Artwork Materials Research Articles

Aging of a Poly(vinyl acetate)-Based White Glue and Its Durability in Contemporary Artworks.

While extensive research has focused on understanding the degradation mechanisms of Poly(vinyl acetate) (PVAC) paint under different environmental conditions, limited attention has been paid to the long-term stability of PVAC-based white glues, especially when used in artworks. This study investigates the accelerated degradation, under simulated photoaging, and isothermal treatment of a commercial PVAC-based white glue considered representative of this class of materials used in contemporary artworks to predict its durability and assess its behavior in art objects. Through accelerated aging experiments and comparison with natural aging observed in artworks, the study reveals the formation of chromophores and the release of plasticizers as key processes; in particular, the progressive darkening was considered an early indicator of degradation processes, before structural changes could be detected by FTIR or NMR spectroscopies. The plasticizer loss induces an increase in glass transition temperature, from 7 °C to temperatures higher than room temperature, affecting the adhesive's cohesive strength and contributing to the detachment of materials in artworks. The findings underscore the importance of preventive conservation measures to mitigate degradation issues in PVAC-based artworks.

On the reliability of historic books as sources of reference samples of early synthetic dyes – The case of “The Coal Tar Colours of the Farbwerke vorm. Meister, Lucius & Brüning, Höchst on the Main, Germany – A General Part” (1896)

The swatches present in the popular book “The Coal Tar Colours of the Farbwerke vorm. Meister Lucius & Brüning, Höchst on the Main, Germany – A General Part”, published in 1896, were analysed by high performance liquid chromatography coupled to diode array detector and high-resolution tandem mass spectrometry (HPLC-DAD-MS/MS) with the aim to identify the synthetic dyes and reveal the correspondences and discrepancies between the information reported in the labels and the actual chemical composition of the samples.The research resulted in guidelines to be followed to connect commercial dye names with Colour Index (C.I.) constitution numbers and produced a molecular database of more than 250 molecules, whose high-resolution mass spectrometric details are reported here for the first time in some cases. Out of 120 samples analysed, ca. 40% did not exactly correspond to the expected dye(s) according to the labels, thus raising awareness of the challenges related to the reliability of historic sources of reference materials and the need to study the composition of these historic samples before using them for chemical research purposes. Furthermore, molecular databases of synthetic dyes are fundamental for the correct identification of these materials in historic textiles, objects and works of art. Thus, the results of this research are extremely useful to all researchers studying dyed objects produced from the second half of the 19th century onwards.

INFRA-ART: An Open Access Spectral Library of Art-related Materials as a Digital Support Tool for Cultural Heritage Science

Easily accessible characterization techniques such as X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), or Raman spectroscopy, are at this moment the most commonly used analytical tools in heritage and conservation science. Materials identification in works of art is a fundamental step for understanding an object's history or an artist's technique. Comprehensive characterization and diagnosis of the various constituent materials in artworks can provide valuable information on the artist's working methods, as well as significant evidence for dating, provenance attribution, or forgery detection. The development of databases with high-quality data on the pure substances used as artists’ materials is of utmost importance for the identification and characterization of unknown samples. However, there are relatively few open access spectra libraries dedicated exclusively to the cultural heritage field. To address this need, within the frame of the postdoctoral project INFRA-ART, an open access spectral library of art-related materials has been developed. The database is an ongoing compilation of spectra that contains at this moment over 1,000 high-quality attenuated total reflection–FTIR, Raman, and XRF spectra associated with over 500 known reference materials. In this article, a summary of the database structure and design, functionality, and use is presented, in view of the dissemination of this new open access spectral library to the scientific community.

A Hydroalcoholic Gel-Based Disinfection System for Deteriogenic Fungi on the Contemporary Mixed Media Artwork Poesia by Alessandro Kokocinski

The disinfection of deteriogenic microorganisms and the removal of induced chromatic alterations in artworks are still open challenges in the field of conservation. For this purpose, a new alcoholic hydrogel was tested to remove an extensive fungal attack from a multimaterial collage by the artist Alessandro Kokocinski and to mitigate chromatic changes caused by the contamination of its poster paper and plywood support layers. A Gellan gum-based hydrogel was used, which was modified by adding a high concentration of alcohol (66.7% ethanol), to give the system an effective disinfecting agent in addition to the detergent capacity of the gel for water-sensitive works of art. It was successfully tested on samples mimicking the complex stratigraphy of the artwork under study. To create replica mock-ups, the artwork materials and stratigraphy were investigated through diagnostic and laboratory techniques such as multispectral imaging, X-ray fluorescence spectroscopy, Fourier transform infrared spectroscopy, and pyrolysis coupled with gas-chromatography-mass spectrometry. The treatment was shown to have a disinfecting effect on the test samples and did not alter their structure, allowing us to apply the method to the artwork. Here, the hydrogel successfully removed and inhibited fungal proliferation in addition to mitigating the color changes caused by fungi.

