Paint Cross-sections Research Articles

Discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's The Night Watch: analytical study and historical contextualization

This article reports on the discovery of pararealgar and semi-amorphous pararealgar in Rembrandt's masterpiece The Night Watch. A large-scale research project named Operation Night Watch was started in 2019. A variety of non-invasive analytical imaging techniques, together with paint sample research, has provided new information about Rembrandt's pigments, materials, and techniques as well as the current condition of the painting. Macroscopic X-ray fluorescence, macroscopic X-ray powder diffraction and reflectance imaging spectroscopy identified the presence of arsenic sulfide pigments and degradation products of these pigments in the doublet sleeves and embroidered buff coat worn by Lieutenant Willem van Ruytenburch (central figure to the right of Captain Frans Banninck Cocq). Examination by light microscopy of two paint samples taken from this area shows a mixture of large sharp-edged tabular yellow and orange to red pigment particles, and scanning electron microscopy-energy dispersive X-ray analysis identified these particles as containing arsenic and sulfur. Using micro-Raman spectroscopy, the yellow particles were identified as pararealgar, and the orange to red particles as semi-amorphous pararealgar. Synchrotron-based X-ray diffraction allowed visualization of the presence of multiple degradation products associated with arsenic sulfides throughout the paint layer. The discovery of pararealgar and semi-amorphous pararealgar is a new addition to Rembrandt's pigment palette. To contextualize our findings and to hypothesize why, how, and where Rembrandt obtained the pigments, we studied related historical sources. A comprehensive review of historical sources gives insight into the types of artificial arsenic sulfides that were available and suggests that a broader range of arsenic pigments could have been available in Amsterdam in the seventeenth century than previously thought. This is supported by the use of a very similar mixture of pigments by Willem Kalf (1619–1693), a contemporary artist based in Amsterdam. Together with the condition of the particles in the paint cross sections, this brings us to the conclusion that Rembrandt intentionally used pararealgar and semi-amorphous pararealgar, together with lead–tin yellow and vermilion, to create an orange paint.

Chemical Mapping of the Degradation of Geranium Lake in Paint Cross Sections by MALDI-MSI.

Matrix assisted laser desorption ionization-mass spectrometry imaging (MALDI-MSI) has become a powerful method to extract spatially resolved chemical information in complex materials. This study provides the first use of MALDI-MSI to define spatial-temporal changes in oil paints. Due to the highly heterogeneous nature of oil paints, the sample preparation had to be optimized to prevent molecules from delocalizing. Here, we present a new protocol for the layer-specific analysis of oil paint cross sections achieving a lateral resolution of 10 μm and without losing ionization efficiency due to topographic effects. The efficacy of this method was investigated in oil paint samples containing a mixture of two historic organic pigments, geranium lake and lead white, a mixture often employed in the work of painter Vincent Van Gogh. This methodology not only allows for spatial visualization of the molecules responsible for the pink hue of the paint but also helps to elucidate the chemical changes behind the discoloration of paintings with this composition. The results demonstrate that this approach provides valuable molecular compositional information about the degradation pathways of pigments in specific paint layers and their interaction with the binding medium and other paint components and with light over time. Since a spatial correlation between molecular species and the visual pattern of the discoloration pattern can be made, we expect that mass spectrometry imaging will become highly relevant in future degradation studies of many more historical pigments and paints.

Multi-Scale X-ray Imaging of the Pigment Discoloration Processes Triggered by Chlorine Compounds in the Upper Basilica of Saint Francis of Assisi.

