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Author Janssens, K.; Alfeld, M.; Van der Snickt, G.; De Nolf, W.; Vanmeert, F.; Monico, L.; Legrand, S.; Dik, J.; Cotte, M.; Falkenberg, G.; van der Loeff, L.; Leeuwestein, M.; Hendriks, E.
Title Examination of Vincent van Gogh's paintings and pigments by means of state-of-the-art analytical methods Type H2 Book chapter
Year 2014 Publication Abbreviated Journal
Volume Issue Pages 373-403 T2 - Science and art : the painted surface
Keywords H2 Book chapter; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Abstract Recent studies in which X-ray beams of macroscopic to (sub) microscopic dimensions were used for non-destructive analysis and characterization of pigments, paint micro samples and/or entire paintings by Vincent van Gogh are concisely reviewed. The overview presented encompasses the use of laboratory and synchrotron radiation-based instrumentation and deals with the use of several variants of X-ray fluorescence (XRF) as a method of elemental analysis and imaging as well as with the combined use of X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS). Microscopic and macroscopic XRF are variants of the method that are well suited to visualize the elemental distribution of key elements, mostly metals, present in paint multi layers, either on the length scale from 1–100 μm inside micro samples taken from paintings or on the 1–100 cm length scale when the (subsurface) distribution of specific pigments in entire paintings is concerned. In the context of the characterization of van Gogh's pigments subject to natural degradation, the use of methods limited to elemental analysis or imaging usually is not sufficient to elucidate the chemical transformations that have taken place. However, at synchrotron facilities, combinations of μ-XRF with related methods such as μ-XAS and μ-XRD have proven themselves to be very suitable for such studies. Their use is often combined with microscopic Fourier transform infra-red (μ-FTIR) spectroscopy since this method delivers complementary information at more or less the same length scale as the X-ray microprobe techniques. Also in the context of macroscopic imaging of works of art, the complementary use of X-ray based and infra-red based imaging appears very promising; some recent developments are discussed.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Editor
Language Wos Publication Date 2020-02-24
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN ISBN 978-1-84973-818-7 Additional Links UA library record
Impact Factor Times cited Open Access
Notes Approved no
Call Number UA @ admin @ c:irua:190782 Serial 7943
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Author Christiansen, T.; Cotte, M.; de Nolf, W.; Mouro, E.; Reyes-Herrera, J.; De Meyer, S.; Vanmeert, F.; Salvado, N.; Gonzalez, V.; Lindelof, P.E.; Mortensen, K.; Ryholt, K.; Janssens, K.; Larsen, S.
Title Insights into the composition of ancient Egyptian red and black inks on papyri achieved by synchrotron-based microanalyses Type A1 Journal article
Year 2020 Publication Proceedings Of The National Academy Of Sciences Of The United States Of America Abbreviated Journal P Natl Acad Sci Usa
Volume 117 Issue 45 Pages 27825-27835
Keywords A1 Journal article; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Abstract A hitherto unknown composition is highlighted in the red and black inks preserved on ancient Egyptian papyri from the Roman period (circa 100 to 200 CE). Synchrotron-based macro-X-ray fluo-rescence (XRF) mapping brings to light the presence of iron (Fe) and lead (Pb) compounds in the majority of the red inks inscribed on 12 papyrus fragments from the Tebtunis temple library. The iron-based compounds in the inks can be assigned to ocher, notably due to the colocalization of Fe with aluminum, and the detection of hematite (Fe2O3) by micro-X-ray diffraction. Using the same techniques together with micro-Fourier transform infrared spectroscopy, Pb is shown to be associated with fatty acid phosphate, sulfate, chloride, and carboxylate ions. Moreover, microXRF maps reveal a peculiar distribution and colocalization of Pb, phosphorus (P), and sulfur (S), which are present at the micrometric scale resembling diffused “coffee rings” surrounding the ocher particles imbedded in the red letters, and at the submicrometric scale concentrated in the papyrus cell walls. A similar Pb, P, and S composition was found in three black inks, suggesting that the same lead components were employed in the manufacture of carbon-based inks. Bearing in mind that pigments such as red lead (Pb3O4) and lead white (hydrocerussite [Pb-3(CO3)(2)(OH)(2)] and/or cerussite [PbCO3]) were not detected, the results presented here suggest that the lead compound in the ink was used as a drier rather than as a pigment. Accordingly, the study calls for a reassessment of the composition of lead-based components in ancient Mediterranean pigments.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Editor
Language Wos 000590753400016 Publication Date 2020-10-27
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0027-8424; 1091-6490 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 11.1 Times cited Open Access
Notes Approved Most recent IF: 11.1; 2020 IF: 9.661
Call Number UA @ admin @ c:irua:174323 Serial 8107
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Author Monico, L.; d'Acapito, F.; Cotte, M.; Janssens, K.; Romani, A.; Ricci, G.; Miliani, C.; Cartechini, L.
