This paper provides an overview over the application of scanning macro-XRF with mobile instruments for the investigation of historical paintings. The method is compared to synchrotron based macro-XRF ...imaging and Neutron Activation Auto-Radiography. Full-Field XRF imaging instruments, a potential future alternative to scanning macro-XRF, and confocal XRF, providing complementary depth profiles and developing into a 3D imaging technique itself, are described with the focus on investigations of historical paintings. Recent developments of X-ray radiography are presented and the investigation of cultural heritage objects other than paintings by MA-XRF is summarized. In parallel to XRF, hyperspectral imaging in the visible and range has developed into a technique with comparable capabilities, providing insight in chemical compounds, where XRF imaging identifies the distribution of elements. Due to the complementary nature of these techniques the latter is summarized. Further, progress and state of the art in data evaluation for spectroscopic imaging is discussed. In general it could be observed that technical capabilities in MA-XRF and hyperspectral imaging have reached a plateau and that with the availability of commercial instruments the focus of recent studies has shifted from the development of methods to applications of the instruments. Further, that while simple instruments are easily available with medium budgets only few groups have high-end instrumentation available, bought or in-house built.
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•Comprehensive review of scanning macro XRF investigations of historical paintings•Comparison of synchrotron based and X-ray tube based scanning macro XRF•Comparison of scanning macro XRF with Neutron Activation Autoradiography•Discussion of full field XRF imaging and confocal XRF•Comparison with hyperspectral imaging in the visible and near IR ranges
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.
Motivated by the challenge of capturing complex hierarchical chemical detail in natural material from a wide range of applications, the Maia detector array and integrated realtime processor have been ...developed to acquire X-ray fluorescence images using X-ray Fluorescence Microscopy (XFM). Maia has been deployed initially at the XFM beamline at the Australian Synchrotron and more recently, demonstrating improvements in energy resolution, at the P06 beamline at Petra III in Germany. Maia captures fine detail in element images beyond 100 M pixels. It combines a large solid-angle annular energy-dispersive 384 detector array, stage encoder and flux counter inputs and dedicated FPGA-based real-time event processor with embedded spectral deconvolution. This enables high definition imaging and enhanced trace element sensitivity to capture complex trace element textures and place them in a detailed spatial context. Maia hardware and software methods provide per pixel correction for dwell, beam flux variation, dead-time and pileup, as well as off-line parallel processing for enhanced throughput. Methods have been developed for real-time display of deconvoluted SXRF element images, depth mapping of rare particles and the acquisition of 3D datasets for fluorescence tomography and XANES imaging using a spectral deconvolution method that tracks beam energy variation.
In this manuscript, we address the problem of studying layer structure in X-ray Fluorescence (XRF) elemental maps of paintings through the incorporation of reflectance imaging spectral data in the ...visible or near IR range. We propose a conceptually flexible approach, which involves an initial clustering step for the visible hyperspectral reflectance data (RIS) and the formation of a synthetic surface XRF image. Considering the difference of the full and synthetic surface XRF images, surface and subsurface correlated features are then identified. Results are demonstrated on real and simulated data.
Caspar David Friedrich (1774–1840), one of the most famous German 19th c. painters, created paintings throughout his artistic life using different paint palettes, including many new pigments from the ...turn from the 18th to the 19th century. In that regard especially blue and yellow pigments are the focus of this non‐invasive chemical study using X‐ray fluorescence imaging, as these are a landscape painter's major colours. Four paintings from the collection of the Alte Nationalgalerie, Staatliche Museen zu Berlin‐Stiftung Preußischer Kulturbesitz, spanning over two important decades of Friedrich's artistic career, were investigated in situ to determine the chemical composition of the blue pigments used in the sky and the yellow hues used in the sunsets and moonlight. The results indicate the use of iron based yellow pigments as well as smalt based blue pigments in Friedrich's early works, while chromium‐based yellow pigments and cobalt blue are used in later paintings. The finding of cadmium sulphide in a painting dated in 1817, probably as a historical retouching, is interesting and requires further research. This in situ non‐invasive imaging study, although limited to one analytical technique, shows Friedrich's introduction of new synthetic pigments into his paint palette, which varies over the time. These results are important to better understand the painting technique of Caspar David Friedrich and his contemporaries.