In this paper, the chromatic alteration of various types of paints, present on mural painting fragments derived from the vaults of The Upper Basilica of Saint Francis of Assisi in Italy (12th-13th century), is studied using synchrotron radiation. Six painted mural fragments, several square centimeters in size, were available for analysis, originating from the ceiling paintings attributed to Cimabue and Giotto; they correspond to originally white, blue/green, and brown/yellow/orange areas showing discoloration. As well as collecting macroscopic X-ray fluorescence and diffraction maps from the entire fragments in the laboratory and at the SOLEIL synchrotron, corresponding paint cross-sections were also analyzed using microscopic X-ray fluorescence and powder diffraction mapping at the PETRA-III synchrotron. Numerous secondary products were observed on the painted surfaces, such as (a) copper tri-hydroxychloride in green/blue areas; (b) corderoite and calomel in vermillion red/cinnabar-rich paints; (c) plattnerite and/or scrutinyite assumed to be oxidation products of (hydro)cerussite (2PbCO3·Pb(OH)2) in the white areas, and (d) the calcium oxalates whewellite and weddellite. An extensive presence of chlorinated metal salts points to the central role of chlorine-containing compounds during the degradation of the 800-year-old paint, leading to, among other things, the formation of the rare mineral cumengeite (21PbCl2·20Cu(OH)2·6H2O).

Comparison of ATR-FTIR and O-PTIR Imaging Techniques for the Characterisation of Zinc-Type Degradation Products in a Paint Cross-Section.

ATR–FTIR (attenuated total reflection–Fourier-transform infrared) microscopy with imaging is widely used in the heritage field to characterise complex compositions of paint cross-sections. However, some limitations include the need for ATR crystal contact with the sample and the inability to resolve particle size below the IR diffraction limit. Recently, a novel O-PTIR (optical-photothermal infrared) spectroscopy technique claimed to open a new avenue for non-invasive, efficient, and reliable analysis at sub-micron resolution. O-PTIR produces transmission-like FTIR spectra for interpretation, without the need to touch the sample, which are highly favourable attributes for analysing heritage samples. This paper reports the comparison of O-PTIR and ATR–FTIR techniques applied to a cross-section embedding a thin paint fragment that delaminated from a late 19th to early 20th-century oil portrait. The hazy paint fragment consisted of zinc soaps (both crystalline and amorphous), gordaite (NaZn4Cl(OH)6SO4·6H2O), and zinc lactate, that could not all be well-resolved with ATR–FTIR imaging. With O-PTIR analysis, the degradation compounds could be resolved at sub-micron resolution with an equivalent or better signal-to-noise ratio. This case study shows how the two techniques can be used to obtain comprehensive information at a broad level with ATR–FTIR and a detailed level with O-PTIR.

An Investigation of the Grounds in Nineteenth-Century Chinese Export Oil Paintings

ABSTRACT This article summarises the findings of the first technical art historical study conducted on the oil paintings of nineteenth-century Chinese painters. Twelve paint cross-sections from export oil paintings were examined and compared in order to establish the painters’ use of materials to make the preparatory layers of paintings. The research focuses on the characteristics of the composition of the ground and structure of the build-up ground layers. Attenuated total reflection (ATR) in conjunction with Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) were performed to analyse the pigments, fillers, binding media, and additives used in the preparatory layers. The findings are also considered in relation to what is known about Chinese export oil painting techniques and materials of the era.

A multi-analytical approach for precise identification of alkyd spray paints and for a better understanding of their ageing behaviour in graffiti and urban artworks

Contemporary graffiti and murals became an artistic expression worthy of attention worldwide as well as their conservation. The application of spray paints with increasing technical performance mirrors the variety of the chemical composition of these increasingly common painting materials. An insight into the formulation and the ageing process is extremely important to predict and prevent the possible decay phenomena observed on outdoor urban artworks. This paper aims to investigate the relationship between the macroscopic outcomes and the chemical changes occurring on spray paints after the ageing by a multi-analytical approach. A systematic artificial ageing procedure was performed on multiple sets of concrete mock-ups painted with three different alkyd-based spray paints and in three different light-sensitive colours. The colour variation was assessed by colorimetric measurements, the changes in the paint cross section were observed by scanning electron microscopy, Fourier transform infrared spectroscopy (FTIR) was applied both to characterize the spray paints and to detect the chemical changes of the organic compounds during the ageing. A significant and innovative contribution to this research is the application of the evolved gas analysis-mass spectrometry (EGA-MS) and pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) with tetramethylammonium hydroxide in double-shot mode. These two analytical methodologies allowed an accurate classification of the different alkyd-based binders, the identification of plasticizers, organic pigments and other components often hard to spot in complex formulations, and an analysis of their fate following ageing.