Title Total electron yield (TEY) detection mode Cr K-edge XANES spectroscopy as a direct method to probe the composition of the surface of darkened chrome yellow (PbCr1-xSxO4) and potassium chromate paints Type A1 Journal article
Year 2023 Publication Nuclear instruments and methods in physics research: B: beam interactions with materials and atoms Abbreviated Journal
Volume 539 Issue Pages 141-147
Keywords A1 Journal article; Engineering sciences. Technology; Antwerp X-ray Imaging and Spectroscopy (AXIS)
Abstract The darkening of chromate-pigments, including chrome yellows (PbCr1-xSxO4), is a surface phenomenon affecting late 19th-early 20th c. paintings, such as those by Van Gogh. Exploring analytical strategies that contribute to a deep understanding of darkening is therefore significant for the long-term conservation of unique masterpieces. Here, we examined the capabilities of Cr K-edge XANES spectroscopy collected at the same time in X-ray fluorescence yield (XFY) and total electron yield (TEY) detection modes to selectively study the surface composition of darkened oil paint mock-ups composed of chrome yellow (PbCr0.2S0.8O4) or potassium chromate. By discussing advantages and drawbacks in using XFY/TEY modes in relation to XFY & mu;-XANES analysis from sectioned samples, we aim at assessing if TEY-XANES spectroscopy: (i) is a selective surface method to determine the abundance of different Cr-species from paint fragments; (ii) can contribute to optimize the analytical strategy by limiting time consuming sample preparation procedures; (iii) can decrease the probability of radiation damage.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Editor
Language Wos 001041485400001 Publication Date 2023-04-10
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0168-583x ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 1.3 Times cited Open Access OpenAccess
Notes Approved Most recent IF: 1.3; 2023 IF: 1.109
Call Number UA @ admin @ c:irua:198427 Serial 8944
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Author Mayda, S.; Monico, L.; Krishnan, D.; De Meyer, S.; Cotte, M.; Garrevoet, J.; Falkenberg, G.; Sandu, I.C.A.; Partoens, B.; Lamoen, D.; Romani, A.; Miliani, C.; Verbeeck, J.; Janssens, K.
Title A combined experimental and computational approach to understanding CdS pigment oxidation in a renowned early 20th century painting Type A1 Journal article
Year 2023 Publication Chemistry of materials Abbreviated Journal
Volume 35 Issue 24 Pages 10403-10415
Keywords A1 Journal article; Electron microscopy for materials research (EMAT); Condensed Matter Theory (CMT); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Abstract Cadmium sulfide (CdS)-based yellow pigments have been used in a number of early 20th century artworks, including The Scream series painted by Edvard Munch. Some of these unique paintings are threatened by the discoloration of these CdS-based yellow oil paints because of the oxidation of the original sulfides to sulfates. The experimental data obtained here prove that moisture and cadmium chloride compounds play a key role in promoting such oxidation. To clarify how these two factors effectively prompt the process, we studied the band alignment between CdS, CdCl2, and Cd-(OH)Cl as well as the radicals center dot OH and H3O center dot by density functional theory (DFT) methods. Our results show that a stack of several layers of Cd-(OH)Cl creates a pocket of positive holes at the Cl-terminated surface and a pocket of electrons at the OH-terminated surface by leading in a difference in ionization energy at both surfaces. The resulting band alignment indicates that Cd-(OH)Cl can indeed play the role of an oxidative catalyst for CdS in a moist environment, thus providing an explanation for the experimental evidence.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Editor
Language Wos 001133000900001 Publication Date 2023-12-08
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0897-4756; 1520-5002 ISBN Additional Links UA library record; WoS full record
Impact Factor 8.6 Times cited Open Access
