactant/Good-Solvent Mixtures: A Mechanistic Insight and Its Implications for the Conservation of Cultural Heritage.

Aqueous nanostructured fluids (NSFs) have been proposed to remove polymer coatings from the surface of works of art; this process usually involves film dewetting. The NSF cleaning mechanism was studied using several techniques that were employed to obtain mechanistic insight on the interaction of a methacrylic/acrylic copolymer (Paraloid B72) film laid on glass surfaces and several NSFs, based on two solvents and two surfactants. The experimental results provide a detailed picture of the dewetting process. The gyration radius and the reduction of the Tg of Paraloid B72 fully swollen in the two solvents is larger for propylene carbonate than for methyl ethyl ketone, suggesting higher mobility of polymer chains for the former, while a nonionic alcohol ethoxylate surfactant was more effective than sodium dodecylsulfate in favoring the dewetting process. FTIR 2D imaging showed that the dewetting patterns observed on model samples are also present on polymer-coated mortar tiles when exposed to NSFs.

Microemulsions, Micelles, and Functional Gels: How Colloids and Soft Matter Preserve Works of Art.

Colloid science provides fundamental knowledge to fields such as the pharmaceutical, detergency, paint, and food industry. An exciting application is art conservation, which poses a challenge owing to the complex range of interfacial interactions involved in restoring artefacts. Currently, the majority of the most performing and environmentally safe cleaning and consolidation agents for artworks belong to soft matter and colloids. The development and application of increasingly complex systems, from microemulsions to semi-interpenetrating hydrogels containing such fluids, is presented. These systems have been used on diverse artefacts, from Renaissance frescos to works by Picasso and Pollock. Chemical design can be implemented to meet the requirements of curators, and knowledge of the colloid structure and dynamics can overcome serendipitous approaches of traditional conservation practice. Future perspectives for soft matter and colloid science in the field of cultural heritage preservation are also summarized.

Photochemistry of Artists' Dyes and Pigments: Towards Better Understanding and Prevention of Colour Change in Works of Art.

The absorption of light gives a pigment its colour and its reason for being, but it also creates excited states, that is, new molecules with an energy excess that can be dissipated through degradation pathways. Photodegradation processes provoke long-term, cumulative and irreversible colour changes (fading, darkening, blanching) of which the prediction and prevention are challenging tasks. Of all the environmental risks that affect heritage materials, light exposure is the only one that cannot be controlled without any impact on the optimal display of the exhibit. Light-induced alterations are not only associated with the pigment itself but also with its interactions with support/binder and, in turn, are further complicated by the nature of the environmental conditions. In this Minireview we investigate how chemistry, encompassing multi-scale analytical investigations of works of art, computational modelling and physical and chemical studies contributes to improve our prediction of artwork appearance before degradation and to establish effective preventive conservation strategies.

Miniaturized Biosensors to Preserve and Monitor Cultural Heritage: from Medical to Conservation Diagnosis.

The point-of-care testing concept has been exploited to design and develop portable and cheap bioanalytical systems that can be used on-site by conservators. These systems employ lateral flow immunoassays to simultaneously detect two proteins (ovalbumin and collagen) in artworks. For an in-depth study on the application of these portable biosensors, both chemiluminescent and colorimetric detections were developed and compared in terms of sensitivity and feasibility. The chemiluminescent system displayed the best analytical performance (that is, two orders of magnitude lower limits of detection than the colorimetric system). To simplify its use, a disposable cartridge was designed ad hoc for this specific application. These results highlight the enormous potential of these inexpensive, easy-to-use, and minimally invasive diagnostic tools for conservators in the cultural heritage field.

Mobile NMR: An essential tool for protecting our cultural heritage.

