Tian Siyu, Ma Wenhua, Li Hua, Wang Chunyan, Xia Yin, Lan Desheng, Zhou Ping, Hu Daodao
Engineering Research Center of Historical and Cultural Heritage Protection, Ministry of Education, School of Materials Science and Engineering, Shaanxi Normal University, Xi'an, 710062, China.
Emperor Qin Shihuang's Mausoleum Site Museum, Lintong, Xi'an, 710600, China.
Sci Rep. 2024 Jul 30;14(1):17572. doi: 10.1038/s41598-024-68442-3.
Since the Qin terracotta warriors were unearthed, polyamide 650 cross-linked E-44 epoxy resin binder has been employed to bond and restore them. In this paper, the chemical aging of the binders service in indoor natural environment during the past 30 years in the terracotta warriors was studied by means of infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis. The results indicated that the binders did not emerge the characteristic peak of carbonyl stretching vibration at 1700 cm in the IR spectra of all determined binders, and their thermal decomposition curves did not emerge any abnormal changes, and the thermal decomposition mainly occurred above 300 °C. There are evident ceramic grains attached to the surface of the binders being peeled off for sampling. These results that the binders service in the Qin terracotta warriors did not exhibit an observable chemical aging and still has strong adhesion. Generally, discrepancies were observed between natural aging and accelerated artificial aging due to the ineffectiveness of the latter to reproduce the effects of complex weather conditions. Compared to artificially accelerated aging, the evaluation results in a long-term natural aging of the binder which is used for restoration of the life-size Qin terracotta warriors, providing in the present investigation, are more reliable in terms of predicting the safety of restored terracotta warriors.
自兵马俑出土以来,一直采用聚酰胺650交联E-44环氧树脂粘结剂对其进行粘结修复。本文利用红外光谱、X射线光电子能谱和热重分析等手段,研究了兵马俑室内自然环境中粘结剂在过去30年里的化学老化情况。结果表明,在所有测定的粘结剂红外光谱中,粘结剂均未出现1700 cm处羰基伸缩振动的特征峰,其热分解曲线也未出现任何异常变化,热分解主要发生在300℃以上。用于取样的粘结剂表面有明显附着的陶粒脱落。这些结果表明,兵马俑中的粘结剂未表现出明显的化学老化,仍具有较强的粘结力。一般来说,自然老化和加速人工老化之间存在差异,因为后者无法再现复杂天气条件的影响。与人工加速老化相比,本研究中对用于修复真人大小兵马俑的粘结剂进行长期自然老化的评估结果,在预测修复后兵马俑的安全性方面更可靠。