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Article Dans Une Revue Materials Année : 2022

Distinguishing Genuine Imperial Qing Dynasty Porcelain from Ancient Replicas by On-Site Non-Invasive XRF and Raman Spectroscopy

Distinguer les vraies porcelaines impériales de la Dynastie Qing de leurs répliques anciennes par spectroscopies non-invasives de fluorescence des rayons X et Raman

Michele Gironda
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  • PersonId : 1221520
Gulsu Simsek Franci
Pauline D’abrigeon

Résumé

: The combined use of non-invasive on-site portable techniques, Raman microscopy and X-ray fluorescence spectroscopy, on seven imperial bowls and two decorated dishes, attributed to the reigns of the Kangxi, Yongzheng, Qianlong, and Daoguang emperors (Qing Dynasty), allows identifying the coloring agents/opacifiers and composition types of the glazes and painted enamels. Particular attention is paid to the analysis of the elements used in the (blue) marks and those found in the blue, yellow, red, and honey/gilded backgrounds on which or in reserve, a floral motif is principally drawn. The honey-colored background is made with gold nanoparticles associated with a lead- and arsenic-based flux. One of the red backgrounds is also based on gold nanoparticles, the second containing copper nanoparticles, both in lead-based silicate enamels like the blue and yellow backgrounds. Tin and arsenic are observed but cassiterite (SnO2) is only clearly observed in one of the painted decors (dish) and in A676 yellow whereas lead(calcium/potassium) arsenate is iden-tified in most of the enamels. Yellow color is achieved with Pb-Sn-Sb pyrochlore (Naples yellow) with various Sb content although green color is mainly based on lead-tin oxide mixed with blue enamel. The technical solutions appear very different from one object to another, which leads one to think that each bowl is really a unique object and not an item produced in small series. The visual examination of some marks shows they are made in overglaze (A608, A616, A630, A672). It is obvious that different types of cobalt sources are used for the imprinting of the marks: cobalt rich in manganese for bowl A615 (Yongzheng reign), cobalt rich in arsenic for bowl A613 (but not the blue mark), cobalt with copper (A616), and cobalt rich in arsenic and copper (A672). So, we have a variety of cobalt sources/mixtures. The high purity of cobalt used for A677 bowl indicates a pro-duction after ~1830-1850.
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hal-03759687 , version 1 (24-08-2022)

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Philippe Colomban, Michele Gironda, Gulsu Simsek Franci, Pauline D’abrigeon. Distinguishing Genuine Imperial Qing Dynasty Porcelain from Ancient Replicas by On-Site Non-Invasive XRF and Raman Spectroscopy. Materials, 2022, 15 (16), ⟨10.3390/ma15165747⟩. ⟨hal-03759687⟩
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