What is 'cultural heritage'? Is it simply our legacy of physical artifacts - or is it our collective legacy as human societies - how we want to be remembered by future generations? With time, negligence, and even military conflict working to erase the past, we must ask: Can a better understanding of our shared heritage assists us in addressing cultural differences in the present day? And how can science both help us understand the historic record and work to preserve it? In this perspective article, we examine an emerging scientific method, mobile nuclear magnetic resonance (NMR), which can help us examine in a non-invasive way important objects and sites of our cultural heritage. Following these investigations, one can envisage ways for protecting our global heritage for future generations. For this purpose, we examine how this method can be used to non-destructively explore historical artifacts, which can lead to understanding the science behind the creation of these treasured items - paintings, frescoes, parchments, historical buildings, musical instruments, ancient mummies, and other artifacts. This perspective article follows few relevant examples from the scientific literature where mobile NMR has been applied in a non-invasive way to analyze objects of cultural heritage. One can envision possible future advancements of this technique and further applications where portable NMR can be used for conservation of cultural heritage. Copyright © 2016 John Wiley & Sons, Ltd.

Uncovering Art's Vanishing Hues with Surface-Enhanced Raman Scattering: Drawing Inspiration from the Past for the Future.

The aesthetic and historical significance of art is well recognized; art can stoke emotions, invite close inquiry, and connect us to the past. However, works of art are also complex material objects that present unique challenges and opportunities for the scientific community. Identifying "fugitive" organic pigments in traditional oil paintings, for example, presents a particularly complex analytical challenge that is critical to address for their conservation and long-term preservation. In this Perspective, we discuss the benefits and technical challenges of applying surface-enhanced Raman scattering (SERS) spectroscopy to the ultrasensitive identification of fugitive pigments in paintings as well as future developments in SERS we envision that are inspired by the past.

Sponge-like Cryogels from Liquid-Liquid Phase Separation: Structure, Porosity, and Diffusional Gel Properties.

Macroporous gels find application in several scientific fields, ranging from art restoration to wastewater filtration or cell entrapment. In this work, two-component sponge-like cryogels are challenged to assess their cleaning performances and to investigate how pores size and connectivity affect physico-chemical properties. The gels were obtained through a freeze-thaw process, exploiting a spontaneous polymer-polymer phase-separation occurring in the pre-gel solution. During the freezing step, a highly hydrolyzed polyvinyl alcohol (H-PVA) forms the hydrogel walls. The secondary components, namely a partially hydrolyzed polyvinyl alcohol (L-PVA) or polyvinyl pyrrolidone (PVP), act as modular porogens, being partially extracted during gel washing. H-PVA/L-PVA and H-PVA/PVP mixtures were studied by confocal laser scanning microscopy to unveil sols and gels morphology at the micron-scale, while small angle X-ray scattering was used to get insights about characteristic dimensions at the nanoscale. The gelation mechanism was investigated through rheology measurements, and the characteristic exponents were compared to De Gennes' scaling laws gathered from percolation. In the field of art conservation, these sponge-like gels are ideal systems for the cleaning of artistic painted surfaces. Their interconnected pores allow the diffusion of cleaning fluids at the painted interface, facilitating dirt uptake and/or detachment. This study uncovered a direct relationship linking a gel's cleaning performance to its apparent tortuosity. These findings can pave the way to fine-tuning systems with enhanced cleaning abilities, not restricted to the restoration of irreplaceable priceless works of art, but with possible application in diverse research fields.

Nanocomposite Organogel for Art Conservation─A Novel Wax Resin Removal System.

We describe a new, safe, and effective method for removing wax resin adhesive from the canvases of paintings conserved by the once widely used Dutch Method, which involved attaching a new canvas to the back of a painting using an adhesive made of beeswax and natural resin. First, a low-toxicity cleaning mixture for dissolving the adhesive and removing it from the canvases was developed, and then a nanocomposited organogel was obtained. The ability of the organogel to remove the adhesive from canvases was investigated on the lining of the 1878 painting "Battle of Grunwald" by Jan Matejko, with promising results. Additionally, we found that the organogel can be used several times with no visible loss of cleaning ability. Finally, the effectiveness and safety of the method were confirmed on two oil paintings (one from the National Museum in Warsaw): all the wax resin adhesive was removed and the painting regained its original brightness and vivid colors.

