Microanalytical identification of Pb-Sb-Sn yellow pigment in historical European paintings and its differentiation from lead tin and Naples yellows

Hradil, David; Grygar, Tomáš Matys; Hradilová, Janka; Bezdička, Petr; Grünwaldová, Veronika; Fogaš, Igor; Miliani, Costanza

doi:10.1016/j.culher.2007.07.001

Cited by 76 publications

(87 citation statements)

References 13 publications

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“…[1,2,6,8,9] Two different lead antimonates doped with tin (PV TY 1 and PV TY 60) were synthesized using Sb 2 O 3 or Sb 2 S 3 , in order to evaluate the possible meaning of 'antimony' in historical recipes, which theoretically meant metallic, oxide and/or sulfide antimony. Moreover, the possible effect of the presence of lead carbonate instead of lead oxide as a starting material on the final structure was taken into account in PV TY 60.…”

Section: Methodsmentioning

confidence: 99%

“…Only recently the existence of the modified structure been confirmed, also suggesting that its use was not necessarily restricted to 17th century Roman artistic production. In particular, using micro-Raman spectroscopy RuizMoreno et al [4] and Sandalinas et al [5] identified the ternary oxide in an Italian 17th century painting and a 16th century majolica, while using X-ray fluorescence (XRF) and XRD investigations Hradil et al [6] detected it in five Mid-European paintings from the 18th to 19th centuries.…”

Section: Introductionmentioning

confidence: 99%

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Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc

Rosi

Manuali

Miliani

et al. 2008

J Raman Spectroscopy

115

165

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Yellow pyroantimonates Pb-Sb, Pb-Sb-Sn and Pb-Sb-Zn were synthesized by solid-state reactions at high temperature and characterized by X-ray diffraction and Raman spectroscopy. The lattice size of cubic pyrochlores increases with Sn and Zn doping and with Pb overstoichiometry, indicating the replacement of Sb 5+ by the larger cations. This fact permits the understanding of the corresponding Raman spectral modifications as a consequence of the changes in the local symmetry of the Sb-O polyhedra, justifying the exploitation of Raman spectroscopy to noninvasively identify structural modifications of pyroantimonate pigments in artworks.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc

Rosi

Manuali

Miliani

et al. 2008

J Raman Spectroscopy

115

165

View full text Add to dashboard Cite

show abstract

“…Tin-rich Pb-antimonate are testified in the literature both in glass [17,20,56,57], where they are interpreted as Pb-antimonates, and in painting pigments, classified as "triple oxides of Sn, Pb and Sb" [58,59]. Many hypotheses were advanced to explain the presence of tin in Pb-antimonate [17,18].…”

Section: Yellow and Green Tesseraementioning

confidence: 99%

A Mosaic of Colors: Investigating Production Technologies of Roman Glass Tesserae from Northeastern Italy

Maltoni

Silvestri

2018

Minerals

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In the current study, a set of 60 glass tesserae from two disrupted Roman mosaics located in Pordenone and Trento (northeastern Italy) are analyzed, with the aim of investigating the coloring and opacification techniques, with a focus on the causes of specific textural features. All the available colors and textures were selected for archaeometric analyses, in order to guarantee the full characterization of both assemblages and comparisons between the two sites. The applied analytical protocol comprises micro-textural and preliminary chemical characterizations of the tesserae by means of OM and SEM-EDS, mineralogical analysis of the opacifiers by XRD and chemical analysis of the glassy matrices by EPMA; in addition, on specific tesserae, micro-Raman spectroscopy, FORS, and EPR were also performed to clarify the type of opacifer, coloring ion and oxidation state, respectively. Results show that both the base-glass and the coloring/opacification techniques identified are consistent with the presumed Roman dating of the mosaics. All the tesserae are natron-based and chemically comparable with major Roman compositional groups, except for red samples. Antimony-based opacifiers are identified in most of the blue, turquoise, white, yellow and green tesserae, and copper-based opacifiers in the red ones; cobalt and copper are the most frequent ionic colorants used to obtain various shades of blue, turquoise and green colors. Despite the general comparability of both assemblages with the published data on glass tesserae coeval in age, the present study shows differences in the technological solutions used for obtaining the same color, and less common coloring and opacification techniques in three samples from Pordenone. The banded textures of some tesserae were also carefully investigated, and multiple factors influencing the changes in color (different distribution or relative abundance of opacifiers, crystal size, micro-texture, chemical composition of glassy matrix) are identified.

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“…However, we may not exclude that copper filings [30,31] were added and during the firing process in oxidising atmosphere turned into tenorite. Burnt Cu was widely used in ancient and medieval glasses and glazes [29]. There is also a Renaissance recipe of Piccolpasso (The Three Books of the Potter's Art, para.…”

Section: Opacifiers and Colorantsmentioning

confidence: 99%

“…9) and lead-tin yellow type I (SEM/EDS, µ-XRD- Fig. 10), which were probably added as a mixture [29]. According to recipes, these two yellow pigments were used in the mixture known as giallolino which originated from Germany (Alemagna).…”

Section: Opacifiers and Colorantsmentioning

confidence: 99%

Gothic green glazed tile from Malbork Castle: multi-analytical study

2017

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Looking at the façade of a historical building, it is often difficult to distinguish between the original decoration and later additions. One such building is the Holy Virgin Mary Church at the Malbork Castle (Northern Poland), built between 1276 and 1406. During the latest restoration works, ceramic tiles with some remnants of the green glaze, decorating the Holy Virgin Mary Church façade, were studied in situ using portable X-ray fluorescence spectrometry. Micro-samples were analyzed in laboratory by scanning electron microscopy with energy dispersive X-ray spectrometry (SEM-EDS) and wavelength-dispersive X-ray spectrometry (SEM-WDS), micro-Raman spectroscopy and powder X-ray micro-diffraction. We found that what was originally thought to be a paint layer was in fact a heavily deteriorated SiO 2 -PbO glaze. White, yellow and black pigments were found to have been added into the glaze as opacifiers and colorants. Copper and iron were used as glaze colorants. The originally added pigments were transformed into new phases, such as antimony-doped tin oxide. The technology used to produce the glazed tiles was identified. All the results collectively confirmed the medieval origin of the green glazed tiles.

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Microanalytical identification of Pb-Sb-Sn yellow pigment in historical European paintings and its differentiation from lead tin and Naples yellows

Cited by 76 publications

References 13 publications

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc

A Mosaic of Colors: Investigating Production Technologies of Roman Glass Tesserae from Northeastern Italy

Gothic green glazed tile from Malbork Castle: multi-analytical study

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Microanalytical identification of Pb-Sb-Sn yellow pigment in historical European paintings and its differentiation from lead tin and Naples yellows

Cited by 76 publications

References 13 publications

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb2Sb2O7 doped with tin and zinc

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb2Sb2O7 doped with tin and zinc

A Mosaic of Colors: Investigating Production Technologies of Roman Glass Tesserae from Northeastern Italy

Gothic green glazed tile from Malbork Castle: multi-analytical study

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Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc

Raman scattering features of lead pyroantimonate compounds. Part I: XRD and Raman characterization of Pb₂Sb₂O₇ doped with tin and zinc