Macroscopic x-ray fluorescence imaging spectroscopy (MA-XRF) and reflectance imaging spectroscopy (RIS) are important tools in the analysis of cultural heritage objects, both for conservation and art historical research purposes. The elemental and molecular distributions provided by MA-XRF and RIS respectively, are particularly useful for the identification and mapping of pigments in easel paintings. While MA-XRF has relatively established data processing methods based on modeling of the underlying physics, RIS data cannot be modeled with sufficient precision and its processing has considerable room for improvements. This work seeks to improve RIS data processing workflows in the short wavelength infrared range (SWIR, 1000–2500 nm) with a novel method that fits Gaussian profiles to pigment-specific absorption features, and we compare its performance to MA-XRF for the task of semi-quantitative pigment mapping, evaluating their limits of detection (LODs) and the matrix effects that affect their signals. Two pigments are considered in this work, lead white and blue verditer, which are mapped in SWIR RIS using the first overtone of -OH stretching of their primary compounds, hydrocerussite (Pb₃(CO₃)₂(OH)₂) and azurite (Cu₃(CO₃)₂(OH)₂), at 1447 and 1497 nm respectively, and in MA-XRF using the Pb-L and Cu-K fluorescence signals. The methods are evaluated using two sets of custom-prepared paint samples, as well as a 16th-century painting, discussing the identification, mapping, and semi-quantitative analysis of the considered pigments. We found SWIR RIS to be a pigment-specific method with a longer linear range but inferior LODs and penetration depth when compared to MA-XRF, the latter is often not capable of discriminating between different pigments with identical elemental markers. We furthermore present a novel color scale that allows the simultaneous visualization of signals above and below a confidence limit.

@en

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.

@en

We demonstrate multi-scale multi-parameter optical coherence tomography (OCT) imaging and visualization of Johannes Vermeer’s painting Girl with a Pearl Earring. Through automated acquisition, OCT image segmentation, and 3D volume stitching we realize OCT imaging at the scale of an entire painting. This makes it possible to image, with micrometer axial and lateral resolution, an entire painting over more than 5 orders of length scale. From the multi-scale OCT data we quantify multiple parameters in a fully automated way: the surface height, the scattering strength, and the combined glaze and varnish layer thickness. The multi-parameter OCT data of Girl with a Pearl Earring shows various features: Vermeer’s brushstrokes, surface craquelure, paint losses, and restorations. Through an interactive visualization of the Girl, based on the OCT data and the optical properties of historical reconstructions of Vermeer’s paint, we can virtually study the effect of the lighting condition, viewing angle, zoom level and presence/absence of glaze layer. The interactive visualization shows various new painting features. It demonstrates that the glaze layer structure and its optical properties were essential to Vermeer to create an extremely strong light to dark contrast between the figure and the background that gives the painting such an iconic aesthetic appeal.@en

During the Second World War the German occupants of the Netherlands made ample use of the Scheveningen prison near The Hague, popularly nicknamed the Oranjehotel. One former death cell in this infamous prison (Doodencel 601) has been preserved in its original condition, showing wartime inscriptions on the cell walls. Interestingly, a small section of the wall has been given an additional plaster layer, presumably covering inscriptions. Here, we report on the visualization of this enigmatic text, which so far had escaped the reach of historians. Our visualization methodology was threefold. First, we determined the cell-wall stratigraphy and its composition based on a sample cross-section. Second, we prepared a physical model wall, mimicking the layering of the original cell wall. Third, we tested a combination of raking light photography and infrared thermography on the model wall. Applying this methodology on the original wall revealed the inscriptions, including the author’s name Daniël de Blocq van Scheltinga, a prominent Nazi collaborator, as well as a calendar and an important date of his post-war trial in the fall of 1945. Our visualizations flawlessly dovetail with archival findings. Together, they offer an intimate view of an early post-war inmate of the Scheveningen prison, whose message was covered up once the cell was transformed into a war monument in 1946.

@en

Rembrandt (1606–1669) is renowned for his impasto technique, involving his use of lead white paint with outstanding rheological properties. This paint was obtained by combining lead white pigment (a mixture of cerussite PbCO ₃ and hydrocerussite Pb ₃(CO ₃) ₂(OH) ₂) with an organic binding medium, but the exact formulation used by Rembrandt remains a mystery. A powerful combination of high-angle and high-lateral resolution x-ray diffraction was used to investigate several microscopic paint samples from four Rembrandt masterpieces. A rare lead compound, plumbonacrite (Pb ₅(CO ₃) ₃O(OH) ₂), was detected in areas of impasto. This can be considered a fingerprint of Rembrandt's recipe and is evidence of the use of an alkaline binding medium, which sheds a new light on Rembrandt's pictorial technique.