Environmentally friendly ZnO/Castor oil polyurethane composites for the gas-phase adsorption of acetic acid.

HYPOTHESIS: Acetic acid, a common pollutant present in museums and art galleries, can irreversibly damage works of art. Herein, a sustainable and scalable synthesis of zinc oxide-castor oil polyurethane hybrids (ZnO/COPs), to be used as acetic acid removers in the preventive conservation of Cultural Heritage, is reported. EXPERIMENTS: The adsorption capacities of ZnO/COPs were studied in saturated acetic acid atmosphere, at low acetic acid gas concentration, and inside a wooden crate (naturally emitting acetic acid) representative of those used in the storage deposits of museums and art collections. FINDINGS: Upon exposure, acetic acid interacts with the castor oil polyurethane and diffuses to the surface of ZnO particles where is stably fixed as zinc acetate crystals. Zinc acetate domains form homogeneously on the surface and are distributed evenly within the ZnO/COPs, thanks to weak interactions between the polyurethane matrix and acetic acid that favour the transport of the acid up to reach the zinc oxide surfaces, resulting in a synergistic effect. The ZnO/COPs composites showed significantly enhanced adsorption capacities of acetic acid surpassing those of the activated carbon benchmark, with the advantage of being easily handled and movable, without the health issues and risks associated to the use of non-confined micro/nano-powders.

Biodeterioration and cellulolytic activity by fungi isolated from a nineteenth-century painting at the National Theatre of Costa Rica.

Living organisms can induce deterioration of cultural heritage. Conservation strategies aimed at avoiding damage and aiding restoration, require a comprehensive knowledge of structure, chemical composition, and identity of microorganisms that colonize artworks. The National Theatre of Costa Rica (NTCR), a building with historic architecture, houses several oil paintings from the nineteenth century, some with visible signs of biodeterioration. One of them is a large format painting on canvas called La Danza (size 9.83 × 5.13 m) from 1896 by Italian artist Vespasiano Bignami, located on the ceiling of the theatre's foyer. In the present study, we undertook a physicochemical and microbiological study of La Danza to identify the fungal species that inhabit the artwork and are responsible for the damage observed. Scanning electron microscope (SEM) images and attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectroscopic data indicated that the canvas material is made of hemp, the binder contains linseed oil and lead white, and a material in the inner face of the canvas is mainly composed of beeswax. Fungi were isolated onto potato dextrose agar (PDA) and carboxymethyl cellulose (CMC) agar, and then identified with molecular (BTUB, nrDNA ITS, and TEF1 regions) and morphological methods. Four isolates belonging to the genera Myxospora, Pestalotiopsis, Ustilago, and aff. Penicillium, were obtained. Qualitative tests showed cellulolytic activity in all isolated specimens, confirming their possible role in biodeterioration of the canvas. Phylogenetic and morphological data revealed a new species of Myxospora we name here as Myxospora theatro sp. nov., in reference to NTCR. The findings broaden the knowledge of fungi capable of inhabiting and damaging cultural heritage. They also provide valuable information to develop strategies for conservation and restoration of oil paintings on canvas.

Nanostructured fluids for polymeric coatings removal: Surfactants affect the polymer glass transition temperature.

