Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings

Paint cross-sections of five 16th century paintings with areas of discoloured smalt oil paint were investigated. Semi-quantitative SEM-EDX analysis revealed that potassium was relatively low in all discoloured smalts, while cobalt remained at an approximately steady level. Reflection light...

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Main Authors: Jaap J. Boon, Katrien Keune, Jaap van der Weerd, Muriel Geldof, J.R.J. van Asperen de Boer
Format: Article
Language:deu
Published: Swiss Chemical Society 2001-11-01
Series:CHIMIA
Subjects:
Online Access:https://www.chimia.ch/chimia/article/view/3516
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author Jaap J. Boon
Katrien Keune
Jaap van der Weerd
Muriel Geldof
J.R.J. van Asperen de Boer
author_facet Jaap J. Boon
Katrien Keune
Jaap van der Weerd
Muriel Geldof
J.R.J. van Asperen de Boer
author_sort Jaap J. Boon
collection DOAJ
description Paint cross-sections of five 16th century paintings with areas of discoloured smalt oil paint were investigated. Semi-quantitative SEM-EDX analysis revealed that potassium was relatively low in all discoloured smalts, while cobalt remained at an approximately steady level. Reflection light microscopy demonstrated the presence of partially discoloured smalt particles with a remaining blue core. Imaging SIMS demonstrated that cobalt has a uniform distribution in the glass particles. Potassium however shows relatively high levels in the oil paint matrix around the discoloured glass particles and an uneven distribution in smalt particles with a blue core. These blue cores always have a higher K level compared to the discoloured rim of the particle. The loss of potassium from smalt in oil paint is interpreted as a leaching process which lowers the basicity of the glass below a critical level for colour maintenance. The colour change of the smalt is thus an indicator of a change in alkalinity inside the glass. The critical level appears to be near a K:Co of about 1:1 in 16th century potash glass on the basis of semi-quantitative SEM-EDX data. The migrated K is thought to be accommodated on the many fatty acid groups of the mature oil network ionomer in the aged oil paint. Ca was observed in a number of blue remaining smalts which suggest a role in preservation of the blue glass or retardation of the leaching process. It is estimated that the colour change is an early phenomenon possibly related to the early stages of oxidation and hydrolysis of the cross-linking oil paint. The differences in potassium levels in the remaining blue part of the smalt particles point to variability in the quality of the base potash glass in the 16th century. Analysis of partially discoloured smalt from two panels of a triptych by Dirck Barendsz (1534–1592) demonstrated that he had access to two chemically different smalts.
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spelling doaj.art-d77b591c8c3e4521a601ca6ea9d44d262022-12-21T17:23:29ZdeuSwiss Chemical SocietyCHIMIA0009-42932673-24242001-11-015511Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century PaintingsJaap J. BoonKatrien KeuneJaap van der WeerdMuriel GeldofJ.R.J. van Asperen de Boer Paint cross-sections of five 16th century paintings with areas of discoloured smalt oil paint were investigated. Semi-quantitative SEM-EDX analysis revealed that potassium was relatively low in all discoloured smalts, while cobalt remained at an approximately steady level. Reflection light microscopy demonstrated the presence of partially discoloured smalt particles with a remaining blue core. Imaging SIMS demonstrated that cobalt has a uniform distribution in the glass particles. Potassium however shows relatively high levels in the oil paint matrix around the discoloured glass particles and an uneven distribution in smalt particles with a blue core. These blue cores always have a higher K level compared to the discoloured rim of the particle. The loss of potassium from smalt in oil paint is interpreted as a leaching process which lowers the basicity of the glass below a critical level for colour maintenance. The colour change of the smalt is thus an indicator of a change in alkalinity inside the glass. The critical level appears to be near a K:Co of about 1:1 in 16th century potash glass on the basis of semi-quantitative SEM-EDX data. The migrated K is thought to be accommodated on the many fatty acid groups of the mature oil network ionomer in the aged oil paint. Ca was observed in a number of blue remaining smalts which suggest a role in preservation of the blue glass or retardation of the leaching process. It is estimated that the colour change is an early phenomenon possibly related to the early stages of oxidation and hydrolysis of the cross-linking oil paint. The differences in potassium levels in the remaining blue part of the smalt particles point to variability in the quality of the base potash glass in the 16th century. Analysis of partially discoloured smalt from two panels of a triptych by Dirck Barendsz (1534–1592) demonstrated that he had access to two chemically different smalts. https://www.chimia.ch/chimia/article/view/3516Imaging simsOil paintPotash glass leachingPotassium cobalt ratioSmalt discoloration
spellingShingle Jaap J. Boon
Katrien Keune
Jaap van der Weerd
Muriel Geldof
J.R.J. van Asperen de Boer
Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
CHIMIA
Imaging sims
Oil paint
Potash glass leaching
Potassium cobalt ratio
Smalt discoloration
title Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
title_full Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
title_fullStr Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
title_full_unstemmed Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
title_short Imaging Microspectroscopic, Secondary Ion Mass Spectrometric and Electron Microscopic Studies on Discoloured and Partially Discoloured Smalt in Cross-sections of 16th Century Paintings
title_sort imaging microspectroscopic secondary ion mass spectrometric and electron microscopic studies on discoloured and partially discoloured smalt in cross sections of 16th century paintings
topic Imaging sims
Oil paint
Potash glass leaching
Potassium cobalt ratio
Smalt discoloration
url https://www.chimia.ch/chimia/article/view/3516
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