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Laser-based techniques for the non-invasive characterisation of grisaille paints on stained-glass windows
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Resumo(s)
Grisaille was the first paint applied on stained-glass panels, used in Europe since the twelfth century. Historical written sources described the use of iron and copper together with a high lead-silica base glass in the grisailles production. This project aims to study the evolution of the grisaille paint composition throughout time and the changes in the raw materials used in their production using non-destructive and non-invasive techniques. To achieve this objective, 23 grisaille samples dated from the 13th to the twentieth centuries from nine different countries (Portugal, Poland, United Kingdom, Sweden, Norway, Belgium, Low Countries, Germany, and France) were studied by means of micro particle-induced X-ray emission (μ-PIXE), micro energy dispersive X-ray fluorescence (μ-EDXRF), laser-induced breakdown spectroscopy (LIBS), laser-induced fluorescence (LIF), non-linear optical microscopy (NLOM) in the modality of multiphoton excitation fluorescence (MPEF) and optical microscopy (OM). The results showed that it was possible to identify compositional differences and patterns throughout the samples when compared with literature results. The preference for using copper in central and south-central European countries and the addition of new compounds (CoO, Cr2O3, MnO) as colouring agents since the nineteenth century was verified. The LIBS analyses allow the identification of boron on two samples, confirming the change of base glass components since the seventeenth century. The NLOM-MPEF showed the capability of this technique to measure the grisaille paint layers’ thickness. This non-invasive multi-analytical and complementary approach proves itself efficient in identifying changes in the grisaille’s composition throughout time, which can be interpreted as changes in the raw materials and manufacture used in the production of these paint materials.
Descrição
This research has been funded by the H2020 European project IPERION HS (Integrated Platform for the European Research Infrastructure ON Heritage Science, GA 871034), by the Spanish State Research Agency (AEI) through project PID2019-104124RB-I00/AEI/, by the Fundação de Ciência e Tecnologia de Portugal (project ref. UIDB/EAT/00729/2020, LA/P/0008/2020, researcher grant CEECIND/02249/2021 and by project TOP Heritage-CM (S2018/NMT-4372) from Community of Madrid.
The authors wish to thank all that allow us access to samples to develop this study: Joost Caen (Antwerp University, Belgium) Elisabeth Sinnerud and Marie Louise Anker (Nidarosdomen, Norway), Linda Kvarnström and Emma Newman (Stained-Glass Studio, Uppsala Cathedral, Sweden), Marta Kaminska (Jan Matejko Academy of Fine Arts Krakow, Poland), Leonie Seliger (Restoration Atelier Canterbury, UK), to Glasmalerei Otto Peters (Germany) and to Pedro Redol (Batalha Monastery, Portugal). The authors are also grateful to Trinitat Pradell and Mingyue Yuan (Universitat Politècnica de Catalunya, Spain) for the preparation of the samples and the optical microscopy analysis.
Publisher Copyright:
© 2023, The Author(s).
Palavras-chave
Grisaille Laser spectroscopies Multi-analytical characterisation Non-linear optical microscopy Stained-glass windows Thickness measurements Conservation Chemistry (miscellaneous) Archaeology Materials Science (miscellaneous) Archaeology Computer Science Applications Spectroscopy