HYPOTHESIS: Nanostructured fluids (NSFs) based on water, organic solvents and surfactants are a valid alternative to the use of neat unconfined organic solvents for polymer coatings removal in art conservation. The physico-chemical processes underpinning their cleaning effectiveness in terms of swelling/dewetting of polymer films were identified as key in this context. The role of surfactants on polymers' dewetting was considered to be mainly restricted to the lowering of interfacial tensions. However, recent experiments evidenced that surfactants have an important role in swelling polymer films. EXPERIMENTS: Five different amphiphiles were selected, namely: sodium dodecylsulfate, dimethyldodecyl amine oxide, hexaoxyethylene decyl ether (C9-11E6), pentadecaoxyethylene dodecyl ether (C12E15), and methyoxypentadecaoxyethylene dodecanoate (C11COE15CH3). They were combined with a carefully selected organic solvents' mixture (1-butanol/butanone/dimethyl carbonate) to formulate new NSFs, differing for the surfactant only, and used to perform cleaning tests on surfaces coated with Paraloid B72® and Primal AC33®. Here for the first time, polymer swelling induced by surfactants was quantified and correlated with the glass transition temperature of the two polymers by differential scanning calorimetry, before and after the exposure to the fluids. Confocal laser scanning microscopy and small-angle X-ray scattering provided additional insights on the interaction mechanism. FINDINGS: Nonionics were proven more efficient than zwitterionic/ionic amphiphiles in the polymer swelling, and, overall, methyoxy pentadecaoxyethylene dodecanoate resulted the most effective among the selected surfactants. A direct relation between the effect of surfactants on the polymers' glass transition temperature and cleaning capacity was established. This finding, fundamental to understand the interaction mechanism between NSFs and polymer coatings or paint layers, is key to achieve a selective, effective and complete removal of polymer coatings, as recently shown in the removal of vandalism and over-paintings from street art.

Density Functional Theory (DFT) as a Nondestructive Probe in the Field of Art Conservation: Small-Molecule Adsorption on Aragonite Surfaces.

Humans have incorporated minerals in objects of cultural heritage importance for millennia. The surfaces of these objects, which often long outlast the humans that create them, are undeniably exposed to a diverse mixture of chemicals throughout their lifetimes. As of yet, the art conservation community lacks a nondestructive, accurate, and inexpensive flexible computational screening method to evaluate the potential impact of chemicals with art, as a complement to experimental studies. In this work, we propose periodic density functional theory (DFT) studies as a way to address this challenge, specifically for the aragonite phase of calcium carbonate, a mineral that has been used in pigments, marble statues, and limestone architecture since ancient times. Computational models allow art conservation scientists to better understand the atomistic impact of small-molecule adsorbates on common mineral surfaces across a wide variety of environmental conditions. To gain insight into the surface adsorption reactivity of aragonite, we use DFT to investigate the atomistic interactions present in small-molecule-surface interfaces. Our adsorbate set includes common solvents, atmospheric pollutants, and emerging contaminants. Chemicals that significantly disrupt the surface structure such as carboxylic acids and sulfur-containing molecules are highlighted. We also focus on comparing adsorption energies and changes in surface bonds, which allows for the identification of key features in the electronic structure presented in a projected-density-of-state analysis. The trends outlined here will guide future experiments and allow art conservators to gain a better understanding of how a wide range of molecules interact with an aragonite surface under variable conditions and in different environments.

Long-term monitoring of fresco paintings in the cathedral of Valencia (Spain) through humidity and temperature sensors in various locations for preventive conservation.

We describe the performance of a microclimate monitoring system that was implemented for the preventive conservation of the Renaissance frescoes in the apse vault of the Cathedral of Valencia, that were restored in 2006. This system comprises 29 relative humidity (RH) and temperature sensors: 10 of them inserted into the plaster layer supporting the fresco paintings, 10 sensors in the walls close to the frescoes and nine sensors measuring the indoor microclimate at different points of the vault. Principal component analysis was applied to RH data recorded in 2007. The analysis was repeated with data collected in 2008 and 2010. The resulting loading plots revealed that the similarities and dissimilarities among sensors were approximately maintained along the three years. A physical interpretation was provided for the first and second principal components. Interestingly, sensors recording the highest RH values correspond to zones where humidity problems are causing formation of efflorescence. Recorded data of RH and temperature are discussed according to Italian Standard UNI 10829 (1999).