Notes The experimental research on the cadmium yellow powders/paint mock-ups and The Scream (ca. 1910) was financially supported by the European Union, research projects IPERION-CH (H2020-INFRAIA-2014-2015, GA no. 654028) and IPERION-HS (H2020-INFRAIA-2019-1, GA no. 871034) and the project AMIS within the program Dipartimenti di Eccellenza 2018-2022 (funded by MUR and the University of Perugia). For the beamtime grants received, the authors thank the ESRF-ID21 beamline (experiments HG64 and HG95), the DESY-P06 beamline, a member of the Helmholtz Association HGF (experiments I-20130221 EC and I-20160126 EC), and the project CALIPSOplus under the GA no. 730872 from the E.U. Framework Programme for Research and Innovation Horizon 2020. All of the staff of the MUNCH Museum (Conservation Department) is acknowledged for their collaboration. The computational resources and services used in this work were provided by the VSC (Flemish Supercomputer Center) and the HPC infrastructure of the University of Antwerp (CalcUA), both funded by the FWO – Vlaanderen and the Flemish Government, Department EWI. Approved Most recent IF: 8.6; 2023 IF: 9.466
Call Number UA @ admin @ c:irua:202836 Serial 8999
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Author Monico, L.; Rosi, F.; Vivani, R.; Cartechini, L.; Janssens, K.; Gauquelin, N.; Chezganov, D.; Verbeeck, J.; Cotte, M.; D'Acapito, F.; Barni, L.; Grazia, C.; Buemi, L.P.; Andral, J.-L.; Miliani, C.; Romani, A.
Title Deeper insights into the photoluminescence properties and (photo)chemical reactivity of cadmium red (CdS1-xSex) paints in renowned twentieth century paintings by state-of-the-art investigations at multiple length scales Type A1 Journal article
Year 2022 Publication The European Physical Journal Plus Abbreviated Journal Eur Phys J Plus
Volume 137 Issue 3 Pages 311
Keywords A1 Journal article; Electron microscopy for materials research (EMAT); Antwerp X-ray Imaging and Spectroscopy (AXIS)
Abstract Cadmium red is the name used for denoting a class of twentieth century artists' pigments described by the general formula CdS1-xSex. For their vibrant hues and excellent covering power, a number of renowned modern and contemporary painters, including Jackson Pollock, often used cadmium reds. As direct band gap semiconductors, CdS1-xSex compounds undergo direct radiative recombination (with emissions from the green to orange region) and radiative deactivation from intragap trapping states due to crystal defects, which give rise to two peculiar red-NIR emissions, known as deep level emissions (DLEs). The positions of the DLEs mainly depend on the Se content of CdS1-xSex; thus, photoluminescence and diffuse reflectance vis-NIR spectroscopy have been profitably used for the non-invasive identification of different cadmium red varieties in artworks over the last decade. Systematic knowledge is however currently lacking on what are the parameters related to intrinsic crystal defects of CdS1-xSex and environmental factors influencing the spectral properties of DLEs as well as on the overall (photo)chemical reactivity of cadmium reds in paint matrixes. Here, we present the application of a novel multi-length scale and multi-method approach to deepen insights into the photoluminescence properties and (photo)chemical reactivity of cadmium reds in oil paintings by combining both well established and new non-invasive/non-destructive analytical techniques, including macro-scale vis-NIR and vibrational spectroscopies and micro-/nano-scale advanced electron microscopy mapping and X-ray methods employing synchrotron radiation and conventional sources. Macro-scale vis-NIR spectroscopy data obtained from the in situ non-invasive analysis of nine masterpieces by Gerardo Dottori, Jackson Pollock and Nicolas de Stael allowed classifying the CdS1-xSex-paints in three groups, according to the relative intensity of the two DLE bands. These outcomes, combined with results from micro-/nano-scale electron microscopy mapping and X-ray analysis of a set of CdS1-xSex powders and artificially aged paint mock-ups, indicated that the relative intensity of DLEs is not affected by the morphology, microstructure and local atomic environment of the pigment particles but it is influenced by the presence of moisture. Furthermore, the extensive study of artificially aged oil paint mock-ups permitted us to provide first evidence of the tendency of cadmium reds toward photo-degradation and to establish that the conversion of CdS1-xSex to CdSO4 and/or oxalates is triggered by the oil binding medium and moisture level and depends on the Se content. Based on these findings, we could interpret the localized presence of CdSO4 and cadmium oxalate as alteration products of the original cadmium red paints in two paintings by Pollock.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Editor
Language Wos 000765807600002 Publication Date 0000-00-00
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 2190-5444 ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 3.4 Times cited 3 Open Access OpenAccess
