A Silver Monochrome “Concetto spaziale” by Lucio Fontana: A Spectroscopic Non- and Micro-Invasive Investigation of Materials

In several of his artworks, for instance the Venezie cycle, Fontana employed metallic paints; previous investigations on such materials highlighted the use of different synthetic binders and of thick paint layers below the metal one, having different colours to change the visual perception of the metallic surface. In the present work, a monochrome silver “Concetto spaziale” by the Italo–Argentine artist belonging to a private collection recently gifted to the museum of the Church of San Fedele in Milano, Italy, was investigated to deepen the knowledge of this particular group of Fontana’s paintings. The artwork was initially visually inspected in visible and ultraviolet (UV) light. Subsequently, a non-invasive spectroscopic investigation was performed by X-ray fluorescence (XRF), reflection Fourier-transform infrared (FTIR) and Raman spectroscopy. A minute fragment of silver-coloured paint was taken from the reverse of the painting, near the cut edge, and examined by scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM-EDX) and micro-Fourier-transform Raman (FT-Raman) spectroscopy. The analytical data made it possible to identify the composition of the metallic paint layer and of the underlying dark one, both from the point of view of the pigments and of the binders used, also highlighting the potential of the non-invasive and micro-invasive methods adopted in the investigation.     

The identification of synthetic organic pigments in modern paints and modern paintings using pyrolysis-gas chromatography-mass spectrometry

A collection of more than 70 synthetic organic pigments were analysed using pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS). We report on the analysis of diketo-pyrrolo-pyrrole, isoindolinone and perylene pigments which are classes not previously reported as being analysed by this technique. We also report on a number of azo pigments (2-naphthol, naphthol AS, arylide, diarylide, benzimidazolone and disazo condensation pigments) and phthalocyanine pigments, the Py-GC-MS analysis of which has not been previously reported. The members of each class were found to fragment in a consistent way and the pyrolysis products are reported. The technique was successfully applied to the analysis of paints used by the artist Francis Bacon (1909-1992), to simultaneously identify synthetic organic pigments and synthetic binding media in two samples of paint taken from Bacon's studio and micro-samples taken from three of his paintings and one painting attributed to him.     

Monet's painting under the microscope.

An oil painting by Claude Monet, Port-Goulphar, Belle-Ile 1887 (collection of the Art Gallery of New South Wales), was examined to determine both the identity of the pigments used by the artist in this painting and his technique of mixing colors and laying paint on the canvas. The extremely complex construction of the painting was revealed by optical microscopy, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDS), and X-ray mapping (XRM) analysis of cross sections of paint flakes excised from damaged regions of Port-Goulphar, Belle-Ile. Nine different pigments were found on the painting. Many of the identified colors were modern pigments that became available only late in the 19th century as a result of scientific advances in pigment chemistry. Although similar colors were available in a natural mineral form, they lacked the vivid color of their manufactured counterparts. The use of these new synthetic metallic oxide colors by Monet accounts for the brilliance of his paintings. In addition, a separation between successive paint layers was observed in some areas of paint chip cross sections, indicating that oil-based paint was applied to paint that had dried, and consequently, Port-Goulphar, Belle-Ile was painted over a long period of time. This observation is contrary to the general perception of Monet's technique of painting freely and quickly.     

Alkyd paints in art: Characterization using integrated mass spectrometry

Alkyd resins have been commonly used as binders in artist paints since the 1940s. The characterization of alkyds in samples from artworks can help to solve attribution and dating issues, investigate decay processes, and contribute to the planning of conservation strategies. Being able to assess the components of industrially formulated paint materials and to differentiate between different trademarks and producers is extremely interesting and requires multi-analytical approaches.     

Characterization of “oil on copper” paintings by energy dispersive X-ray fluorescence spectrometry

Energy dispersive X-ray fluorescence is a common analytical tool for layer thickness measurements in quality control processes in the coating industry, but there are scarce microanalytical applications in order to ascertain semi-quantitative or quantitative information of painted layers. “Oil on copper” painting becomes a suitable material to be analysed by means of X-ray fluorescence spectrometry, due to the metallic nature of substrate and the possibility of applying layered models as used in coating industry. The aim of this work is to study the suitability of a quantitative energy dispersive X-ray fluorescence methodology for the assessment of the areal distribution of pigments and the characterization of painting methods on such kind of pictorial artworks. The method was calibrated using standard reference materials: dried droplets of monoelemental standard solutions laid on a metallic plate of copper. As an example of application, we estimated pigment mass distribution of two “oil on copper” paintings from the sixteenth and eighteenth centuries. Pictorial layers have been complementarily analysed by X-ray diffraction. Apart of the supporting media made of copper or brass, we could identify two different superimposed layers: (a) a preparation layer mainly composed by white lead and (b) the pictorial layer of variable composition depending on the pigments used by the artist on small areas of the painting surface. The areal mass distribution of the different elements identified in the painting pigments (Ca, Cr, Mn, Fe, Zn, Cd, Hg and Pb) have been determined by elemental mapping of some parts of the artworks.     

