Artwork Materials Research Articles

Matter and Movement’s Presence: Notes on Heidegger, Francesco Mosca, and Bernini

Abstract The role of actual works of art with philosophical writing is often reduced to the status of example or illustration. As such the materiality of art work is rarely discussed let alone deployed as the basis of philosophical reflection. In this paper works by Francesco Mosca, and Bernini are used to question Heidegger’s writings on sculpture. What such an approach opens up is the possibility that art may set the measure for philosophy.

A remote scanning Raman spectrometer for in situ measurements of works of art

In conservation science, one of the main concerns is to extract information from an artistic surface without damaging it. Raman spectroscopy has emerged in recent years as a reliable tool for the non-destructive analysis of a wide range of inorganic and organic materials in works of art and archaeological objects. Nevertheless, the technique is still mainly limited to the analysis of micro-samples taken from artistic surfaces. The development of an instrument able to perform non-contact analysis of an area of a few square centimeters aims to further increase the employment of this technique. This paper describes the development of a prototype Raman scanning spectrometer based on a diode laser, a 2D scanning mirror stage and a custom optical system, which can map a surface of 6 cm in diameter at a working distance of 20 cm. The device exhibits collecting optics with a depth of field close to 6 cm, which makes the Raman system suitable for the analysis of non-flat surfaces and three-dimensional objects. In addition, the overall dimensions and weight of the instrument have been limited in order to make the device transportable and, in principle, usable for in situ measurements. Details on the design of the device, with particular emphasis on the collecting optical system, and on results of the characterization tests carried out to assess its performances are reported. Finally, an example of an application involving the identification of pigments from a model painting is presented.

Study of the GC–MS determination of the palmitic–stearic acid ratio for the characterisation of drying oil in painting: La Encarnación by Alonso Cano as a case study

The correct identification of drying oils plays an essential role in providing an understanding of the conservation and deterioration of artistic materials in works of art. To this end, this work proposes the use of peak area ratios from fatty acids after ensuring that the linear responses of the detector are tested. A GC–MS method, previously reported in the literature, was revisited to its developed and validated in order to identify and quantify of eight fatty acids that are widely used as markers for drying oils in paintings, namely myristic acid (C14:0), palmitic acid (C16:0), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), suberic acid (2C8), azelaic acid, (2C9) and sebacic acid (2C10). The quaternary ammonium reagent m-(trifluoromethyl)phenyltrimethylammonium hydroxide (TMTFAH) was used for derivatization prior to GC–MS analysis of the oils. MS spectra were obtained for each methyl ester derivative of the fatty acids and the characteristic fragments were identified. The method was validated in terms of calibration functions, detection and quantification limits and reproducibility using the signal recorded in SIR mode, since two of the methyl derivatives were not totally separated in the chromatographic run. The proposed method was successfully applied to identify and characterise the most widely used drying oils (linseed oil, poppy seed oil and walnut oil) in the painting La Encarnación. This 17th century easel painting is located in the main chapel of the cathedral in Granada (Spain) and was painted by the well-known artist of the Spanish Golden Age, Alonso Cano (1601–1667).

Bright Light: Microspectrofluorimetry for the Characterization of Lake Pigments and Dyes in Works of Art

Color is an important component in the perception of beauty and in an artist's original intent when creating a work. Better conservation of our cultural heritage requires detailed knowledge of artwork materials and the complex evolution they have endured over time. Organic dyes have been used from ancient times, and their characterization is a challenge that has been successfully addressed over the past few years by the development of advanced techniques, such as microspectrofluorimetry. In this Account, we describe the application of microspectrofluorimetry to the study of medieval illuminations, paint cross sections, millenary textiles, and wall paintings. In our research into color in medieval Portuguese illuminations, we chose to emphasize the importance of the experimental design and the use of microspectrofluorimetry in the context of other analytical techniques, such as microFTIR, microRaman, and micro-X-ray fluorescence (microXRF). Within this framework, we were able to unveil the full complexity of a medieval colorant and to address issues not yet explored, such as the influence of Arab, Jewish, and Christian cultures on the production and underlying technology of Portuguese illuminations. The analysis of individual pigment particles or aggregates (by excitation with an 8 mum diameter spot) in paint cross sections from works by Vincent van Gogh and Lucien Pissarro highlights the technique's advantage of high spatial resolution. Its high spectral resolution proved to be useful not only for better characterizing the dyes used to color Andean textiles but also for detecting mixtures of relevant chromophores; the emission signals for the reds in Paracas and Nasca textiles were shown to be due to the presence of purpurin and pseudopurpurin. Finally, the complexity of the study of yellow dyes and the importance of accurate historical reproductions is addressed in a study of Asian organic colorants on historic Chinese wall paintings. Microspectrofluorimetry offers high sensitivity, selectivity, fast data acquisition, good spatial resolution, and the possibility of in-depth profiling. It has proved to be an invaluable analytical tool in identifying dyes and lake pigments in works of art. As Saint-Exupéry's protagonist said in Le Petit Prince, "L'essentiel est invisible pour les yeux," or "What is essential is invisible to the eye"--but it may be unveiled with kind love, a prepared mind, and a little help from microspectrofluorimetry.