Notes g The research was financially supported by the EU FP7 and Horizon 2020 Projects CHARISMA (FP7-INFRASTRUCTURES, GA No. 228330), IPERION-CH (H2020-INFRAIA-2014-2015, GA No. 654028), IPERION-HS (H2020-INFRAIA-2019-1, GA No. 871034) and ESTEEM3 (Research and innovation programme, GA No. 823717) and the Italian project AMIS (Dipartimenti di Eccellenza 2018–2022, funded by MIUR and Perugia University). For the beamtime grants received, we thank ESRF-ID21 (Experiment No. HG156 and in-house beamtimes) and the CERIC-ERIC Research Infrastructure for the investigations at ESRF-BM08 (LISA) beamline (Proposal Id: 20207042). D.C. acknowledges TOP/BOF funding of the University of Antwerp.; esteem3reported; esteem3TA Approved Most recent IF: 3.4
Call Number UA @ admin @ c:irua:187375 Serial 7060
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Author da Pieve, F.; Hogan, C.; Lamoen, D.; Verbeeck, J.; Vanmeert, F.; Radepont, M.; Cotte, M.; Janssens, K.; Gonze, X.; Van Tendeloo, G.
Title Casting light on the darkening of colors in historical paintings Type A1 Journal article
Year 2013 Publication Physical review letters Abbreviated Journal Phys Rev Lett
Volume 111 Issue 20 Pages 208302-208305
Keywords A1 Journal article; Electron microscopy for materials research (EMAT); AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Abstract The degradation of colors in historical paintings affects our cultural heritage in both museums and archeological sites. Despite intensive experimental studies, the origin of darkening of one of the most ancient pigments known to humankind, vermilion (α-HgS), remains unexplained. Here, by combining many-body theoretical spectroscopy and high-resolution microscopic x-ray diffraction, we clarify the composition of the damaged paint work and demonstrate possible physicochemical processes, induced by illumination and exposure to humidity and air, that cause photoactivation of the original pigment and the degradation of the secondary minerals. The results suggest a new path for the darkening process which was never considered by previous studies and prompt a critical examination of their findings.
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Corporate Author Thesis
Publisher Place of Publication (up) New York, N.Y. Editor
Language Wos 000327244500003 Publication Date 2013-11-15
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0031-9007;1079-7114; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 8.462 Times cited 30 Open Access
Notes Vortex; ERC FP7; COUNTATOMS; ECASJO_; Approved Most recent IF: 8.462; 2013 IF: 7.728
Call Number UA @ lucian @ c:irua:111396UA @ admin @ c:irua:111396 Serial 287
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Author Monico, L.; Janssens, K.; Miliani, C.; Brunetti, B.G.; Vagnini, M.; Vanmeert, F.; Falkenberg, G.; Abakumov, A.; Lu, Y.; Tian, H.; Verbeeck, J.; Radepont, M.; Cotte, M.; Hendriks, E.; Geldof, M.; van der Loeff, L.; Salvant, J.; Menu, M.;
Title Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of spectromicroscopic methods : 3 : synthesis, characterization, and detection of different crystal forms of the chrome yellow pigment Type A1 Journal article
Year 2013 Publication Analytical chemistry Abbreviated Journal Anal Chem
Volume 85 Issue 2 Pages 860-867
Keywords A1 Journal article; Electron microscopy for materials research (EMAT); AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Abstract The painter, Vincent van Gogh, and some of his contemporaries frequently made use of the pigment chrome yellow that is known to show a tendency toward darkening. This pigment may correspond to various chemical compounds such as PbCrO4 and PbCr1-xSxO4, that may each be present in various crystallographic forms with different tendencies toward degradation. Investigations by X-ray diffraction (XRD), mid-Fourier Transform infrared (FTIR), and Raman instruments (benchtop and portable) and synchrotron radiation-based micro-XRD and X-ray absorption near edge structure spectroscopy performed on oil-paint models, prepared with in-house synthesized PbCrO4 and PbCr1-xSxO4, permitted us to characterize the spectroscopic features of the various forms. On the basis of these results, an extended study has been carried out on historic paint tubes and on embedded paint microsamples taken from yellow-orange/pale yellow areas of 12 Van Gogh paintings, demonstrating that Van Gogh effectively made use of different chrome yellow types. This conclusion was also confirmed by in situ mid-FTIR investigations on Van Goghs Portrait of Gauguin (Van Gogh Museum, Amsterdam).