Time-of-flight secondary ion mass spectrometry imaging in cultural heritage: A focus on old paintings.

Time-of-flight secondary ion mass spectrometry (TOF-SIMS) imaging is a surface analysis technique that identifies and spatially resolves the chemical composition of a sample with a lateral resolution of less than 1 μm. Depth analyses can also be performed over thicknesses of several microns. In the case of a painting cross section, for example, TOF-SIMS can identify the organic composition, by detecting molecular ions and fragments of binders, as well as the mineral composition of most of the pigments. Importantly, the technique is almost not destructive and is therefore increasingly used in cultural heritage research such as the analysis of painting samples, especially old paintings. In this review, state of the art of TOF-SIMS analysis methods will be described with a particular focus on tuning the instruments for the analysis of painting cross sections and with several examples from the literature showing the added value of this technique when studying cultural heritage samples.

Micro reflectance imaging spectroscopy for pigment identification in painting cross sections

Micro reflectance imaging spectroscopy for pigment identification in painting cross sections

Characterization of Green Paints in Ming and Qianlong Dynasties' Lin'xi Pavilion by Complimentary Techniques.

During conservation of the painted ceiling decoration of Lin’xi Pavilion in the Forbidden City, two distinct paint campaigns were isolated as a unique case study into architectural paint materials during both the Ming and Qing dynasties. Paint samples and cross sections from both paint generations were analyzed with SEM-EDX, time of flight-secondary ion mass spectrometry (ToF-SIMS), XRD, FTIR, and Raman spectroscopies. Similar organic and inorganic materials characteristic of these time periods were identified. The pigments of interest found in both paint generations were botallackite and atacamite polymorphs. This suggests a shift from natural mineral sources to synthetic copper-based pigments for these larger architectural projects.

Polymorph identification in green Chinese architectural paints using Raman imaging and multivariate curve resolution

AbstractDistinguishing the polymorphs of basic copper chlorides is useful to inform how these materials were used as pigments in Western artworks. Raman imaging spectroscopy and multivariate curve resolution‐alternating least squares (MCR‐ALS) were employed to distinguish the minerals used in green pigments of several Chinese architectural paintings (12th–19th centuries). MCR‐ALS generated component spectra for the Raman datasets, which allowed the resolution of trace materials separated from background features. This method established the mixtures of atacamite and botallackite polymorphs and their relative ratios in five paint samples and identified the mineral azurite, a basic copper carbonate in one sample. These findings identify and suggest a shift to synthetic basic copper chloride pigments in Chinese architectural paints based on the spectroscopically resolved spectra of these mixtures. Thus, this methodology has successfully been applied to paint cross sections to distinguish components and to inform on the materiality and history of objects.

Chemometrics in forensic science

Chemometrics in forensic science

Ag-Nanostars for the Sensitive SERS Detection of Dyes in Artistic Cross-Sections—Madonna della Misericordia of the National Gallery of Parma: A Case Study

In historical paintings, the detection of low amounts of pigments and dyes by Raman spectroscopy can sometimes be challenging, in particular for fluorescent dyes. This issue can be overcome by using SERS (surface-enhanced Raman spectroscopy) which takes advantage of the properties of nanostructured metal surfaces to quench fluorescence and enhance Raman signals. In this work, silver nanostars (AgNSs) are applied for the first time to real art samples, in particular to painting cross-sections, exploiting their effective SERS properties for pigment identification. The case study is the Madonna della Misericordia of the National Gallery of Parma (Italy). Cross-sections were analyzed at first by optical microscopy, SEM-EDS, and micro-Raman spectroscopy. Unfortunately, in some cross-sections, the application of conventional Raman spectroscopy was hindered by an intense background fluorescence. Therefore, AgNSs were deposited and used as SERS-active agent. The experimentation was successful, allowing us to identify a modern dye, namely copper phthalocyanine. This result, together with the detection of other modern pigments (titanium white) and expert visual examination, allowed to reconstruct the painting history, postdating its realization from the 15th century (according to the Gallery inventory) to 19th century with a heavy role of recent (middle 20th century) restoration interventions.

