Articlediamond2003

Characterization of Natural Resin Films and Identification of Ancient Coating

61 citations0/0 files storedJournal of the Mass Spectrometry Society of Japan

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Cultural Heritage Materials Analysis Archaeology and ancient environmental studies Polymer Synthesis and Characterization

Abstract

Typical Japanese natural resin films, i.e., oriental lacquer films, cashew resin films, and drying oil polymers were characterized, and also an ancient coating was identified using two-stage pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). Urushiol, laccol, and thitsiol components, which are the main constituents of the respective oriental lacquers, were detected by the pyrolysis at 400°C. Additionally, the pyrolysis products, which reflect the structure of the urushiol, laccol, and thitsiol polymers, were detected by pyrolysis at 500°C after pyrolysis at 400°C. All the results have shown a significant progress occurring in the side chain-side chain C-C coupling and aromatic nucleus-side chain C-O coupling of urushiol, laccol, and thitsiol concurrently with the formation of the respective lacquer films. The cashew resin film was found to be terminated with saturated cardols and cardanols by the pyrolysis at 400°C. Furthermore, pyrolysis at 500°C revealed that the autoxidative side chain-side chain C-C coupling accelerated the cross-linking of trienyl- and dienylcardanols during the polymerization. The C4-C18 free fatty acids were detected by the pyrolysis of the drying oil polymers. These pyrolysis products are significant markers for a drying oil polymer. The drying oil polymer is terminated with saturated fatty acids, especially with hexadecanoic acid and octadecanoic acid. Based on these results, the ancient coating sample obtained from the surface of a wooden dish excavated at Tobarikyu, Kyoto prefecture, Japan was identified as Rhus vernicifera lacquer combined with an drying oil, presumably added as the solvent. Py-GC/MS was proved to be effective for the characterization of natural resin films and identification of organic coatings of historic artifacts.

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References

1999Long‐term behavior of oil‐based varnishes and paints I. Spectroscopic analysis of curing drying oils 1993The potential of pyrolysis—gas chromatography/mass spectrometry in the recognition of ancient painting media 1996Characterization of Rhus vernicifera and Rhus succedanea lacquer films and their pyrolysis mechanisms studied using two-stage pyrolysis-gas chromatography/mass spectrometry

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2009Determination of the type of lacquer on East Asian lacquer ware 2016Some observations on the composition of Chinese lacquer 2015Characterization and identification of urushi using in situ pyrolysis/silylation–gas chromatography–mass spectrometry 2021Analytical pyrolysis applied to the characterisation and identification of Asian lacquers in cultural heritage samples – A review 2014Characterising native plant resins from Australian Aboriginal artefacts using ATR-FTIR and GC/MS 2009Applying pyrolysis-gas chromatography/mass spectrometry to the identification of oriental lacquers: study of two lacquered shields 2017The degradation of Burmese lacquer (thitsi) as observed in samples from two cultural artefacts 2015Characterisation of oriental lacquers from Rhus succedanea and Melanorrhoea usitata using in situ pyrolysis/silylation-gas chromatography mass spectrometry

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