自然老化与人工做旧老蜜蜡的宝石学鉴别特征

Gemmological Identification Characteristics of Natural Ageing and Artificial Aged Beeswax Amber

  • 摘要: 蜜蜡是一种黄色-棕色的半透明至不透明琥珀, 老蜜蜡是指经历了一定时间(几十至上百年)的佩戴、盘玩或搁置在自然环境下经风化作用使颜色变深, 视觉上显"老"的蜜蜡, 因其具有较高的文化价值和商业价值, 深受收藏者和大众的喜爱, 且存量有限, 其价格一直居高不下。近年来市场上出现了大量的用普通蜜蜡经加热处理, 通过控制加热的速率、温差等参数, 或者叠加了其他技术而形成的人工做旧老蜜蜡, 其外观近似年代久远的老蜜蜡。目前学术界缺乏对人工做旧老蜜蜡的系统性研究。本文采用宝石显微观察、红外光谱、光致发光光谱、紫外-可见-近红外光谱对清代自然老化老蜜蜡与人工做旧老蜜蜡进行了系统研究, 总结了二者的鉴别特征。主要结论如下: (1)人工做旧老蜜蜡表面大多光滑, 有时可见快速加热形成的黑色碳化凹坑等, 有些人工做旧老蜜蜡也可人工打磨出较一致的凹凸不平外观, 而自然老化老蜜蜡大多表面粗糙, 具有不规则凹凸不平的外观; (2)人工做旧老蜜蜡的龟裂纹只能做出一组, 且裂隙较老蜜蜡形态规则, 裂纹可大、可小, 深度较浅; 自然老化老蜜蜡的龟裂纹形态自然、均匀、紧密, 一般分为2~3级, 1级主裂隙深而宽, 显微镜下呈深色大裂隙, 2级裂纹的深度和宽度小于主裂纹, 3级细微龟裂纹分布于被主裂纹或2级裂纹分割成的小块区域内。自然老化老蜜蜡的3级或2级龟裂纹同时存在, 是人工做旧老蜜蜡目前无法实现的工艺, 也是鉴别它们的重要依据; (3)人工做旧蜜蜡断口处的老化层厚度(≤ 0.2 mm)远小于自然老化老蜜蜡(≥ 0.8 mm); (4)红外光谱中, 自然老化老蜜蜡的由于表面粗糙, 红外光谱变形明显, "波罗的海肩"(1 260~1 160 cm-1)不显著, 而该特征峰在人工处理老蜜蜡中则较明显, 与其老化层过薄有关。其次, 1 566 cm-1处的吸收峰在自然老化老蜜蜡中出现的几率较高, 推测与波罗的海琥珀老化后生成的琥珀酸有关。(5)老蜜蜡和人工做旧老蜜蜡的光致发光光谱相似, 但两种样品的发光中心强度比断口处(内芯)均有大幅下降, 详细对比二者的特征谱峰波长有较小的差异, 但易受仪器精度和人为操作影响, 鉴定意义需进一步统计验证; (6)紫外-可见-近红外光谱二者基本一致, 没有鉴定意义。本文的研究结果对自然老化和人工处理的老蜜蜡鉴别有实用价值。

     

    Abstract: Beeswax amber is a kind of translucent to opaque amber with yellow to brown colour. The old beeswax amber refers to a kind of beeswax that has been worn, played or left in the natural environment for a certain period of time (tens to hundreds of years) and has been darkened by natural weathering, which is visually "old". Among them, natural old beeswax is greatly appreciated by certain collectors and the public due to its high cultural value and commercial value, and its price has always been high since its stock is limited. In recent years, there has been a large number of artificial aged beeswax amber through heating treatment of ordinary beeswax, controlling the processing parameters such as the heating rate and temperature difference, or overlapping other technologies, the artificial aged beeswax displays the appearance similar to that of natural ageing beeswax amber. At present, there is a lack of systematically academic research on the artificial aged beeswax amber. This article conducts a systematic study on the Qing Dynasty natural ageing beeswax amber and artificially aged beeswax amber via gemstone microscopy, infrared spectroscopy, photoluminescence spectroscopy, and ultraviolet visible near-infrared (UV-Vis-NIR) spectroscopy, and summarizes the identification characteristics of them. The main conclusions are as follows: (1) The surface of artificially aged beeswax amber is mostly smooth, and sometimes accompanied by black carbonization pits formed by rapid heating. However, the surface of naturally ageing beeswax amber is mostly rough, with an irregular and uneven appearance. Some manually made beeswax amber can also be artificially polished to create a more consistent uneven appearance; (2) There is only one set of turtle cracks can be made on the artificially aged beeswax amber, and the turtle cracks are more regular in shape than the natural ageing beeswax amber. The turtle cracks can be large, small, and shallow in depth; The morphology of turtle cracks in natural ageing beeswax amber is natural, uniform, and compact, generally divided into 2-3 levels. The first level main crack is deep and wide, and appears as a dark large crack under the microscope. The depth and width of the second level crack are smaller than the main crack, and the third level fine turtle cracks are distributed in small areas divided by the main or secondary cracks. The coexistence of Level 3 or Level 2 turtle cracks in naturally ageing beewax amber is a process that cannot be achieved by artificially aged beeswax amber, and it is also an important basis for identifying them; (3) The thickness of the ageing layer (≤ 0.2 mm) at the fracture surface of artificially aged beeswax amber is much smaller than that of naturally ageing beeswax amber (≥ 0.8 mm); (4) In the infrared spectrum, due to the rough surface of the naturally ageing beeswax amber, the infrared spectrum deformation is obvious, and the "Baltic shoulder" (1 260-1 160 cm-1) is not significant. However, the characteristic peaks are more obvious in the artificially aged beeswax amber, which is related to the thin ageing layer. Secondly, the absorption peak at 1 566 cm-1 has a higher probability of appearing in naturally aged beeswax amber, which is speculated to be related to the succinic acid generated after the ageing of Baltic amber. (5) The photoluminescence spectra of naturally ageing beeswax amber and artificially aged beeswax amber are similar, but the luminescence center intensity of both samples significantly decreases compared to that of the fracture (inner). There is a small difference in the characteristic spectral peak wavelength between these two, but which are easily affected by instrument accuracy and human operation, and the identification significance needs further statistical verification; (6) The UV-Vis-NIR spectra are basically consistent and have no identification significance. The research results of this article are of practical value for the identification of natural aging and artificially aged beeswax amber.

     

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