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Benito, P.; de Nolf, W.; Nuyts, G.; Janssens, K.; et al. |
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Title |
Role of coating-metallic support interaction in the properties of electrosynthesized Rh-based structured catalysts |
Type |
A1 Journal article |
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Year |
2014 |
Publication |
ACS catalysis |
Abbreviated Journal |
Acs Catal |
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Volume |
4 |
Issue |
10 |
Pages |
3779-3790 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Rh-structured catalysts for the catalytic partial oxidation of CH4 to syngas were prepared by electrosynthesis of Rh-containing hydrotalcite-type (HT) compounds on FeCrAlloy foams followed by calcination at 900 degrees C. During the calcination the simultaneous decomposition of the layered HT structure and formation of the protective FeCrAlloy outer shell in alumina occurred. Here, we studied the role of the coating-metallic support interaction in the properties of the catalysts after calcination, H-2 reduction, and catalytic tests, by a combination of electron (FEG-SEM/EDS) and synchrotron X-ray (XRF/XRPD and XRF/XANES) microscopic techniques. The characterization of crystalline phases in the metallic support and coating and distribution of Rh active species was carried out on several samples prepared by modifying the Rh content in the electrolytic solution (Rh/Mg/Al = 11.0/70.0/19.0, 5.0/70.0/25.0, 0/70.0/30.0 atomic ratio). A sample was also prepared with no aluminum in the electrolytic solution (Rh/Mg/Al = 13.6/86.4/0.0 atomic ratio) and calcined at 550 and 900 degrees C. The interaction between the elements of the metallic support and the catalytic coating increased the film adhesion during the thermal treatment and catalytic tests and modified the catalyst crystalline phases. A chemical reaction between Al corning from the foam and Mg in the coating occurred during calcination at high temperature leading to the formation of spinel phases in which rhodium is solved, together with some Rh2O3 and Rh. The metallic support was oxidized forming the corundum scale and chromium oxides, moreover t-Al2O3 was identified. For the Rh11.0Mg70.0Al19.0 catalyst the inclusion of Rh in the spinel phase decreased its reducibility in the H-2 pretreatment. The reduction continued during catalytic tests by feeding diluted CH4/O-2/He gas mixtures, evidenced by the catalyst activation. While under concentrated gas mixtures the deactivation occurred, probably by oxidation. |
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000345735200053 |
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2014-09-24 |
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2155-5435 |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
10.614 |
Times cited |
13 |
Open Access |
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Notes |
; The authors thank the scientists who assisted during the conducted experiments: D. Grolimund and C. N. Borca for the mu XRF/XRPD experiments performed at MicroXAS Beamline of SLS, M. Janousch for the mu XRF/XANES experiments at Phoenix Beamline of the SLS, M. Salome for the mu XRE/XANES experiments at ID21 Beamline of the ESRF, and I. Guerra for the FEG-SEM/EDS experiments at Granada University. Thanks must go to Porvair for supplying FeCrAlloy foams. The financial support from the Ministero per l'Istruzione, l'Universita e la Ricerca (MIUR, Roma, I) is gratefully acknowledged. ; |
Approved |
Most recent IF: 10.614; 2014 IF: 9.312 |
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Call Number  |
UA @ admin @ c:irua:122215 |
Serial |
5820 |
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Van der Stighelen, K.; Janssens, K.; van der Snickt, G.; Alfeld, M.; Van Beneden, B.; Demarsin, B.; Proesmans, M.; Marchal, G.; Dik, J. |
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Title |
Young Anthony van Dyck revisited : a multidisciplinary approach to a portrait once attributed to Peter Paul Rubens |
Type |
A3 Journal article |
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Year |
2014 |
Publication |
Art matters : international journal for technical art history |
Abbreviated Journal |
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Volume |
6 |
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Pages |
21-35 |
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Keywords |
A3 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Part of the collection of the Rubens House in Antwerp is a portrait of young Anthony van Dyck, alternatively attributed to Peter Paul Rubens and his pupil Anthony van Dyck. In order to reconstruct the genesis of the portrait in a manner that improves upon past investigations, a number of high-end technological methods, such as X-radiography, X-ray computer tomography, mammographic tomosynthesis and macroscopic X-ray fluorescence, have been employed to render the overpainted layers visible again. The results of the interdisciplinary examinations of the portrait of the youthful Van Dyck are impressive. The combined results allow the later additions to be peeled away until the original composition can be reached. Several pentimenti are easily discernible and refer to a rather immature hand that makes the authorship of Peter Paul Rubens very unlikely. What emerges is a portrait of an ambitious young man with a luxuriant head of hair and a slightly turned-up collar. The hat and cape were added later. The facial features are more recognisable and the execution of the bold curls points irrefutably in the direction of Anthony van Dyck as the author of his own portrait. |
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Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:122562 |
Serial |
5922 |
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Author |
Monico, L.; Janssens, K.; Hendriks, E.; Brunetti, B.G.; Miliani, C. |
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Title |
Raman study of different crystalline forms of PbCrO4 and PbCr1-xSxO4 solid solutions for the noninvasive identification of chrome yellows in paintings : a focus on works by Vincent van Gogh |
Type |
A1 Journal article |
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Year |
2014 |
Publication |
Journal of Raman spectroscopy |
Abbreviated Journal |
J Raman Spectrosc |
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Volume |
45 |
Issue |
11-12 |
Pages |
1034-1045 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Chrome yellows, a class of pigments frequently used by painters of the Impressionism and Post-impressionism period, are known for their different chemical stability; the latter depends on the chemical composition (PbCrO4, PbCr1-xSxO4) and crystalline structure (monoclinic or orthorhombic) of the material. The possibility to distinguish among different forms of this pigment is therefore relevant in order to extend knowledge on the corresponding degradation process that is observed on several original paintings. For this purpose, three paintings conserved at the Van Gogh Museum (Amsterdam) were analyzed using noninvasive Raman spectroscopy, while equivalent investigations employing bench-top instrumentation were performed to obtain information from micro-samples originating from these works of art. In each painting, the chrome yellow was identified either as monoclinic PbCrO4 or in the form of monoclinic PbCr1-xSxO4 (x<0.25) or S-rich orthorhombic PbCr1-xSxO4 (x similar to 0.5). Our ability to make this fairly subtle distinction is based on a Raman study of several oil paint model samples made up of monoclinic and/or orthorhombic crystalline forms of PbCrO4 and PbCr1-xSxO4 (0.1x0.8). These paints were studied using several excitation wavelengths (namely 785.0, 532.0, 514.5, and 488nm). Because of the absence of the resonance Raman effect, which strongly enhances the chromate symmetric stretching band, and the absence of any laser-induced photodecomposition, it is advantageous to acquire data at 785.0nm. The band-shape and the position of the chromate bending modes proved to be more sensitive to the solid solution composition and crystalline structure than the stretching modes and can be used as distinctive spectral markers to discriminate among the different chrome yellow forms that are present. Copyright (c) 2014 John Wiley & Sons, Ltd. |
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000346912700008 |
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2014-07-17 |
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ISSN |
0377-0486 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
2.969 |
Times cited |
34 |
Open Access |
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Notes |
; This research was supported by Interuniversity Attraction Poles Programme – Belgian Science Policy (S2-ART project S4DA) and also presents results from GOA 'XANES meets ELNES' (Research Fund University of Antwerp, Belgium), FWO (Brussels, Belgium) projects no. G.0704.08 and G.01769.09. Support from the Italian projects PRIN (SICH Sustainability in Cultural Heritage: from diagnosis to the development of innovative system for consolidation, cleaning and protection) and PON (ITACHA Italian advanced technologies for cultural heritage applications) is also acknowledged. The analysis of the paintings Sunflowers gone to seed, Bank of the Seine, and Portrait of Gauguin was performed within the mobile laboratory access activity of the FP7 programme CHARISMA supported by EC (Grant Agreement 228330). LM acknowledges the Italian National Research Council (CNR) for the financial support in the framework of the Short Term Mobility Programme 2013. Thanks are expressed to Muriel Geldof, Cultural Heritage Agency of The Netherlands, for selecting and sharing the information on the cross-sections and to the staff of the Van Gogh Museum for the agreeable cooperation. ; |
Approved |
Most recent IF: 2.969; 2014 IF: 2.671 |
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Call Number |
UA @ admin @ c:irua:122841 |
Serial |
5798 |
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De Vis, K.; Jacobs, P.; Caen, J.; Janssens, K. |
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Title |
The use of glass bricks in architecture in the 19th and 20th centuries : a case study |
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P2 Proceeding |
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2010 |
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Pages |
194-201 |
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Keywords |
P2 Proceeding; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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978-0-87290-182-7 |