Easy-to-Make Polymer Hydrogels by UV-Curing for the Cleaning of Acrylic Emulsion Paint Films.

The cleaning of acrylic emulsion paint surfaces poses a great challenge in the conservation field, due to their high water sensitivity. In this article, we present easy-to-make polymer hydrogels, made by UV-photopolymerization, that show excellent cleaning properties. The formulation of hydrogels obtained by UV-curing and their performance as dry cleaners for acrylic paints was investigated. First, different hydrogel formulations based on functional acrylic monomers were used to formulate a series of UV cross-linked hydrogels by fast UV photopolymerization. Their effectiveness on surface dirt removal was investigated by SEM microscopy and colorimetry. The hydrogels showed excellent cleaning properties and controlled water release, and they still performed satisfactorily after several cleaning uses. The obtained UV-hydrogels were compared to the well-known agar gels, showing benefits in terms of reducing excess water. This article shows that easy-to-make UV-cured hydrogels are an efficient tool for the cleaning of surface dirt from water-sensitive paintings, overcoming the limits of traditional cleaning methods.

Graphene Quantum Dots-Ornamented Waterborne Epoxy-Based Fluorescent Adhesive via Reversible Addition-Fragmentation Chain Transfer-Mediated Miniemulsion Polymerization: A Potential Material for Art Conservation.

Epoxy-based adhesives have gotten significant attention in the conservation of antiquities and repair or reconstruction of artifacts due to their excellent adhesion strength. However, it has become hard to detect repaired work in artifacts due to the transparent nature of epoxy-based adhesives. Hence, the making of fluorescent adhesives has become an exciting topic for art conservators. Here, we have synthesized a new kind of waterborne epoxy-based fluorescent adhesive decorated with graphene quantum dots (GQDs) via reversible addition-fragmentation chain transfer (RAFT)-mediated surfactant-free miniemulsion polymerization. In this case, a new block copolymer (BCP), poly(1-vinyl-2-pyrrolidone)-block-poly(glycidyl methacrylate), has been synthesized via surfactant-free RAFT-mediated miniemulsion polymerization using a polymerization-induced self-assembly technique. The GQDs were prepared from citric acid by a hydrothermal process, and this was used for making a fluorescence-active BCP/GQD nanocomposite emulsion. The obtained BCP/GQD nanocomposite adhesive was transparent and showed blue fluorescence under ultraviolet-visible light, indicating the easy detection of its mark on the artifacts. The BCP and BCP/GQD emulsions were applied to adhere ceramic and glass substrates, and their adhesion strength was evaluated by lap shear tests. The BCP/GQDs showed better adhesion strength than the BCP only, indicating better adhesive performance. Additionally, the synthesis process was carried out in aqueous media, indicating the sustainability and environment-friendliness of the process. We believe that this kind of new waterborne epoxy-based fluorescent adhesive will provide a new contrivance among art conservators to repair or reconstruct artifacts.

Surfactants Mediate the Dewetting of Acrylic Polymer Films Commonly Applied to Works of Art.

The removal of hydrophobic polymer coatings from artistic surfaces is a ubiquitous challenge in art restoration. Over the years, nanostructured fluids (NSFs), aqueous surfactant solutions containing a good solvent for the polymer, have been successfully applied in polymer removal interventions; however, the precise role of the surfactant in promoting polymer film dewetting is not fully understood. This contribution addresses the interaction of a NSF of water/propylene carbonate containing a nonionic surfactant with an acrylic polymer film commonly used in art conservation. Combining confocal microscopy and fluorescence correlation spectroscopy, we monitored the penetration of the fluid into the polymer film, defining its compositional changes and following the polymer swelling. The ensemble of results highlights that the surfactant role is twofold: (i) at the polymer-support interface, it promotes the detachment of the polymer film from the underlying support; (ii) inside the polymer film, it accelerates polymer swelling by increasing the chains' mobility.