The Identification of Multiple Crystalline Zinc Soap Structures Using Infrared Spectroscopy.

The formation of crystalline zinc soaps (zinc salts of fatty acids) in oil paint layers is a common sign of paint degradation. In this study, we have used infrared spectroscopy to systematically identify differences in structure and composition of crystalline zinc soap phases, and report data analysis methods for structure attribution in challenging oil paint samples. Supported by reported crystal structures, it was possible to distinguish two distinct types of zinc soap geometry: a highly symmetrical packing for long-chain saturated soaps (type B) and an alternating packing for zinc soaps with short, unsaturated, or dicarboxylic chains (type A). These two types of packing can be identified by a single or split asymmetric COO stretch vibration band. With this new information, we studied the structure and composition of zinc soaps formed in a zinc white model paint and in a cross-section from the painting Equations in Space by Lawren Harris. Using non-negative matrix factorization, band integration and band position maps, it was possible to clearly identify zinc azelate in the model paint and map its spatial distribution. The same methods showed that the paint cross-section contained both types of zinc soap structure within the same paint layer, with the less symmetrical structure appearing only at the interface with the ground layer. The results give valuable information on the internal chemistry of oil paint layers, and the demonstrated methods can find widespread application for in-depth analysis of infrared microscopy data.

The role of smalt in complex pigment mixtures in Rembrandt\u2019s Homer 1663: combining MA-XRF imaging, microanalysis, paint reconstructions and OCT

As part of the NWO Science4Arts REVISRembrandt project (2012–2018), novel chemical imaging techniques were developed and applied to the study of Rembrandt’s late experimental painting technique (1651–1669). One of the unique features in his late paintings is his abundant use of smalt: a blue cobalt glass pigment that he often combined with organic lake pigments, earth pigments and blacks. Since most of these smalt-containing paints have discolored over time, we wanted to find out more about how these paintings may have originally looked, and what the role of smalt was in his paint. This paper reports on the use of smalt in complex pigment mixtures in Rembrandt’s Homer (1663), Mauritshuis, The Hague. Macroscopic X-ray fluorescence imaging (MA-XRF) assisted by computational analysis, in combination with SEM-EDX analysis of paint cross-sections, provides new information about the distribution and composition of the smalt paints in the painting. Paint reconstructions were carried out to investigate the effect of different percentages of smalt on the overall color, the drying properties, translucency and texture of the paint. Results show that the influence of (the originally blue) smalt on the intended color of the paint of the Homer is minimal. However, in mixtures with high percentages of smalt, or when combined with more transparent pigments, it was concluded that the smalt did produce a cooler and darker paint. It was also found that the admixture of opaque pigments reduced the translucent character of the smalt. The drying tests show that the paints with (cobalt-containing) smalt dried five times faster compared to those with glass (without cobalt). Most significantly, the texture of the paint was strongly influenced by adding smalt, creating a more irregular surface topography with clearly pronounced brushstrokes. Optical coherence tomography (OCT) was used as an additional tool to reveal differences in translucency and texture between the different paint reconstructions. In conclusion, this study confirmed earlier assumptions that Rembrandt used substantial amounts of smalt in his late paintings, not for its blue color, but to give volume and texture to his paints, to deepen their colors and to make them dry faster.

Degradation of emerald green: scientific studies on multi-polychrome Vairocana Statue in Dazu Rock Carvings, Chongqing, China

