# Non-invasive on-site Raman and XRF study of the 17th-18th century painted enamelled Chinese metal wares and porcelains: Comparison with French enamelling technology

Philippe Colomban, Burcu Kirmizi, Bing Zhao, Jean-Baptiste Clais, Michele Gironda, Vincent Cochet

► To cite this version:

Philippe Colomban, Burcu Kirmizi, Bing Zhao, Jean-Baptiste Clais, Michele Gironda, et al. Non-invasive on-site Raman and XRF study of the 17th-18th century painted enamelled Chinese metal wares and porcelains: Comparison with French enamelling technology. 5th International Conference on Innovation in Art Research and Technology (inArt 2022), Jun 2022, Paris, France. hal-03964497

HAL Id: hal-03964497

https://hal.science/hal-03964497

Submitted on 1 Feb 2023

HAL is a multi-disciplinary open access
archive for the deposit and dissemination of sci-
entific research documents, whether they are pub-
lished or not. The documents may come from
teaching and research institutions in France or
abroad, or from public or private research centers.

L'archive ouverte pluridisciplinaire HAL, est
destinée au dépôt et à la diffusion de documents
scientifiques de niveau recherche, publiés ou non,
émanant des établissements d'enseignement et de
recherche français ou étrangers, des laboratoires
publics ou privés.

<figure><img src="image_1.png" /></figure>

Distributed under a Creative Commons Attribution 4.0 International License
# Non-invasive on-site Raman and XRF study of the 17th-18th century painted enamelled Chinese metal wares and porcelains: Comparison with French enamelling technology

Philippe Colombanª, Burcu Kırmızıᵇ, Bing Zhaoᶜ, Jean-Baptiste Claisᵈ, Michele Girondaᵉ, Vincent Cochetf

<figure><img src="image_2.png" /></figure>

a Sorbonne Université, CNRS, MONARIS UMR8233, 4 Place Jussieu, 75005 Paris, France

b Yıldız Technical University, Dept. of Conservation and Restoration of Cultural Property, Beşiktaş 34349 Istanbul, Turkey

c CNRS, Collège de France, CRCAO, UMR8155, 75005 Paris, France

d Musée du Louvre, Département des objets d'art, quai F. Mitterand, 75001 Paris, France

e XGLab S.R.L - Bruker, 23 Via Conte Rosso, 20134 Milan, Italy

f Château de Fontainebleau, 77300 Fontainebleau, France

<figure><img src="image_3.png" /></figure>

<figure><img src="image_4.png" /></figure>

ENAMEL
FRANCE CHINA

<figure><img src="image_5.png" /></figure>

SCIENCES
SORBONNE
UNIVERSITÉ

<figure><img src="image_6.png" /></figure>

## Background and Scope of the Study

Both Chinese and European historical records report that French Ambassador of Louis XIV and the French Jesuit missionaries were hosted at the Kangxi Court during the 17th century, and they presented outstanding enamelled artefacts as gifts to the Chinese emperor. Among these presents were enamelled metal objects which offer a complex realistic painted decor of enamels. It is also known that according to the demand of Kangxi Emperor, this advanced enamelling technology was taught to Chinese craftsmen at the workshops inside the Beijing Forbidden Palace. Royal archives mention that pigments and ingredients required to make such enamels were imported from Europe and this trade was regularly followed [1-2].

In this study, we present the non-invasive on-site study of 10 enamelled metal wares dating to the 17th-18th centuries (Qing Dynasty) from the collections of Musée du Louvre and Château de Fontainebleau (Musée Chinois) by non-invasive mobile Raman microspectroscopy and portable X-ray fluorescence spectroscopy. These metal wares were produced by cloisonné and/or painted enamel techniques. The objective of the study is to compare the enamelling technology used in these artefacts, regarding the different types of enamels with the identification of pigments/opacifiers and glass compositions used [3].

The study is expected to provide arguments to identify the use of imported enamels and/or enamel recipes from Europe to China at the end of the 17th century under the guidance of Jesuits as reported in the historical records.

[1] B. Zhao, G.Y. Wang, I. Biron, P. Colomban, L. Hilaire-Pérez, La circulation des techniques de l'émail entre la France et la Chine du XVIIème au XIXème siècle. *Le CNRS en Chine Bulletin*, 21, 20-25. 2016

[2] C.F. Shih, Evidence of East-West exchange in the eighteenth century: The establishment of painted enamel art at the Qing Court in the reign of Emperor Kangxi. *Natl. Palace Mus. Res. Q.* 24, 45-94, 2007

[3] P. Colomban, B. Kırmızı, B. Zhao, J-B. Clais, Y. Yang, V. Droguet, Non-invasive on-site raman study of pigments and glassy matrix of 17th-18th century painted enamelled Chinese metalwares: Comparison with French enamelling technology, *Coatings*, 10(5), 2020

## Analytical Techniques

* Mobile Raman set-up (HORIBA Jobin-Yvon, Longjumeau France)

* 532 nm Ventus 300 mW laser (Laser Quantum) and x50 (NIKON) and x200 (Mitutoyo Corp.) long working distance objectives.