Computational Chemistry Meets Cultural Heritage: Challenges and Perspectives

Chemistry is central to addressing topics of interest in the cultural heritage field, offering particular insight into the nature and composition of the original materials, the degradation processes that have occurred over the years, and the attendant physical and chemical changes. On the one hand, the chemical characterization of the constituting materials allows researchers to unravel the rich information enclosed in a work of art, providing insight into the manufacturing techniques and revealing aspects of artistic, chronological, historical, and sociocultural significance. On the other hand, despite the recognized contribution of computational chemistry in many branches of materials science, this tool has only recently been applied to cultural heritage, largely because of the inherent complexity of art materials. In this Account, we present a brief overview of the available computational methods, classified on the basis of accuracy level and dimension of the system to be simulated. Among the discussed methodologies, density functional theory (DFT) and time-dependent DFT represent a good compromise between accuracy and computational cost, allowing researchers to model the structural, electronic, and spectroscopic properties of complex extended systems in condensed phase. We then discuss the results of recent research devoted to the computer simulation of prototypical systems in cultural heritage, namely, indigo and Maya Blue, weld and weld lake, and the pigment minium (red lead). These studies provide insight into the basic interactions underlying the materials properties and, in some cases, permit the assignment of the material composition. We discuss properties of interest in the cultural heritage field, ranging from structural geometries and acid-base properties to IR-Raman vibrational spectra and UV-vis absorption-emission spectra (including excited-state deactivation pathways). We particularly highlight how computational chemistry applications in cultural heritage can complement experimental investigations by establishing or rationalizing structure-property relations of the fundamental artwork components. These insights allow researchers to understand the interdependence of such components and eventually the composition of the artwork materials. As a perspective, we aim to extend the simulations to systems of increasing complexity that are similar to the realistic materials encountered in works of art. A challenge is the computational investigation of materials degradation and their associated reactive pathways; here the possible initial components, intermediates, final materials, and various deterioration mechanisms must all be simulated.

X-ray diffraction studies of Pompeian wall paintings using synchrotron radiation and dedicated laboratory made systems

The full identification of artwork materials requires not only elemental analysis but also structural information of the compounds as provided by X-ray diffraction (XRD). This is easily done when taking samples (or micro-samples) from artworks. However, there is an increasing interest in performing non-destructive studies that require adapted XRD systems. Comparative study of synchrotron high-resolution X-ray powder diffraction (SR-HRPD) and laboratory non-destructive systems (portable XRD and micro-XRD) is the main objective of this work. There are no qualitative differences among the three systems as for detected phases in the Pompeian wall paintings that were studied, except in the case of minority phases which only were detected by SR-HRPD. The identified pigments were goethite, hematite, cinnabar, glauconite, Pompeian blue, together with calcite, dolomite and aragonite. Synchrotron XRD diagrams show better resolution than the others. In general, the peak widths in the diagrams obtained with the portable XRD system are similar to those obtained by micro-diffraction equipment. Factors such as residual divergence of X-ray sources, incidence angle and slit or collimator size are discussed in relation with the quality of XRD diagrams.