The Russian avant-garde painting palette--documentary and physicochemical study of inorganic colorants

In the present article an attempt is being made to elucidate the inorganic colorants encountered in the Russian avant-garde painting palette by a combined art historical, documentary and physicochemical investigation; and to examine the influence of environmental factors on the chromatic profile originally sought by the artist. The overall approach based on written sources is confirmed by measurements on representative paintings from the Costakis Collection in the State Museum for Contemporary Art, Thessaloniki. The documentary research deals with the influences of Orthodox iconography, folkloric art, and occidental modernist tendencies on the Russian avant-garde palette; and is studying the effects of contradictory historical processes in the chromatic profile of individual paintings. In the experimental section a series of colorants are investigated concerning the effects of accelerated ageing on experimental painting tables, prepared as watercolour and gouache layers on paper ground. The resulting samples are subject to colorimetric, and spectroscopic measurements; and analogous analytical procedures are applied on samples taken from selected paintings belonging to the Costakis Collection. A systematic comparative study of all data permits evaluating the materials used as to their stability towards exstrincic factors, and proposing degradation routes, in order to assist museum curators and conservators in every concrete case related to the broad spectrum of pigments examined.     

Multispectral and hyperspectral image analysis of elemental and micro-Raman maps of cross-sections from a 16th century painting

Spectroscopic imaging is well suited to the study of micro-samples from artworks, where the sample material is limited and the maximum amount of information needs to be obtained. In this study, a new approach to imaging elemental data from energy dispersive X-ray analysis maps was used in conjunction with micro-Raman spectroscopic imaging to characterise the paint layers within micro-samples. Cross-sections from the 16th century painting Portrait of a Youth were found to contain vermilion, lead-tin yellow type 1 and a blue-green pigment consistent with terre-verte. The mid-preparatory layer (imprimatura) contains a high proportion of elements and mineral inclusions that indicates a clay-type composition. The ground layer was identified as anhydrite with large gypsum inclusions. The pigments and composition of the preparatory layers are consistent with those used by Italian Renaissance artist Dosso Dossi.     

Using Non‐Destructive Analysis Techniques to Examine the Artworks of Taiwanese Artist Cheng‐Po Chen (1895‐1947)

This study employed the non‐destructive techniques to analyze and examine the artworks of the Taiwanese artist Cheng‐Po Chen (1895‐1947) for disclosing the damage to Chen's artworks and determine his creation habits. Ten pieces of artworks that required restoration were examined using ultraviolet examination techniques. Based on the differences in their fluorescence characteristics, various parts of these works were shown to have been retouched, thus, original and retouched regions were distinguished. Examining these works using Infrared instrument revealed that Chen did not use charcoal to prepare drafts, and he directly applied oil paint to the canvases. Subsequently, these two examination techniques were adopted to examine sketches. The results showed that residues imprinted on them cause of storage methods were organic materials from charcoal and not carbon granules. The X‐ray examination identified numerous creations beneath the surface of several artworks. The X‐ray fluorescence spectrometer was used for elemental analysis of the pigments. The results corresponded with the pigments listed in Chen's purchase form, thus, we summarized the composition of palettes used by Chen. In general, this study acquired a considerable amount of information from the pigment examinations and established a database of the pigments that Chen commonly employed in his artworks.     

Raman identification of yellow synthetic organic pigments in modern and contemporary paintings: reference spectra and case studies

The characterization of the binding media and pigments in modern and contemporary paintings is important for designing safe conservation treatments, as well as for determining suitable environmental conditions for display, storage and transport. Raman spectroscopy is a suitable technique for the in situ non-destructive identification of synthetic organic pigments in the presence of the complex binding media characteristic of synthetic resin paints or colour lithographic inks. The precise identification of a pigment by comparing its spectrum to that of a reference is necessary when conservation treatments with aqueous solutions or organic solvents are being considered for a work of art, since solubility properties can sometimes vary within the same pigment group. The Raman spectra of 21 yellow synthetic organic pigments, belonging to the monoazo, monoazo lakes, diarylide, disazo condensation, benzimidazolone, bisacetoacetarylide, azo-methine metal complex, isoindolinone and isoindoline groups are presented. Since modern artists frequently mixed paint developed for other applications, in addition to colorants developed as artists' paints, other synthetic organic pigments were included in the spectral database. Two monoazo pigments, Pigment Yellow 1 and Pigment Yellow 3, a benzimidazolone, Pigment Yellow 154 and a phthalocynanine, Pigment Green 7, were identified in sample cross-sections from four modern and contemporary paintings in the collection of The Museum of Modern Art in Ljubljana, Slovenia.     