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Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124194 |
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5892 |
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Cagno, S.; Nuyts, G.; De Vis, K.; Caen, J.; Van Mol, W.; Bongaers, E.; Pauwels, B.; Janssens, K. |
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Title |
The browning of stained glass windows : characterization of Mn-corrosion bodies and evaluation of cleaning methods |
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P3 Proceeding |
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2011 |
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P3 Proceeding; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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978-88-97484-01-1 |
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UA library record |
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Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124196 |
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5494 |
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Anitha, A.; Brasoveanu, A.; Duarte, M.F.; Hughes, S.M.; Daubechies, I.; Dik, J.; Janssens, K.; Alfeld, M. |
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Title |
Virtual underpainting reconstruction from X-ray fluorescence imaging data |
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P1 Proceeding |
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Year |
2011 |
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1239-1243 |
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P1 Proceeding; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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UA library record; WoS full record; WoS citing articles |
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; ; |
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Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124612 |
Serial |
5905 |
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Benito, P.; Monti, M.; de Nolf, W.; Nuyts, G.; Janssens, K.; et al. |
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Title |
Improvement in the coating homogeneity in electrosynthesized Rh structured catalysts for the partial oxidation of methane |
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A1 Journal article |
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Year |
2015 |
Publication |
Catalysis today |
Abbreviated Journal |
Catal Today |
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Volume |
246 |
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154-164 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The precipitation of Rh/Mg/Al and Rh/Al hydroxides on the surface of FeCrAlloy foams by a base electrogeneration method was investigated to improve the properties of the deposited film (homogeneity and composition) and therefore the performances of the structured catalysts, obtained by calcination, in the Catalytic Partial Oxidation of CH4 to syngas. The work focussed on decreasing current gradients within open-cell foam cylinders by increasing the number of electrical contacts from 1 to 3 points to promote a more homogeneous precipitation of the hydroxides. Electrochemical and catalytic tests as well as SEM/EDS and mu-XRFIXRD analyses allowed to correlate the effect of the number of electrical contact points with materials properties. Lastly, syntheses were performed on Pt plates to study the effect of the electrical behaviour and shape of the support on the composition of the film. A more homogeneous coating of the foam surface was achieved by adopting a configuration with 3 contact points since the reduction of nitrates and water molecules that generates the basic media in the vicinity of the support was enhanced. Layer thicknesses up to 5-15 mu m were deposited; however, the sequential precipitation of a film with composition closer to the expected one and a layer enriched in Al and Rh (outer layer) was not avoided. The improvement in the coating gave rise to enhanced performances for a sample prepared at -1.1 V for 3000 s. Contrarily, the low adherence of the outer layer in a sample prepared at -1.2 V for 2000 s during both calcination and catalytic tests may be responsible of the unexpected decrease in catalytic performances. The same sequential precipitation was observed by performing the syntheses on Pt plates, showing that the electrical nature the support did not play a key role on this phenomenon. (C) 2014 Elsevier B.V. All rights reserved. |
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Wos |
000349998300020 |
Publication Date |
2014-10-31 |
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Edition |
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ISSN |
0920-5861 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
4.636 |
Times cited |
14 |
Open Access |
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Notes |
; The financial support from the Ministero per l'Istruzione, l'Universita e la Ricerca (MIUR, Roma, I) is gratefully acknowledged. The authors thank D. Grolimund and C.N. Borca for assisting the mu XRF/XRD conducted experiments at MicroXAS Beamline of SLS Thanks are due to Porvair for supplying FeCrAlloy foams. ; |
Approved |
Most recent IF: 4.636; 2015 IF: 3.893 |
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Call Number |
UA @ admin @ c:irua:124616 |
Serial |
5656 |
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Author |
Vanmeert, F.; van der Snickt, G.; Janssens, K. |
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Title |
Plumbonacrite identified by X-ray powder diffraction tomography as a missing link during degradation of red lead in a Van Gogh painting |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Angewandte Chemie: international edition in English |
Abbreviated Journal |
Angew Chem Int Edit |
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Volume |
54 |
Issue |
12 |
Pages |
3607-3610 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Red lead, a semiconductor pigment used by artists since antiquity, is known to undergo several discoloration phenomena. These transformations are either described as darkening of the pigment caused by the formation of either plattnerite (β-PbO2) or galena (PbS) or as whitening by which red lead is converted into anglesite (PbSO4) or (hydro)cerussite (2 PbCO3⋅Pb(OH)2; PbCO3). X-ray powder diffraction tomography, a powerful analytical method that allows visualization of the internal distribution of different crystalline compounds in complex samples, was used to investigate a microscopic paint sample from a Van Gogh painting. A very rare lead mineral, plumbonacrite (3 PbCO3⋅ Pb(OH)2⋅PbO), was revealed to be present. This is the first reported occurrence of this compound in a painting dating from before the mid 20th century. It constitutes the missing link between on the one hand the photoinduced reduction of red lead and on the other hand (hydro)cerussite, and thus sheds new light on the whitening of red lead. |
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000351178300008 |
Publication Date |
2015-02-20 |
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ISSN |
1433-7851; 0570-0833 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
11.994 |
Times cited |
24 |
Open Access |
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Notes |
; The authors acknowledge L. Van der Loeff and M. Leeuwestein (Kroller-Muller Museum) for providing the paint sample. We thank Dr. J. Jaroszewicz (WUT) for performing the CT measurements. This research was carried out at the light source PETRA III at DESY, a member of the Helmholtz Association (HGF). We thank Dr. G. Falkenberg and the members of his team for their assistance in using beam line P06. We acknowledge financial support from the University of Antwerp GOA projects “XANES meets EELS” and “SOLARPaint”, as well as from BELSPO (Brussels) Project S2-ART and FWO (Brussels) project “ESRF-Dubble”. ; |
Approved |
Most recent IF: 11.994; 2015 IF: 11.261 |
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Call Number |
UA @ admin @ c:irua:124620 |
Serial |
5774 |
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Bertrand, L.; Schoeeder, S.; Anglos, D.; Breese, M.B.H.; Janssens, K.; Moini, M.; Simon, A. |
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Title |
Mitigation strategies for radiation damage in the analysis of ancient materials |
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A1 Journal article |
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Year |
2015 |
Publication |
Trends in analytical chemistry |
Abbreviated Journal |
Trac-Trend Anal Chem |
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66 |
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128-145 |
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A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The study of materials in cultural heritage artifacts and micro-samples benefits from diagnostic techniques based on intense radiation sources, such as synchrotrons, ion-beam accelerators and lasers. While most of the corresponding techniques are classified as non-destructive, investigation with photons or charged particles entails a number of fundamental processes that may induce changes in materials. These changes depend on irradiation parameters, properties of materials and environmental factors. In some cases, radiation-induced damage may be detected by visual inspection. When it is not, irradiation may still lead to atomic and molecular changes resulting in immediate or delayed alteration and bias of future analyses. Here we review the effects of radiation reported on a variety of cultural heritage materials and describe the usual practice for assessing short-term and long-term effects. This review aims to raise awareness and encourage subsequent research activities to limit radiation side effects. |
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000352248200020 |
Publication Date |
2014-12-22 |
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ISSN |
0165-9936 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
8.442 |
Times cited |
35 |
Open Access |
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Notes |
