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What Technology Does an Xray Use to See Below the Surface of a Work of Art Jishka

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Examination of historical paintings by land-of-the-fine art hyperspectral imaging methods: from scanning infra-red spectroscopy to computed Ten-ray laminography

  • Frederik Vanmeert1,
  • Geert Van der Snickti,
  • Matthias Alfeldone,ii,
  • Wout De Nolf1,
  • Joris Dik3 &
  • Koen Janssens1

Heritage Scientific discipline book two, Commodity number:xiii (2014) Cite this article

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Abstract

The development of advanced methods for non-destructive selective imaging of painted works of art at the macroscopic level based on radiation in the X-ray and infrared range of the electromagnetic spectrum are concisely reviewed. Such methods allow to either record depth-selective, element-selective or species-selective images of entire paintings. Camera-based 'total field' methods (that record the prototype data in parallel) can exist discerned next to scanning methods (that build upwardly distributions in a sequential manner by scanning a beam of radiations over the surface of an artefact). Six methods are discussed: on the ane hand, macroscopic X-ray fluorescence and X-ray diffraction imaging and X-ray laminography and on the other hand macroscopic Mid and Near Infrared hyper- and full spectral imaging and Optical Coherence Tomography. These methods can be considered to be improved versions of the well-established imaging methods employed worldwide for exam of paintings, i.e., X-ray radiography and Infrared reflectography. Possibilities and limitations of these new imaging techniques are outlined.

Introduction

Historical paintings are considered to exist among the most precious cultural heritage artefacts and have been the subject of intensive studies for decades. Scientific studies on such artefacts are highly relevant, in order to optimize the preservation of the paintings for coming generations and/or to gain more profound insights in their creation process [one–iii]. This review focusses on the examination of easel paintings, i.e., painted renditions realized on a moveable substrate. Easel painting consists typically of a support, ground, paint and varnish layers, applied on top of one some other. Canvasses and wooden panels are the nigh popular supports, but as well other materials such as thin copper plates, paper, stone and glass take been used. Ofttimes the pictorial layers are very thinly painted out, making some of them semi-transparent. Micrometers below a painting's surface, a wealth of data may be nowadays about the creative process followed by the artist while making the work of art. Many painterly effects can critically depend on the layer build-upward: e.g., the translucent shine of colorful tissues, the proposition of shadow in mankind tones or the disarming illusion of an object'south texture may exist realized past deliberately including the optical contribution of lower layers. Additionally, knowledge about the stratigraphy of a painting often is highly relevant in conservation when stability problems such every bit pigment discoloration or delamination are studied. Thus, the study of a painting, its limerick and stratigraphy is a common research theme shared past curators, conservators and conservation scientists. However, this data, comprised of structural and compositional aspects, is usually not like shooting fish in a barrel to obtain in a non-invasive manner. Next to the visible surface layers, subsurface layers may include underdrawings, underpaintings, and adjustments made in the course of painting. Together, all these layers determine the current appearance of the work of art. In a growing number of cases conservators take discovered abandoned compositions underneath paintings, illustrating the artist's exercise of reusing a canvas or panel. Imaging methods that can "read" this subconscious information without any damage to the artwork are therefore valuable for fine art-historical research [ii] while also being very useful during restoration activities.

The standard methods for studying the inner structure of painted works of fine art are X-ray radiography (XRR) and infrared reflectography (IRR), penetrative illumination techniques that are optionally complemented with the microscopic analysis of cross-sectioned samples. Both methods are full field imaging methods, employing epitome plates or cameras that are sensitive in the advisable range of the electromagnetic spectrum for recording the prototype information (encounter Figure 1A). Since these methods all have their limitations, recently, a number of new approaches based on 10-ray and Infra-cherry-red radiations for imaging the buildup of hidden paint layer systems have been put into practice; some of these methods make apply of scanning pencil beams over the painting while recording data either in manual or reflection mode (see Effigy 1B, C). 2 major motivations can be discerned for the evolution of these more advanced versions: (a) the want to know more than nigh the creative process and/or the artist's way of working that accept led to a given work of art and (b) the demand to assess and predict the current and future condition of a work of art. Motivation (a) is essentially of art-historical nature and seeks to reconstruct (better) the past/history of an artwork while motivation (b) is more strongly linked to preventive conservation and to conservation technology, and therefore mostly concerned with the future of the artwork [1]. Of course, for conservation, an agreement of the history of a work of fine art and the artist's intent is fundamental, since it provides the basis for assessing the current condition of the art work and for deciding which interventions are (not) appropriate [4]. In what follows, we mainly review recent activities that involve the use of strongly penetrative radiation (from either the 10-ray or IR range of the EM spectrum); the interested reader is referred to reviews [one–iv] for a broader treatment of the topic, including related spectroscopic investigations. Also Liang'south 2012 review of multispectral and hyperspectral imaging using mainly visual radiations is a useful complementary resource in this respect [five].