@en

The background of Vermeer’s Girl with a Pearl Earring (c. 1665, Mauritshuis) has, until recently, been interpreted as a flat dark space. The painting was examined in 2018 as part of the research project The Girl in the Spotlight using a combination of micro- and macro-scale analytical techniques. The stratigraphy of the background was determined from samples mounted as cross-sections, and its material composition was analysed using electron microscopy and chromatographic techniques. The underlayer contains mainly charcoal black, and the glaze contains two organic colourants—indigo and weld—and a copper drier. Deterioration of the glaze has made features in the background difficult to discern with the naked eye. Complementary imaging techniques were able to visualise Vermeer’s signature, and the suggestion of folded fabric (possibly a curtain) on the right side of the painting. The distribution of the layer(s) in the background were imaged using: infrared reflectography (900–1100 nm), multi-scale optical coherence tomography scanning, macroscopic X-ray fluorescence and 3D digital microscopy. Vermeer applied the black underlayer vigorously with overlapping brushstrokes that varied in thickness. When he applied the glaze on top, it levelled out to make a smooth flat surface. The visual effect of the background contrasts the figure of the Girl and projects her forward in space, closer to the viewer.

@en

Until the 19th century, lead white was the most important white pigment used in oil paintings. Lead white is typically composed of two crystalline lead carbonates: hydrocerussite [2PbCO₃·Pb(OH)₂] and cerussite (PbCO₃). Depending on the ratio between hydrocerussite and cerussite, lead white can be classified into different subtypes, each with different optical properties. Current methods to investigate and differentiate between lead white subtypes involve invasive sampling on a microscopic scale, introducing problems of paint damage and representativeness. In this study, a 17th century painting GirlwithaPearlEarring(by Johannes Vermeer, c. 1665, collection of the Mauritshuis, NL) was analyzed with a recently developed mobile and noninvasive macroscopic x-ray powder diffraction (MA-XRPD) scanner within the project Girl in the Spotlight. Four different subtypes of lead white were identified using XRPD imaging at the macroscopic and microscopic scale, implying that Vermeer was highly discriminatory in his use of lead white.

@en

A seventeenth-century canvas painting is usually comprised of varnish and (translucent) paint layers on a substrate. A viewer’s perception of a work of art can be affected by changes in and damages to these layers. Crack formation in the multi-layered stratigraphy of the painting is visible in the surface topology. Furthermore, the impact of mechanical abrasion, (photo)chemical processes and treatments can affect the topography of the surface and thereby its appearance. New technological advancements in non-invasive imaging allow for the documentation and visualisation of a painting’s 3D shape across larger segments or even the complete surface. In this manuscript we compare three 3D scanning techniques, which have been used to capture the surface topology of Girl with a Pearl Earring by Johannes Vermeer (c. 1665): a painting in the collection of the Mauritshuis, the Hague. These three techniques are: multi-scale optical coherence tomography, 3D scanning based on fringe-encoded stereo imaging (at two resolutions), and 3D digital microscopy. Additionally, scans were made of a reference target and compared to 3D data obtained with white-light confocal profilometry. The 3D data sets were aligned using a scale-invariant template matching algorithm, and compared on their ability to visualise topographical details of interest. Also the merits and limitations for the individual imaging techniques are discussed in-depth. We find that the 3D digital microscopy and the multi-scale optical coherence tomography offer the highest measurement accuracy and precision. However, the small field-of-view of these techniques, makes them relatively slow and thereby less viable solutions for capturing larger (areas of) paintings. For Girl with a Pearl Earring we find that the 3D data provides an unparalleled insight into the surface features of this painting, specifically related to ‘moating’ around impasto, the effects of paint consolidation in earlier restoration campaigns and aging, through visualisation of the crack pattern. Furthermore, the data sets provide a starting point for future documentation and monitoring of the surface topology changes over time. These scans were carried out as part of the research project ‘The Girl in the Spotlight’.