The spontaneous degradation of pigments in painting may occur depending on environment, especially the surrounding condition of high humidity and soluble salts. Even some of these are well studied, more investigations are still in need for heritage science. Paint cross sections from Vairocana Statue in Dazu Rock Carvings, one of World Cultural Heritage, Chongqing, China are studied by optical microscopy (OM), Raman spectroscopy (Raman) and mapping, and scanning electron microscopy coupled with energy dispersive X-ray analysis (SEM–EDS). Ultramarine blue, emerald green, synthetic atacamite, vermilion, red lead, gold foil, orpiment, cerussite, gypsum and barite are identified as pigments. Moreover, lavendulan (NaCaCu5(AsO4)4Cl·5H2O) and mimetite (Pb5(AsO4)3Cl) are degradation products of emerald green (Cu(C2H3O2)2·3Cu(AsO2)2) and cerussite(PbCO3) originally used as green pigment with mixture. These secondary products are formed via multistep progresses as degradation of emerald green and cerussite, oxidation of arsenite ((AsO2)−), migration of arsenate ((AsO4)3−) and precipitation reaction of these ions with other necessary ions from environmental conditions. Based on the pigment and paint layer stratigraphy analysis, the paintings of the statue have been executed at least four times and the most recent may be after 1850s. The formation of lavendulan give rise to a highlight for identification of green copper-arsenic containing pigments and characterization of degradation in complex conditions.

A study of \u201cThe Portrait of F.P. Makerovsky in a Masquerade Costume\u201d by Dmitry Levitsky from the collection of the State Tretyakov Gallery

This paper reports on activities carried out as part of a pre-conservation studies of the painting by Dmitry Levitsky, “The Portrait of F.P. Makerovsky in a Masquerade Costume” (1789, the State Tretyakov Gallery). Samples were taken and prepared for further study within the following algorithm. Using optical microscopy of cross-sections of the samples taken, structural elements of layered compositions were revealed and external differences between them were established. X-ray fluorescence spectroscopy was used to evaluate the elemental composition of the painting surface and cross-sections of samples. Scanning electron microscopy combined with energy dispersive X-ray spectroscopy was used to clarify the elemental composition of each of the structural elements of the samples taken, their submicro- and microdimensional inclusions, to map the distribution of chemical elements over the studied surface, and to determine the dispersion of organic and inorganic components contained in the material. Micro-FTIR was used to identify functional groups and to determine the main classes of inorganic compounds, as well as binders, used, including in the local analysis of micro-inclusions. The list of specific chemical compounds in the composition of the studied paint layers and grounds, which included an examination of the varnish coating, was determined with micro-Raman spectroscopy using data obtained by the above methods. As a result of the study, complementary information was obtained on the chemical composition of the inorganic components used, of the binder and of the varnish coating, which is required for further conservation of this work of art.

The examination of Van Gogh\u2019s chrome yellow pigments in \u2018Field with Irises near Arles\u2019 using quantitative SEM\u2013WDX

In this paper we present the results of quantitative measurements on the pigment chrome yellow (PbCr1−xSxO4 with 0 ≤ x ≤ 0.8) using scanning electron microscopy-wavelength dispersive X-ray analysis (SEM–WDX). Traditionally, Optical Microscopy (OM) in combination with scanning electron microscopy-energy dispersive X-ray analysis (SEM–EDX) is used for the identification of many pigments in paint cross-sections based on their particle characteristics and elemental composition. However, in the case of chrome yellow, the lead (Pb) and sulphur (S) peaks overlap, which makes quantitative analysis unreliable. SEM–WDX does not suffer from this problem and we have demonstrated that this technique can distinguish different types of chrome yellow based on the quantification of the sulphur-content of the pigment. This identification can be performed on paint cross-sections, allowing for distinction between chrome yellows in different paint layers. In addition, our study showed that the different types of chrome yellow can still be identified even in low concentrations. Van Gogh made wide use of different hues of chrome yellow. Using this method, we have identified the types of chrome yellow he used in Field with Irises near Arles, which we have been able to correlate with the information in his letters. Raman spectroscopy of the same samples confirmed the SEM–WDX results, but evidenced a higher sensitivity of the latter technique in revealing small amounts of sulphur-rich PbCr1−xSxO4 in mixtures with PbCrO4. SEM–WDX is also more accurate, because it allows the lead(II) sulphate fraction to be determined within 1 mol% absolute, whereas with Raman spectroscopy only relatively broad ranges can be defined. The on-going research of Van Gogh’s paintings as part of a cataloguing project—a collaboration between the Van Gogh Museum, the Cultural Heritage Agency of the Netherlands and Shell—opens the way for a comprehensive comparison of the chrome yellows used by Van Gogh using SEM–WDX.

