湖北江陵九店战国墓出土墨的科学分析

Scientific Research on Warring States Ink Unearthed From Jiangling Jiudian Tomb in Hubei Province

湖北江陵九店战国墓M56出土墨为我国早期制墨原料和工艺研究提供了重要的实物资料,但出土至今一直未对其进行分析和研究,关于墨类型、墨中添加剂及胶结物等信息尚未知。为此,应用傅里叶变换红外吸收光谱仪(FTIR)、透射电镜(TEM)和热裂解气相色谱质谱法(Py-GC/MS)对江陵九店战国墨的形貌特征和化学成分进行科学分析和研究。结果表明:(1)红外光谱在1595 cm-1附近有烟炱CC骨架振动吸收峰,另有羧酸羰基CO(1 716 cm-1)和醇类物质中C—O(1 031和1 092 cm-1)键的伸缩振动,以及表面OH, COOH中O—H(3 421 cm-1)的伸缩振动,表明江陵九店战国墨中含有羧酸和醇类物质;(2)在透射电镜下对墨的形貌特征和颗粒大小均匀性进行分析,结果表明江陵九店战国墨颗粒近圆形,边缘光滑,大小分布不均匀,与松烟墨的特征相似;(3)应用热裂解气相色谱质谱法(Py-GC/MS)对江陵九店战国墨的化学成分进行分析,检测出一系列多环芳烃类化合物(PAHs)、松木类物质燃烧化合物(惹烯、脱氢松香酸甲酯等)、樟脑和雪松油类的芳香化合物(α-柏木烯,β-雪松烯、花侧柏烯、雪松醇)等,其中PAHs的相对含量及松木燃烧化合物表明江陵九店战国墨为松烟墨。另外,Py-GC/MS检测结果表明江陵九店战国墨中有樟脑和雪松油添加剂。研究认为,我国在战国时期已有用樟脑和雪松油作为添加剂于松烟墨的制造中。

The ink unearthed from the Warring States tomb M56 of Jiudian village, Jiangling County in Hubei province provides important material objects for researching the early ink materials and technologies in China. However, the types of ink, additives and binding media in ancient ink are still unknown. In this paper, Infrared Spectrometer(FTIR), Transmission Electron Microscopy(TEM), and Pyrolysis-Gas Chromatography/Mass Spectrometry(Py-GC/MS) were used to analyze the morphology and chemical composition of the Warring States ink. The results show:(1) the FTIR analysis reveals that there are the vibration absorption peaks of soot CC skeleton near 1 595 cm-1, carboxylic acid carbonyl CO(1 716 cm-1), alcohol C—O(1 031 and 1 092 cm-1) bonds, and O—H(3 421 cm-1) in OH and COOH, which indicates that there are carboxylic acids and alcohol in the Warring States ink;(2) the TEM results show that the characteristic of Warring States ink is similar to pine wood soot ink;(3) the results of Py-GC/MS show that there are a series of polycyclic aromatic hydrocarbons(PAHs), pyrolysis compounds of pine wood(retene and methyl dehydroabietate), camphor and cedar oil-related aromatic compounds(cedr-8-ene, beta-cedrene, cuparene and cedrol). Among these, the content of PAHs and the characteristic compounds of pine wood indicates that the Warring States ink is pine wood soot ink. Besides, camphor and cedar oil are used as additives in Warring States ink. This study shows that camphor and cedar oil existed in pine wood soot ink as additives during the Warring States period in China.