Colomban Philippe, Gironda Michele, Simsek Franci Gulsu, d'Abrigeon Pauline
MONARIS UMR8233, Sorbonne Université, CNRS, 4 Place Jussieu, 75005 Paris, France.
XGLab S.R.L-Bruker, 23 Via Conte Rosso, 20134 Milan, Italy.
Materials (Basel). 2022 Aug 20;15(16):5747. doi: 10.3390/ma15165747.
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 the identification of 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 (SnO) is clearly observed in one of the painted decors (dish) and in A676 yellow, whereas lead (calcium/potassium) arsenate is identified in most of the enamels. Yellow color is achieved with Pb-Sn-Sb pyrochlore (Naples yellow) with various Sb contents, 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 that they were made in overglaze (A608, A616, A630, A672). It is obvious that different types of cobalt sources were 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). Thus, we have a variety of cobalt sources/mixtures. The high purity of cobalt used for A677 bowl indicates a production after ~1830-1850.
对七件御碗和两件装饰盘运用非侵入式现场便携式技术、拉曼显微镜和X射线荧光光谱法进行分析，这些器物可追溯至康熙、雍正、乾隆和道光皇帝在位时期（清朝），从而能够鉴定出釉料和彩绘珐琅的着色剂/遮光剂以及成分类型。特别关注对（蓝色）标记中使用的元素以及在绘制有花卉图案的蓝色、黄色、红色和蜜色/金色背景中发现的元素的分析。蜜色背景是由与铅基和砷基助熔剂相关联的金纳米颗粒制成。其中一种红色背景同样基于金纳米颗粒，另一种含有铜纳米颗粒，它们都存在于类似于蓝色和黄色背景的铅基硅酸盐珐琅中。观察到了锡和砷，但在一件彩绘装饰（盘子）以及A676黄色中清晰地观察到了锡石（SnO），而在大多数珐琅中鉴定出了砷酸铅（钙/钾）。黄色是通过含有不同锑含量的Pb-Sn-Sb焦绿石（拿不勒斯黄）实现的，尽管绿色主要基于与蓝色珐琅混合的铅锡氧化物。不同器物的技术解决方案差异很大，这让人认为每只碗都是独一无二的，而非小批量生产的物品。对一些标记的目视检查表明它们是釉上彩（A608、A616、A630、A672）。显然，不同类型的钴源被用于标记的印制：碗A615（雍正时期）使用富含锰的钴，碗A613（但蓝色标记除外）使用富含砷的钴，碗A616使用含铜的钴，碗A672使用富含砷和铜的钴。因此，我们有多种钴源/混合物。用于A677碗的钴的高纯度表明其生产时间约在1830 - 1850年之后。