; We wish to acknowledge the support of this initiative by the International Atomic Energy Agency. We gratefully thank Professor Manfred Schreiner of the Institute of Natural Sciences and Technology in the Arts (Akademie den bildenden Kunst, Vienna, Austria) for helpful discussions and insights on this work. We thank all colleagues who accepted to have their work reproduced in this review. IPANEMA at Synchrotron SOLEIL, the Hungarian Academy of Science and IESL-FORTH were supported within the Research Infrastructure program CHARISMA of the 7th Framework Programme of the EU (Grant Agreement no. 228330). MM's contribution is based upon work supported by the National Science Foundation under Grant numbers CHE 1241672 and CHE 1440849. We thank Chris McGlinchey and Lauren Klein (Museum of Modern Art, New York, USA) for their critical rereading of the manuscript. ; |
Approved |
Most recent IF: 8.442; 2015 IF: 6.472 |
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Call Number |
UA @ admin @ c:irua:124627 |
Serial |
5729 |
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Author |
Legrand, S.; Vanmeert, F.; van der Snickt, G.; Alfeld, M.; de Nolf, W.; Dik, J.; Janssens, K. |
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Title |
Examination of historical paintings by state-of-the-art hyperspectral imaging methods : from scanning infra-red spectroscopy to computed X-ray laminography |
Type |
A1 Journal article |
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Year |
2014 |
Publication |
Heritage science |
Abbreviated Journal |
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Volume |
2 |
Issue |
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Pages |
13-11 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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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 full field methods (that record the image data in parallel) can be discerned next to scanning methods (that build up distributions in a sequential manner by scanning a beam of radiation over the surface of an artefact). Six methods are discussed: on the one 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 examination of paintings, i.e., X-ray radiography and Infrared reflectography. Possibilities and limitations of these new imaging techniques are outlined. |
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Publication Date |
2014-05-30 |
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Series Issue |
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Edition |
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ISSN |
2050-7445 |
ISBN |
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Additional Links |
UA library record |
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Impact Factor |
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Times cited |
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Open Access |
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Notes |
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Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124629 |
Serial |
5619 |
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Author |
Cosyns, P.; Cagno, S.; Janssens, K.; Nys, K. |
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Title |
Un verre méditerranéen pour la production de bracelets laténiens en Europe septentrionale : résultats danalyses SEM-EDX et LA-ICP-MS de bracelets en verre La Tène tardive de Odijk, Tiel et Geldermalseren-Hondsgemet |
Type |
A3 Journal article |
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Year |
2014 |
Publication |
Bulletin AFAV |
Abbreviated Journal |
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Volume |
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Issue |
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Pages |
13-19 |
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Keywords |
A3 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Additional Links |
UA library record |
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Impact Factor |
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Times cited |
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Open Access |
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Notes |
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Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124631 |
Serial |
5884 |
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Author |
Vermeulen, M.; Sanyova, J.; Janssens, K. |
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Title |
Identification of artificial orpiment in the interior decorations of the Japanese tower in Laeken, Brussels, Belgium |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Heritage science |
Abbreviated Journal |
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Volume |
3 |
Issue |
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Pages |
Unsp 9 |
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Keywords |
A1 Journal article; Art; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
In this paper, we used a multi-technique approach in order to identify the arsenic sulfide pigment used in the decorative panels of the Japanese tower in Laeken, Belgium. Our attention was drawn to this particular pigment because of its relatively good conservation state, despite its known tendency to fade over time when exposed to light. The pigment was used with different painting techniques, bound with oil and urushi in the lacquers and with an aqueous binder in the mat relief panels. In the latter case it is always applied as an underlayer mixed with ultramarine blue. This quite unusual pigment mixture also shows a good state of preservation. In this study, the orpiment used for the Japanese tower has been identified as an amorphous arsenic sulfide glass (AsxSx) with the aid of light microscopy, PLM, SEM-EDX and Raman microscopy. The pigment features different degrees of As4S4 monomer units in its structure, also known as realgar-like nano-phases. This most likely indicates different synthesis processes as the formation of these As4S4 monomers is dependent of the quenching temperature (Tq) to which the artificial pigment is exposed during the preparation phase. |
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Wos |
000356920400001 |
Publication Date |
2015-02-25 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
2050-7445 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
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Times cited |
17 |
Open Access |
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Notes |
; We cordially thank Gunter Grundmann for his precious advice regarding PLM and arsenic sulfide glass. This research is made possible with the support of the Belgian Science Policy Office (BELSPO) through the research program Science for a Sustainable Development – SDD, “Long-term role and fate of metal-sulfides in painted works of art – S2ART” (SD/RI/04A). ; |
Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:124904 |
Serial |
5649 |
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| Permanent link to this record |
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Author |
Silva, A.L.M.; Carvalho, M.L.; Janssens, K.; Veloso, J.F.C.A. |
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Title |
A large area full-field EDXRF imaging system based on a THCOBRA gaseous detector |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
2 |
Pages |
343-352 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
By taking advantage of the attractive features in terms of gain, position and energy resolution of the 2D-THCOBRA detector, a new large area Full-Field X-ray Fluorescence Imaging (FF-XRFI) system for EDXRF imaging applications was developed. The proposed FF-XRFI system has an active area of 10 x 10 cm(2) and can be used to examine macroscopic samples with a moderately good energy resolution (< 1.6 keV FWHM at 8 keV) and a suitable spatial resolution (similar to 500 mu m FWHM). This combination of characteristics allows us to record elemental distribution maps from the surface of different sample types by combining image and energy information. Two different approaches were used for X-ray optics, one based on a single pinhole and another based on a parallel multiple-hole collimator. To illustrate the system capabilities, some sample examples were imaged and studied. |
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Place of Publication |
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Wos |
000349145700003 |
Publication Date |
2014-10-24 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
11 |
Open Access |
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Notes |
; The authors thank Stijn Legrand for acquisition of the MAXRF maps shown in Fig. 15. This work was partially supported by projects CERN/FP/123604/2011 FEDER, COMPETE and FCT (Lisbon) programs. A. L. M. Silva is supported by the QREN programme Mais Centro – Programa Operacional Regional do Centro, FEDER and COMPETE, through the project Biomaterials for Regenerative Medicine (CENTRO-07-ST24-FEDER-002030). ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:125297 |
Serial |
5452 |
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Author |
Radepont, M.; Coquinot, Y.; Janssens, K.; Ezrati, J.-J.; de Nolf, W.; Cotte, M. |
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Title |
Thermodynamic and experimental study of the degradation of the red pigment mercury sulfide |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
3 |
Pages |
599-612 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The red pigment mercury sulfide, called cinnabar or vermilion, is well known to suffer from an alteration giving rise to a grey, grey-white or black color at the surface of degraded works of art. This phenomenon can dramatically affect the esthetical value of artworks. This work aims at assessing the factors (light, halides) influencing the instability of red mercury sulfide and understanding (by combining thermodynamic and experimental approaches) the chemical equilibria governing the formation and evolution of the different degradation compounds. From the thermodynamic study of the Hg-S-Cl-H2O system, it was concluded that Hg(0), Hg3S2Cl2, and Hg2Cl2 can be formed from the reaction of alpha-HgS with ClO(g). In the second part, the artificial ageing experiments presented were carried out on model samples following the conditions assessed in the first part, in order to reproduce natural ageing observed on red mercury sulfide. Similarly to degradation compounds detected on original works of art, mercury chlorine compounds such as calomel (Hg2Cl2) and corderoite (alpha-Hg3S2Cl2) were identified on the surface of alpha-HgS model samples, when exposed to light and a sodium hypochlorite solution. Sulfates were detected as well, and more particularly gypsum (CaSO4 center dot 2H(2)O) when Ca was originally present in the model sample. The relationship between color and composition is discussed as well. |
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Wos |
000350650800005 |
