光谱学与光谱分析 |
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Using Raman Spectrum Analysis to Research Corrosive Productions Occurring in Alloy of Ancient Bronze Wares |
JIA La-jiang1, JIN Pu-jun2* |
1. Postdoctoral Station of History of Science &Technology, Northwest University, Xi’an 710069, China 2. School of Materials Science and Engineering, Shaanxi Normal University, Xi’an 710062, China |
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Abstract The present paper analyzes the interior rust that occurred in bronze alloy sample from 24 pieces of Early Qin bronze wares. Firstly, samples were processed by grinding, polishing and ultrasonic cleaning to make a mirror surface. Then, a confocal micro-Raman spectrometer was employed to carry out spectroscopic study on the inclusions in samples. The conclusion indicated that corrosive phases are PbCO3, PbO and Cu2O, which are common rusting production on bronze alloy. The light-colored circular or massive irregular areas in metallographic structure of samples are proved as Cu2O, showing that bronze wares are not only easy to be covered with red Cu2O rusting layer, but also their alloy is easy to be eroded by atomic oxygen. In other words, the rust Cu2O takes place in both the interior and exterior parts of the bronze alloy. In addition, Raman spectrum analysis shows that the dark grey materials are lead corrosive products——PbCO3 and PbO, showing the corroding process of lead element as Pb→PbO→PbCO3. In the texture of cast state of bronze alloy, lead is usually distributed as independent particles between the different alloy phases. The lead particles in bronze alloy would have oxidation reaction and generate PbO when buried in the soil, and then have chemical reaction with CO2-3 dissolved in the underground water to generate PbCO3, which is a rather stable lead corrosive production. A conclusion can be drawn that the external corrosive factors (water, dissolved oxygen and carbonate, etc) can enter the bronze ware interior through the passageway between different phases and make the alloy to corrode gradually.
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Received: 2013-12-23
Accepted: 2014-03-19
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Corresponding Authors:
JIN Pu-jun
E-mail: jinpj@snnu.edu.cn
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