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对苯二酚(C_6H_4(OH)_2)热溶液受空气中氧的氧化作用,生成对苯醌(C_6H_4O_2)与醌氢醌(C_6H_4O_2·C_6H_4(OH)_2),具有弱氧化性,可将铜镜(成分)样品表面金属氧化生成色黑而光亮的氧化物膜。经扫描电镜分析,氧化物表层中铜锡含量亦别于原合金成分,即表层中由于铜的流失而导致铜的含量低于原合金,锡的含量则反而高于原合金。经对笨二酚处理后的样品表面X射线衍射分析的谱图中亦有四个较宽的弥散峰,其位置与出土黑漆古铜镜及用腐殖酸处理过的铜镜样品表面X射线衍射分析谱图极为相近。由于所用对苯二酚不含硅、铁、镁等杂质,故处理所得样品表面氧化物膜经电子探针分析亦不含这些元素,说明腐殖酸不是导致铜镜表面产生黑漆古的唯一物质。唯腐殖酸处理过的样品表面氧化物膜与出土黑漆古铜镜表面膜一样,均含有硅、铁、铝、镁等杂质。邻苯二酚、间苯二酚、对苯醌及丹宁酸等亦可使铜镜样品表面得到类似于黑漆古的光亮表面膜,多数为褐色。具有黑漆古表层的铜镜样品及其基体的X射线衍射分析结果表明,九种具有黑(或褐)漆古表层的铜镜与铜镜成分样品除具有基体衍射峰外,在相近的2θ角附近均有四个较宽的弥散峰,而所用的样品基体的X射线衍射分析结果却无弥散峰,证明弥散峰是因黑(或褐)漆古表层中含有SnO_2微晶所引起的,微晶的尺寸在3-5 nm间。其中一块系湖南战国时期墓葬出土的已经穿透腐蚀的黑漆古铜镜残片,研细后的粉末X射线衍射分析结果亦存在铜镜基体的强衍射峰,表明铜镜黑漆古表层中除有金属氧化物主要是SnO_2外,尚有较多的为二氧化锡所包藏而未被氧化的原铜锡合金颗粒。从而证明,黑漆古表层并非全部均由金属氧化物主要为二氧化锡所构成,其中尚包藏了大量大小不等的原合金颗粒。
The hydroquinone (C_6H_4 (OH) _2) hot solution is oxidized by the oxygen in the air to generate p-benzoquinone (C_6H_4O_2) and quinhydrone (C_6H_4O_2 · C_6H_4 (OH) _2) The metal surface of the mirror (component) sample is oxidized to form a black and bright oxide film. Scanning electron microscopy analysis, the oxide layer of copper and tin content is also different from the original alloy composition, that is due to the loss of copper in the surface of the copper content is lower than the original alloy, tin content is higher than the original alloy. There are also four broader diffusion peaks in the X-ray diffraction analysis of the stupid phenol-treated sample. The position and the black bronze mirror and the surface of the copper mirror treated with humic acid Ray diffraction analysis of the spectra are very similar. As hydroquinone does not contain impurities such as silicon, iron, magnesium, the oxide film on the surface of the treated sample is also free of these elements by electron probe analysis, indicating that the humic acid is not the only one that causes black paint on the copper mirror surface substance. The only humic acid treated sample surface oxide film and the black painted bronze mirror surface film, all contain silicon, iron, aluminum, magnesium and other impurities. Catechol, resorcinol, p-benzoquinone and tannic acid can also make copper mirror surface of the sample similar to the black lacquer ancient bright surface film, the majority of brown. X-ray diffraction analysis of copper mirror samples and their substrates with black lacquer antiquated surface shows that the copper and copper mirror component samples of the nine black (or brown) lacquer palaeohigh surface coatings have similar diffraction peaks at 2θ There are four broad diffuse peaks near the corners, while the X-ray diffraction analysis results of the sample matrix used have no diffuse peaks, which proves that the diffuse peaks are caused by the SnO 2 crystallites in the ancient surface of the black (or brown) The size of the crystallites is between 3-5 nm. One of them is a black-painted bronze mirror fragment that has been eroded by the burials unearthed from the tombs of the Warring States Period in Hunan Province. The results of powder X-ray diffraction analysis after grinding show that there is also a strong diffraction peak of the copper mirror base, There are mainly metal oxides SnO_2, there are still more for the stannum oxide is not oxidized copper-tin alloy particles. Thus, not all of the black lacquer ancient surface is composed of metal oxide mainly composed of tin dioxide, which still contains a large number of different sizes of the original alloy particles.