Surface-enhanced Raman scattering (SERS) was investigated for applications in the analysis of anthraquinone dyes used in works of art. Two SERS procedures were developed and evaluated with frequently used anthraquinone dyes, alizarin, carminic acid and lac dye. The first procedure involves the removal of a microscopic fragment containing alizarin from a painting, and a layer of silver nanoparticles was thermally evaporated directly on the fragment to induce SERS signal from alizarin. The applicability of this procedure for analyzing solid samples of color layer from paintings was discussed in detail. In the second procedure, a SERS-active substrate was prepared by spin-coating an alumina-nanoparticle layer onto a glass slide, followed by thermally evaporating a layer of silver nanoparticles on top of the alumina layer. Aliquots of dye solutions were delivered onto this substrate where intense SERS spectra characteristic of alizarin, carminic acid, and lac dye were obtained. The effects of two parameters, the concentration of the alumina suspension, and the thickness of the silver nanoparticle layer, on the performance of the Ag-Al2O3 substrate were examined with alizarin as the model compound. Comparative studies with other common SERS substrates showed larger enhancement and improved reproducibility for the Ag-Al2O3 substrate. The potential applicability of the Ag-Al2O3 substrate for the analysis of real artifact objects was illustrated by the identification of alizarin extracted from a small piece of textile dyed with traditional methods and materials. The limit of detection for alizarin was estimated to be 7×10-15 g from tests using solutions of known concentration.
The identification of natural dyes found in archaeological objects and in works of art as textile dyes and lake pigments is a demanding analytical task. To address the problems raised by the very low dye content of dyed fibers and lake pigments, and by the requirement to remove only microscopic samples, surface enhanced Raman scattering techniques were investigated for application to museum objects. SERS gives excellent results with the majority of natural dyes, including: alizarin, purpurin, laccaic acid, carminic acid, kermesic acid, shikonin, juglone, lawsone, brazilin and brazilein, haematoxylin and haematein, fisetin, quercitrin, quercetin, rutin, and morin. In this study, limits of detection were determined for representative dyes and different SERS supports such as citrate reduced Ag colloid and silver nanoisland films. SERS was successfully used to identify natural madder in a microscopic fragment from a severely degraded 11th Century Byzantine textile recently excavated in Amorium, Turkey.
Conference Committee Involvement (3)
Advanced Environmental, Chemical, and Biological Sensing Technologies V
10 September 2007 | Boston, MA, United States
Advanced Environmental, Chemical, and Biological Sensing Technologies IV
1 October 2006 | Boston, Massachusetts, United States
Advanced Environmental, Chemical, and Biological Sensing Technologies III