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atw Vol. 65 (2020) | Issue 4 ı April RESEARCH AND INNOVATION 228 | Fig. 5. A landscape painting with a large oak tree, assigned to a 19 th century artist. available with additional options like automated scanning of the surface of the painting and automated recording of the data from the investigated object. Further optimizations are precise, very small irradiation spots in so- called Micro-XRF instruments using collimating X-ray lenses. The advantage is at hand: The area under investigation is much better characterised and the imaging resolution is higher, while the scanning over the whole surface reveals a complete image of the elemental distribution. These X-ray images seem much better achievable than to expend high efforts for neutron activation radiographies, although it should be reminded that low-Z elements are difficult or not at all detectable in XRF because of the attenuation of their characteristic X-rays in the paint layers. Modern scanning Micro-XRF instruments are operated in investigations of important art objects like in the actual analysis prior to the restoration of Rembrandt´s painting “Night Watch” of the Rijksmuseum in Amsterdam [12]. In the following example measured at TÜV NORD – the case of a landscape painting from the 19 th Century – the power of X-ray radiography combined with XRF analysis is demonstrated (Figures 5 and 6). The painting, showing several traces of old damages, had been restored earlier and by this occasion had been relined (this means, a second canvas was glued on the backside). The XRF results from the elements in the paint layers were consistent for the pigments expected like iron (pigment Siena or Umber) and manganese ( pigment Umber). The detection of chromium (pigment Chrome Green from the beginning of the 19 th century, or the improved version of hydrated chromium oxide, which became known as Viridian Green during the 1860’s) allows to date the painting into the 19 th century. Before the introduction of these chromium pigments, green colors in paintings were mostly based on copper pigments like Azurite, Malachite or Verdigris, however, the element copper was not detected in the XRF spectra of this painting. It is worth noting, that similar XRF pigment analysis is well suited to detect fake paintings if the forger used modern pigments like Titanium White (available since ca. 1920) or various Cadmium pigments (not available before the very late 19 th Century), as it was discovered in a number of cases of art forgery. The most prominent case might be the forger Wolfgang Beltracci who specialized on fakes of Expressionism painters from around 1900 and probably sold hundreds of fakes into the art market. In one of his forged paintings of the famous painter Campendonk, the pigment Titanium White was measured in a technical investigation with XRF, which proved that the painting was a fake and thereby uncovered one of the largest cases of art forgery. In the landscape painting of Figure 5, surprisingly a high amount of mercury (an element, which is umambiguously assigned to the red pigment Cinnabar) was detected. The idea, that Cinnabar could have been used in one of the paint layers below the visible surface was at hand. By means of the digital X-ray radiography of the painting, it was discovered that the artist had used an older canvas with a mythological or religious figural scenery for his work (see Figure 6) and that the overpainted and hidden composition is well consistent with the use of Cinnabar pigment, which often occurs in (red) clothes of the figures. As it was stated above, X-ray radiography is not limited to paintings and this is shown in the following case [13]. Near the village of Schortens in Friesland, a part of North-West- Germany, a large cemetery field from the early middle-ages had been discovered in the 1970’s. The archaeological findings, attributed to a period from the 5 th to the 12 th Century, consisted of cinerary urns including a variety of corroded metallic artefacts and are conserved in museums today (Landesmuseum Natur und Mensch Oldenburg and Landesmuseum Hannover). However, most of the metallic artefacts were never investigated, although the presumed keys, buckles, knives or even swords given to the graves of the dead would reveal additional knowledge about the life in these early populations of North- West- Germany, before and during the Christianisation phase. The effort to restore such objects is very high and restoration is under the risk of damaging the objects during the delicate procedures involved. Hence, a non-destructive imaging by X-rays was chosen in order to reveal first insight into the corroded pieces and prepare a decision basis for later restoring. As an example for the results, Figure 7 shows the amazing pictures of a so-called needle tubule, which was an important part of women´s equipment in the early middle ages, | Fig. 6. X-ray radiography (30 kV, 4 mAs, © TÜV NORD EnSys) of the painting from Fig.5, showing the older and overpainted composition as well as structural information. Research and Innovation Radiation in Art and Cultural Heritage ı Frank Meissner and Andrea Denker