Application of the Kubelka—Munk Correction for Self-Absorption of Fluorescence Emission in Carmine Lake Paint Layers

The variations of the fluorescence emission of carmine lake travelling through an absorbing and scattering medium, such as a paint layer, were investigated by ultraviolet (UV)-visible absorption, fluorescence spectroscopy, and imaging techniques. Samples of the lake were studied in dilute and saturated solutions, on a reference test panel and a real case study. Relevant spectral modifications have been observed as a function of the lake concentration mainly consisting of a fluorescence quenching, red shift of emission maxima, and deformation of emission band. The application of a correction factor based on the Kubelka-Munk model allowed fluorescence spectra obtained in solution and on painted samples of known composition to be compared and correlated, highlighting that the fluorescence of the lake within paint layers is affected by both self-absorption and aggregation phenomena. This approach has been successfully applied on a painting by G. Vasari for the noninvasive identification of carmine lake. The results reported here emphasize the necessity of taking physical phenomena into account in the interpretation of the fluorescence spectra for a proper and reliable characterization and identification of painting materials in works of art.

Unilateral NMR applied to the conservation of works of art

In conventional NMR, samples from works of art in sizes above those considered acceptable in the field of art conservation would have to be removed to place them into the bore of large superconducting magnets. The portable permanent-magnet-based systems, by contrast, can be used in situ to study works of art, in a noninvasive manner. One of these portable NMR systems, NMR-MOUSE(R), measures the information contained in one pixel in an NMR image from a region of about 1 cm(2), which can be as thin as 2-3 microm. With such a high depth resolution, profiles through the structures of art objects can be measured to characterize the materials, the artists' techniques, and the deterioration processes. A novel application of the technique to study a deterioration process and to follow up a conservation treatment is presented in which micrometer-thick oil stains on paper are differentiated and characterized. In this example, the spin-spin relaxation T (2) of the stain is correlated to the iodine number and to the degree of cross-linking of the oil, parameters that are crucial in choosing an appropriate conservation treatment to remove them. It is also shown that the variation of T (2) over the course of treatments with organic solvents can be used to monitor the progress of the conservation interventions. It is expected that unilateral NMR in combination with multivariate data analysis will fill a gap within the set of high-spatial-resolution techniques currently available for the noninvasive analysis of materials in works of art, where procedures to study the inorganic components are currently far more developed than those suitable for the study of the organic components.

Lasers in the Analysis of Cultural Heritage Materials

This article reviews laser-based analytical techniques, which find applications in the field of cultural heritage diagnostics, providing information about the chemical composition of materials, at the atomic or molecular level. Lasers are intense sources of light featuring unique characteristics that have been exploited in order to enhance the performance of certain spectroscopic techniques such as Raman or fluorescence spectroscopy, or even produce new schemes of analysis, including, for instance, non-linear or remote sensing spectroscopy as well as laser ablative sampling and excitation. In parallel, with advances in laser and detector technology, compact, mobile instrumentation is becoming available that permits broader use of such laser-based techniques for analysis of materials in works of art and archaeological findings.

Fully-Non-Contact Masking-Based Holography Inspection on Dimensionally Responsive Artwork Materials.

Environmental control in galleries and museums is a necessity and is informed by the knowledge of ongoing processes of deterioration which can threaten the integrity and stability of artworks. Invisible dimensional changes in many works of art occur following environmental fluctuations as materials respond to the changes in humidity and temperature. The constant influence of dimensional changes usually remains invisible until displacement generates visible deterioration and irreversible damage. This paper exploits fully non contact coherent interferometry in a sequential masking procedure for visualising and studying surface deformation which is the direct effect of dimensional alterations induced by humidity changes. Surface deformation during dimensional displacements of constituent materials may occur on any artwork within an unstable environment. In this context, the presented research study explores the diagnostic potential of fully non contact sensors for the direct structural assessment of environmental effects as they occur in real time on works of art. The method is employed to characterise material responses, complementing and improving understanding of material behaviour in unstable environments.

Portable Equipment for Luminescence Lifetime Measurements on Surfaces

The prototype of a portable instrument, based on the time-correlated single-photon counting method, purposely assembled for in situ measurements of luminescence lifetimes on artwork surfaces, is here presented. Preliminary tests have been carried out using the portable instrument and the results have been compared with those obtained using a bench instrument. In this way we have proven that the prototype provides lifetime measurements with good precision. It is also shown that fluorescence lifetime determinations, coupled with steady-state fluorescence spectra, allow the distinguishing, on laboratory samples, of different red organic lakes having similar fluorescence spectra, achieving new boundaries in the nondestructive diagnosis of artwork materials. The first in situ application of the technique on an original work of art, The Book of Kells, held at Trinity College Library, Dublin, highlighted the diagnostic potential of coupled steady-state and time-resolved luminescence spectroscopy in the identification of organic colorants.

