Evaluation of the “added value” of SIMS: A mass spectrometric and spectroscopic study of an unusual Naples yellow oil paint reconstruction

Keune, Katrien; Hoogland, Frank; Boon, Jaap J.; Peggie, David A.; Higgitt, Catherine

doi:10.1016/j.ijms.2008.10.016

Cited by 36 publications

(33 citation statements)

References 14 publications

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“…Even if such techniques are destructive and cannot always be applied to precious historical samples, they are of interest to understand reaction processes on model paints. A comparison of pros and cons of many analytical techniques applied to the study of interactions between the Naples yellow (lead antimonate) pigment and oil (in particular the detection of metal carboxylates) can be found here (Keune et al, 2009). Beyond the scope of paintings, Corkery gives a very detailed review of uses, identification, and characterization of metal soaps, through history (Corkery, 1998).…”

Section: Identification Of Metal Soaps In Paintings: a Dramatic Evolumentioning

confidence: 99%

Lead soaps in paintings: Friends or foes?

Cotte

Checroun

Nolf

et al. 2016

Studies in Conservation

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The origin(s) and role(s) of metal soaps in paints are a worldwide concern today. These hybrid compounds, containing both fatty acid chains and metals associated with a carboxylate function, are increasingly identified in paints. As reviewed in the first part of this work, the presence of metal soaps in paints is differently interpreted in scientific publications: metal soaps are sometimes considered to play a positive role as anchor points, during paint drying processes; they can also be considered as responsible for many degradation processes (protrusions, efflorescences, darkening, etc.). Their origins are also interpreted in various ways. In some paintings (in particular from the twentieth century), they have sometimes introduced on purpose, as additives, to modify the physical properties of the painting materials. In older paintings, metal soaps are usually thought to result from an uncontrolled reaction of oil with lead-based pigments, in particular lead white, red lead, and lead tin yellow. In the second part of this work, the review of historical recipes of lead-based paint shows an important number of recipes based on controlled mixing of oil with lead driers. In the third part, the experimental reproduction of such traditional recipes using walnut oil and litharge (PbO) shows that lead soaps can be formed, both in about one hour at ∼100°C, or in about one month at room temperature. It shows as well that after a few years, litharge is no longer detected in the paint medium, while different lead carbonates are. Finally, the micro-infrared spectroscopy and micro-X-ray diffraction re-analysis of protrusions from a nine-year model painting shows together with lead soaps, the presence of Pb 5 (CO 3 ) 3 (OH) 2 O ('synthetic plumbonacrite'), an unusual phase recently observed in a protrusion from a painting by Vincent Van Gogh. This work highlights (i) the multiple origins and roles of metal soaps in paints and (ii) the importance of combining the analysis of fragments from historical paintings with the analysis and reproduction of historical recipes. In particular, we show that the components detected today in historical paintings may severely differ from those originally used or prepared by the painter, complicating the assessment of the painter's intentions. More than the presence of metal soaps, the key questions to be tackled should be about their origins and (re)mobilization.

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Section: Identification Of Metal Soaps In Paintings: a Dramatic Evolumentioning

confidence: 99%

Lead soaps in paintings: Friends or foes?

Cotte

Checroun

Nolf

et al. 2016

Studies in Conservation

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“…It has been successfully used for several Cultural Heritage studies regarding detection and localization of both organic and inorganic compounds as it offers a high sensitivity and selectivity and an excellent lateral resolution (from the micrometer down to few hundreds of nanometers). Furthermore, sample integrity is preserved and identification and localization of a large variety of compounds is possible . The presence of dried blood and snake urine in the patina of African statuettes, an unexpected use of starch in a Rembrandt's painting ground layer as well as the identification of atacamite and copper carboxylates in a XVI th century's altarpiece were all revealed thanks to mass spectrometry imaging.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, sample integrity is preserved and identification and localization of a large variety of compounds is possible. [18] The presence of dried blood and snake urine in the patina of African statuettes, [19] an unexpected use of starch in a Rembrandt's painting ground layer [20] as well as the identification of atacamite and copper carboxylates in a XVI th century's altarpiece [21] were all revealed thanks to mass spectrometry imaging. In addition, the limited damage is a significant advantage since the sample, which is often inestimable and unique, can then be further analyzed by other chemical imaging methods to obtain complementary information.…”