The painting Saul and David, considered to date from c. 1652 and previously attributed to Rembrandt van Rijn and/or his studio, is a complex work of art that has been recently subjected to intensive ...investigation and conservation treatment. The goal of the research was to give insight into the painting's physical construction and condition in preparation for conservation treatment. It was also anticipated that analysis would shed light on authenticity questions and Rembrandt's role in the creation of the painting. The painting depicts the Old Testament figures of King Saul and David. At left is Saul, seated, holding a spear and wiping a tear from his eye with a curtain. David kneels before him at the right playing his harp. In the past, the large sections with the life-size figures were cut apart and later reassembled. A third piece of canvas was added to replace a missing piece of canvas above the head of David. As part of the investigation into the authenticity of the curtain area, a number of paint micro samples were examined with LM and SEM–EDX. Given that the earth, smalt and lake pigments used in the painting could not be imaged with traditional imaging techniques, the entire painting was also examined with state of the art non-destructive imaging techniques. Special attention was devoted to the presence of cobalt-containing materials, specifically the blue glass pigment smalt considered characteristic for the late Rembrandt. A combination of quantitative electron microprobe analysis and macroscopic X-ray fluorescence scanning revealed that three types of cobalt-containing materials are present in the painting. The first type is a cobalt drier that was found in the overpaint used to cover up the canvas inset and the joins that were added in the 19th century. The other two Co-containing materials are part of the original paint used by Rembrandt and comprise two varieties of smalt, a K-rich glass pigment that derives its gray–blue color by doping with Co-ions. Smalt paint with a higher Ni content (NiO:CoO ratio of around 1:4) was used to depict the blue stripes in Saul's colorful turban, while smalt with a lower Ni content was employed (NiO:CoO ratio of around 1:5) for the broad expanses of Saul's garments. The presence of two types of smalt not only supports the recent re-attribution of the painting to Rembrandt, but also that the picture was painted in two phases. Saul's dark red garment is painted in a rough, “loose” manner and the now discolored smalt-rich layer was found to have been partially removed during a past restoration treatment/s. In contrast, the blue-green smalt in the turban is much better preserved and provides a colorful accent. While the use of different types of smalt in a Rembrandt painting has been previously identified using quantitative EDX analysis of paint cross-sections, to the best of our knowledge this is the first time such a distinction has been observed in a 17th-century painting using non-destructive imaging techniques. In addition to the XRF-based non-invasive elemental mapping, hyperspectral imaging in the visual to near-infrared (VNIR) region was also carried out.
•The painting ‘Saul and David’ was examined by Macroscopic-XRF and hyperspectral imaging.•The results show where in the painting the Cobalt-containing pigment smalt was used.•The results also show which areas of the painting are not original•Results show that Rembrandt employed two types of smalt, probably during two different periods, a finding consistent with quantitative analyses of paint micro samples.•For the first time, the occurrence of different types of smalt in the same painting was demonstrated by means of non-destructive imaging methods.
In 17th century Old Master Paintings, the underpainting generally refers to the first sketch of a composition. The underpainting is applied to a prepared ground using a monochrome, brown oil paint to ...roughly indicate light, shade and contours. So far, methods to visualize the underpainting—other than in localized cross-sections—have been very limited. Neither infrared reflectography nor neutron induced autoradiography have proven to be practical, adequate visualization tools. Thus, although of fundamental interest in the understanding of a painting’s genesis, the underpainting has virtually escaped all imaging efforts. In this contribution we will show that 17th century underpainting may consist of a highly heterogeneous mixture of pigments, including copper pigments. We suggest that this brown pigment mixture is actually the recycled left-over of a palette scraping. With copper as the heaviest exclusive elemental component, we will hence show in a case study on a
Portrait of an Old Man
attributed to Rembrandt van Rijn how scanning macro-XRF can be used to efficiently visualize the underpainting below the surface painting and how this information can contribute to the discussion of the painting’s authenticity.
We examined 2 hypotheses regarding why some young women do not maintain their espoused occupational aspirations in male-dominated fields from late adolescence through young adulthood. The first ...hypothesis concerns attitudes towards math and science; the second concerns the desire for job flexibility. The sample of young women (N = 104) was taken from a larger longitudinal investigation of approximately 1,000 young women from a midwestern metropolitan area in Michigan, USA, who were followed from age 18 (in 1990) to age 25 (1997). Findings suggest that desire for a flexible job, high time demands of an occupation, and low intrinsic value of physical science were the best predictors of women changing their occupational aspirations out of male-dominated fields. These results suggest that despite the women's movement and more efforts in society to open occupational doors to traditional male-jobs for women, concerns about balancing career and family, together with lower value for science-related domains, continue to steer young women away from occupations in traditionally male-dominated fields, where their abilities and ambitions may lie.
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