Address
Corporate Author Thesis
Publisher Place of Publication (up) Washington, D.C. Editor
Language Wos 000313668400031 Publication Date 2012-10-10
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0003-2700;1520-6882; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 6.32 Times cited 79 Open Access
Notes Goa; Fwo Approved Most recent IF: 6.32; 2013 IF: 5.825
Call Number UA @ lucian @ c:irua:108707UA @ admin @ c:irua:108707 Serial 631
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Author Monico, L.; van der Snickt, G.; Janssens, K.; de Nolf, W.; Miliani, C.; Verbeeck, J.; Tian, H.; Tan, H.; Dik, J.; Radepont, M.; Cotte, M.
Title Degradation process of lead chromate in paintings by Vincent van Gogh studied by means of synchrotron X-ray spectromicroscopy and related methods : 1 : artificially aged model samples Type A1 Journal article
Year 2011 Publication Analytical chemistry Abbreviated Journal Anal Chem
Volume 83 Issue 4 Pages 1214-1223
Keywords A1 Journal article; Electron microscopy for materials research (EMAT); AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation)
Abstract On several paintings by artists of the end of the 19th century and the beginning of the 20th Century a darkening of the original yellow areas, painted with the chrome yellow pigment (PbCrO4, PbCrO4·xPbSO4, or PbCrO4·xPbO) is observed. The most famous of these are the various Sunflowers paintings Vincent van Gogh made during his career. In the first part of this work, we attempt to elucidate the degradation process of chrome yellow by studying artificially aged model samples. In view of the very thin (1−3 μm) alteration layers that are formed, high lateral resolution spectroscopic methods such as microscopic X-ray absorption near edge (μ-XANES), X-ray fluorescence spectrometry (μ-XRF), and electron energy loss spectrometry (EELS) were employed. Some of these use synchrotron radiation (SR). Additionally, microscopic SR X-ray diffraction (SR μ-XRD), μ-Raman, and mid-FTIR spectroscopy were employed to completely characterize the samples. The formation of Cr(III) compounds at the surface of the chrome yellow paint layers is particularly observed in one aged model sample taken from a historic paint tube (ca. 1914). About two-thirds of the chromium that is present at the surface has reduced from the hexavalent to the trivalent state. The EELS and μ-XANES spectra are consistent with the presence of Cr2O3·2H2O (viridian). Moreover, as demonstrated by μ-XANES, the presence of another Cr(III) compound, such as either Cr2(SO4)3·H2O or (CH3CO2)7Cr3(OH)2 [chromium(III) acetate hydroxide], is likely.
Address
Corporate Author Thesis
Publisher Place of Publication (up) Washington, D.C. Editor
Language Wos 000287176900011 Publication Date 2011-02-14
Series Editor Series Title Abbreviated Series Title
Series Volume Series Issue Edition
ISSN 0003-2700;1520-6882; ISBN Additional Links UA library record; WoS full record; WoS citing articles
Impact Factor 6.32 Times cited 113 Open Access
Notes Iuap; Fwo Approved Most recent IF: 6.32; 2011 IF: 5.856
Call Number UA @ lucian @ c:irua:88794UA @ admin @ c:irua:88794 Serial 632
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