@en

Over the past several decades the painting An Old Man in Military Costume by Rembrandt Harmensz van Rijn (ca. 1630–31; J. Paul Getty Museum, 78.PB.246) has been the subject of a number of investigations carried out in order to better visualize a second painting beneath the surface figure. The underlying image–the head and shoulders of a man wearing a cloak–is oriented 180 degrees from the upper image and appears to be fairly complete. Scanning macro x-ray fluorescence (XRF) spectroscopy reveals the face is painted with lead white and a mercury-containing pigment (likely vermilion), and the cloak is painted with a copper-containing pigment. Following the revelation and digital color reconstruction of the underlying figure, a number of questions still remained. Here, through the use of infrared reflectance imaging spectroscopy (i.e., hyperspectral imaging) and macro-XRF imaging spectroscopy, together with cross-sections taken from targeted areas, the sequence of painting in both compositions was explored. Of particular interest was the discovery of evidence of multiple attempts to situate the lower figure, and the subsequent application of a blocking-out layer over the lower figure before the artist rotated the panel and executed the upper figure. In addition, examination of the placement of the two images on the panel adds to our understanding of the subtle complexities of Rembrandt's working process.

@en

High fidelity reproductions of paintings provide new opportunities to museums in preserving and providing access to cultural heritage. This paper presents an integrated system which is able to capture and fabricate color, topography and gloss of a painting, of which gloss capturing forms the most important contribution. A 3D imaging system, utilizing stereo imaging combined with fringe projection, is extended to capture spatially-varying gloss, based on the effect of specular reflectance polarization. The gloss is measured by sampling the specular reflection around Brewster’s angle, where these reflections are effectively polarized, and can be separated from the unpolarized, diffuse reflectance. Off-center gloss measurements are calibrated relative to the center measurement. Off-specular gloss measurements, following from local variation of the surface
normal, are masked based on the height map and corrected. Shadowed regions, caused by the 3D relief, are treated similarly. The area of a single capture is approximately 180x90mm at a resolution of 25x25μm. Aligned color, height, and gloss tiles are stitched together off-line, registering overlapping color regions. The resulting color, height and gloss maps are inputs for the poly-jet 3D printer. Two paintings were reproduced to verify the effectiveness and efficiency of the proposed system. One painting was scanned four times, consecutively rotated by 90 degrees, to evaluate the influence of the scanning system geometric configuration on the gloss measurement. Experimental results show that the method is sufficiently fast for practical application, i.e. to scan a whole painting within eight hours, during closing hours of a museum. The results can well be
used for the purpose of physical reproduction and other applications needing first-order estimates of the appearance (e.g. conservation diagnostics and condition reports). Our method to extend appearance scanning with gloss measurements is a valuable addition in the quest for realistic reproductions, in terms of its practical applicability - number of images needed for reconstruction and speed - and its perceptual added value, when added to color and topography reproduction.@en

Additive Manufacturing (commonly known as 3D printing) technology has become a global phenomenon. In the domain of heritage, 3D printing is seen as a time and cost efficient method for restoring vulnerable architectural structures. The technology can also provide an opportunity to reproduce missing or destroyed cultural heritage, in the cases of conflicts or environmental threats. This project takes the Hippolytuskerk in the Dutch village of Middelstum, as a case study to explore the limits of the existing technology, and the challenges of 3D printing of cultural heritage. Architectural historians, modelling experts, and industrial scientists from the universities of Delft and Eindhoven have engaged with diverse aspects of 3D printing, to reproduce a selected part of the 15th century church. This experimental project has tested available technologies to reproduce a mural on a section of one of the church’s vault with maximum possible fidelity to material, colors and local microstructures. The project shows challenges and opportunities of today’s technology for 3D printing in heritage, varying from the incapability of the scanning technology to capture the existing cracks in the required resolution, to the high costs of speciality printing, and the limited possibilities for combining both printing techniques for such a complex structure.