Strengthening Literacy of Cultural Arts and Crafts in the Material of Sculpture for 6th-grade Elementary School Students through Learning Video Media

The purpose of this study was to determine and improve students' understanding of literacy through learning video media. Based on previous research, there are not too many studies that discuss Strengthening Literacy for Learning Arts, Culture and Crafts in Sculpture Artwork Materials for 6th-grade elementary school students. This study uses a quantitative approach to pre-experimental design in the form of pre-test and post-test. Based on the results of the research that has been carried out, before providing an understanding of the material of Sculpture in the students' understanding of Cultural Arts and Crafts learning, the results of the pre-test only reached an average value of 61.0% then an increase occurred after the learning video media was given, the post-test results the test given increased by 90.28%. The results showed that the difference was 29.28%. So, it can be concluded that the use of instructional video media on the material of sculptures learning Arts, Culture and Crafts can improve students' knowledge literacy.

Rapid Characterization of Proteinaceous Binders Used in Artwork and Cultural Heritage Materials by Surface-Enhanced Raman Spectroscopy (SERS)

The identification and characterization of binders in art and cultural heritage materials such as manuscripts, drawings, and paintings provide important information for dating, authentication, and conservation. However, the common methods are usually invasive and require micro-sampling. Here, a simple and rapid method was established based on surface-enhanced Raman spectroscopy (SERS) for quasi-uninvasive determination of proteinaceous binders with a portable Raman spectrometer. Initially, silica sol was prepared via a one-step synthesis and deposited on the germination paper to obtain a silica film. After being cut and wetted, 5-mm × 5-mm pieces of silica film were attached to the surface of the test object. The proteinaceous binders were extracted from the test objects with the interaction between silica, followed by SERS analysis using silver nanoparticles as the substrate. Scanning electron microscopic and optical microscopic images confirm that the surface of the samples was uninvasively damaged after extraction. The feasibility and reproducibility of this method were confirmed using paint models. The minimum detectable concentration of bovine serum albumin in the paint models was 0.005% (w/w). The method was successfully applied to determine the proteinaceous binders in fresh or aged paint replicas. Due to advantages that include rapid, quasi-non-invasive, and on-site analysis, this protocol is promising for the determination of proteinaceous binders employed in culture heritage materials.

Light Conductivity of Materials in New Media Art Works

Based on the application of materials in installation art, this paper briefly introduces the light conductivity of different materials and the function of light in an installation. It also analyzes the complementary relationship between light and materials, so as to provide support and reference for the development of new media art in China.

Evaluation and optimization of the potential of a handheld Raman spectrometer: in situ, noninvasive materials characterization in artworks

AbstractDecades of technological and methodological advances in Raman spectroscopy have brought this technique from laboratory innovation to a well‐established analytical tool with increasing applicability to the study of cultural heritage objects. Enduring research in the field of miniaturization has given rise to new generations of mobile, portable, and handheld spectrometers that have deeply transformed the way in which scientists approach materials analysis. Although sometimes limited in terms of performance and flexibility compared with their benchtop counterparts, miniaturized instruments are typically compact and light, user‐friendly, and equipped with fiber optics and batteries, thus enabling the operator to easily transport them and collect data in the field in a timely manner. In this work, a new handheld Raman spectrometer was evaluated for the in situ, noninvasive analysis of organic and inorganic materials in artworks from five prestigious New York City museums. Relevant examples include the following: the investigation of indigotin‐containing plant dyes in Romano‐Egyptian funerary portraits from the Brooklyn Museum; the detection and identification of natural blue colorants and mineral pigments in Medieval and Renaissance manuscripts from The Morgan Library & Museum; the study of a yellow pigment and a proteinaceous inlay material on a 12th‐century Korean lacquered box in the collection of The Metropolitan Museum of Art; the characterization of synthetic organic dyes and pigments used by Henri Matisse in one of his cutouts belonging to The Museum of Modern Art; and the identification of different plastics, fillers, and pigments in a work by Jeff Koons in the holdings of the Whitney Museum of American Art.