Figure 1
figure 1

Schematic representation of (A) full field imaging and (B) scanning pencil-beam imaging methods: these can operate in either (C) transmission or reflection geometry; of (D) conventional computed X-ray tomography (employing cone axle illumination) and (East) computed X-ray laminography (employing parallel beam irradiation). Adapted from [4] and [2].

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Ten-ray based methods

The variants of XRR that will exist discussed below in more than detail are called Macroscopic 10-ray fluorescence (MA-XRF), the related method of Macroscopic Ten-ray diffraction (MA-XRD) and Computed X-ray laminography (CXL). All are non-destructive techniques, eliminating the need to remove fabric from the artefacts for their examination. The first ii allow for element- or (crystal) phase-selective imaging at the length scale of the paintings themselves while the third method is suitable for depth selective micro imaging.

Macroscopic 10-ray fluorescence analysis (MA-XRF)

XRF is a well-established method of quantitative chemical element assay that is based on the ionization of the atoms of the material existence irradiated past an energetic beam of primary X-rays [6, 7]. Characteristic radiation emitted by the ionized atoms contains information on the nature and the abundance of the elemental constituents present. The technique is particularly efficient for studying loftier-Z elements in low-Z matrices. Since XRF meets a number of the requirements of the 'ideal method' for non-destructive assay of cultural heritage materials [8], analysis of objects of artistic and/or archaeological value with conventional XRF is fairly mutual. Several textbooks cover the fundamental and methodological aspects of the method and its many variants [ix]. XRF on cultural heritage and archaeological materials and artefacts is mainly used in reflection geometry. MA-XRF has recently been implemented to determine the distribution of pigments on easel paintings over large areas. Annotation that this method is not depth-selective and so that projected pigment distributions (nowadays at and/or below the visible paint surface) are obtained. In 2008, Dik et al. used a 38.5-keV Ten-ray beam of 0.5 mm in diameter to record XRF spectra from a 17.5×17.five cm2 area of the painting Patch of Grass by Vincent van Gogh; this was done to visualize the portrait below the visible mural [10]. While most of the elemental maps recorded from Patch of Grass reflect the individual paint strokes that plant the multicolored meadow, reconstruction of the flesh tones of the subconscious head of a woman was possible by combining the Sb (yellowish-orange, Naples Yellow) and Hg (cherry, vermillion) distributions. Following this initial and promising result, the MA-XRF setup at the synchrotron facility was employed to examine paintings by Rembrandt van Rijn [xi], Philipp Otto Runge [12] and several other paintings by Van Gogh [13, 14]. A self-portrait by Australian artist Sir Arthur Streeton (1867–1943) that he covered at a later phase with heavy brushstrokes of pb white pigment has been re-visualized by Howard et al. [15] at the Australian Synchrotron radiation facility, making use of a multiple element detector system offering very fast scanning possibilities. 1 of the developments permitting the employ of the MA-XRF method on a larger calibration has been the construction of mobile (i.e., 10-ray tube based) MA-XRF scanners [14, 16–18] that tin exist used inside the museum or pic gallery where the works of fine art ordinarily are displayed or conserved. Alfeld et al. [18] has designed and optimized such a device, reporting element sensitivities that are of same club of magnitude every bit those of the SR-based setup employed to scan Patch of Grass. Since the SR setup employed monochromatic 38.5 keV radiations while the mobile device employs the complete bremsstrahlung spectrum of Mo- or Rh-anode tubes bombarded with 45–l kV electrons, the SR setup shows higher One thousandα-sensitivities for heavy elements (such every bit Ag, Cd, Sn, Sb) while the reverse is true for elements with atomic number below twoscore (Zr). The availability of the mobile MA-XRF scanner permitted the investigation of a number of paintings 'in their native environment' that normally would have been nearly impossible to transport to synchrotron facilities, either considering they were too big, also frail, too valuable or all of these. A MA-XRF scanner is commercially available from Bruker Nano GmbH (Berlin, Federal republic of germany) under the proper name 'M6 Jetstream' [19]. Using this device, several paintings past 15thursday, 17th, 19thursday and twentyth C. artists such as Memling, Rembrandt, Hals, Van Gogh, Magritte, Mondriaan and Pollock could exist examined successfully in various museums in Holland, Belgium and the Usa.