atw Vol. 65 (2020) | Issue 4 ı April [9] Bildanalyse in der Kunst A. Beck in: Forschung mit Röntgenstrahlen F.H.W. Heuck, E. Macherauch (Eds.) Springer, Berlin, Heidelberg (1995) ISBN 978-3-642-78842-0 [10] Die Bedeutung der Gemäldedurchleuchtung mit Röntgenstrahlen für die Kunstgeschichte C. Wolters in: Veröffentlichungen zur Kunstgeschichte Bd. 3 Prestel-Verlag, Frankfurt (1938) [11] https://www.nga.gov/features/bazille-hiddencompositions.html Webpage of the National Gallery of Art, Washington, date: Feb.17 th , 2020 [12] https://www.rijksmuseum.nl/en/the-first-scan Webpage of the Rijksmuseum, Amsterdam, date: Feb.14 th , 2020 [13] https://www.archaeologie-online.de/nachrichten/ kulturgut-unter-dem-roentgengeraet-4419/ Authors Dr. Frank Meissner TÜV NORD EnSys Große Bahnstraße 31 22525 Hamburg Prof. Dr. Andrea Denker Helmholtz-Zentrum Berlin Hahn-Meitner-Platz 1 14109 Berlin RESEARCH AND INNOVATION 229 | Fig. 7. The digital X-ray radiography (70 kV, 5 mAs, ©TÜV NORD EnSys) of a corroded tubule (above), found in a cinerary urn shows that the tubule contains a needle. It was given to the buried ashes of its owner, most likely a woman from the 5 th to 7 th century (Landesmuseum Natur und Mensch, Oldenburg) usually tied to their belts. These tubules contained a stitching needle which was thus readily available for sewing and repair work. By means of digital X-ray radiography, the needle inside the tubule and also some remnants of a thread are clearly identified, see Figure 7. Archeologists are gaining information by these X-ray images which would otherwise not be available. 3 Summary Nuclear methods and X-rays applications are not limited to industry or medicine, but have found entrance into the investigation of art and cultural heritage objects. Worldwide, a number of institutes work on projects or even support devoted working groups in order to use reactor neutrons, accelerator particle beams and X-rays from synchrotrons or X-ray tubes in the research of paintings and historical artefacts. In the case of X-rays, mobile equipment for radiography and XRF analysis has large advantages for valuable or non-transportable objects since they can be used on-site. Neutrons from reactor facilities allow complementary techniques, which reveal striking additional information about the objects, provided the objects are transported to the reactor site. Some established methods in art and cultural heritage were described to shine on these interesting radiation applications, which are well suited to answer questions deriving from art history, archeology, conservators and many other professionals in this field. Literature [1] Synchrotron Radiation and Neutrons in Art and Archeology, 9 th International Conference, 22-25 February 2021 in Los Angeles [2] Why use neutrons? Schillinger, B. Restaur. Archäol. 8 (2015): 1–7 [3] Neutron Imaging in Cultural Heritage Research at the FRM II Reactor of the Heinz Maier-Leibnitz Center Schillinger, B.; Beaudet, A.; Fedrigo, A.; Grazzi, F.; Kullmer, O.; Laaß, M.; Makowska, M.; Werneburg, I.; Zanolli, C. J. Imaging 4 (2018): 22. [4] Neutron activation autoradiography and scanning macro-XRF of Rembrandt van Rijn’s Susanna and the Elders (Gemäldegalerie Berlin): a comparison of two methods for imaging of historical paintings with elemental contrast M. Alfeld, C. Laurenze-Landsberg, A. Denker, K. Janssens, P. Noble Appl. Phys. A (2015) 119:795-805 [5] Scanning macro-x-ray fluorescence analysis and Neutron Activation Auto Radiography: Complementary imaging methods for the investigation of historical paintings M. Alfeld, C. Laurenze-Landsberg, A. Denker, K. Janssens, P. Noble Berliner Beiträge zur Archäometrie, Kunsttechnologie und Konservierungswissenschaft, Band 23 (2015): 9-14 [6] The Examination of Paintings by Rembrandt with Neutron Autoradiography and a comparison of Neutron Autoradiography with Scanning Macro-XRF C. Laurenze-Landsberg Restaurierung und Archäologie 8 (2015), 99-114 [7] Neutron Autoradiography of Paintings, ‘The Hermit’ by an unknown artist and ‘Armida abducts the sleeping Rinaldo’ (c.~1637) by Nicolas Poussin B. Schröder-Smeibidl, C. Laurenze-Landsberg, C. Schmidt, L. A. Mertens in: Non-destructive testing and analysis of museum objects A. Denker, A. Adriaens, M. Dowsett, A. Giumlia-Mair (Editors) Fraunhofer IRB Verlag, ISBN 978-3-8167-7178-4 [8] BENSC neutrons for “Cultural Heritage” Research: Neutron Autoradiography of Paintings C. Laurenze-Landsberg, L.A. Mertens, C. Schmidt, B. Schröder-Smeibidl Notiziario Neutroni e Luce di Sincrotrone 11 no. 1 (2006): 24-27 Research and Innovation Radiation in Art and Cultural Heritage ı Frank Meissner and Andrea Denker
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