Gas chromatography/mass spectrometry techniques for the characterisation of organic materials in works of art

AbstractThe power of GC/MS to resolve, characterise and quantify complex mixtures of organic compounds with high sensitivity has made it an indispensable analytical tool to address detailed questions about the chemical constituents of works of art. This paper provides an overview of the technique and its particular suitability to material studies of art and historical artefacts, and reviews its diverse research applications concerning the organic composition of artists’ and conservation materials. Options with regard to sample preparation by chemical derivatisation, pyrolysis techniques, and methods for the analysis of volatile organic compounds are discussed, as well as various approaches to the treatment and interpretation of data. The greatest value is gained from GC/MS when it is used as a complementary technique, informed by and in synergy with other methods of analysis.

Characterization of proteins in cultural heritage using MALDI–TOF and LC–MS/MS mass spectrometric techniques

AbstractIdentification of proteinaceous materials in artworks is of high interest to restorers-conservators, art historians and archaeologists, because it helps to shed light on the used painting techniques, to attribute unknown artworks, to make conclusions on prehistoric diets, etc. The chapter is devoted to the mass spectrometry instrumentation, evaluation of obtained data and it is showing several examples of the application of matrix-assisted laser desorption/ionization–time-of-flight and liquid chromatography–electrospray ionization–quadrupole–time-of-flight mass spectrometers on cultural heritage samples.

Multivariate analysis of Raman spectra of carbonaceous black drawing media for the in situ identification of historic artist materials

AbstractThe identification of black drawing materials in works of art on paper is often important for their conservation and crucial to gain insight about artists' methodologies and the historic use of drawing materials. Traditionally, conservators and curators have had to rely upon visual observation with multiple wavelengths of light and magnification to characterize the materials in drawings, a challenging task further complicated if the media have been manipulated by the artist. The use of carbon‐based pigments in black drawing materials, ranging from charcoals and chalks to pastels and crayons, can be verified in situ using Raman microspectroscopy based on the presence of the two broad spectral bands characteristic of carbonaceous materials. However, the subtle differences in these spectral features between pigments can be difficult to discern, especially in cases with high background fluorescence. Here, we utilized principal component analysis to distinguish a group of 14 reference black drawing materials, both contemporary and historic, in the Raman spectral region of 800–2,000 cm−1. The model generated successfully differentiates between charcoal, chalk, and fabricated stick media, with sensitivity to both the Raman bands of carbon‐based materials as well as the fluorescent background profile. We validated the model using Raman spectra of black media on 19th‐century French drawings from the J. Paul Getty Museum collection that were previously classified visually by microscopic evaluation.

In-depth examination and analysis of Domenico Cresti's oil on wall paintings in Santa Maria della pace in Rome

Abstract This study closely examines Domenico Cresti's oil-based wall paintings in Santa Maria della Pace in Rome using a novel analytical technique that allows for the simultaneous characterization of organic and inorganic materials in works of art. ToF-SIMS was successfully used to obtain high-resolution spatial maps of cross-sectional paint samples and served as a complimentary technique to Raman spectroscopy and scanning electron microscopy-energy dispersive X-ray spectroscopy. Analysis of Cresti's wall paintings using imaging ToF-SIMS revealed the presence of specific amino, acids as well as fatty acids, fragments that were mapped to discrete paint and ground layers. ToF-SIMS was also used to characterize proteinaceous materials that were presumably used during a previous restoration campaign. These analytical results allowed for direct comparison between Cresti's wall painting technique to those described primary sources, specifically those cited by Giorgio Vasari and Filippo Baldinucci.

Uncontrolled Bush Burning in the Niger Delta Region of Nigeria: Potential Causes and Impacts on Biodiversity

The Niger Delta region of Nigeria is one of the largest wetland and biodiversity hotspots in Africa that inhabit several endemic species. Biodiversity including plants, animals and microbes have several economic importance to human and its ecosystem. Of recent, the intensity of bush burning in the Niger Delta has increased. Bush burning is among the leading cause of decline in composition and abundance of biodiversity. This study evaluated the potential causes of bush burning, impacts on biodiversity and possible options for mitigation in the Niger Delta region of Nigeria. The study found that quest for bush meat (i.e. major source of animal protein), burning of solid wastes, precarious discharge of cigarette remains and deliberate uncontrolled in-situ burning by farmers as the leading cause of bush burning. Bush burning portends adverse effects like; habitat fragmentation, destruction of medicinal plant, extinction of species in the wild, loss of food sources, loss of raw material that can be useful for several art work, wood fuel, construction and shelter materials, and disruption of ecological processes including biogeochemical cycling. The paper concludes by suggesting pasture management, wastes management, sensitization, enactment and implementation of bush burning laws and specifying punishment for offenders, and introduction of biodiversity conservation techniques in school curriculum as potential option for mitigation.