Publication Date |
2015-01-02 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
26 |
Open Access |
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Notes |
; The authors gratefully acknowledge the ESRF for granting beamtime under proposal no. EC720. Michel Dubus is thanked for providing precious advices concerning ageing protocols. This research was supported by Belgian Science Policy project S2-ART (BELSPO S4DA), the GOA “SOLARPAINT” (Research Fund University of Antwerp, Belgium) and FWO (Brussels, Belgium) projects no. G.0C12.13, G.0704.08 and G.01769.09. ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:125474 |
Serial |
5877 |
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Author |
Monico, L.; Janssens, K.; Alfeld, M.; Cotte, M.; Vanmeert, F.; Ryan, C.G.; Falkenberg, G.; Howard, D.L.; Brunetti, B.G.; Miliani, C. |
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Title |
Full spectral XANES imaging using the Maia detector array as a new tool for the study of the alteration process of chrome yellow pigments in paintings by Vincent van Gogh |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
3 |
Pages |
613-626 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
A combination of synchrotron radiation (SR) micro X-ray fluorescence (m-XRF) and XRF mode X-ray absorption near edge structure (XANES) measurements at the Cr K-edge already allowed us to establish that the photo-reduction of chromates to Cr(III) compounds is the cause of darkening of chrome yellow pigments (PbCr1-xSxO4, 0 <= x <= 0.8) in a number of paintings by Vincent van Gogh and in corresponding artificially aged paint models. A silicon drift detector (SDD) was employed to record the Cr-K XRF radiation in these X-ray micro beam-based measurements. However, in view of the limited count rate capabilities and collection solid angle of a single device, m-XRF and m-XANES employing single element SDDs (or similar) are primarily suited for collection of spectral data from individual points. Additionally, collection of XRF maps via point-by-point scanning with relatively long dwell times per point is possible but is usually confined to small areas. The development of the 384 silicon-diode array Maia XRF detector has provided valuable solutions in terms of data acquisition rate, allowing for full spectral (FS) XANES imaging in XRF mode, i.e., where spectroscopic information is available at each pixel in the scanned map. In this paper, the possibilities of SR Cr K-edge FS-XANES imaging in XRF mode using the Maia detector are examined as a new data collection strategy to study the speciation and distribution of alteration products of lead chromate-based pigments in painting materials. The results collected from two micro-samples taken from two Van Gogh paintings and an aged paint model show the possibility to perform FS-XANES imaging in practical time frames (from several minutes to a few hours) by scanning regions of sample sizes of the same order (more than 500 mm). The sensitivity and capabilities of FS-XANES imaging in providing representative chemical speciation information at the microscale (spatial resolution from similar to 2 to 0.6 mm) over the entire scanned area are demonstrated by the identification of Cr(OH) 3, Cr(III) sulfates and/or Cr(III) organometallic compounds in the corresponding phase maps, as alteration products. Comparable Cr-speciation results were obtained by performing equivalent higher spatial resolution SR m-XRF/single-point m-XANES analysis using a more conventional SDD from smaller regions of interest of each sample. Thus, large-area XRF mode FS-XANES imaging (Maia detector) is here proposed as a valuable and complementary data collection strategy in relation to “ zoomed-in” high-resolution m-XRF mapping and single-point m-XANES analysis (SDD). |
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Wos |
000350650800006 |
Publication Date |
2014-12-17 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
28 |
Open Access |
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Notes |
; This research was supported by the Interuniversity Attraction Poles Programme – Belgian Science Policy (S2-ART project S4DA), GOA “SOLARPAINT” (Research Fund University of Antwerp, Belgium) and FWO (Brussels, Belgium) project no. G.0C12.13, G.0704.08 and G.01769.09. Support from the Italian projects PRIN (SICH Sustainability in Cultural Heritage: from diagnosis to the development of innovative system for consolidation, cleaning and protection) and PON (ITACHA Italian advanced technologies for cultural heritage applications) is also acknowledged. For the grants received thanks are expressed to ESRF (experiments EC-799, EC-1051) and DESY (experiment H-20000043). Part of this research was undertaken at the XFM beamline at the Australian Synchrotron, Victoria, Australia (experiment M4604). LM acknowledges the CNR for the financial support received in the framework of the Short Term Mobility Programme 2013. Thanks are expressed to Ella Hendriks (Van Gogh Museum, Amsterdam), Muriel Geldof (Cultural Heritage Agency of The Netherlands) and Margje Leeuwestein (Kroller-Muller Museum, Otterlo) for selecting and sharing the information on the cross-section taken from the paintings The Bedroom and Falling Leaves (Les Alyscamps). All the staff of the Van Gogh Museum and the Kroller-Muller Museum are acknowledged for their agreeable cooperation. ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:125475 |
Serial |
5628 |
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Author |
Nuyts, G.; Cagno, S.; Bugani, S.; Janssens, K. |
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Title |
Micro-XANES study on Mn browning: use of quantitative valence state maps |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
3 |
Pages |
642-650 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Historical glass, especially non-durable medieval glass, can undergo corrosion. This sometimes results in the formation of dark-coloured manganese-rich inclusions that reduce the transparency of the glass. While unaltered bulk glass contains manganese mainly present in the +II valence state, inside the inclusions Mn is present in higher valence states (+III to +IV). Two different strategies may be considered by conservators when aiming to improve the transparency. One is based on the reduction of highly oxidised black/brown compounds using mildly reducing solutions, while the other focuses more on the extraction of manganese from the inclusions by the application of chelating agents. In this paper, a method for quantitative mapping of the Mn speciation inside partially corroded historical windowpanes based on X-Ray Absorption Near-Edge Structure (XANES) spectroscopy is discussed. The calibration of such Mn valence state maps based on the combo method, a fairly reliable way to determine the oxidation state, is described in more detail. This method is used to evaluate the effect of reducing treatments on historical glass, dated to the 14th century and originating from Sidney Sussex College (Cambridge, UK), suffering from Mn browning. Glasses were examined by means of Synchrotron Radiation (SR) based microscopic X-Ray Absorption Near-Edge Structure (mXANES) spectroscopy and microscopic X-Ray Fluorescence (mXRF). X-Ray elemental distribution maps of glass cross-sections are recorded at different energies, while Mn K-edge spectra are used to convert these into Mn valence state (VS) maps. Such valence state maps will allow evaluation of a reducing treatment. |
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Wos |
000350650800009 |
Publication Date |
2015-02-23 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
8 |
Open Access |
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Notes |
; This research was supported by the Interuniversity Attraction Poles Programme Belgian Science Policy (IUAP VI/16) and partially by the Research Council of Norway through its Centres of Excellence funding scheme, project number 223268/ F50. The text also presents results of Center of Excellence AGRECHEM (Research Fund University of Antwerp, Belgium) and from the Fund for Scientific Research (FWO, Brussels, Belgium) projects no. G.0C12.13 and G.01769.09. We gratefully acknowledge ESRF for granting beamtime (experiment EC768) and the beamline scientists of ID21 for their support. The authors also want to thank Leonie Seliger of Canterbury Cathedral, UK, the Sidney Sussex College Council and Bursar Charles Larkum for providing the archaeological samples of the Franciscan Friary which are kept in store for Sidney Sussex College in Cambridge (UK). ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:125476 |
Serial |
5719 |
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Author |
Alfeld, M.; Janssens, K. |
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Title |
Strategies for processing mega-pixel X-ray fluorescence hyperspectral data: a case study on a version of Caravaggio's painting Supper at Emmaus |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
3 |
Pages |
777-789 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Technical progress in the fields of X-ray sources, optics and detectors is constantly enhancing the pace of data acquisition in XRF imaging. This enlarges the size of the hyperspectral datasets and the number of their sub-parts. This paper describes the challenges in processing large XRF datasets featuring several million pixels/spectra and the strategies developed to overcome them. During the investigation of historical paintings by scanning macro-XRF the main challenges are the correct identification of all spectral features in a dataset and its timely processing. For the identification of spectral features different approaches are discussed, i.e. the use of sum spectra, maximum pixel spectra and of chi(2)(r) maps. For the time-efficient, artefact-free evaluation of XRF imaging data, different software packages are evaluated and intercompared (AXIL, PyMCA, GeoPIXE and the in-house written datamuncher). The process of data evaluation is illustrated on a large dataset (3.4 MPixels) acquired during the investigation of a version of Caravaggio's Supper at Emmaus (143 x 199.5 cm(2)). This 17th century painting is currently the largest object entirely scanned with macroscopic XRF. |
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Wos |
000350650800026 |
Publication Date |
2015-02-12 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
67 |
Open Access |
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Notes |