As an example, Figure 2 shows results obtained past scanning the left and right panels of the Moreel tryptich, a 15thursday C altarpiece painted past Hans Memling. It was painted for the highly respected Moreel family of Bruges, whose members had lived in the city since the 13thursday century. William Moreel, Seigneur of Oost Cleyhem, was one of the wealthiest and nigh politically active men in Bruges. He served equally burgomaster of the city in 1478 and as treasurer in 1489. William Moreel and his 2d wife Barbara had eighteen children. Long earlier their death effectually 1500, they ordered the alterpiece shown in Figure 2A for their funerary chapel in the Church of St. Jacques in Bruges, founded in 1484. The lower frame of the wings and the center console bear the same date. On the interior wings, the Moreel family is painted as kneeling devotees; the parents are represented with 16 of their children – the other two presumably were born after 1484. On the left, William Moreel is shown with his v sons behind him and flanked by his name patron saint, William of Acquitaine. On the right panel, Mrs. Moreel and her daughters kneel next to her patron saint St. Barbara. Of the 11 daughters depicted, the oldest wears the habit of a Dominican nun.

Effigy two
figure 2

The Moreel Triptych, 1485, H. Memling (Groeninge Museum, Bruges, Belgium). (A) Photograph; (B) the M6 MA-XRF scanning in front of the correct console; (C-Eastward) MA-XRF images of part of the left panel, showing Mrs. Moreel and her daughters (ca 60x40 cm2); (F) close-upwards of the right panel, showing W. Moreel and his sons (ca 40x40 cm2); (K-H) corresponding MA-XRF images; (I) scheme clarifying the shift of the position of the eldest son; step size: one mm in both directions; dwell time: 0.5 s/pixel.

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Since the X-ray radiographs of the side panels, recorded several decades ago, advise that changes were made to the representation and position of the minor characters in both wings, MA-XRF was used to vizualise whatever pentimenti in the tryptich to allow for a ameliorate agreement of its development under the paw of Memling. Some of the MA-XRF results obtained with the M6 scanner (see Figure 2B) are shown in Figure 2C-F. Normally, the MA-XRF Pb-Lα distribution (Figure 2C) resembles the XRR image but shows the distribution of lead white (and other lead containing pigments, if whatsoever) in a more clear manner. When because the copper distribution (green, Figure 2E), nosotros observe that in the original version of the right panel, only 4 daughters were depicted against a landscaped background, painted with ane of more Cu-containing dark-green pigments. Much more than of the hill/backyard to the correct of Mrs. Moreel was originally visible; in the landscape, positions were left open for her portrait and that of her (commencement) four daughters. The faces of the boosted 7 daughters were painted on top of the verdant background in a afterward phase. The mercury map (crimson, Figure 2d) shows that initially, Mrs. Moreel's hat was less elongated. Finally, in the atomic number 82 distribution, it tin be seen (grey/white, Effigy 2C) that she and her oldest girl originally wore more revealing dresses, equally is nonetheless the case for the second girl (to the right of the nun). In left console of the Moreel tryptich (Figure 2F) changes were made to the positions of the male children backside William Moreel: an additional portrait (of his quaternary son) was inserted betwixt that of the two boys already in the groundwork while the eldest son was moved closer to his father (Effigy 2I). The latter changes are particularly visible in the Lead and Sr images (Figure 2G and H). From the to a higher place we tin can conclude that the process of creating this altar piece went through at to the lowest degree two major stages, a outset in which the relatively young Moreel family unit was represented in a balanced manner against a green landscape. In order to include in a second phase all the younger children, some of the balance of the representation was sacrified by the artist. This too allowed a number of minor aspects (such as the dress of the eldest girl) of the painting to be brought up-to-engagement. The above shows how the use of MA-XRF opens up the possibility for art-historians and conservators alike to explore in greater depth and with unprecedented detail the creative process that led to paintings of this blazon past Hans Memling and other artists.