Revealing the composition of organic materials in polychrome works of art: the role of mass spectrometry-based techniques.

The most recent advances in the identification and determination of organic constituents in paintings and other polychrome objects using mass spectrometry (MS)-based techniques are reviewed. The latest achievements in gas chromatography (GC)-MS and pyrolysis (Py-) GC-MS are mainly related to sample pretreatment protocols and to the employment of double-shot or laser desorption pyrolysis, respectively. MS techniques based on soft ionization methods such as matrix assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) are discussed. So far, MALDI and ESI MS have been mainly used in the characterization of proteinaceous materials, but further applications are definitely emerging, e.g., in the fields of lipids, resins, and organic colorants analysis. Chemical imaging by time-of-flight secondary ion mass spectrometry (TOF SIMS), formerly applied to the detection and localization of lipid binders and inorganic materials, has been recently extended to proteins. Finally, the potential of niche techniques such as direct temperature resolved mass spectrometry (DTMS) and direct analysis in real time (DART) MS are outlined.

Mesocycles in conserving plastics

Analysis suggests that progress in conservation of plastics objects and artworks can be described by a series of overlapping mesocycles. Focus has been placed for periods of 5–10 years each on determining the degradation pathways in the 1990s, developing strategies to inhibit those pathways from the late 1990s and, since 2006 on actively stabilizing and treating the symptoms of degradation. The primary driving forces behind the direction and rate of progress within each of these three mesocycles have been different and specific. The controlling factor in understanding degradation pathways for heritage plastics has been the origin of the data describing lifetimes. By contrast, mesocycles in developing suitable storage and display microclimates for plastics have mirrored preventive conservation practices for natural polymeric materials. The rate of the third mesocycle, interventive conservation, has been driven by the need to balance the requirements for reversibility in conservation practices with the artist's intent and significance. Developments within each of the three mesocycles from the 1990s to date are discussed in this article. Environmental science and toxicology of waste plastics offer a novel source of information about real time degradation in terrestrial and marine microenvironments that seems likely to contribute to the conservation of similar materials in contemporary artworks.

Analytical Approaches Based on Gas Chromatography Mass Spectrometry (GC/MS) to Study Organic Materials in Artworks and Archaeological Objects.

Gas chromatography/mass spectrometry (GC/MS), after appropriate wet chemical sample pre-treatments or pyrolysis, is one of the most commonly adopted analytical techniques in the study of organic materials from cultural heritage objects. Organic materials in archaeological contexts, in classical art objects, or in modern and contemporary works of art may be the same or belong to the same classes, but can also vary considerably, often presenting different ageing pathways and chemical environments. This paper provides an overview of the literature published in the last 10years on the research based on the use of GC/MS for the analysis of organic materials in artworks and archaeological objects. The latest progresses in advancing analytical approaches, characterising materials and understanding their degradation, and developing methods for monitoring their stability are discussed. Case studies from the literature are presented to examine how the choice of the working conditions and the analytical approaches is driven by the analytical and technical question to be answered, as well as the nature of the object from which the samples are collected.

Scientific studies for the restoration of a wood painting of the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto di Palermo

The Ritratto muliebre, referring to Venus, is a panel painting, oil on wood, attributed to unknown artist and probably dated to the second half of 16th century, today conserved in the Galleria Interdisciplinare Regionale della Sicilia—Palazzo Mirto of Palermo.The aim of this research was to assess the techniques used to decorate the wooden painting and to verify the state of conservation of the artwork's materials but also to identify the previous treatments. This study was the essential condition to plane and perform the correct restoration.For this reason, an integrated analytical approach based on the use of non-invasive and micro-invasive techniques was used, with the aim to obtain a characterization of the wooden panel, to elucidate the painting technique, including the stratigraphic sequence of the pigments and the organic binders, the state of preservation, the possible decay processes, and the possible additions made during previous restorations.In addition to the imaging diagnostics techniques and the microchemical spot tests, micro-fragments of the painted material, original or not, were analyzed by several analytical techniques: optical microscopy, scanning electron microscopy (SEM-EDAX), FT-IR spectroscopy, and X-ray photoelectron spectroscopy (XPS).The results of all analyses revealed that the portrait is a small panel painting made by an unknown painter in the second half of 16th century, with a traditional painting technique: a single wooden panel, two preparatory layers (“ammannitura”), a sort of priming (“imprimitura”), an underdrawing, a paint layer composed of oil as binding medium and pigments common in 16th century.