@en

Twentieth century paints often contain titanium dioxide and zinc oxide based white pigments that can range from photostable to highly photocatalytic. Photocatalytic pigments can cause the degradation of paint upon UV exposure, whereas photostable pigments may be benign or can protect paintings from degradation. Hence, knowing whether or not a pigment is photocatalytic is of high importance for risk assessment and the subsequent decision making process concerning storage and exposure conditions of objects. Here we present a proof of principle, focused on titanium white paints, for an easy-to-use and low-tech application of a commercial photocatalytic activity indicator ink (PAII) on embedded paint samples or cross sections. This test determines, qualitatively, if a photocatalytic pigment is present in a white paint sample. The PAII paint sample staining application shows an obvious color change, within five minutes of UV irradiation, for paint samples containing photocatalytic pigments. A microscope with a camera and a UV source are the only necessary equipment for the application of this method. A quantitative image processing protocol is also proposed as an extension of the staining method by applying open source software analysis to measure the color change using photographs. The test was evaluated on reference paints with well-characterized pigments and applied on samples from modern paintings by Piet Mondriaan, Robert Ryman, and Lucebert, indicating the presence of harmful photocatalytic pigments in these cases. The novel application of a commercial ink on paint samples offers a simple test, not just for assessment of photocatalytic activity of titanium white pigments, but which may in future be applied for the detection of photoactive forms of zinc white and other potentially harmful semiconductor pigments in art objects.

@en

Late paintings of Rembrandt van Rijn (1606–1669) offer intriguing problems for both art historians and conservation scientists. In the research presented here, the key question addressed is whether observed stylistic differences in paint handling can be correlated with material differences. In Saul and David, in the collection of the Royal Picture Gallery Mauritshuis in The Hague, NL, the stylistic differences between the loose brushwork of Saul’s cloak and the more detailed depiction of his turban and the figure of David have been associated with at least two painting stages since the late 1960s, but the attribution of each stage has been debated in the art historical literature. Stylistic evaluation of the paint handling in the two stages, based on magnified surface examination, is further described here. One of the research goals was to determine whether the stylistic differences could be further differentiated with macroscale and microscale methods of material analysis. To address this, selected areas of the painting having pronounced stylistic differences were investigated with two macroscopic chemical imaging methods, X-ray fluorescence and reflectance imaging spectroscopies. The pigments used were identified and their spatial distribution was mapped. The mapping results show that the passages rendered in more detail and associated stylistically with the first painting stage, such as the orange-red color of David’s garment or the Greek key design in Saul’s turban, were painted with predominately red ochre mixed with vermilion. The regions of loose, bold brushwork, such as the orange-red slashing strokes in the interior of Saul’s cloak, associated with the second painting stage, were painted with predominately red ochre without vermilion. These macroscale imaging results were confirmed and extended with scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM–EDX) analysis of three cross-sections taken from regions of stylistic differences associated with the two painting stages, including one sample each from the right and left sleeve of David, and one from the interior of Saul’s cloak. SEM–EDX also identified a trace component, barium sulfate, associated with the red ochre of the second stage revisions. Combining mapping information from two spectroscopic imaging methods with localized information from microscopic samples has clearly shown that the stylistic differences observed in the paint handling are affiliated with differences in the chemical composition of the paints.[Figure not available: see fulltext.].@en

The discoloration rate of chrome yellow (CY), a class of synthetic inorganic pigments (PbCr_1−xS_xO₄) frequently used by Van Gogh and his contemporaries, strongly depends on its sulfate content and on its crystalline structure (either monoclinic or orthorhombic). Macroscopic X-Ray powder diffraction imaging of selected areas on Van Gogh's Sunflowers (Van Gogh Museum, Amsterdam) revealed the presence of two subtypes of CY: the light-fast monoclinic PbCrO₄ (LF-CY) and the light-sensitive monoclinic PbCr_1−xS_xO₄ (x≈0.5; LS-CY). The latter was encountered in large parts of the painting (e.g., in the pale-yellow background and the bright-yellow petals, but also in the green stems and flower hearts), thus indicating their higher risk for past or future darkening. Overall, it is present in more than 50 % of the CY regions. Preferred orientation of LS-CY allows observation of a significant ordering of the elongated crystallites along the direction of Van Gogh's brush strokes.

@en

Being able to link captured material characteristics and fabricable material appearance attributes is important for creating life-like reproductions. In this paper we propose a method for gloss calibration, and an approach for gloss gamut mapping, as part of an integrated approach for color, topography and gloss reproduction. For gloss calibration, gloss calibration targets were printed in the primary printing colors (CMYK and White), with uniform gloss in equal distant gloss levels. These targets were scanned using the proposed gloss scanner. To create the gloss gamut map, a monotonic curve was fitted to the mean gloss scan values at different gloss levels. Analysis of fitted curves indicated that the gloss mapping is independent of the diffuse colors. As a case study, the painting ‘Fruit Still Life’ by Cornelis de Heem was scanned, and the measured gloss was mapped to printable gloss levels using the relation described by the fitted curve. The printed result shows good correspondence to the painting’s appearance, with clearly distinguishable gloss features for the in-gamut glass values.@en

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863-68), Marguerite de Conflans en Toilette de Bal (1870-1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies-Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV-Vis-NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies-Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.