Macroscopic XRD (MA-XRD)

A fundamental limitation of MA-XRF stems from the fact that XRF but provides information that allows distinguishing betwixt different chemic elements, only does not allow making the more subtle difference between, e.g. 2 different atomic number 82-oxide pigments such equally minium (Pb3O4) and litharge (PbO). By performing macroscopic scans while signals other than X-ray fluorescence emission are recorded, this limitation may be circumvented. The first instance of XRD-based imaging of works of art was reported past Dooryhee et al. [xx], making apply of synchrotron radiation in reflection mode. De Nolf et al. [21] have employed very high energy radiation (86 keV) for scanning transmission X-ray pulverisation diffraction mapping of the distribution of pigments in mockups and original Netherlandish paintings. They concluded that highly specific identification and visualization of most pigments, even those containing the same feature metals (e.g., Fe in hematite and goethite) is possible, provided the angular resolution of the setup is sufficiently loftier. An additional advantage is that at loftier energy, absorption of the primary and of the diffracted beams is nearly negligible. Recently, this MA-XRD capability was successfully transferred to the laboratory by making utilize of a combination of a compact mirror-focussed X-ray source (Ag-IμS, Incoatec GmbH, Hamburg, D), emitting monochromatic Ag-Chiliadα radiations of 22 keV and a single photon counting diffraction camera (Pilatus 200 Yard, Dectris GmbH, Switzerland) [Vanmeert F, Janssens G, De Nolf W, Legrand S, Van der Snickt G, Dik J: Scanning Macroscopic X-ray powder diffraction imaging (MA-XRPD): transfer from the synchrotron to the laboratory, submitted] (come across Figure 3A). As an case of the imaging possibilities of this newly constructed device, Figure 3B shows the distribution of the Pb-containing pigments hydrocerussite [2PbCO3 · Pb(OH)ii] and Naples' yellow [PbiiSb2O7] in a re-create of a bizarre painting entitled The Education of Mary (original painted 1630–1635 by P.P. Rubens). The images accept a spatial resolution of 0.5 mm. Both the MA-XRF Hg distribution and the MA-XRD Cinnabar (α-HgS) image show that this red paint was merely used very sparingly to pigment Mary's lips and to create a faint blush on her cheeks. The use of lead antimonate (constitute in nature as the mineral bindheimite) to render the halo around Mary's head is consistent with a mid-xviiith to tardily-19thursday century appointment of origin of this smaller copy of the original Rubens painting. The higher specificity of XRD allows readily distinguishing and identifying the pigments in a straight and positive manner while this is merely possible in an indirect way on the footing of the corresponding MA-XRF images (Effigy 3C). The higher free energy of the diffracted X-rays equally opposed to that of the characteristic XRF radiation also allows to probe deeper for representations that may be hidden below the surface.

Figure 3
figure 3

Paradigm MA-XRD setup at the Academy of Antwerp. A) Photograph showing the micro-focus X-ray tube source (Southward), equipped with a double curved mirror G and detector for recording manual XRD (Dane) and XRF (D2) information: these components are positioned close to a painting mounted on a motorized stage; B) MA-XRD and C) MA-XRF images obtained by scanning a item of the painting shown in D): scan size: 78×75 mm2, image step size: 0.v mm in both directions, Dwell time: 2 s/pixel. Adjusted from [Vanmeert F, Janssens K, De Nolf W, Legrand Southward, Van der Snickt Thousand, Dik J: Scanning Macroscopic X-ray powder diffraction imaging (MA-XRPD): transfer from the synchrotron to the laboratory, submitted].