; The authors would like to thank W. de Nolf, A. Rothkirch, C. Ryan, A. Sole, B. Vekemans, P. van Espen and L. Vincze for their fruitful discussions over the years. Furthermore, the authors thank D. Swetzoff for his support. M. Alfeld was from 2009 to 2013 the recipient of a Ph.D. fellowship of the Research Foundation-Flanders (FWO, Brussels). ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:125477 |
Serial |
5848 |
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Author |
Alfeld, M.; Laurenze-Landsberg, C.; Denker, A.; Janssens, K.; Noble, P. |
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Title |
Neutron activation autoradiography and scanning macro-XRF of Rembrandt van Rijn's Susanna and the Elders (Gemaldegalerie Berlin) : a comparison of two methods for imaging of historical paintings with elemental contrast |
Type |
A1 Journal article |
| |
Year |
2015 |
Publication |
Applied physics A : materials science & processing |
Abbreviated Journal |
Appl Phys A-Mater |
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Volume |
119 |
Issue |
3 |
Pages |
795-805 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Imaging methods with elemental contrast are of great value for the investigation of historical paintings, as they allow for study of sub-surface layers that provide insight into a painting's creation process. Two of the most important methods are neutron activation autoradiography (NAAR) and scanning macro-XRF (MA-XRF). Given the differences between these methods in the fundamental physical phenomena exploited, a theoretical comparison of their capabilities is difficult and until now a critical comparison of their use on the same painting is missing. In this paper, we present a study of Rembrandt van Rijn's painting Susanna and the Elders from the Gemaldegalerie in Berlin employing both techniques. The painting features a considerable number of overpainted features and a wide range of pigments with different elemental tracers, including earth pigments (Mn/Fe), Azurite (Cu), lead white (Pb), vermilion (Hg) and smalt (Co, As). MA-XRF can detect all elements above Si (Z = 14), suffers from few spectral overlaps and can be performed in a few tens of hours in situ, i.e. in a museum. NAAR requires the stay of the painting at a research facility for several weeks, and inter-element interferences can be difficult to resolve. Also, only a limited number of elements contribute to the acquired autoradiographs, most notably Mn, Cu, As, Co, Hg and P. However, NAAR provides a higher lateral resolution and is less hindered by absorption in covering layers, which makes it the only method capable of visualizing P in lower paint layers. |
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Wos |
000354189200001 |
Publication Date |
2015-04-13 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0947-8396 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
1.455 |
Times cited |
11 |
Open Access |
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Notes |
; This research was supported by the Interuniversity Attraction Poles Programme-Belgian Science Policy (IUAP VI/16). The text also presents the results of GOA “XANES meets ELNES” (Research Fund University of Antwerp, Belgium) and from FWO (Brussels, Belgium) Project Nos. G.0704.08 and G.01769.09. M. Alfeld received from 2009 to 2013 a PhD fellowship of the Research Foundation-Flanders (FWO). ; |
Approved |
Most recent IF: 1.455; 2015 IF: 1.704 |
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Call Number |
UA @ admin @ c:irua:126034 |
Serial |
5745 |
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Author |
Caen, J.; Legrand, S.; van der Snickt, G.; Janssens, K. |
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Title |
Macro X-ray fluorescence (MA-XRF) scanning : a new and efficient method for documenting stained-glass panels |
Type |
P3 Proceeding |
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Year |
2015 |
Publication |
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Abbreviated Journal |
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Keywords |
P3 Proceeding; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES) |
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ISBN |
978-2-9543731-1-9 |
Additional Links |
UA library record |
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Impact Factor |
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Times cited |
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Open Access |
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Notes |
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Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:126832 |
Serial |
5697 |
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| Permanent link to this record |
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Author |
De Vis, K.; Janssens, K.; Jacobs, P.; Caen, J. |
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Title |
Dealing with architectural glasses : maintenance, monitoring and emergency treatment |
Type |
P3 Proceeding |
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Year |
2015 |
Publication |
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Abbreviated Journal |
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Volume |
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Issue |
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Pages |
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Keywords |
P3 Proceeding; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES) |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
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ISBN |
978-2-9543731-1-9 |
Additional Links |
UA library record |
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Impact Factor |
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Times cited |
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Open Access |
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Notes |
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Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:126833 |
Serial |
5565 |
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| Permanent link to this record |
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Author |
Storme, P.; Selucká, A.; Rapouch, K.; Mazík, M.; Vanmeert, F.; Janssens, K.; Van de Voorde, L.; Vekemans, B.; Vincze, L.; Caen, J.; De Wael, K. |
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Title |
Composition and corrosion forms on archaeological and non-archaeological historic printing letters from the Moravian Museum, Memorial of Kralice Bible, the Czech Republic and the Museum Plantin-Moretus Antwerp, Belgium |
Type |
P1 Proceeding |
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Year |
2015 |
Publication |
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Abbreviated Journal |
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Volume |
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Issue |
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Pages |
59-65 |
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Keywords |
P1 Proceeding; Engineering sciences. Technology; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation); Antwerp Cultural Heritage Sciences (ARCHES) |
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Abbreviated Series Title |
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Edition |
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ISSN |
978-2-87522-152-0; 0770-8505 |
ISBN |
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Additional Links |
UA library record |
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Impact Factor |
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Times cited |
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Open Access |
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Notes |
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Approved |
Most recent IF: NA |
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Call Number |
UA @ admin @ c:irua:126909 |
Serial |
5535 |
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Author |
Monico, L.; Janssens, K.; Cotte, M.; Romani, A.; Sorace, L.; Grazia, C.; Brunetti, B.G.; Miliani, C. |
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Title |
Synchrotron-based X-ray spectromicroscopy and electron paramagnetic resonance spectroscopy to investigate the redox properties of lead chromate pigments under the effect of visible light |
Type |
A1 Journal article |
| |
Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
7 |
Pages |
1500-1510 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Light-induced redox processes have been established as the cause of the chromatic alterations of a number of artists' pigments used from the 15th to the 20th century. Despite the fact that a general comprehension of the mechanisms has been provided through the characterization of photo-degraded compounds, both exhaustive information on the wavelength-dependence of the alteration process of the pigments and experimental evidence in how visible light may influence the formation pathways of specific secondary compounds are still lacking. Establishing an analytical protocol for the study of wavelength-dependence of pigments on photo-redox pathways is relevant for the safe illumination of paintings, especially in view of the possible use of spectrally tunable light sources such as white light emitting diodes (WLEDs). In this work, we propose an integrated approach based on a combination of diffuse reflectance UV-visible, synchrotron radiation (SR)-based micro X-ray fluorescence (m-XRF)/X-ray absorption near edge structure (m-XANES) and electron paramagnetic resonance (EPR) spectroscopies to study the photo-redox process of Cr(VI) -> Cr(III) for lead chromate yellows (PbCr1-xSxO4, 0 <= x <= 0.8) under exposure to different monochromatic light. In view of the thin (3-5 mm) alteration layer that is formed at the paint surface after light exposure, SR-based Cr K-edge mu-XANES/mu-XRF analysis was employed to obtain information on the abundance, nature and distribution of the alteration of Cr(III)-compounds at the micrometricscale level. On the other hand, EPR spectroscopy was used as a complementary tool to the SR-based X-ray methods due to its sensitivity for revealing species containing one or more unpaired electrons and for distinguishing different coordination geometries of paramagnetic centers, such as Cr(V)-species. Semi-quantitative indications about the darkening of the paint surface were obtained by UV-Vis spectroscopy. An abundance of reduced Cr down to around 50% was detected at the aged surface of chrome yellow paints. The reduction process was favored not only by wavelengths shorter than 460 nm (i.e., where the pigment shows its maximum absorption) but also by light in the 490-530 nm range. The first evidence of the presence of Cr(V)-intermediates in the Cr(VI) -> Cr(III) reduction reaction allowed the risks of inducing photo-degradation of the 490-530 nm wavelength range to be explained. |
