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Six rare porcelains of the Qing Dynasty, in particular, dishes ordered respectively for Philibert Orry, the Duke of Penthièvre and a tureen from the service of Louis XV, with royal coat-of-arms, were analyzed non-invasively by Raman microspectrometry. A coffee pot with a rare decoration attributed to Cornelius Pronk was also analyzed as well as two plates, one decorated with an Imari-style pattern and the second post-decorated in the Low-Countries/Holland. The enamel types and coloring or opacifying agents were identified on the basis of combined Raman and SEM-EDXS analysis previously published as well as new section and surface analysis of five plate samples representative of different technologies (blue-and-white, Famille rose). The use of lead oxide for the preparation of overglaze is demonstrated. For the first time, the use of borax in the blue overglaze according to the recipe from the 1753 manuscripts of French chemist Jean Hellot is demonstrated on Chinese porcelain. This fact, like the use of cobalt free of manganese, demonstrates the use of European ingredients and/or recipes for ceramics exported from China to Europe. The highlighting of the use of different recipes or raw materials for porcelain from the same period can therefore be the signature of different workshops. For instance, three different Raman signatures of red decoration were identified from the hematite vibration modes: very narrow modes for Pronk’ coffee pot and Louis XV tureen, broad for Orry’ dish and intermediate for the others. Three workshops are thus expected. It is interesting to note that the use of arsenic for the realization of white enamels corresponds to the latest objects, made after 1738. China was therefore in the 18th century both an importer of European know-how, design and an exporter of enameled products made with imported technologies to Europe.

Chinese porcelain with an optically clear colored glaze, imported to Europe from the Kangxi period (1662–1722, Qing Dynasty) onwards was highly collected by the French Elite of the 18th century. The bright colors with a clear, shiny glaze were unlike anything produced in Europe at that time. The colors of enamelled artifacts (on biscuits or already glazed porcelain) can be fully monochrome or consist of associations of large monochromatic areas with or without application of gilding. Non-invasive portable XRF and mobile Raman analyses have previously shown their effectiveness in the characterization of (colored) glassy silicates. In this study, we compare the Raman signatures of twenty-one Chinese artifacts fully—or with major monochrome area (sancai)—decorated with blue, turquoise (or celectian blue), honey-yellow, green, eggplant, and red color. Different types of glazes are identified and confirmed by pXRF: lead-rich, lead-poor-alkali, lead-doped alkali, and alkali-based compositions. However, an unexpected low level of lead is observed in the turquoise glazes, likely to optimize the gloss. Raman spectroscopy appears more reliable to compare the Pb content than pXRF. This work presents Raman spectral signatures of glazes that can potentially be used for non-invasive object classification and counterfeit detection.