Identification of complex structures of paintings on canvas by NMR: Correlation between NMR profile and stratigraphy

Paintings on canvas are complex structures created by superimposing layers of different composition. Investigations on the structure of these artworks can provide essential information on their state of conservation, pictorial technique, possible overpaintings, and in planning a proper conservation plan. Standard methods of investigation consist in sampling a limited number of fragments for stratigraphic analyses. Despite the recognized validity of these methods, they are affected by evident limitations. Nuclear magnetic resonance (NMR) profiling, often named NMR stratigraphy, is an NMR relaxometry technique applied by single-sided portable devices developed to overcome the disadvantages of microinvasive stratigraphic analyses. The potential of this approach on artworks, including wall paintings and a few examples of painted canvas, is described in the literature. In this study, NMR profiles of painting on canvas were examined by analyzing transverse relaxation time data by T₂ quasi-continuous distributions and the results compared with standard stratigraphic cross-sections analysis. Combining signal intensity and T₂ quasi-continuous distributions, the identification of textile, preparatory, and paint layers was enhanced. The diction “NMR stratigraphy” for these inhomogeneous layered artworks is also discussed. Indeed, unlike the stratigraphic cross-sections, NMR profiles provide information on a volume (flat slice), rather than on a surface, and the collected signal can derive from nonuniform and partially overlapping layers. This study paves the way for extensive investigations on relaxation time quasi-continuous distributions in various binder/pigment mixtures in order to improve the reliability of NMR profile as an innovative, non–invasive, and nondestructive method for analyzing paintings on canvas.     

A joint application of ATR-FTIR and SEM imaging with high spatial resolution: Identification and distribution of painting materials and their degradation products in paint cross sections

A series of paint cross sections from an oil painting are studied by attenuated total reflection in conjunction with Fourier transform infrared spectroscopy (ATR-FTIR) and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX). The imaging modes of both methods were employed to show their potential in the detection of various painting materials and their distribution in the paint cross sections. The goal of this work is to evaluate FTIR and SEM-EDX spectroscopy in order to understand the limitations and strengths of both approaches. It has been revealed that both techniques are complementary in the identification of pigments, extenders and binding media used by an artist. FTIR spectroscopy is also a powerful tool in the studies on degradation products that are formed due to ageing or deterioration of works of art. We attempted to identify such secondary products present in the paint cross section. Cadmium oxalate and a high concentration of zinc palmitate/stearate were detected for the first time with the use of ATR-FTIR imaging technique. These results can complement studies on the conservation issue and provide an insight into understanding the mechanisms of chemical processes that appear in art works.     

Chromatographic,Microscopic, and Spectroscopic Characterization of a Wooden Architectural Painting from the Summer Palace,Beijing, China

The wooden construction painting is a type of an ancient decorative art on Chinese ancient structures. Comprehensive reports concerning the composition of these materials are rather limited. Here multiple analytical methods were applied to systematically explore the morphology and materials. Several paintings were characterized using a morphological microscope. Scanning electron microscopy–energy dispersive spectrometry (SEM-EDS), X-ray fluorescence (XRF), and X-ray diffraction (XRD) detected emerald green and ultramarine in the paint layers. Gas chromatography–mass spectrometry (GC-MS) indicated that the binding medium in the first layer was composed of blood. Our study helps to comprehensively understand the preparation of the wooden construction paintings in the renowned Summer Palace and provide a scientific basis for its restoration and related archeology work.     

Application of time-of-flight secondary ion mass spectrometry to automobile paint analysis.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) provides a method of elemental analysis that can distinguish among automotive paint samples of the same or nearly the same color. TOF-SIMS survey spectra were employed to determine the relative abundances of elements in the surface layers of the paint chips. The depth profile of paint samples permitted the analysis of small paint chips, the reproducible results for specific elements, and the identification of each car paint. Seventy-three samples of blue, red, white, and silver automobile paints from the major manufacturers in Korea were investigated using high resolution TOF-SIMS technique. It was found that paints of the same color produced by different manufacturers could be distinguished by this technique. TOF-SIMS is a reliable, nondestructive, and small area analyzing method for characterization of the elemental composition of automotive paint chips.     

Gas chromatography/mass spectrometry of oils and oil binders in paintings

A GC/MS procedure has been developed, optimized, and applied to characterization of oil binders in paintings. The procedure involves hydrolysis of lipids to fatty acids (FAs) and derivatization of FAs to fatty acid methyl esters (FAMEs) by a solution of sodium methanolate in methanol at an elevated temperature. FAMEs are analyzed by temperature-programed GC followed by full-scan MS. Old and dried samples are subjected to extraction of nonpolymerized FAMEs into dichloromethane prior to hydrolysis. The method provides a good repeatability of results and has been applied to the characterization of common plant oils used in paintings, to commercial oil and tempera paints, to model painting samples, and to samples taken from real paintings. The fresh oils and binders can readily be identified and characterized. The ratio of the methyl esters of palmitic and stearic acids can be used to characterize oil binders in old works of art.     