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Wos |
000356971900004 |
Publication Date |
2015-04-15 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
17 |
Open Access |
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Notes |
; This research was supported by the Italian projects PRIN-(SICH) and PON- (ITACHA) and by Belgian Science Policy project S2-ART (BELSPO S4DA), the GOA “SOLARPAINT” (Research Fund Antwerp University, Belgium) and FWO (Brussels, Belgium) projects no. G.0C12.13, G.0704.08 and G.01769.09. ESRF is acknowledged for the grants received (experiments HG18 and HG26). L.S. and L.M. acknowledge the financial support of Ente-CRF and CNR-Short Term Mobility Programme 2013, respectively. ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:127059 |
Serial |
5862 |
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Author |
Ceglia, A.; Nuyts, G.; Meulebroeck, W.; Cagno, S.; Silvestri, A.; Zoleo, A.; Nys, K.; Janssens, K.; Thienpont, H.; Terryn, H. |
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Title |
Iron speciation in soda-lime-silica glass: a comparison of XANES and UV-vis-NIR spectroscopy |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Journal of analytical atomic spectrometry |
Abbreviated Journal |
J Anal Atom Spectrom |
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Volume |
30 |
Issue |
7 |
Pages |
1552-1561 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Scientific analyses of ancient glasses have been carried out for many years using elemental chemical analysis. However, it is known that the control of the redox conditions in the glass melt has a strong implication on the final hue of glass because it affects Fe2+/SFe. Therefore an increasing number of studies on the redox conditions have been published in recent years by means of synchrotron based Xray absorption spectroscopy. This is a technique which is not easily accessible and requires dedicated facilities. In this paper we describe an alternative approach by means of optical absorption spectroscopy. We synthesised 10 soda-lime-silica glasses with known redox conditions and iron concentration to calibrate the absorption at 1100 nm as a function of Fe2+ concentration. The linear extinction coefficient was also determined. These glasses were also studied by means of X-ray Absorption Near Edge Structure (XANES) spectroscopy. Electron paramagnetic resonance spectroscopy was additionally used as an ancillary method to verify the quality of our data. Furthermore 28 samples from real archaeological samples were analysed by XANES and optical spectroscopy as a case study. The Fe2+/SFe values obtained were compared and demonstrated that the two techniques were in good agreement with each other. Optical spectroscopy can be applied in situ with moderate sample preparation to determine the concentration of Fe2+. To investigate the redox conditions, especially as a first screening approach, this methodology is an important tool to take into consideration before applying more sophisticated techniques such as XANES, which is more elaborate and requires high-tech resources. |
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Wos |
000356971900009 |
Publication Date |
2015-04-15 |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0267-9477 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.379 |
Times cited |
20 |
Open Access |
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Notes |
; The research leading to these results has received funding from the European Union Seventh Framework Programme FP7/2007-2013 under grant agreement no. 265010. For more information please visit the NARNIA website: http:// narnia-itn.eu/. This work was partly supported by the Research Council of Norway through its Centres of Excellence funding scheme, project number 223268/ F50. We are grateful to the ESRF for granting beamtime and Dipanjan Banerjee for his help at the beamline. We are thankful to the R&D department of AGC Glass Europe, in particular Dr Benoit Cherdon, Dr Dominique Michiels and Ms Dominique Delleuze, for preparing glass for us and providing us the chemical information. A special thanks to M. Fialin for the help with EPMA measurements in CAMPARIS. We want to express our gratitude to F. Farges and A. Berry for sharing their XANES spectra with us. Thanks to Anne Isabelle for reading this paper and giving comments. Finally we are grateful to two anonymous reviewers who contributed to improve this paper. ; |
Approved |
Most recent IF: 3.379; 2015 IF: 3.466 |
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Call Number |
UA @ admin @ c:irua:127060 |
Serial |
5679 |
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Author |
Benito, P.; Nuyts, G.; Monti, M.; de Nolf, W.; Fornasari, G.; Janssens, K.; Scavetta, E.; Vaccari, A. |
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Title |
Stable Rh particles in hydrotalcite-derived catalysts coated on FeCrAlloy foams by electrosynthesis |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Applied catalysis : B : environmental |
Abbreviated Journal |
Appl Catal B-Environ |
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Volume |
179 |
Issue |
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Pages |
321-332 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Rh-based structured catalysts for the Catalytic Partial Oxidation of CH4 to syngas were prepared by electrosynthesis of Rh/Mg/Al hydrotalcite-type compounds on FeCrAlloy foams and calcination. The effects of Rh content, total metal concentration, and partial replacement of Mg2+ by Ni2+ in the electrolytic solution on coating thickness, Rh speciation, metallic particle size, and catalytic activity were investigated by SEM/EDS, mu-XRF/XANES and tests under diluted and concentrated reaction conditions. The amount of Rh species, present as Mg (RhxAl1-x)(2)O-4, depended on the thickness of the electrosynthesised layer as well as the Rh particle size and dispersion. Smaller and more dispersed particles were obtained by decreasing the Rh concentration in the electrolytic solution from Rh/Mg/Al=11/70/19 to 5/70/25 and 2/70/28 atomic ratio% (a.r.%) and in thinner rather than thicker layers. Despite the improvement in metallic particles features, the CH4 conversion was negatively affected by the low amount of active sites in the coating, the high metal support interaction and possibly the oxidation of metallic particles and carbon formation. A larger amount of solid containing well dispersed Rh particles was deposited by increasing the total metal concentration from 0.03 M to 0.06 M with the Rh/Mg/Al=5/70/25 a.r.%, and the catalytic performances were enhanced. The partial replacement of Mg2+ by Ni2+ gave rise to a very active bimetallic Rh/Ni catalyst, CH4 conversion and selectivity to syngas were above 90%, however, it slightly deactivated with time-on-stream. (C) 2015 Elsevier B.V. All rights reserved. |
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Place of Publication |
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Wos |
000359873800036 |
Publication Date |
2015-05-19 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0926-3373 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
9.446 |
Times cited |
14 |
Open Access |
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Notes |
; The Authors acknowledge M. Salome for helping during the mu XRF/XANES experiments at ID21 Beamline of the ESRF, the Department of Structural Characterisation of CNR-IMM of Bologna for the access to the FEG-SEM facility and Dr F. Ospitali for the scientific support. Thanks are due to Farrel Lytle database for providing the necessary Rh metal spectrum (rhfoil.a99 in http:// ixs.iit.edu/data/FarrelLytledata/). The financial support from the Ministero per l'Istruzione, l'Universita e la Ricerca (MIUR, Roma, Italy) and the University of Bologna (FARB program) is gratefully acknowledged. ; |
Approved |
Most recent IF: 9.446; 2015 IF: 7.435 |
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Call Number |
UA @ admin @ c:irua:127777 |
Serial |
5846 |
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Author |
Odin, G.P.; Vanmeert, F.; Farges, F.; Gand, G.; Janssens, K.; Romero-Sarmiento, M.-F.; Steyer, J.S.; Vantelon, D.; Rouchon, V. |
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Title |
Alteration of fossil-bearing shale (Autun, France; Permian), part II : monitoring artificial and natural ageing by combined use of S and Ca K-edge XANES analysis, Rock-Eval pyrolysis and FTIR analysis |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Annales de paléontologie |
Abbreviated Journal |
Ann Paleontol |
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Volume |
101 |
Issue |
3 |
Pages |
225-239 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Fossil-bearing shale specimens that include sulfides in their compositions are chemically reactive and sometimes also mechanically fragile. This decay is often related to iron sulfate efflorescence resulting from the oxidation of sulfide compounds. The processes underlying these degradations are poorly known, thus impeding the elaboration of curative or preventive treatments. The present contribution aims to identify the origin of museum specimen alterations. It focuses on the Flouest collection housed at the Museum National d'Histoire Naturelle (MNHN, Paris, France) and originating from the Autun Basin (Saone-et-Loire, France, Permian). To evaluate the alteration of MNHN specimens, it appeared necessary to compare their composition with that of unaltered shale so as to identify chemical changes occurring during ageing. Therefore, new material was collected in the Autun Basin, among others on the locality of Muse that corresponds to the same lithostratigraphic unit as that of the MNHN specimens. This material was, if necessary, artificially aged. The first part of this work, presented elsewhere, deals with the use of Xray diffraction and Mossbauer spectroscopy for characterizing iron reactivity and speciation. It leads to the conclusion that the reactivity of iron in the shale matrix was limited and could not account for the large efflorescence of iron (II) sulfate occurring nearby the fossil. The second part presented here focuses on the use of S K-edge X-ray Absorption Near Edge Structure (XANES) spectroscopy for characterizing sulfur speciation and reactivity. Measurements were performed on the shale matrix and on thin layers of maceral found in the proximity of damaged areas. As sulfur