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Computed 10-ray Laminography (CXL)

A limitation shared past MA-XRF, MA-XRD and XRR is the fact that they provide projection images, i.due east., they exercise non reveal information on the distribution of (one or more) pigments in a single layer merely rather in a series of superimposed paint layers. To split out the contributions from the different pigment layers, a tomographic data drove approach [22, 23] or, in the example of (MA-)XRF, a confocal detection geometry [24, 25] may be employed. Computed X-ray tomography (CXT) involves the recording of a series of two-dimensional radiographies under many different orientations of the sample relative to the X-ray source-detector axis; the principle is illustrated in Effigy 1D for the case of cone-axle illumination [26]. For CXT, the shape of artefacts being examined should be such that under all observation/irradiation angles, the total path length the transmitted radiations must follow through the absorbing material does non vary more than than, say, an order of magnitude. In case of paintings and other objects that are much more extended along two dimensions (length, width) than along the third (depth), conventional CXT therefore cannot exist employed; during the rotating motion of the painting relative to the source-detector axis, in a item orientation, its entire length or width would be in the radiations path, blocking all transmission. A way of circumventing this trouble is to employ the related method of computed X-ray laminography (CXL), originally developed for inspection of complex, flat, multilayered objects such as printed circuit boards [27–29]. CXL makes use of a rotation around an centrality that is non perpendicular to the radiations source/detector axis only that is tilted relative to it (Effigy 1E). By performing experiments on mock-up paintings, Krug et al. [30] demonstrated that voids and hidden compartments inside paintings can exist inspected in a non-destructive manner via this technique. Figure four illustrates how CXL allows high-resolution imaging of the local sub-surface microstructure in paintings in a non-invasive and non-destructive way. Results of feasibility tests on a painting mockup (consisting of an oak panel, a chalk basis superimposed with vermilion and lead white pigment layers, meet Figure 4AB) show that achieving lateral and depth resolutions of up to a few micrometres is possible. Based on assimilation and stage contrast, the method tin provide high-resolution 3D maps of the paint stratigraphy (Figure 4C), including the wooden substrate, and visualize modest features, such as pigment particles, voids, cracks, cells in the wood support etc. (Figure 4D). In resulting virtual cross sections (Figure 4EF) the local density and chemical limerick of the different paint layers are visible due to increased attenuation of X-rays past elements of college diminutive number. A typical CXL scan consists of 1000 to 3600 radiographs, each with a size of 2048 by 2048 pixels and a pixel size of 0.28 to 1.4 micrometers. While each prototype is only exposed for 0.1 southward, the speed with which the painting can exist rotated is limited; thus, per data ready of the order of 1 h of total drove time was required.

Figure 4
figure 4

Mockup painting used for evaluating CXL. A: Visual photograph; B: detail of A, showing a stroke of atomic number 82 white covering the red surface of the painting; C: 3D rendering of CXL data, showing the reconstructed volume; D: series of virtual laminographic sections a-d, parallel to the wood/paint surface at the depth indicated in E: (a) superficial lead white, (b) pigment particles in the ruby pigment; (c) spherical voids in the basis layer; (d) cells in the wood back up; console (e) shows the corresponding radiography of the volume shown in C; East, F: virtual cross sections obtained by applying a maximum (Eastward) or a minimum (F) filter of 750 images, oriented perpendicular to the axis of the forest cells. Adjusted from [32].

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Thus, this method is well adapted to report the temporal evolution of the stratigraphy in examination specimens and offers an alternative to destructive sampling of original works of fine art. In a style very like to that used with high magnification optical microscopes, the laminographic technique allows to obtain detailed morphological images at whatsoever depth in an (optically opaque) paint layer stack [31, 32]. CXL thus presents a not-invasive and non-subversive alternative to sampling and polishing where such fine structure needs to be preserved. The technique has a high potential in studying conservation problems on test specimens or original works of art, where the microstructure of carrier, ground or paint is of importance but sample removal is to be avoided.

