James Ensor's pigment use: artistic and material evolution studied by means of portable X‐ray fluorescence spectrometry

Snickt, Geert Van der; Janssens, Koen; Schalm, Olivier; Aibéo, Cristina; Kloust, Hauke; Alfeld, Matthias

doi:10.1002/xrs.1235

Cited by 28 publications

(2 citation statements)

References 19 publications

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“…Chrome Yellows (CY) are a family of synthetic yellow pigments of PbCr (1Àx) S x O 4 formula, which were introduced in 1809 by Vaquelin and made commercially available since around 1815. 1,2 CY suddenly entered into the palette of nineteenthcentury masters, including J. Constable, 3 J. M. W. Turner, 4 V. van Gogh, 5,6 G. Seraut, 7 C. Pissarro, 8 P. Cezanne, 9 J. Ensor, 10 who highly appreciated its bright and opaque colour ranging from deep yellow to lemon yellow. Pure PbCrO 4 is the reference compound, CrO 4 2À being responsible for the characteristic deep yellow colour of the pigment; it shows a monoclinic crystal structure (Scheme 1, le).…”

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Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

2016

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Section: Introductionmentioning

confidence: 99%

Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

2016

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“…C hrome yellows belong to a class of synthetic inorganic yellow-orange pigments that became popular as artists' materials from the second quarter of the 19th century; they are often encountered in masterpieces by famous painters, such as Paul Cezanne (1839−1906), 1 Vincent van Gogh (1853− 1890), 2 and James Ensor (1860−1949). 3 This pigment is also employed for industrial purposes, such as painting of vehicles and airplanes, in printing inks, and for coloring rubber and paper. So, it can be released into the environment through degradation and corrosion as a result of industrial use and service life of colored products.…”

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Unique Optoelectronic Structure and Photoreduction Properties of Sulfur-Doped Lead Chromates Explaining Their Instability in Paintings

et al. 2017

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Chrome yellow refers to a group of synthetic inorganic pigments that became popular as an artist's material from the second quarter of the 19th century. The color of the pigment, in which the chromate ion acts as a chromophore, is related to its chemical composition (PbCrSO, with 0 ≤ x ≤ 0.8) and crystalline structure (monoclinic/orthorhombic). Their shades range from the yellow-orange to the paler yellow tones with increasing sulfate amount. These pigments show remarkable signs of degradation after limited time periods. Pure PbCrO (crocoite in its natural form) has a deep yellow color and is relatively stable, while the coprecipitate with lead sulfate (PbCrSO) has a paler shade and seems to degrade faster. This degradation is assumed to be related to the reduction of Cr(VI) to Cr(III). We show that, when the the sulfur(S)-content in chrome yellow increases, the band gap increases. Typically, when increasing the band gap, one might assume that a decrease in photoactivity is the result. However, the photoactivity relative to the Cr content and, thus, Cr reduction of sulfur-rich PbCrSO is found to be much higher compared to the sulfur-poor or nondoped lead chromates. This discrepancy can be explained by the evolution of the crystal and electronic structure as a function of the sulfur content: first-principles density functional theory calculations show that both the absorption coefficient and reflection coefficients of the lead chromates change as a result of the sulfate doping in such a way that the generation of electron-hole pairs under illumination relative to the total Cr content increases. These changes in the material properties explain why paler shade yellow colors of this pigment are more prone to discoloration. The electronic structure calculations also demonstrate that lead chromate and its coprecipitates are p-type semiconductors, which explains the observed reduction reaction. Because understanding this phenomenon is valuable in the field of cultural heritage, this study is the first joint action of photoelectrochemical measurements and first-principles calculations to approve the higher tendency of sulfur-rich lead chromates to darken.

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Raman study of different crystalline forms of PbCrO₄ and PbCr_1−xS_xO₄ solid solutions for the noninvasive identification of chrome yellows in paintings: a focus on works by Vincent van Gogh

Monico

Janssens

Hendriks

et al. 2014

J Raman Spectroscopy

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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 ~ 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 (0.1 ≤ × ≤ 0.8). These paints were studied using several excitation wavelengths (namely 785.0, 532.0, 514.5, and 488 nm). 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 785.0 nm. 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 © 2014 John Wiley & Sons, Ltd.

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James Ensor's pigment use: artistic and material evolution studied by means of portable X‐ray fluorescence spectrometry

Cited by 28 publications

References 19 publications

Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Unique Optoelectronic Structure and Photoreduction Properties of Sulfur-Doped Lead Chromates Explaining Their Instability in Paintings

Raman study of different crystalline forms of PbCrO₄ and PbCr_1−xS_xO₄ solid solutions for the noninvasive identification of chrome yellows in paintings: a focus on works by Vincent van Gogh

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James Ensor's pigment use: artistic and material evolution studied by means of portable X‐ray fluorescence spectrometry

Cited by 28 publications

References 19 publications

Structural and electronic properties of the PbCrO4 chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Structural and electronic properties of the PbCrO4 chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Unique Optoelectronic Structure and Photoreduction Properties of Sulfur-Doped Lead Chromates Explaining Their Instability in Paintings

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

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Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Structural and electronic properties of the PbCrO₄ chrome yellow pigment and of its light sensitive sulfate-substituted compounds

Raman study of different crystalline forms of PbCrO₄ and PbCr_1−xS_xO₄ solid solutions for the noninvasive identification of chrome yellows in paintings: a focus on works by Vincent van Gogh