The mobile Raman analysis @ Musée chinois

* Portable Elio XRF instrument (XGLab Bruker, Italy)

* 40 kV tube voltage, 100 µA current, 40 s acquisition time

<figure><img src="image_7.png" /></figure>

<figure><img src="image_8.png" /></figure>

The on-site pXRF analysis @ Musée chinois

<figure><img src="image_9.png" /><figcaption>康熙帝</figcaption></figure>

<figure><img src="image_10.png" /><figcaption>Kangxi Emperor</figcaption></figure>

<figure><img src="image_11.png" /></figure>

<figure><img src="image_12.png" /><figcaption>Qianlong Emperor</figcaption></figure>

<figure><img src="image_13.png" /><figcaption>Qianlong mark on the base</figcaption></figure>

<caption>Details of the painted
enamel medallion</caption>

<figure><img src="image_14.png" /><figcaption>F1448C @ Chateau de Fontainebleau, Musée Chinois
H:27 cm / D:26 cm</figcaption></figure>

<figure><img src="image_15.png" /><figcaption>Ewer, painted and cloisonné enamel on gold body
Qianlong reign (1736-1795)</figcaption></figure>

<figure><img src="image_16.png" /></figure>

<figure><img src="image_17.png" /><figcaption>F1467 @ Chateau de Fontainebleau, Musée Chinois
H:40 cm / D:20 cm</figcaption></figure>

<figure><img src="image_18.png" /><figcaption>Raman spectra of the F1467 ewer (A-B-C)</figcaption></figure>

<figure><img src="image_19.png" /></figure>

## Results-Discussion

### The Kangxi tripod with cloisonné (C) enamels:

* Glassy Si-O Matrix

* Variations of lead-alkali type of glass: a) the strongest component at ~1030 to 1050 cm⁻¹, b) rather similar intensity of ~975 and 1045 cm⁻¹ components, c) the strongest component at ~1065–1070 cm⁻¹, d) the strongest component at ~1080–1100 cm⁻¹

* Pigments and Opacifiers

* **White:** Fluorite (320 cm⁻¹)

* **Blue:** Co²⁺ ions

* **Yellow:** Pb-Sn pyrochlore (~135,320,435 cm⁻¹)

* **Light green:** Pb-Sb-Sn(Zn) pyrochlore (~135,251,337,375,470 cm⁻¹) + Cassiterite (631,780 cm⁻¹) + Co²⁺ ions

* **Red:** Cu° nanoparticles (fluorescence)

❖ The Kangxi tripod mostly displays the characteristics of Chinese technology with fluorite opacification and copper red. Only the yellow and green enamels are made with European ingredients/techniques.

### The Qianlong ewer with cloisonné (C) / painted (P) enamels:

* Glassy Si-O Matrix (C)

* Lead-alkali type of glass with the strongest component at ~1070 cm⁻¹

* Pigments and Opacifiers (C)

* **Blue:** Co²⁺ ions

* **Yellow:** Pb-Sn pyrochlore (~135,330,445,520 cm⁻¹)

* **Green:** Pb-Sn pyrochlore (~135,330,450,520 cm⁻¹) + Co²⁺ ions

* **Pink:** Au° nanoparticles (fluorescence) + arsenate (815 cm⁻¹)

* Glassy Si-O Matrix (P)

* Lead-alkali type of glass with the strongest components at ~980 cm⁻¹ and 1040 cm⁻¹

* Pigments and Opacifiers (P)

* **White:** Lead arsenate (~820 cm⁻¹)

* **Blue:** Co²⁺ ions + lead arsenate (~820 cm⁻¹)

* **Yellow:** Pb-Sb pyrochlore (~130,340,455,506 cm⁻¹)

* **Green:** Pb-Sn/Pb-Sb-(Zn) pyrochlore (~135,335,450,510 cm⁻¹) + Co²⁺ ions + Cassiterite (632,775 cm⁻¹)

* **Orange:** Hematite (225, 410,1318 cm⁻¹)

❖ The Qianlong ewer represents the use of European ingredients/ techniques with the lead pyrochlore pigment, gold nanoparticles and European cobalt ores (rich in As).

## Conclusion

This analytical study confirms the capability of on-site Raman analysis with mobile set-up for characterization of the sophisticated enamelled wares from China. The 17th-18th century turn marks the period of close contact between Europe and China through the Jesuits hosted at the Chinese Court. The results particularly contribute to identification of the artefacts where ingredients or recipes from Europe had been used for enamelling.

It is significant that cassiterite was probably used as an opacifier in some of the metal wares. Lead arsenate detected in some of the 17th-18th century blue enamels is related to the use of arsenic-rich European cobalt ores.

❖ This work has been carried out in the framework of the LIA CNRS-Palace Museum and Campus France PHC Cai Yuanpei programs in preparation of ANR EnamelFC. Vincent Cochet, former Head of the Château de Fontainebleau, and Site, Sarah Paronetto, keeper at Château de Fontainebleau and Catherine Gougeon from Musée du Louvre are acknowledged for their contribution.

<figure><img src="image_20.png" /></figure>

<figure><img src="image_21.png" /><figcaption>Representative pXRF spectra recorded on the R975 bottle for the metal and enamelled areas</figcaption></figure>

<figure><img src="image_22.png" /></figure>

<figure><img src="image_23.png" /><figcaption>R975 @ Musée du Louvre
Qianlong period
H:26.5 cm / D:14 cm</figcaption></figure>