Methods based on infrared radiation

IRR was introduced in the 1960'south by J.R.J. van Asperen de Boer, using PbS-based Vidicon tubes as recording devices and has seen of import technological improvements over the by years [33–35]. An infra-red (IR) source of around i.ii μm is used to illuminate objects; this radiation will readily penetrate through a number of commonly occurring paint constituents such as atomic number 82 white, while becoming strongly captivated by others such equally carbon blackness. The radiation (0.9-1.vii μm) reflected by the illuminated objects is now typically recorded with a InGaAs (or equivalent) camera, assuasive for rapid acquisition of high definition images with a resolution up to 0.1 mm, covering areas of typically 0.5 × 0.five thousand2. Over the past decades, IRR has go a routine class of analysis in many painting collections, almost exclusively for the study of carbon-based underdrawings in paintings from the 16th century and earlier. In such artefacts, IR-absorbing carbon black tracery is often applied on IR-reflective chalk or gypsum grounds, resulting in a potent contrast in the reflectograms. Exam of 17th or 18th century paintings with IRR tends to exist less rewarding considering these later paintings oftentimes were set up in sketchy touches of earth pigments, or underdrawn in white chalk. These pigments are very poor infrared absorbers. Furthermore, many 17thursday century paintings were painted on colored grounds that poorly reflect IR. Another limiting cistron is that many of the paints contain infrared absorbing pigments, such as carbon black, that get in difficult to distinguish the underlying drawings from the covering paint layers. Adjacent to the acquisition of full field reflection images by IR-sensitive cameras, scanning may also be employed. Already in 2006, Saunders et al. [35] devised a camera system that acquired 25 Mpixel IRRs with a lateral resolution of 100 μm; it incorporated a small-scale (320 × 256 pixel) moving InGaAs sensor of which the images were stitched together. This lightweight camera, suitable for in-situ measurements, is commercially available (OSIRIS camera) and is sensitive in the 0.ix-1.7 μm wavelength range. The camera itself does non offering whatsoever ways of wavelength dispersion or selection, but via assimilation filters the spectral range finer acquired can be adjusted to optimize the vizualisation of underdrawing textile. Daffara et al. have described an advanced scanner that records 14 bands from 0.7 to 2.3 μm and that allows for multispectral imaging of large paintings, achieving a spatial resolution of 0.5 mm [36]. Fast movement of the scanner head in front of the painting allows recording IRR maps of ane grand2 areas within a catamenia of several hours at maximum resolution.

Delaney et al. have more than recently described a novel virtually-infrared (NIR) system that allows for hyperspectral imaging in 342 narrow wavelength bands situated in the ane.0-ii.5 μm (4000–10000 cm-one) range [37–41]. The system incorporates a scan mirror, an imaging lens, a manual grating spectrometer + relay lens and a cryo-cooled (640 × 512 pixel) InSb sensor. The surface area examined is scanned one-dimensionally by rotation of the mirror while the other camera dimension is used for wavelength dispersion. In a number of cases where the results of MA-XRF do non significantly differ from those obtained past XRR, for example in the case where very thick overpainted layers of lead white are present, this system has allowed to obtain contrast-rich imaging information. This complementarity was recently underscored during the examination of a painting past R. Magritte, called Le Portrait (1934, Museum of Mod Art, New York City, USA) past means of a combination of traditional XRR, MA-XRF and NIR-hyperspectral imaging [Van der Snickt 1000, Martins A, Duffy M, McGlinchey C, Coddington J, Delaney JK, Janssens K, Dik J: Multimodal examination of 'Le portrait' past R. Magritte past ways of Ten-ray and Infrared hyperspectral imaging methods reveals an overpainted representation, submitted]. The combined employ of the resulting images allowed art historians of MoMA to identify the piece of work present beneath the surface equally La Pose Enchantée, a painting erroneously believed lost that was made by Magritte in 1927 merely overpainted in 1935.

Also in the mid infrared (MIR) range, a tendency towards hyperspectral imaging and fifty-fifty full spectrum recording at all pixel positions is discernable. Promising results have been recently reported by Rosi et al. [42] using a novel hyperspectral imaging system (Hi90, Bruker Optics), originally developed for the remote identification and mapping of hazardous compounds. It is based on a focal-plane assortment mercury cadmium telluride (FPA-MCT) detector having 256×256 pixels. This device operates in the 900–1300 cm-i (7.7-11.0 μm) spectral range and allows for the parallel recording of series of MIR spectra (with adequate spectral resolution -iv cm-1), corresponding to each pixel of the investigated area. It was successfully used for mapping of both organic and inorganic compounds in a painting by A. Burri. Daffara et al. also have reported on a device operating in the 2000–3000 cm-1 (three.three-5.0 μm) range [43].

