pXRF Data Evaluation Methodology for On-Site Analysis of Precious Artifacts: Cobalt Used in the Blue Decoration of Qing Dynasty Overglazed Porcelain Enameled at Customs District (Guangzhou), Jingdezhen and Zaobanchu (Beijing) Workshops

Abstract

In a noninvasive determination, Raman and XRF analyses showed the possibility of identifying specific phases and elements characteristic of the use of recipes and ingredients imported from Europe, according to the information documented in Chinese and European archives. Two sets of objects, supposed to have been produced during the Qing Dynasty (1662–1912) at the Forbidden City (‘imperial bowls’ of the Baur Foundation, Geneva) and in the customs district of Guangzhou (Musée Ariana, Geneva), were analyzed with pXRF and also for some objects with Raman microspectroscopy also on-site. The heterogeneity of the colored zones, in three spatial directions, requires the development of a new methodology. We focused particular attention on the cobalt used in the colored areas and marks, drawn either on the body layer (standard underglaze) or on the glaze itself (overglaze). Comparison is made with previous data on Chinese and Vietnamese porcelains from the Yuan (1271–1368) and Ming Dynasty (1368–1644) periods. Combined data for objects attributed to Guangzhou from the Kangxi and Yongzheng periods indicates the use of the same raw materials containing cobalt, associated with arsenic, nickel, zinc, copper and bismuth, according to the European sources. Similarity of the glaze composition and impurities promotes the production of the glazed body with the same raw materials as those used at Jingdezhen. A consistent shift in data for Qianlong style items, which are significantly richer in manganese, is compatible with their partial mixing with Asian cobalt. The deliberate selection of conflicting objects—namely, examples belonging to the other places of production or different periods—are well-observed outside the ‘Guangzhou’ cluster. Some artifacts have anachronistic purity characteristics that support a production after ca. 1850. For instance, two objects on which certain attributions had been made concerning the stylistic analysis are definitive examples of ceramics using a refined ‘cobalt’, and therefore now may be assigned to the later production period of the first half of the 19th century.