Studying pigments on painted plaster in Minoan,Roman and Early Byzantine Crete. A multi-analytical technique approach

Wall paintings spanning two millennia of Cretan painting history and technology were analysed in an effort to determine similarities and evolutions of painting materials and technology. A multi-technique approach was employed that combined the use of (a) laser-induced breakdown spectroscopy (LIBS) and Raman microspectroscopy, based on mobile instrumentation, appropriate for rapid, routine-level object characterization, and (b) non-destructive X-ray diffractometry (XRD), performed directly on the wall painting fragment, which provides detailed information on the minerals constituting the paint. Elemental analysis data obtained through LIBS were compared with molecular and crystal structure information from Raman spectroscopy and XRD. Cross-sections from selected samples were also investigated by means of optical microscopy and scanning electron microscopy coupled to micro-probe analysis and X-ray mapping that enabled identification of several mineral components of the paint confirming the results of the XRD analysis. In parallel, replica wall paintings, created with known pigments and binding media for reference purposes, were examined with optical microscopy and stain tested for organic materials. The overall study shows that the LIBS and Raman techniques offer key advantages, such as instrument mobility and speed of data collection and interpretation that are particularly important when dealing with on-site investigations. Thus, they are capable of providing important compositional information in an effective manner that enables quick surveying of wall paintings and permit targeted sample selection for further analysis by advanced laboratory techniques.     

Tryptic peptide analysis of protein binders in works of art by liquid chromatography-tandem mass spectrometry

A proteomics approach was used for the identification of protein binders in historical paints: the proteins were digested enzymatically into peptides using trypsin before being separated and detected by high performance liquid chromatography-electrospray ionisation tandem mass spectrometry (HPLC-ESI-MS/MS). Mascot (Matrix Science) was used to analyse the resulting data and for protein identification. In contrast to amino acid analysis, amino acid sequences could be studied that retain much more information about the proteins. The best extraction strategy was selected based on the number of peptides that were identified in the protein content of paint replicas using different methods. The influence of pigments on the extraction method was studied and the analytical characteristics of the selected method were determined. Finally this method was applied to historical paint microsamples on the anonymous early 15th century panel painting Crucifixion with St Catherine and St Barbara (Calvary of the Tanners), the St Catherine Altarpiece by Joes Beyaert (c. 1479) and two paintings by Pieter Brueghel the Younger (1617-1628).     

External proton beam analysis of layered objects

Ion-beam analysis for determining the elemental composition and to obtain depth information has been carried out with MeV protons in air by means of simultaneous external PIXE and RBS. Stainless steel products of extended size and a historic painting are analyzed non-destructively. These objects include systems of layers with areal densities up to some ten mg/cm(2). Depth information is obtained by PIXE using energy variation of the primary proton beam and in addition directly from RBS for the outermost near-surface region. Main and secondary elements as well as impurities can be determined together with areal densities. Particularly, the knowledge on the depth distribution of the pigments in paintings provides information on paint techniques.     

Effect of pigment concentration on NMR relaxometry in acrylic paints

Acrylic emulsion paint is among the most common media employed by 20th century artists. Since early acrylic paintings have begun to require the attention of conservators, scientists are working to characterize the properties of these paints to facilitate conservation efforts. In this study, we report an investigation of the physical and chemical properties of acrylic emulsion paints using single-sided NMR in conjunction with gloss measurements and scanning electron microscopy-energy dispersive spectrometry. Combining the data from these techniques gives insight into pigment-base interactions and the acrylic curing process, showing that as pigment concentration is increased in paints, the amount of acrylic base adsorbed to pigment particles increases, resulting in films with differing relaxation times. This research both emphasizes and contextualizes the utility of NMR relaxometry in studying cultural heritage objects and prompts further study into the effects of pigment concentration on the curing and conservation of paint films.     

Application of emission spectrometer with laser sampler to microanalysis of pigments from Hubert Robert’s canvas painting

Laser-induced breakdown spectroscopy has been applied to layer-by-layer pigment material microanalysis from the different sections of Hubert Robert’s (1733–1808) painting “Landscape of a Pool with an Obelisk and Ruins of an Aqueduct”. This painting consists of two sections and, therefore, requires thorough examination of the pigments from both sections in order to identify their authenticity. The data obtained on the elemental composition of the paint layers including the ground layer alongside with art examination have formed the basis for the identification, attribution and restoration of both investigated sections of the painting.