基于多种分析方法对古陶瓷修复胶结材料的分析鉴定

The Identification and Analysis of the Modern Binding Media Based on Multiple Analytical Methods

文物中的天然有机胶结材料研究是文化遗产保护研究的热点之一,但是文物修复用的现代胶结材料的分析鉴定在文物保护中也是非常重要的。了解古陶瓷修复所用粘结材料的成分对于古陶瓷的后续修复十分必要。针对这一问题,采用傅里叶变换红外光谱法(FTIR)、热裂解气相色谱质谱联用(Py-GC/MS)技术和热辅助水解甲基化裂解气相色谱质谱(THM-Py-GC/MS)技术对一批古陶瓷修复用的未知胶结材料进行分析。研究发现,该胶结材料的红外光谱在1252和829 cm^(-1)处的特征吸收峰符合环氧化合物的特征吸收峰范围,并且与红外谱库中环氧树脂标准谱图相匹配,表明该胶结材料为环氧树脂类的胶粘剂,且其中检测出吡啶类化合物、苯甲酸酯类化合物和伯醇类化合物等添加剂。之后,应用Py-GC/MS和THM-Py-GC/MS技术对该胶结材料的化学成分进行分析,检测出该胶结材料为双酚A型环氧树脂。为了改善环氧树脂胶粘剂的性能,还检测出该胶结材料中加入了胺类固化剂、邻苯二甲酸二异辛酯增塑剂、邻苯二甲酸二异辛酯非活性稀释剂。THM-Py-GC/MS技术因为其中的甲基化试剂会影响该胶结材料中胺类固化剂的分析与鉴定,所以直接Py-GC/MS方法更适合环氧树脂类胶粘剂的分析与鉴定。该研究展示了利用多种科学技术手段确定了古陶瓷文物修复用的现代胶结材料种类,所建立的适用于分析鉴定古代天然胶结材料的Py-GC/MS实验方法同样也适用于环氧树脂类胶粘剂的快速识别,同时为文物未知修复材料的鉴定提供了新视角。

The study of natural organic binders in historical objects is one of the research highlights in cultural heritage.However,identifying and classifying modern binding media used for restoration is also very important in heritage conservation.It is necessary for the subsequent restoration of ancient ceramics to understand the composition of the binding media used in the restoration of ancient ceramics.To address this problem,a batch of modern binding media for restoring ancient ceramics was analyzed by Fourier Transform infrared spectroscopy(FTIR),Pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS)and thermally assisted hydrolysis-methylation pyrolysis-gas chromatography-mass spectrometry(THM-Py-GC/MS)techniques.The results showed that the characteristic absorption peaks of the infrared spectrum of the binding media at 1252 and 829 cm^(-1) were in line with the range of characteristic absorption peaks of epoxy compounds and matched with the standard spectrum of epoxy resin in the infrared spectrum library,which indicated that the binding media was an epoxy adhesive.Moreover,additives such as pyridine compounds,benzoate compounds and primary alcohol compounds are also added to the binding media.Then,the chemical composition of the binding media was analyzed by applying Py-GC/MS and THM-Py-GC/MS techniques,and the binding media was detected as a bisphenol A-type epoxy resin.Moreover,to improve the performance of the epoxy resin adhesive,amine curing agent,diisooctyl phthalate plasticizers and diisooctyl phthalate inactive diluent were also detected to be added to the binding media.THM-Py-GC/MS technique affects the analysis and identification of amine curing agents in this binding media due to the presence of methylation reagents,whereas the Py-GC/MS technique is more suitable for the analysis and characterization of epoxy adhesives.In this study,the use of the Py-GC/MS technique can identify the types of modern binding media used for the restoration of ancient ceramic relics,providing a new approach for the analysis and identification of epoxy resin adhesives,as well as a new perspective for the identification of unknown restoration materials for cultural relics.