In view of these promising results, and in analogy of the MA-XRF and MA-XRD scanners discussed above, Legrand et al. [44, 45] have recently explored the possibilities and limitations of a prototype macroscopic MIR-FTIR scanner, based on the Alpha Bruker FTIR spectrometer. The latter is a compact, calorie-free-weight FTIR spectrometer operating in the 400–7500 cm-1 (1.3-25.0 μm) range, incorporating a globar IR-source and a deuterated triglycine sulphate (DTGS) detector that tin can be fitted with a reflection style accessory. The curved mirrors in the latter produce a roughly circular IR beam of ca ii×2 mm2 with which a single spot on a painting may be interrogated. During the scanning functioning, the entire spectrometer is moved in an XY fashion in front of the painting while series of FTIR spectra are recorded in reflection fashion from many points. Effigy 5 compares results obtained by MA-rFTIR and MA-XRF from a small-scale (8 × viii cm) twentyth century, unvarnished folk-art panel painting of Antillean origin. Information technology is built up of a number of strongly contrasting coloured areas and has a fairly simple stratigraphy, in about cases consisting of but one paint layer applied on a calcite basis. MA-XRF analysis of this painting (meet Figure 5, lower row) reveals the presence of the elements cadmium, selenium and barium in the ruby and orange regions, strongly suggesting that the pigment employed here is cadmium lithopone (CdSe + BaSO4). Cadmium-based pigments have, due to the heavy atomic mass of cadmium, their cardinal bands in the far-IR (FIR) region and therefore cannot be detected with the MIR setup. The map in Figure 5B (1173–1260 cm-one) however, shows that the distribution of the sulphate ion via its symmetric stretching vibration mode (νthree-And soiv 2-) is strongly correlated to the Cd MA-XRF maps of Figure 5F, corroborating the hypothesis near the presence of cadmium lithopone in the orange areas. The MA-XRF-data too show that the principal yellow pigment present in this painting contains the elements lead and chromium; in the FTIR spectra, it is identified by its chromate- (ν4-CrO4 ii- at 888 cm-1) and sulphate- (ν4-SO4 2- at 604 and 630 cm-1) ion bands equally chrome yellow (in its pale PbCr1-xDue southxO4 form), a pigment that is in utilise since the 19th century [46]. Accordingly, the map in Effigy 5C, based on the CrOfour 2- asymmetric stretch (890–950 cm-1) shows a skillful correlation with the chromium XRF prototype (Figure 5G). By means of the rFTIR maps, it was also possible to identify the blueish and green pigments present in this painting in an unambiguous manner as phthalocyanine-based compounds. Since this group of pigments was only discovered in the 1930s, their presence confirms the presumed twentythursday century origin of the painting. The metal-ligand ring at 898 cm-1 suggest that copper is the metal ion in the circuitous, a hypothesis that is confirmed by the MA-XRF copper map of Figure 5H. The phthalocyanine-blueish (PB15) distribution (Effigy 5D) tin be visualized by means of its C-H out-of-aeroplane bending style at 729–740 cm-i. Phthalocyanine green (PG7) is a partially chlorinated version of PB15 and this exchange results in a shift of the C-H out-of-airplane angle mode band of this pigment towards higher wavenumbers, in this example to 747–762 cm-1 (Figure 5E). For confirmation, the copper and chlorine XRF-maps are also shown in Effigy 5H and I. While the MA-XRF copper map resembles the sum distribution of both pigments, the chlorine distribution of Figure 5I only resembles the FTIR map of PG7. It is possible to conclude from the above that the species-specific MA-rFTIR maps permit visualization of the distribution of these highly similar pigments in a straightforward and reliable manner, even though in its current implementation, very long conquering times are required for this. Considering these results, that illustrate the advantages of recording total spectral data at all positions of an examined painting expanse may entail, information technology is expected that hyper- and full spectral imaging of paint surfaces in the IR fingerprint region will open up new and broad perspectives for non-invasive analysis.

Figure five
figure 5

Antillean folk art painting (8×8 cm 2 ), of assumed twenty th Century origin. A) Visual prototype; MA-rFTIR chemical distribution images: B) cadmium lithopone (1173–1260 cm-1), C) chrome yellow (890–950 cm-1), D) phthalocyanine bluish (729–740 cm-1) and Due east) phthalocyanine dark-green (747–762 cm-1); MA-XRF elemental distribution maps of F) cadmium, K) chromium, H) copper and I) chlorine: lighter tones bespeak higher levels of net pseudo absorbance or X-ray fluorescence intensity; J) Photograph of MA-rFTIR device in front of a big canvass, scanned area: 76×76 mmtwo, stride size: ane mm in both directions, dwell time: 8 due south/pixel. Adjusted from [44].

