**Investigation of the Pigments and Glassy Matrix of Painted Enamelled Qing Dynasty Chinese Porcelains by Noninvasive On-Site Raman Microspectrometry**

### **Philippe Colomban 1,\* , Burcu Kırmızı 1,2 , Bing Zhao <sup>3</sup> , Jean-Baptiste Clais <sup>4</sup> , Yong Yang <sup>5</sup> and Vincent Droguet <sup>6</sup>**


Received: 24 July 2020; Accepted: 14 August 2020; Published: 17 August 2020

**Abstract:** A selection of 15 Chinese painted enameled porcelains from the 18th century (Qing dynasty) was analyzed on-site by mobile Raman and XRF microspectroscopy. The highly prized artifacts are present in the collections of the Musée du Louvre in Paris and Musée Chinois at Fontainebleau Castle in France. In the painted enamels, pigments such as Naples yellow lead pyrochlore, hematite, manganese oxide and carbon and opacifiers such as lead arsenates were detected. The glassy matrices of the enamels mainly belonged to lead-rich and lead-alkali glass types according to the Raman spectra obtained. The glaze and body phases of the porcelain artifacts were also analyzed. The detection of lead arsenate apatite in some of the blue enamels was significant, indicating the use of arsenic-rich European cobalt ores (smalt) and possibly mixing with Asian cobalt. This characteristic phase has also been identified in French soft-paste porcelains and glass decor and high-quality Limoges enamels from the same period. Based on the shape of the Raman scattering background, the presence of colloidal gold (Au◦ nanoparticles) was identified in red, orange and pink enamels. Different types of Naples yellow pigments were also detected with Sb-rich, Sn-rich and mixed Sb–Sn–(Zn, Fe?) compositions in the yellow enamels. The results were compared to previous data obtained on Chinese *cloisonné* and painted enameled metalware and Limoges enamels as well as French enameled watches.

**Keywords:** porcelain; enamels; China; 18th century; Raman microspectroscopy; pXRF; pigments; arsenic; cobalt; Naples yellow
