Non-Invasive Study of Gold Nanoparticles in Famille rose and Ruby-Back Qing Porcelain by Luminescence, Low-Wavenumber Raman Scattering and pXRF

Comprehensive studies of Famille rose porcelains, particularly ruby-back pieces, are rare and have generally not addressed the vibrational signatures arising from gold nanoparticles. Due to the high cultural and material value of these artifacts, a strictly non-invasive approach combining X-ray fluorescence (XRF) and Raman (micro-)spectrometry must be employed. If the conservation of porcelain does not pose any difficulties, fakes exist and they must be identified. Preliminary studies show that the presence of metal nanoparticles generates plasmon-related fluorescence. Our results confirm that plasmon fluorescence is more effective than pXRF for detecting colloidal gold, whereas pXRF efficiently identifies associated elements such as arsenic, tin, and, newly observed, antimony; the presence of iron is difficult to demonstrate due to its ubiquitous occurrence. Yellow and green hues, distinct from those produced by Cu2+ ions alone, are mainly due to simple tin yellow (PbSnO3), while the cobalt used originates from a mixture of European smalt (rich in arsenic and potassium) and Asian ores (rich in manganese). Minimal variability was observed among egg-shell porcelains with similar decorations and dimensions, suggesting a common workshop or standardized raw materials and procedures. Two other egg-shell plates employ a different gold preparation technique (addition of Sn and Sb rather than As), which is visually evident in the ruby color.