may be found in association with calcium or organic matter, complementary techniques were implemented, such as FTIR spectroscopy, Rock-Eval pyrolysis (characterization of organic matter content) and Ca K-edge XANES (analysis of calcium speciation) spectroscopy. It was shown that sulfur is mainly related to thioether, sulfoxide, iron sulfide, and sulfates whereas calcium is mainly bound to carboxylate, carbonate and/or sulfate groups. FTIR analysis of the macerals confirmed the presence of vitrinite on damaged MNHN specimens. The low oxygen content of new shale samples determined by Rock-Eval pyrolysis indicates that the organic matter is well preserved, despite the fact that samples come from outcrop surface. In the newly collected material, sulfur is mainly related to organic sulfides (thioether) with a minor occurrence of iron sulfide. In the shale fraction of damaged MNHN specimens, sulfur is mostly oxidized into a mixture of iron and calcium sulfate. However, in the vitrinite layers of the same specimens, a large proportion of sulfur corresponds to organic sulfides. Also the oxidation of sulfur does not occur homogeneously but preferentially in the shale fraction, probably because this latter is porous whereas vitrinite is not. Artificial ageing of new shale material showed that the oxidation of organic sulfides could be reproduced at 90 degrees C, 80% of relative humidity. However, the obtained efflorescence almost exclusively corresponds to calcium sulfate whereas iron (II) sulfates are mostly observed on MNHN specimens. The new material collected on site is probably to be questioned, and future studies will have to select new samples with fossil remains. This will be the object of the third part of this work. (C) 2015 Elsevier Masson SAS. All rights reserved. |
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Wos |
000363821700009 |
Publication Date |
2015-05-09 |
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Series Editor |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0753-3969 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
1.113 |
Times cited |
6 |
Open Access |
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Notes |
; This work was conducted within a PhD work that was supported by a doctoral school grant of the Museum national d'Histoire naturelle, Paris, France. We acknowledge SOLEIL for provision of synchrotron radiation facilities (Proposals ID “20130462” and “20110189”) and we would like to thank Nicolas Trcera, Pierre Lagarde and Anne Marie Flanck for assistance in using beamline LUCIA. ; |
Approved |
Most recent IF: 1.113; 2015 IF: 0.970 |
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Call Number |
UA @ admin @ c:irua:129523 |
Serial |
5462 |
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Author |
Ayalew, E.; Janssens, K.; De Wael, K. |
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Title |
Unraveling the reactivity of minium towards bicarbonate and the role of lead oxides therein |
Type |
A1 Journal article |
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Year |
2016 |
Publication |
Analytical chemistry |
Abbreviated Journal |
Anal Chem |
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Volume |
88 |
Issue |
3 |
Pages |
1564-1569 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Understanding the reactivity of (semiconductor) pigments provides vital information on how to improve conservation strategies for works of art in order to avoid rapid degradation of the pigments. This study focuses on the photoactivity of minium (Pb3O4), a semiconductor pigment, that gives rise to strong discoloration phenomena upon exposure to various environmental conditions. To demonstrate its photoactivity, an electrochemical setup with minium-modified graphite electrode (C|Pb3O4) was used. It is confirmed that minium is a p-type semiconductor which is photoactive during illumination and becomes inactive in the dark. Raman measurements confirm the formation of the degradation products. The photoactivity of a semiconductor pigment is partly defined by the presence of lead oxide (PbO) impurities; these introduce new states in the original band gap. It will be experi-mentally evidenced that the presence of PbO particles in minium leads to an upward shift of the valence band that reduces the band gap. Thus, upon photoexcitation, the electron/hole separation is more easily initialized. The PbO/Pb3O4 composite electrodes demonstrate a higher reductive photocurrent compared to the photocurrent registered at pure PbO or Pb3O4 modified electrodes. Upon exposure to light with energy close to and above the band gap, electrons are excited from the valence band to the conduction band to initialize the reduction of Pb(IV) to Pb(II), resulting in the initial formation of PbO. However in the presence of bicarbonate ions, a significantly higher photoreduction current is recorded since the PbO reacts further to form hydrocerussite. Therefore the presence of bicarbonates in the environment stimulates the photodecomposition process of minium and plays an important role in the degradation process. |
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Wos |
000369471100014 |
Publication Date |
2015-12-31 |
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Series Editor |
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Series Title |
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Abbreviated Series Title |
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Series Volume |
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Series Issue |
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Edition |
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ISSN |
0003-2700; 5206-882x |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
6.32 |
Times cited |
9 |
Open Access |
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Notes |
; The authors acknowledge Sanne Aerts from the Laboratory of Adsorption and Catalysis (LADCA) of the University of Antwerp for her help with the UV-vis-DR. Financial support from the SOLARPAINT BOF-GOA project (University of Antwerp Research Council) is acknowledged. The authors are also indebted to F. Vanmeert for performing the XRD measurements. ; |
Approved |
Most recent IF: 6.32 |
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Call Number |
UA @ admin @ c:irua:129963 |
Serial |
5888 |
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Author |
Cagno, S.; Cosyns, P.; Ceglia, A.; Nys, K.; Janssens, K. |
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Title |
The use of vitrum obsianum in the Roman Empire: some new insights and future prospects |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Periodico di mineralogia |
Abbreviated Journal |
Period Mineral |
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Volume |
84 |
Issue |
3a |
Pages |
465-482 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The research on the use of obsidian in the Mediterranean is extensive but concerns almost exclusively volcanic glass from prehistoric and Bronze Age contexts. The consumption of obsidian during the Roman imperial period, however, has only occasionally received attention. Never a comprehensive account on what the Romans made in vitrum obsianum has been set up, nor have the sources exploited by them been examined. This paper provides a concise overview of the current knowledge on obsidian during the Roman imperial period and offers an introductory outline on potential research. The ancient writers inform us about the use of volcanic glass to create exclusive vessels, gemstones, mirrors and sculpture, but also about the creation of black appearing man-made glass initiated as a cheap and easier workable substitute of obsidian. The archaeological data on the other hand propose a more complex story with the occurrence of obsidian chunks in early Roman secondary glass workshops, and the bulky use of obsidian in late Antiquity to produce tesserae for the creation of wall and vault mosaics. Because it is extremely difficult to visually distinguish natural obsidian from man-made glass imitations we present in this paper data collected by means of non-destructive chemico-physical analyses SEM-EDX, portable X-ray fluorescence (p-XRF) and Raman spectroscopy to easily distinguish man-made glass from natural obsidian. In particular the use of portable instruments makes possible in situ analysis of objects in archaeological depots or museum collections to help defining distribution networks to better understand the shifting consumption patterns in Antiquity. |
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Wos |
000365632500007 |
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ISSN |
0369-8963 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
0.883 |
Times cited |
2 |
Open Access |
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Notes |
; Our sincere gratitude goes to Cecile Evers and Natacha Masar to have granted permission for studying and analysing various obsidian artefacts within the collections of the Royal Museums of Art and History, Brussels (Belgium). We are also very grateful to Roald Doctor, Daniele Foy and Laudine Robin, respectively for having provided the material from Carthage, for the Sidi Jdidi tessera and Lyon. Our appreciation also goes to Ian Freestone and Andrew Meek respectively for having worked out and provided the internal report on the horse foreleg in the British Museum. Finally we wish to thank Jennifer Price, Maria Grazia Diani respectively for the information on the Stanwick fragment and the piece in the Pogliaghi-Varesse collection. This research was supported by the Hercules Foundation (Brussels) with the grant AUHA09004 and FWO (Brussels, Belgium) projects no. G.0C12.13 and G.01769.09 and partly by the Research Council of Norway through its Centres of Excellence funding scheme, project number 223268/ F50. ; |
Approved |
Most recent IF: 0.883; 2015 IF: 0.464 |
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Call Number |
UA @ admin @ c:irua:130244 |
Serial |
5876 |
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Author |
Trentelman, K.; Janssens, K.; van der Snickt, G.; Szafran, Y.; Woollett, A.T.; Dik, J. |
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Title |
Rembrandt's An Old Man in Military Costume: the underlying image re-examined |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Applied physics A : materials science & processing |
Abbreviated Journal |
Appl Phys A-Mater |
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Volume |
121 |
Issue |
3 |
Pages |