Section: Introductionmentioning

confidence: 99%

Cluster TOF‐SIMS imaging of human skin remains: analysis of a South‐Andean mummy sample

et al. 2012

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A skin sample from a South-Andean mummy dating back from the XI(th) century was analyzed using time-of-flight secondary ion mass spectrometry imaging using cluster primary ion beams (cluster-TOF-SIMS). For the first time on a mummy, skin dermis and epidermis could be chemically differentiated using mass spectrometry imaging. Differences in amino-acid composition between keratin and collagen, the two major proteins of skin tissue, could indeed be exploited. A surprising lipid composition of hypodermis was also revealed and seems to result from fatty acids damage by bacteria. Using cluster-TOF-SIMS imaging skills, traces of bio-mineralization could be identified at the micrometer scale, especially formation of calcium phosphate at the skin surface. Mineral deposits at the surface were characterized using both scanning electron microscopy (SEM) in combination with energy-dispersive X-ray spectroscopy and mass spectrometry imaging. The stratigraphy of such a sample was revealed for the first time using this technique. More precise molecular maps were also recorded at higher spatial resolution, below 1 µm. This was achieved using a non-bunched mode of the primary ion source, while keeping intact the mass resolution thanks to a delayed extraction of the secondary ions. Details from biological structure as can be seen on SEM images are observable on chemical maps at this sub-micrometer scale. Thus, this work illustrates the interesting possibilities of chemical imaging by cluster-TOF-SIMS concerning ancient biological tissues.

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“…The application of ToF‐SIMS to art object is instead quite recent: This technique allows the characterization of the molecular composition of the object surface with a limited damage, with high spatial and depth resolution. It gathers more accurate information on the spatial distribution of chemical components than elemental analysis techniques (such as SEM‐EDS) or spectroscopic analysis (such as Raman spectroscopy or FTIR) . These analytical aspects make ToF‐SIMS analysis an interesting tool for chemical characterization in a complex, multilayered painting cross section as the Bosch painting samples investigated here.…”

Section: Introductionmentioning

confidence: 99%

Raman and time of flight secondary ion mass spectrometry investigation answers specific conservation questions on Bosch painting Saint Wilgefortis Triptych

Sodo

Tortora

Biocca

et al. 2018

J Raman Spectroscopy

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Raman spectroscopy and time of flight secondary ion mass spectrometry (ToF-SIMS) were used to answer conservation questions left open after the preliminary analysis performed by the restoration team on the Bosch painting Saint Wilgefortis Triptych, within the project "Bosch in Venice." In this work,we present the results obtained by combining these two techniques on five cross sections, concerning a detailed study of pigments and bindings degradation processes, the identification of organic components (binders/lakes), and the characterization of restoration products. Raman measurements show the presence of degradation products, such as calomel on the red pigment cinnabar, calcium-oxalate, in particular weddellite, localized in a not original external layer, and finally lead soaps in several layers of the investigated samples.Although the detection of lead soaps suggests the use of oils as binders, Raman spectroscopy has given no conclusive information about such binders, neither on the possible presence of red lakes, suggested by independent UV observations. Complementary ToF-SIMS investigations have instead revealed the presence of lead palmitate and stearate in the painting layers along with miristic, palmitic, oleic, and stearic acids, thus confirming the use of an oil medium, likely linseed oil. Additionally, ToF-SIMS shows the presence of polydimethylsiloxane, likely from a previous restoration treatment in the 1990s, in the external layer of the investigated cross sections. Due to experimental difficulties during the analysis of the red lake, we can only hypothesize the presence of alizarin.

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Evaluation of the “added value” of SIMS: A mass spectrometric and spectroscopic study of an unusual Naples yellow oil paint reconstruction

Cited by 36 publications

References 14 publications

Lead soaps in paintings: Friends or foes?

Lead soaps in paintings: Friends or foes?

Cluster TOF‐SIMS imaging of human skin remains: analysis of a South‐Andean mummy sample

Raman and time of flight secondary ion mass spectrometry investigation answers specific conservation questions on Bosch painting Saint Wilgefortis Triptych

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