Progress in the application of ATR-FTIR microscopy to the study of multi-layered cross-sections from works of art

As a non-invasive or micro-invasive technique attenuated total reflectance Fourier transform infrared spectroscopic (ATR-FTIR) microscopy is a valuable tool for the analysis of materials in works of art. An application for which it has received growing interest is in the analysis of paint cross-sections. However, FTIR microscope configurations, objectives' geometries and low spatial resolutions, and issues of sample preparation have often hampered the characterization of individual layers or features in cross-sections. With the use of case studies, it is demonstrated here that an ATR-FTIR microscope featuring a crystal of optimized geometry and a viewing capability feature allows characterization of individual layers, or areas within layers, of 10 microm thickness or less in single measurements. Of particular value is a remote aperturing feature which allows the analysis of selected areas within the contact footprint of the ATR crystal. Since the technique is non-destructive, the same area can be analyzed by complementary microscopic techniques such as Raman spectroscopy and scanning electron microscopy with energy-dispersive spectroscopy. Pyrolysis gas chromatography-mass spectrometry was also used in some cases to corroborate the spectroscopic data. The analyses presented provided data which were important in informing art historical interpretation and conservation of the artworks examined.

Optical characterization of pigments by reflectance spectroscopy in support of UV laser cleaning treatments

The study of optical properties of artwork materials is of fundamental importance for laser-based restoration techniques. In this work, reflectance spectroscopic measurements and colorimetric analyses of painted wooden models were performed to discriminate between pigments on the basis of their spectral features. In particular, the spectral reflection factors of different white pigments were recorded with a fibre optics reflectance spectroscopy module, both before and after excimer laser (248 nm) irradiation. Colour data were obtained and monitored with an integrating sphere spectrophotometer and expressed with the CIE L*a*b* colour coordinates. Moreover, the laser-induced morphological changes of the samples were investigated by scanning electron microscopy.

Experimental problems in Raman spectroscopy applied to pigment identification in mixtures

Raman spectroscopy provides useful information to detect and identify pictorial materials in artworks, although some problems are involved when the identification of individual pigments in mixtures is treated. With the hypothesis of the Principle of superposition, the mixture spectrum should be the direct sum of each pondered individual spectrum. In this work, we will show several mixtures where it can be noticed that the mixture spectrum is not qualitatively proportional to the sum of pondered individual spectra. Also there were some cases where the bands of one of the pigments could not be detected in the mixture spectrum. This non-linear behaviour could be attributed to specific proprieties of each material that are revealed when they interact with each other. We conjecture that, for instance, the different reflectances or the wavelength of the laser source could be determinant factors of the obtained results. In this paper an experimental method has been designed in order to characterize the quantitative behaviour of the Raman bands corresponding to each pigment in a mixture. Adequate coefficients are defined and calculated to facilitate the study of the spectral contribution of the different components of a mixture.

Derivatisation using m-(trifluoromethyl)phenyltrimethylammonium hydroxide of organic materials in artworks for analysis by gas chromatography–mass spectrometry: Unusual reaction products with alcohols

The quaternary ammonium reagent m-(trifluoromethyl)phenyltrimethylammonium hydroxide (TMTFTH) has gained widespread use for the derivatisation for GCMS analysis of organic materials found in artists’ materials, such as oils, plant resins and waxes. This paper discusses products formed from reactions of TMTFTH with alcohols – including fatty alcohols, hydroxyacids, terpenes and glycerol – that have diagnostic value in the analysis of samples from artworks. In addition to methyl ethers, (trifluoromethyl)phenyl ethers were formed to variable degrees from the different types of alcohol. The products were identified from their EI mass spectra. An understanding of these multiple reaction products is important for the interpretation of GCMS data from complex samples, especially in the case of polyfunctional alcohols such as glycerol, which forms a number of methyl, (trifluoromethyl)phenyl and mixed ethers. The significance of the reaction products, and the relative advantages of TMTFTH as compared to alternative ammonium and sulfonium methylating reagents, are discussed.

