Rzeszów University, Institute of Archaeology, Hoffmanowej 8 Str, Rzeszów, Poland.
Spectrochim Acta A Mol Biomol Spectrosc. 2011 Aug 15;79(4):824-30. doi: 10.1016/j.saa.2010.08.068. Epub 2010 Sep 18.
This work aimed at characterization of a black layer covering a Bronze Age (period VI) pot surface. To solve research problems plane polarized light microscopy (PLM), scanning microscopy with X-ray microanalyser (SEM/EDS), Raman and FTIR microspectroscopies were applied. Observation of the black layer under the PLM suggests that we deal with an opaque, isotropic layer, purposely put on leather-hard, burnished surface of a pot. No traces of organic substances that might have modified a pot surface before painting were detected. The black layer coats the pot with a continuous 0.2-0.4 μm thick layer. The black layer must have been applied while warm or hot. It is recognized that the black layer is a true painting layer. Spectroscopic analyses (Raman and FTIR) point that birch tar or a birch-pine tar had been applied. Carbon black should be definitely excluded. The analyzed organic substance is structurally ordered in various degrees, due to varying temperature influence. Some Raman spectra reveal, in second-order region of the spectrum (>2000 cm(-1)), the graphite presence. Scarce points reveal the presence of inorganic admixtures: clay minerals, feldspars and quartz. The next question is: Is it an organic paint or a carbon-based, "mixed" paint? Inorganic admixtures are only casual. Relatively high concentration of alumina is expected to have appeared due to aluminum mobility in acidic environment and this was provided by organic tar/pitch substances. Phosphorus (usually with calcium) mostly concentrates together with clay minerals. Thus, hypothesis on bone powder or ash addition to tar/pitch should be excluded. Some elements may originate not only from inorganic substances but also from wood ashes.
本工作旨在对覆盖在青铜时代(VI 期)陶罐表面的黑色层进行表征。为了解决研究问题,应用了偏光显微镜(PLM)、带有 X 射线微分析仪(SEM/EDS)的扫描显微镜、拉曼和傅里叶变换红外(FTIR)显微光谱学。在 PLM 下观察黑色层表明,我们处理的是一种不透明的各向同性层,是特意涂在陶器半干、抛光表面上的。没有检测到在绘画之前可能改变过陶器表面的有机物质的痕迹。黑色层以 0.2-0.4μm 厚的连续层覆盖在陶器上。黑色层必须是在温热时施加的。可以确定黑色层是真实的绘画层。光谱分析(拉曼和 FTIR)表明,使用了桦木焦油或桦木-松焦油。绝对排除了炭黑。分析得到的有机物质由于温度的不同,在不同程度上具有结构有序性。一些拉曼光谱在光谱的二阶区域(>2000cm(-1))中显示出石墨的存在。少数点显示出无机杂质的存在:粘土矿物、长石和石英。下一个问题是:这是一种有机涂料还是一种基于碳的“混合”涂料?无机杂质只是偶然存在的。由于酸性环境中铝的迁移性,氧化铝的浓度相对较高,这是由有机焦油/沥青物质提供的。磷(通常与钙一起)主要与粘土矿物一起浓缩。因此,应该排除向焦油/沥青中添加骨粉或灰的假说。有些元素可能不仅来自无机物质,也可能来自木灰。