Full size paradigm

It must be mentioned here that the mid-FTIR based methods are severely hampered by the presence of varnish (or other organic comprehend) layers and in practice can but exist employed on paintings that are not varnished or those where the varnish has been temporarily removed. This important limitation is not present with the Ten-ray based imaging methods discussed to a higher place where both primary and secondary (XRF) radiation can easily penetrate any cover layers.

A related and notable evolution of contempo years is the depth selective variant of NIR-based imaging called Optical Coherence Tomography (OCT) [47, 48]. OCT is a betoken scanning system based on the employ of a NIR source coupled to a Michelson interferometer. The source, similar to those used for conventional IRR, illuminates both a reference mirror and the object nether examination. Effective interference occurs when the length of the optical path of the light that is backscattered within the object matches, within the coherence length, the length of the optical path of the radiations reflected by the mirror. The interference measurement therefore enables the decision of the depth at which the reflection took identify within the object. This adds depth-resolution to the infra-red investigation of paintings, allowing mapping of the distribution of specific materials and textile interfaces throughout the paint stratigraphy. The technique proves to be a powerful imaging tool in the written report of thinly painted layers as found in 16th century and earlier paintings [49, fifty]. The technique is particularly valuable for the report of near-surface features, notably translucent layers such every bit glazes and varnish [51].

Conclusions

In this newspaper a cursory overview was presented of recent methodological and instrumental developments regarding the label of painted works of art based on either penetrative X-ray or Infrared radiations. Macroscopic XRF is a variant of the general method of X-ray fluorescence analysis that is well suited to visualize the elemental distribution of key elements, by and large metals, present in areas of effectually 0.5-1 mii or more. This method is not depth-selective then that projected pigment distributions (at and/or below the visible paint surface) are obtained. For depth-selective imaging of the individual layers in a painting, on the other hand 10-ray laminography, a variant of computed 10-ray tomography that is more suitable for exam of flat panels, appears promising. Also past means of October, depth resolved imaging appears possible, albeit in materials that retain a sure transparency. Past ways of infrared radiation, either in the NIR or in the MIR ranges, camera-based or scanning based reflection fashion imaging can exist performed. The data obtained in this way is often complementary to that obtained by means of the X-ray based methods. The combined employ of MA-XRF/XRD scanning with NIR/MIR hyperspectral imaging or MA-rFTIR scanning appears to be a very promising new management for non-invasive imaging of paintings.

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Acknowledgements

The authors admit support from the Hercules fund, Brussels (grant A11/0387), BELSPO (Brussels) through project S2-ART (SD04A) and FWO (Brussels) via grant M.0C12.13. Support was also received from NWO (Den Haag) via the Science4Art plan. Additionally the University of Antwerp Enquiry quango in best-selling for granting a PhD scholarship to S.L. The authors are indebted to the staff of the Groeninge museum for their assist with the MAXRF measurements.

Author information

Affiliations

  1. Department of Chemistry, University of Antwerp, Antwerp, Belgium

    Stijn Legrand, Frederik Vanmeert, Geert Van der Snickt, Matthias Alfeld, Wout De Nolf & Koen Janssens

  2. Photon Science, Deutsches Elektronen Synchrotron (DESY), Hamburg, Deutschland

    Matthias Alfeld

  3. Department of Materials Scientific discipline, Delft University of Technology, Delft, The netherlands

    Joris Dik

Corresponding author

Correspondence to Koen Janssens.

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Competing interests

The authors declare that they have no competing interests.

Authors' contributions

SL and KJ wrote the manuscript which was revised by FVM, GvdS, MA and JD. SL, MA, GvdS and FVM constructed equipment and performed belittling measurements. MA and WDN wrote data processing and reduction software. All authors read and approved the final manuscript.

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Legrand, Due south., Vanmeert, F., Van der Snickt, G. et al. Examination of historical paintings by state-of-the-fine art hyperspectral imaging methods: from scanning infra-red spectroscopy to computed X-ray laminography. herit sci 2, 13 (2014). https://doi.org/ten.1186/2050-7445-2-xiii

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  • DOI : https://doi.org/ten.1186/2050-7445-2-13

Keywords

  • Painting
  • Not-invasive imaging
  • Hyperspectral imaging
  • Full spectral imaging
  • Macroscopic Ten-ray fluoresence
  • Near-infrared
  • Mid-Infrared
  • Computed 10-ray Laminography
  • Optical Coherence Tomography

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