Abstract
Surface Enhanced Raman Scattering (SERS) has become an invaluable tool for the identification of colorants in artworks, due to its enhanced sensitivity and ability to quench fluorescence interference compared to Raman spectroscopy. However, the application of SERS to artwork analysis is still limited by its inherent invasiveness and the need for extraction procedures. In this work non-invasive transparent SERS probes were fabricated by self-assembly of Ag nanoparticles into glass and PDMS surfaces and used for identification of dye content in artistic drawings. SERS measurements were performed directly on the selected analytical surfaces by laser back illumination through the SERS probe. The non-invasiveness of fabricated probes was tested by optical microscopy. It was found that Ag nanoparticle/glass probes left no Ag nanoparticle residue after four consecutive depositions on sacrificial surfaces, whereas Ag nanoparticle/PDMS composites could be deposited and subsequently peeled off the analytical surfaces leaving no contamination traces. The high conformability, flexibility and transparency of Ag nanoparticle/PDMS composites enabled good adhesion to the surface of analyzed artistic drawings and therefore the generation of in situ SERS spectra from artistic drawings. The use of this method allowed identification of main dye components in real artworks comprising a red BIC ballpoint drawing and a Japanese woodblock print.
Highlights
The ability to identify colorants and colorant mixtures in artworks is of fundamental importance to inform application of conservation treatments, display and preservation procedures as well as to allow identification of artworks’ provenance and forgery
Fabrication and characterization of Surface Enhanced Raman Scattering (SERS) composites Ag nanoparticles used in this study were prepared in aqueous solution by reduction of Ag(I) salts with strong reducing agent sodium borohydride and subsequently phase transferred in organic solution
Non-invasive SERS substrates were fabricated by transfer of self-assembled Ag nanoparticles on transparent substrates
Summary
The ability to identify colorants and colorant mixtures in artworks is of fundamental importance to inform application of conservation treatments, display and preservation procedures as well as to allow identification of artworks’ provenance and forgery. SERS has been successfully used for investigations of a large range of heritage materials including archeological textile fibers [6], woodblock prints [8, 9] and has enabled identification of synthetic and organic dye content in Alyami et al Herit Sci (2019) 7:87 polychromic works of art [10, 11], painting samples [12, 13] oil paintings [14] and commercial inks [15] Another advantage of SERS is the availability of lightweight, sensitive and low cost portable instrumentation, whose use is often mandatory for the analysis of large or unmovable artworks
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