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Luo W.,University of Chinese Academy of Sciences | Luo W.,Joint Laboratory of Human Evolution | Si Y.,University of Chinese Academy of Sciences | Si Y.,Joint Laboratory of Human Evolution | And 5 more authors.
Spectrochimica Acta - Part A: Molecular and Biomolecular Spectroscopy | Year: 2011

During July to November, 2006, an important archaeological excavation was conducted in Yun country, Hubei province, southern China. Chinese archaeologists found some remnant of leather materials, covered with red pigments, on a 6th century B.C. Chinese bronze sword. To understand the technology/ies that may have been utilized for manufacturing the leathers, a combined of Raman spectroscopy, FT-IR and XRF was thus applied to the remnant of leather materials. Raman analyses showed that red pigment on the leather was cinnabar (HgS). FT-IR and XRF analyses indicated that the content of some elements, such as Ca (existing as CaCO 3) and Fe (existing as Fe 2O 3), were much higher than those in the surrounding grave soil. The results inferred an application of lime depilation and retting, and the Fe-Al compound salt as tanning agent. And it was furthermore implicated that the Fe-Al salt tanning technique had been developed in the middle and late Spring and Autumn Period of China. © 2011 Elsevier B.V. All rights reserved.

Luo W.,University of Chinese Academy of Sciences | Luo W.,Joint Laboratory of Human Evolution | Li T.,University of Pittsburgh
Journal of Raman Spectroscopy | Year: 2012

A bronze Pan (water vessel), dating back to the 4th-3rd century BC, was excavated at Jiuliandun in Hubei Province, central southern China, in 2002. The Pan attracts wide attention among the Chinese archaeologists and conservators for its uniqueness in style and color, which turns out to be due to a black-brown film of about 1 mm thickness. In the present work, a combined use of X-ray fluorescence (XRF), micro-Raman, and X-ray diffraction (XRD) was employed to determine both chemical and physical compositions of the Pan's film. The results are summarized as follows: (1) The film, as XRF analysis indicates, has high concentrations of chromium (Cr) and iron (Fe); (2) Both Raman and XRD analyses suggest that the element Cr probably exists in the film mainly in the form of chromium oxide (Cr 2O 3). Raman analysis also implies the presence of PbCrO 4·PbO in the film; (3) XRD analysis suggests that the element Fe exists in the film in the form of magnetite (Fe 3O 4). Based on these analytical results and Chinese historical records, we propose that, as early as in the 3rd century BC, people in central southern China might have discovered and intentionally used chromium minerals for bronze surface treatment (such as coating). The source of chromium minerals used in this period was likely Cr-spinel minerals from meteorites. More work remains to be done to test the possibility of using Cr-spinel minerals for bronze production and decoration. Other issues, such as the possibility of forming a chromium-rich film during the underground burial, also need to be solved. Copyright © 2011 John Wiley & Sons, Ltd.

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