Electrospray ionization linear trap quadrupole Orbitrap in analysis of old tempera paintings: application to nineteenth-century Orthodox icons.

Proteomic approach in combination with mass spectrometry demonstrates a great potential for identification of proteinaceous materials in works of art. In this study we used a linear trap quadrupole Orbitrap (LTQ-Orbitrap), a state-of-the-art mass spectrometer for parts per million accuracy analyses of peptides behind tryptic hydrolysis. After the efficiency of the proteomic method was confirmed for reference and model samples, micro-samples from historical paintings were for the first time analysed using this technique. Superior performances of the liquid chromatography-mass spectrometry approach using a LTQ-Orbitrap mass spectrometer allowed identification of egg yolk peptides in two samples from nineteenth-century Orthodox icons, indicating egg tempera as the painting technique. Accurate precursor ion masses, in the range of ±2ppm, and retention times of tryptic peptides strengthen protein identification. Additionally, in all historical samples the presence of animal glues suggested that the ground layer was likely bound using bovine collagen. Comparing to results acquired using matrix-assisted laser desorption/ionization time-of-flight tandem mass spectrometry in our previous study, here we achieved higher ion scores and protein scores, better sequence coverage and more identified proteins. In fact, a combination of the two mass spectrometric techniques provided overlapping and complementary data, related to the detection of peptides with different physicochemical properties.

Evaluation of MidIR fibre optic reflectance: Detection limit, reproducibility and binary mixture discrimination

MidIR fibre optic reflectance (MidIR-FORS) is a promising analytical technique in the field of science conservation, especially because it is non-destructive. Another advantage of MidIR-FORS is that the obtained information is representative, as a large amount of spectral data can be collected. Although the technique has a high potential and is almost routinely applied, its quality parameters have not been thoroughly studied in the specific application of analysis of artistic materials.The objective of this study is to evaluate the instrumental capabilities of MidIR-FORS for the analysis of artwork materials in terms of detection limit, reproducibility, and mixture characterisation. The study has been focused on oil easel painting and several paints of known composition have been analysed. Paint layers include blue pigments not only because of their important role along art history, but also because their physical and spectroscopic characteristics allow a better evaluation of the MidIR-FORS capabilities.The results of the analysis indicate that MidIR-FORS supplies a signal affected by different factors, such as the optical, morphological and physical properties of the surface, in addition to the composition of materials analysed.Consequently, the detection limits established are relatively high for artistic objects (Prussian blue – PB 2.1–6.5%; Phthalocyanine blue - Pht 6.3–10.2%; synthetic Ultramarine blue – UM 12.1%) and may therefore lead to an incomplete description of the artwork.Reproducibility of the technique over time and across surface has been determined. The results show that the major sources of dispersion are the heterogeneity of the pigments distribution, physical features, and band shape distortions. The total dispersion is around 4% for the most intense bands (oil) and increases up to 26% when weak or overlapped bands are considered (PB, Pht, UM). The application of different pre-treatments (cutoff of fibres absorption, Savizky–Golay smoothing algorithm, polynomial baseline offset, Standard Normal Variate algorithm – SNV) to the raw spectra allows improving these results to maximum values of 15%.Finally, the capabilities of PCA and MidIR-FORS to discriminate between binary mixtures were tested. The results demonstrate that it is possible to differentiate mixtures depending on the range of concentration of their components, within specific limits of detection.

Cross-Section and Staining-Based Techniques for Investigating Organic Materials in Painted and Polychrome Works of Art: A Review

The article presents a review of the use of cross-section and staining techniques for investigating natural organic materials (mainly proteinaceous and oil-based binders/varnishes) in painted and polychrome artworks, considering the requirements of conservation practice and routine diagnostics. The reviewed literature calls attention to the importance of using cross sections to prepare samples for optical microscopy and to different properties of embedding resins; the most appropriate instrumental conditions for optical microscopy; and the advantages and disadvantages of the most common staining techniques. A few case studies were selected to illustrate the use of autofluorescence (intrinsic fluorescence) and induced fluorescence (using specific staining tests and fluorophore-labeled antibodies) for mapping and identifying organic paint materials in cross sections. New directions of research in cross-section analyses and fluorescence-based techniques for the identification and mapping of artistic materials are presented. The complementary use of different stains on the same cross section, further exploration of intrinsic and induced fluorescence of aged versus fresh materials, and applicability of cross-section observation and staining as complementary methods for assessing the effectiveness of restoration treatments, such as cleaning and consolidation, are discussed in the last section of the article.