“… I CAME TO UNDERSTAND HOW TO TRANSLATE NATURE INTO COLOUR ACCORDING TO THE FIRE IN MY SOUL”: ALEXEJ JAWLENSKY'S PAINTING TECHNIQUE IN HIS MUNICH OEUVRE

The Russian painter Alexej Jawlensky, who worked in Munich between 1896 and 1914, was an important representative of Expressionism and abstract art in Germany. He was involved with the artistic group Der Blaue Reiter, whose members shared not only ideas about art but also an interest in questions of painting technique and painting materials. This paper aims to illuminate the working process of Jawlensky through research into the characteristics of his painting technique. It examines the paint supports and painting materials in specific works of art from Jawlensky's Munich period. This technical examination, together with the evaluation of written sources reveals the manifold artistic and technological influences that contributed to the development and peculiarities of Jawlensky's art. Comparisons with selected works by Wassily Kandinsky and Gabriele Münter show the strong influence Jawlensky's painting technique had on his artist friends, especially in the years 1908–1909.

Analytical characterization of diterpenoid resins present in pictorial varnishes using pyrolysis–gas chromatography–mass spectrometry with on line trimethylsilylation

A procedure based on the technique of the pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) has been applied, in this work, in order to determine the composition of diterpenoid resin employed in art works. The method is based on the on line derivatization of these resins using hexamethyldisilazane (HMDS). Results obtained were compared with those previously reported in literature from Venice turpentine, Strasbourg turpentine, colophony, sandarac and Manila copal using this same method and with those others from in situ thermally assisted hydrolysis and methylation with tetramethylammonium hydroxide (TMAH). Canada balsam, copper resinate and Copaiba balsam have been also analyzed extending the scope of this method in the field of the analysis of artwork materials. Several non-reported trimethylsilylated derivatives of compounds present in the diterpenoid resins have been identified. An improvement in sensitivity has been obtained by using HMDS as derivatizing reagent, together with a better resolution of the most representative peaks. Additionally, this method reduces the number of pyrolytic fragmentation, recombination, dehydration and isomerization products formed during the pyrolysis process and, in consequence, more simplified chromatograms are obtained. Finally, the reported procedure has been successfully used for characterizing two diterpenoid resin-based varnishes present in the canvas painting "The Betrothal of the Virgin" (Anonymous, 17th century) which is included in the pictorial collection of Saint Joseph Church in Taormina (Italy) and the Magdalena Tryptich (Master of Alzira, 16th century, Valencia, Spain).

Spectroscopic studies of laser ablation plumes of artwork materials

Studies on the plasma plume created during KrF laser (248 nm) ablation of dosimeter tempera samples in vacuum have been carried out to investigate the basic interactions of the laser with paint materials. Time resolved optical emission spectroscopy (OES) was used to measure the translational velocity of electronically excited transients in the plasma plume. Laser-induced fluorescence (LIF) studies using a probe dye laser, allowed to determine the velocities of non-emitting species. The propagation velocities of C 2 in the a 3π u and d 3π g electronic states and of excited atomic species are indicative of a high translational temperature. Differences between the velocities of organic and inorganic species and between emissions from the tempera systems and from the pigments as pellets allow to discuss the participation of photochemical mechanisms in the laser irradiation of the paint systems.

Study of Raman spectra of pigment mixtures

Raman spectroscopy provides useful information for detecting and identifying constituent materials in artworks; but due to the fact that in most cases it is not possible to obtain spectra of single pigments, an informatic tool (named Analyser of Pigments) has been developed to identify all the pigments present in the samples tested 〚M. Breitman, in: Optics and Lasers in Biomedicine and Culture, OWLS V, Springer Verlag, Berlin, 2000, pp. 127–130〛. When mixed pigments do not behave as expected, problems of identification arise. These are the cases we deal with here. A comparative study with different concentrations of two pigments (ultramarine blue and massicot) was carried out. Using our techniques for spectra analyses, it was found that, compared with the theoretical results, some Raman peaks of one pigment were not detected in most of the Raman spectra mixtures 〚M. Breitman, Análisis, Diseño e Identificación de Algoritmos para Reconocimiento de Espectros Raman. Ph.D., June 2000〛. In this work, we present the theory that when the reflection coefficient of one component is larger than the other, a contribution to the spectra of mixture may occur 〚J. Chemom. (1990) 1〛.

Intellectual Property and Indigenous Peoples' Information

ABSTRACTIntellectual property laws deal inadequately with indigenous peoples' information. Although there has been extensive discussion of the issues in relation to artwork and heritage materials, there has been curiously little said about the ownership of cultural and intellectual property in published and archival materials. The complex issues in cultural documentation, primary and moral rights raise significant issues to which libraries and archives must respond.