• Journal of Conservation Science
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• v.35 no.4
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• pp.373-383
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• 2019

We characterized the smelting process and smelting furnace through scanning electron microscopy-energy dispersive spectroscopy, wavelength dispersive X-ray fluorescence, X-ray diffraction, and raman micro-spectroscopy with 13 relics including slags and furnace walls excavated from square-shaped building sites and pits of the Three Kingdoms site at the Ungyo site section I. Our results revealed that the principal components were FeO and SiO₂; and CuO, PbO, and ZnO were contained in small quantities. Furthermore, fayalite, magnetite, augite, copper, and cuprite were found. High contents of FeO or SiO₂ components seem to have been added to form fayalite to remove gangue in the smelting process. The relatively low content of S detected in the copper prills suggests that roasting was performed well. Cristobalite and mullite, which are minerals that indicate high-temperature found in the furnace wall, show that the smelting temperature was higher than 1,250℃. The findings of this study show a high possibility that the Wanju Ungyo site is smelting remains of copper ores, which are nonferrous metals, rather than iron. Various smelting byproducts excavated in this area in the future will help us better understand the copper smelting process that may have been performed since ancient times.

• Journal of Conservation Science
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• v.35 no.2
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• pp.145-152
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• 2019

The metal-manufacturing method and smelting temperature of ancient metal-production processes have been studied by analyzing the principal elements and microstructures of slag. However, the microstructure of slag varies according to the solidification cooling rate and types and relative amounts of various oxides contained within the smelting materials. Hence, there is a need for accurate analysis methods that allow slag to be distinguished by more than its composition or microstructure. In this study, the microstructures of slag discharged as a result of smelting iron sands collected from Pohang and Gyeongju, as well as the slag excavated from the Ungyo site in Wanju, were analyzed by using metalloscopy, scanning election microscopy-energy dispersine X-ray spectroscopy(SEM-EDS) and wavelength dispersive X-ray fluorenscence(WD-XRF). Furthermore, the microcrystals were accurately characterized by performing Raman micro-spectroscopy, which is a technique that can be used to identify the microcrystals of slags. SEM-EDS analysis of Pohang slag indicated that its white polygonal crystals could be Magnetite; however, Raman micro-spectroscopy revealed that these crystals were actually $ulv{\ddot{o}}spinel$. Raman micro-spectroscopy and SEM-EDS were also used to verify that the coarse white dendritic structures observed in the Gyeongju-slag were $W{\ddot{u}}stites$. Additionally, the Wanju slag was observed to have a glassy matrix, which was confirmed by Raman micro-spectroscopy to be Augite. Thus, we have demonstrated that Raman micro-spectroscopy can accurately identify slag microcrystals, which are otherwise difficult to distinguish as solely based on their chemical composition and crystal morphology. Therefore, we conclude that it has excellent potential as a slag analysis technique.