Photoluminescence Properties of Zinc Oxide in Paints: A Study of the Effect of Self-Absorption and Passivation

Clementi, Catia; Rosi, Francesca; Romani, A.; Vivani, Riccardo; Brunetti, Brunetto Giovanni; Miliani, Costanza

doi:10.1366/12-06643

Cited by 48 publications

(42 citation statements)

References 37 publications

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“…Zinc oxide has been ascertained based on the UV-Vis-NIR reflectance profile in Fig. 1b, exhibiting an inflection point at 384 nm [13] and on the luminescence spectra (data not reported herein) showing the sharp band at around 380 nm ascribable to ZnO band gap emission [14] and a broad band at higher wavelengths. The presence of titanium dioxide in the anatase modification, tentatively indicated by the weak inflection point at 372 nm in the reflectance spectrum (Fig.…”

Section: White Paintsmentioning

confidence: 96%

Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies

et al. 2016

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Alchemy (1947, Peggy Guggenheim Collection, Venice) is one of the most materic works by J. Pollock, whose palette is extensive, ranging from white to yellow, red, green, violet, blue, black, and silver. Each layer of color was laid on top of a previously dried one and effectively separated from the lower one forming a quite complex stratigraphy with colors intersecting each other. In this study, a non-invasive multi-technique method combining point analysis with Vis-NIR multispectral imaging has been exploited to give insights on the painting technique of the American abstract expressionist. The molecular identification of pigments, colorants and extenders contained in fifteen different paints has been achieved combining key spectral markers from elemental, electronic and vibrational spectroscopies. For those colors exhibiting similar hues but different chemical compositions, a mapping procedure based on false color rendering, obtained by properly mixing three spectral planes from the Vis-NIR multispectral imaging set, has been successfully applied. Relevant for the understanding of the evolution of Pollock's drip technique is the identification of both traditional oil-based paints and oil-modified alkyd media. Point analysis by reflection FTIR scattered throughout the painting enabled mapping the distinct use of traditional and new binding media among painted, squeezed and dripped paints.

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Section: White Paintsmentioning

confidence: 96%

Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies

et al. 2016

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“…Specically, the n a COO À band is frequently signicantly broadened and shied to higher wavenumbers (between 1570 and 1590 cm À1 ) in ZnO containing paint layers. 7,9,[14][15][16][17] We discuss Attenuated Total Reection Fourier Transform infrared microscopy (m-ATR-FTIR) analysis of a sample from the painting De Houthakker (naar Millet) ('The Woodcutter (aer Millet)') by Vincent van Gogh as a clear example of this phenomenon.…”

Section: Introductionmentioning

confidence: 99%

An infrared spectroscopic study of the nature of zinc carboxylates in oil paintings

Hermans

Keune

Loon

et al. 2015

J. Anal. At. Spectrom.

126

141

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An infrared spectroscopic study of the nature of zinc carboxylates in oil paintingsHermans, J.J.; Keune, K.; van Loon, A.; Iedema, P.D. Published in:Journal of analytical atomic spectrometry DOI:10.1039/c5ja00120jLink to publication Citation for published version (APA):Hermans, J. J., Keune, K., van Loon, A., & Iedema, P. D. (2015). An infrared spectroscopic study of the nature of zinc carboxylates in oil paintings. Journal of analytical atomic spectrometry, 30(7), 1600-1608. DOI: 10.1039/c5ja00120j General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. Download date: 12 May 2018An infrared spectroscopic study of the nature of zinc carboxylates in oil paintings † Joen J. Hermans, * Katrien Keune, Annelies van Loon and Piet D. IedemaThe formation of metal soaps is a major problem for oil paintings conservators. The complexes of either lead or zinc and fatty acids are the product of reactions between common pigments and the oil binder, and they are associated with many types of degradation that affect the appearance and stability of oil paint layers.Fourier transform infrared spectroscopy (FTIR) reveals that a paint sample from The Woodcutter (after Millet) by Vincent van Gogh contains two distinct zinc carboxylate species, one similar to crystalline zinc palmitate and one that is characterized by a broadened asymmetric stretch COO À band shifted to 1570-1590 cm À1 . This observation has been made in many paintings. Although several hypotheses exist to explain the shifted broad carboxylate band, these were not supported by experimental evidence. In this paper, experiments were carried out to characterize the second zinc carboxylate type. It is shown that neither variations in the composition of zinc soaps (i.e. zinc soaps containing mixtures of fatty acids or metals) nor fatty acids adsorbed on pigment surfaces are responsible for the second zinc carboxylate species. X-Ray diffraction (XRD) and FTIR analysis indicate that the broad COO À band represents amorphous zinc carboxylates. These species can be interpreted as either non-crystalline zinc soaps or zinc ions bound to carboxylate moieties on the polymerized oil network, a system similar to ionomers.These findings uncover an intermediate stage of metal soap-related degradation of oil paintings, and lead the way to impr...

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“…This is caused by the reactions between zinc ions of the pigment and fatty acids contained in the binding medium, leading to formation of zinc carboxylates, which are easily detected by Fourier transform infrared spectroscopy (FTIR) [11,12]. Clementi et al worked on different mixtures of zinc white with oils and alkyd medium, observing the generation of a broad band at about 1600 cm −1 with infrared spectroscopy [13]. Based on literature about ZnO functionalized with organic network, the authors suggested that changes in luminescence were due to the absorption of free fatty acids onto the ZnO surface (chemisorbed carboxylates) and oxygen vacancies passivation.…”

Section: Introductionmentioning

confidence: 99%

A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes

et al. 2017

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It is known that oil paintings containing zinc white are subject to rapid degradation. This is caused by the interaction between the active groups of binder and the metal ions of the pigment, which gives rise to the formation of new zinc complexes (metal soaps). Ongoing studies on zinc white paints have been limited to the chemical mechanisms that lead to the formation of zinc complexes. On the contrary, little is known of the photo-physical changes induced in the zinc oxide crystal structure following this interaction. Time-resolved photoluminescence spectroscopy has been applied to follow modifications in the luminescent zinc white pigment when mixed with binder. Significant changes in trap state photoluminescence emissions have been detected: the enhancement of a blue emission combined with a change of the decay kinetic of the well-known green emission. Complementary data from molecular analysis of paints using Fourier transform infrared spectroscopy confirms the formation of zinc carboxylates and corroborates the mechanism for zinc complexes formation. We support the hypothesis that zinc ions migrate into binder creating novel vacancies, affecting the photoluminescence intensity and lifetime properties of zinc oxide. Here, we further demonstrate the advantages of a time-resolved photoluminescence approach for studying defects in semiconductor pigments.

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Photoluminescence Properties of Zinc Oxide in Paints: A Study of the Effect of Self-Absorption and Passivation

Cited by 48 publications

References 37 publications

Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies

Disclosing Jackson Pollock’s palette in Alchemy (1947) by non-invasive spectroscopies

An infrared spectroscopic study of the nature of zinc carboxylates in oil paintings

A Photoluminescence Study of the Changes Induced in the Zinc White Pigment by Formation of Zinc Complexes

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