Beauty is skin deep: the skin tones of Vermeer\u2019s Girl with a Pearl Earring

The soft modelling of the skin tones in Vermeer’s Girl with a Pearl Earring (Mauritshuis) has been remarked upon by art historians, and is their main argument to date this painting to c. 1665. This paper describes the materials and techniques Vermeer used to accomplish the smooth flesh tones and facial features of the Girl, which were investigated as part of the 2018 Girl in the Spotlight research project. It combines macroscopic X-ray fluorescence imaging (MA-XRF), reflectance imaging spectroscopy (RIS), and 3D digital microscopy. Vermeer built up the face, beginning with distinct areas of light and dark. He then smoothly blended the final layers to create almost seamless transitions. The combination of advanced imaging techniques highlighted that Vermeer built the soft contour around her face by leaving a ‘gap’ between the background and the skin. It also revealed details that were otherwise not visible with the naked eye, such as the eyelashes. Macroscopic imaging was complemented by the study of paint cross-sections using: light microscopy, SEM–EDX, FIB-STEM, synchrotron radiation µ-XRPD and FTIR–ATR. Vermeer intentionally used different qualities or grades of lead white in the flesh paints, showing different hydrocerussite/cerussite ratios and particle sizes. Lead isotope analysis showed that the geographic source of lead, from which the different types of lead white were manufactured, was the same: the region of Peak District of Derbyshire, UK. Finally, cross-section analysis identified the formation of new lead species in the paints: lead soaps and palmierite (K2Pb(SO4)2), associated with the red lake.

Investigation of mineralization products of lead soaps in a late medieval panel painting

Metal soaps pose significant concerns in the preservation of paintings made with oil as a binding medium. In highly alkaline environments, metal soap aggregates may undergo mineralization processes with the formation of new phases, such as carbonates, chlorides, oxides and sulfates of the metal cations that are present in pigments or paint additives. In this work, we report new examples of the mineralization of lead soaps in paint-cross sections taken from a late-medieval panel painting owned by the Museum of Cultural History at the University of Oslo. Scientific analyses were carried out with optical microscopy under UV and visible light, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and Raman spectroscopy to investigate and characterize the nature of the compounds present in the samples. Lead (II,IV) oxide, which is presumed to be a secondary product in the mineralization of lead soaps, has been identified in lead-based paint.

Combined Micro- and Macro scale X-ray powder diffraction mapping of degraded Orpiment paint in a 17th century still life painting by Martinus Nellius

The spontaneous chemical alteration of artists’ pigment materials may be caused by several degradation processes. Some of these are well known while others are still in need of more detailed investigation and documentation. These changes often become apparent as color modifications, either caused by a change in the oxidation state in the original material or the formation of degradation products or salts, via simple or more complex, multistep reactions. Arsenic-based pigments such as orpiment (As2S3) or realgar (α-As4S4) are prone to such alterations and are often described as easily oxidizing upon exposure to light. Macroscopic X-ray powder diffraction (MA-XRPD) imaging on a sub area of a still life painting by the 17th century Dutch painter Martinus Nellius was employed in combination with microscopic (μ-) XRPD imaging of a paint cross section taken in the area imaged by MA-XRPD. In this way, the in situ formation of secondary metal arsenate and sulfate species and their migration through the paint layer stack they originate from could be visualized. In the areas originally painted with orpiment, it could be shown that several secondary minerals such as schultenite (PbHAsO4), mimetite (Pb5(AsO4)3Cl), palmierite (K2Pb(SO4)2) and syngenite (K2Ca(SO4)2∙H2O) have formed. Closer inspection of the cross-sectioned paint layer stack with μ-XRPD illustrates that the arsenate minerals schultenite and mimetite have precipitated at the interface between the orpiment layer and the layer below that is rich in lead white, i.e. close to the depth of formation of the arsenate ions. The sulfate palmierite has mostly precipitated at the surface and upper layers of the painting.