Identification of the man-made barium copper silicate pigments among some ancient Chinese artifacts through spectroscopic analysis

• Raman spectroscopy is used to identify ancient barium copper silicate pigments.
• Some artifacts were analyzed in situ by the portable XRF and Raman spectroscopy.
• The technological development of early native glassmaking in China is discussed.

This article describes the complementary application of non-invasive micro-Raman spectroscopy and energy dispersive X-ray fluorescence spectrometry to the characterization of some ancient Chinese silicate artifacts. A total of 28 samples dated from fourth century BC to third century AD were analyzed. The results of chemical analysis showed that the vitreous PbO–BaO–SiO2 material was used to sinter these silicate artifacts. The barium copper silicate pigments including BaCuSi4O10, BaCuSi2O6 and BaCu2Si2O7 were widely identified from colorful areas of the samples by Raman spectroscopy. In addition, other crystalline phases such as Fe2O3, BaSi2O5, BaSO4, PbCO3 and quartz were also identified. The present study provides very valuable information to trace the technical evolution of man-made barium copper silicate pigments and their close relationship with the making of ancient PbO–BaO–SiO2 glaze and glass.

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