801-811 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The painting An Old Man in Military Costume in the J. Paul Getty Museum, by Rembrandt Harmensz van Rijn, was studied using two complementary, element-specific imaging techniques-neutron activation autoradiography (NAAR) and macro-X-ray fluorescence (MA-XRF) mapping-to reveal the second, hidden painting. NAAR provided a strong image of the face and cloak of the underlying figure, along with an indication of the chemical composition. The single-element distribution maps produced by MA-XRF mapping provided additional details into the shape of the underlying image and the composition of the pigments used. The underlying figure's face is richer in mercury, indicative of the pigment vermilion, than the face of the figure on the surface. Likewise, the cloak of the underlying figure is richer in copper than the surface figure though the identity of the copper-containing pigment cannot be determined from these data. The use of iron earth pigments, specifically Si-rich umbers, is indicated through the complementary information provided by the NAAR and MA-XRF maps. These data are used to create a false color digital reconstruction, yielding the most detailed representation of the underlying painting to date. |
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Wos |
000364914100003 |
Publication Date |
2015-08-31 |
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ISSN |
0947-8396 |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
1.455 |
Times cited |
22 |
Open Access |
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Notes |
; The authors gratefully acknowledge the assistance of all those who aided in the examination of this painting over the decades, that has culminated in the work presented here. Particular thanks go to Mark Leonard (former head of Paintings Conservation at the J. Paul Getty Museum) and Henry Prask (NIST) for carrying out the NAAR analysis; John Twilley (former GCI Scientist) for early investigations; Andrea Sartorius (former JPGM Paintings intern) for creating a mock-up painting used in earlier phases of this work; Peter Reishig (former GCI intern) for compiling the NAAR data; Catherine Patterson, Lynn Lee, and David Carson (GCI Science) and Gene Karraker (JPGM Paintings Conservation) for helping with the setup and operation of the M6 Jetstream; and Giacomo Chiari (former head of GCI Science) for performing the XRD analysis. Koen Janssens and Geert van der Snickt acknowledge the Fund Inbev-Baillet Latour for financial support. Joris Dik acknowledges the help of the Netherlands Organization for Scientific Research (NWO) in the form of a VIDI grant in the Innovational Research Incentive Scheme. ; |
Approved |
Most recent IF: 1.455; 2015 IF: 1.704 |
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Call Number |
UA @ admin @ c:irua:130289 |
Serial |
5812 |
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Author |
Pouyet, E.; Cotte, M.; Fayard, B.; Salome, M.; Meirer, F.; Mehta, A.; Uffelman, E.S.; Hull, A.; Vanmeert, F.; Kieffer, J.; Burghammer, M.; Janssens, K.; Sette, F.; Mass, J. |
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Title |
2D X-ray and FTIR micro-analysis of the degradation of cadmium yellow pigment in paintings of Henri Matisse |
Type |
A1 Journal article |
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Year |
2015 |
Publication |
Applied physics A : materials science & processing |
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Volume |
121 |
Issue |
3 |
Pages |
967-980 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
The chemical and physical alterations of cadmium yellow (CdS) paints in Henri Matisse's The Joy of Life (1905-1906, The Barnes Foundation) have been recognized since 2006, when a survey by portable X-ray fluorescence identified this pigment in all altered regions of the monumental painting. This alteration is visible as fading, discoloration, chalking, flaking, and spalling of several regions of light to medium yellow paint. Since that time, synchrotron radiation-based techniques including elemental and spectroscopic imaging, as well as X-ray scattering have been employed to locate and identify the alteration products observed in this and related works by Henri Matisse. This information is necessary to formulate one or multiple mechanisms for degradation of Matisse's paints from this period, and thus ensure proper environmental conditions for the storage and the display of his works. This paper focuses on 2D full-field X-ray Near Edge Structure imaging, 2D micro-X-ray Diffraction, X-ray Fluorescence, and Fourier Transform Infra-red imaging of the altered paint layers to address one of the long-standing questions about cadmium yellow alteration-the roles of cadmium carbonates and cadmium sulphates found in the altered paint layers. These compounds have often been assumed to be photo-oxidation products, but could also be residual starting reagents from an indirect wet process synthesis of CdS. The data presented here allow identifying and mapping the location of cadmium carbonates, cadmium chlorides, cadmium oxalates, cadmium sulphates, and cadmium sulphides in thin sections of altered cadmium yellow paints from The Joy of Life and Matisse's Flower Piece (1906, The Barnes Foundation). Distribution of various cadmium compounds confirms that cadmium carbonates and sulphates are photo-degradation products in The Joy of Life, whereas in Flower Piece, cadmium carbonates appear to have been a [(partially) unreacted] starting reagent for the yellow paint, a role previously suggested in other altered yellow paints. |
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Wos |
000364914100017 |
Publication Date |
2015-06-03 |
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ISSN |
0947-8396; 1432-0630 |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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no |
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Call Number |
UA @ admin @ c:irua:130290 |
Serial |
7382 |
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Author |
Monico, L.; Janssens, K.; Cotte, M.; Sorace, L.; Vanmeert, F.; Brunetti, B.G.; Miliani, C. |
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Title |
Chromium speciation methods and infrared spectroscopy for studying the chemical reactivity of lead chromate-based pigments in oil medium |
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A1 Journal article |
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Year |
2016 |
Publication |
Microchemical journal
T2 – TECHNART Conference, APR 27-30, 2015, Catania, ITALY |
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Microchem J |
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124 |
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272-282 |
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Keywords |
A1 Journal article; AXES (Antwerp X-ray Analysis, Electrochemistry and Speciation) |
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Abstract |
Environmental factors, such as light, humidity and temperature are triggering agents for the alteration of organic and/or inorganic constituents of oil paintings. The oxidation of the organic material is favored by increasing of relative humidity and temperature, whereas processes involving changes of the oxidation states of a number of inorganic pigments (e.g., vermilion, cadmium yellows, zinc yellows, chrome yellows) are mainly activated by light-exposure. In view of the optimization of the long-term conservation and restoration strategies of paintings it is of relevant interest to establish the consequences of thermal parameters (temperature and relative humidity) on the chemical/photochemical-reactivity and the nature of the alteration products of light sensitive-pigments in oil medium. To this aim here we propose a multi-method analytical approach based on the combination of diffuse reflectance UV-Vis, FTIR, synchrotron radiation (SR)-based micro X-ray fluorescence (mu-XRF)/micro-X-ray absorption neat edge structure ()CANES) and electron paramagnetic resonance (EPR) spectroscopies for studying the effects of different relative humidity conditions before and after light exposure on the reactivity of a series of lead chromate-based pigments [such as PbCrO4 center dot PbO (monoclinic), PbCrO4 (monoclinic) and PbCr0.2S0.8O4 (orthorhombic)] in an oil medium. The investigation of paint models was also compared to that of a late 19th century historical orthorhombic PbCr0.4S0.6O4 oil paint. Diffuse reflectance UV-Vis and FTIR spectroscopies were used to obtain information associated with chromatic changes and the formation of organo-metal degradation products at the paint surface. SR-based Cr K-edge mu-XANES/mu-XRF mapping analysis and EPR spectroscopy were employed in a complementary fashion to determine the amount, nature and distribution of Cr(III) and Cr(V)-based alteration compounds within the paints with micrometric spatial resolution. Under the employed thermal aging conditions, lead(II)-carboxylates and reduced Cr-compounds (in abundance of up to about 35% at the surface) have been identified in the lead chromate-based paints. The tendency of chromates to become reduced increased with increasing moisture levels and was favored for the orthorhombic PbCr0.2S0.8O4 compounds. The redox process gave rise to the formation of Cr(V)-species in relative amount much higher than that was formed in the equivalent paint which was exposed only to light. After light-exposure of the thermally aged paints, compounds ascribable to the oxidation of the organic binder were detected for all the types of pigments. Nevertheless, the previous thermal treatment increased the tendency toward photo-reduction of only the PbCr0.2S0.8O4 pigment. For this light-sensitive compound, the thickness variation of the reduced Cr-rich (ca. 70%) photo-alteration layer with moisture levels could be ascribed to a surface passivation phenomenon that had already occurred before photochemical aging. (C) 2015 Elsevier B.V. All rights reserved. |
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000367755600042 |
Publication Date |
2015-09-12 |
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ISSN |
0026-265x; 0026-265x |
ISBN |
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Additional Links |
UA library record; WoS full record; WoS citing articles |
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Impact Factor |
3.034 |
Times cited |
23 |
Open Access |
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Notes |
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Approved |
Most recent IF: 3.034 |
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Call Number |
UA @ admin @ c:irua:131099 |
Serial |
5519 |
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