瓷青纸是我国古代一种名贵的加工纸, 瓷青纸文物存世稀少往往是博物馆的馆藏珍品。 关于瓷青纸相关材料与工艺的文献记载甚少, 对其开展的科技研究工作鲜见, 对其材料组成及制作工艺缺乏系统认知, 难以对瓷青纸文物进行科学的保护、 修复、 复制等工作。 为进一步加深对瓷青纸的认识, 利用视频显微镜、 拉曼光谱仪、 扫描电镜-能谱仪、 赫氏染色法纤维分析等技术对一件明代瓷青纸文物样品进行制作材料及工艺分析。 研究结果表明: 通过拉曼光谱分析, 对比该瓷青纸文物样品纸张染料跟靛蓝的拉曼峰位, 两者的峰位较为匹配, 而在1 570~1 701 cm^-1范围内为C=C键和C=O键和N—H键共轭体系的伸缩振动, 是靛系染料分子特有的特征吸收峰, 而样品纸张染料在1 570 cm^-1出现的强拉曼峰符合靛蓝的拉曼光谱特征, 因此可以确定为靛蓝, 这也与中国历史悠久的种植蓝草、 提取靛蓝作为染料的情况相一致; 通过扫描电镜-能谱分析, 纸张主要元素如S、 Ca、 Al、 Si、 Mg应来源于填料或涂料, 纸张经过了加填以及涂布处理以达到改善纸张不透明度、 透气度、 光泽度的目的, 同时也排除了样品蓝色染料为蓝铜矿、 青金石以及天然群青等蓝色矿物颜料的可能性; 通过赫氏染色法纤维分析, 纸张样品纤维特征为纤维壁上有横节纹、 纤维外壁上有胶质膜、 纤维中有少量草酸钙晶体、 纤维上有较多的黄色无定形蜡状物, 表明纸张纤维与构皮、 桑皮等皮类纤维接近, 瓷青纸的基纸应属于皮纸, 皮纸纤维强度较高, 在染色过程中不易水解导致纸张破损。 该瓷青纸文物样品的制作材料与工艺可以概括为: 将靛蓝染料在经过加填以及涂布处理的皮纸上进行单面染色后上下叠合制成。 通过该研究能够加深对明代瓷青纸造纸材料与工艺的认识, 同时为瓷青纸文物的研究、 保护、 修复、 复制等提供依据。

Porcelain green paper is a famous processing paper in ancient China, and the relic made of porcelain green paper is often museum treasure. There are few records and researches on porcelain green paper, and there is a lack of systematic knowledge of its composition and production technology, making it difficult to carry out scientific protection and restoration of relics made by porcelain green paper. In order to further deepen the understanding of ancient porcelain green paper, three-dimensional video microscopy, Raman spectrometer, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) and fiber analysis were employed to analyse the raw materials and manufacture process of one early Ming dynasty porcelain green paper sample. The result indicated that the dye on the sample matched the Raman peak position of indigo, and in the range of 1 570~1 701 cm^-1, the stretching vibration of the C=C bond, C=O bond and N—H bond conjugate system is the characteristic absorption peak of indigo dye molecules. The sample's strong Raman peak at 1 570 cm^-1 is consistent with the Raman spectral characteristics of indigo, so it can be identified as indigo, which is also consistent with a long history of planting bluegrass and extracting indigo as a dye in China. The scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) analysis indicated that the main elements of paper such as S, Ca, Al, Si, and Mg should come from filler or coating. The paper has been filled and coated in order to improve the paper opacity, permeability, and gloss, but also ruled out the possibility that the sample blue dye is azurite, lapis lazuli or natural ultramarine blue. There are transverse nodules on the fiber wall, a colloidal membrane on the outer fiber wall, a small amount of calcium oxalate crystal in the fiber, and more yellow amorphous wax on the fiber. These characteristics are similar to that of tapa and mulberry bark fibers. Therefore, the base paper of porcelain green paper should belong to the bark paper, the strength of the bark paper fiber is relatively strong, so it is not easy to hydrolyze in the dyeing process. Therefore, the production process of the porcelain green paper is as follows: indigo dye is dyed on one side of the bark paper filled and coated, then superimposed up and down. This study can deepen the understanding of the materials and technology of Ming porcelain green paper making and provide a basis for the research, protection, restoration and reproduction of porcelain green paper relics.