@en

This study reports on the effect of artists’ paint formulation on degradation rates of TiO2-based oil paints. Titanium white oil paint exists in a multitude of different recipes, and the effect of the formulation on photocatalytic binder
degradation kinetics is unknown. These formulations contain, among others, one or both titanium dioxide polymorphs, zinc oxide, the extenders barium sulfate or calcium carbonate and various additives. Most research performed
on the photocatalytic degradation process focusses on pure titanium white-binder mixtures and thus does not take into account the complete paint system. Since photocatalytic oil degradation is a process initiated by the absorption of UV light, any ingredient or combination of ingredients influencing the light scattering and absorption properties of the paint films may affect the degradation rate. In this study three sets of experiments are conducted,
designed using the design of experiments (DoE) approach, to screen for the most important formulation factors influencing the degradation rate. The benefits of using DoE, compared to a more traditional ‘one factor at a time approach’ are robustness, sample efficiency, the ability of evaluate mixtures of multiple components as well as the ability to evaluate factor interactions. The three sets of experiments investigate (1) the influence of the TiO2 type, (2) the impact of different mixtures of two types of TiO2, ZnO and the additive aluminum stearate and (3) the influence of common extenders in combination with photocatalytic TiO2, on the photocatalytic degradation of the oil binder. The impact of the formulation on the degradation rate became apparent, indicating the shortcoming of oversimplified studies. The protective effect of photostable TiO2 pigments, even in a mixture with photocatalytic TiO2 pigments, as well as the negative effect of extenders was demonstrated. Furthermore, the ambiguous role of ZnO (photocatalytic or not) and aluminum stearate is highlighted. Neither can be ignored in a study of degradation behavior of modern oil paints and require further investigation.@en

In the past decade macroscopic X-ray fluorescence imaging (MA-XRF) has become established as a method for the noninvasive investigation of flat painted surfaces, yielding large scale elemental maps. MA-XRF is limited by a lack of specificity, only allowing for indirect pigment identification based on the simultaneous presence of chemical elements. The high specificity of X-ray powder diffraction (XRPD) mapping is already being exploited at synchrotron facilities for investigations at the (sub)microscopic scale, but the technique has not yet been employed using lab sources. In this paper we present the development of a novel MA-XRPD/XRF instrument based on a laboratory X-ray source. Several combinations of X-ray sources and area detectors are evaluated in terms of their spatial and angular resolution and their sensitivity. The highly specific imaging capability of the combined MA-XRPD/XRF instrument is demonstrated on a 15th/16th century illuminated manuscript directly revealing the distribution of a large number of inorganic pigments, including the uncommon yellow pigment massicot (o-PbO). The case study illustrates the wealth of new mapping information that can be obtained in a noninvasive manner using the laboratory MA-XRPD/XRF instrument.

@en

White pigments were abundantly used in 20th century paintings, and relate to several degradation risks such as titanium white mediated photocatalytic binder degradation or zinc soap formation. Knowledge about the white pigments that were used is essential for risk assessments of 20th century collections. In this study, a representative set of 179 paintings in Dutch modern art collections were analyzed by portable X-ray fluorescence spectrometry. Subsequent explorative data analysis was performed, supported by qualitative findings from 140 home-made reference samples. Micro-samples were further investigated by X-ray diffraction and scanning transmission electron microscopy to gain information about crystal structure and surface coating. This study reveals that Dutch 20th century artists were hesitant to use titanium white. In the Netherlands, the use of this pigment is observed convincingly from the 1970s onward and initially mostly in non-oil binders. Additionally, lead white was used until late in the 20th century for paints and grounds but rarely mixed with titanium white in paints. The study also indicated that many CoBrA artists used zinc white, underlining the risk of degradation due to soap formation. Furthermore, this study highlights the different production processes of titanium white. Through the association of titanium with niobium, an impurity only present for sulfate processed pigments, the production process can be identified. The absence of niobium indicates the presence of rutile and is thus a sign of paint stability, as well as a ‘post 1959’ dating. This explorative study illustrates the value of a combination of data analysis approaches, which includes assessment of spectra as well as descriptive, bivariate and multivariate analysis, for medium-sized datasets gathered at similar conditions.@en