• Proceedings of the Korean Institute of Resources Recycling Conference
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• 1993.03a
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• pp.15.2-15
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• 1993

• 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.

• Journal of Conservation Science
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• v.35 no.5
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• pp.392-402
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• 2019

This study interpreted the characteristics of the site and provenance of raw material by performing material characteristics analysis of the slags and tuyeres excavated from the Sinpung site in Wanju, Jeollabuk-do. The major chemical compositions suggested that the slags and tuyeres were created when Cu-Sn-Pb was alloyed. Metal microscope and scanning electron microscopy-energy dispersive spectrometer analyses revealed that the slags and tuyeres were by-products formed in the alloying process. This alloy, created by adding galena to copper and tin ingots, was an intermediary material used in making the finished products. According to the lead isotope ratio analysis result, slags could be made using galena of the southern Zone III region of Korea. Based on the decomposition of mica group minerals and the formation of mullite detected through X-ray diffraction analysis, it is possible to conclude that the tuyeres operated at approximately 1,000℃ as, the mullite was detected on the outside of the tuyeres.

• Journal of Conservation Science
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• v.29 no.2
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• pp.139-147
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• 2013

This study focused on iron making related information through analyzing slags and furnace wall collected from iron production site of Suryong-ri Wonmorongi, Chungju. Total Fe content of slags were from 36.98% to 44.47% and this range was general recovery rate of iron in ancient. Compounds of calcium included slags was supposed to add intentionally during smelting process as deoxidation agent in order that these helped to separate iron from impurities. Furnace wall didn't make of high alumina clay because of low $Al_2O_3$. Microstructure and main components of slags show that No. 1 to 3 slags with fayalite and wustite were products of iron ore smelting. However, No.4 slag is more likely to smelt by iron sand because of ulvospinel with $TiO_2$ in No. 4 slag. Therefore, iron ore were not only used but iron sand in smelting and furnace wall made of general clay with low $Al_2O_3$ content in this area.

• Journal of Conservation Science
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• v.38 no.1
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• pp.33-44
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• 2022

The study, iron-making process was examined through the scientific analysis of six by-products that were obtained during iron making at the Songdu-ri site in Jincheon. The total Fe content of the slags excavated from the Songdu-ri site was 36.29-54.61 wt%, whereas the deoxidation agent was 26.48-49.08 wt%. The compound analysis result indicated that fayalite and wüstite are the main compounds in slag. Furthermore, the microstructure analysis result confirmed the presence of fayalite and wüstite in the slag. It can be inferred from the flat shape in a bright matrix structure of the hammer scales that forging was performed in the latter stage. The Raman micro-spectroscopy results confirmed that the surface was hematite (Fe₂O₄), middle layer was magnetite (Fe₃O₄), and inner layer was wüstite (FeO). The presence of smelting and smithing slags, spheroid hammer scales, and flake hammer scales suggests that at the Songdu-ri site, iron-making process is carried out by division of labor into producing iron bloom through direct smelting, refining and forge welding, and ingot production.

• Journal of Conservation Science
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• v.32 no.2
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• pp.189-202
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• 2016

To figure out the material characteristics about slag and raw materials which are founded in iron product sites in Seosan area, we used XRF, EDS to analysis chemical compositions. Also we observe the microstructure by microscope and SEM. To identify the mineral component, XRD analysis was used and to assume the provenance of the raw material, lead isotope ratio analysis was used. From the results, we figure out that slags are non-ferrous created when metal was refined. Also, main tissue of slags were Fayalite, Galena, Magnetite, and raw materials were identified as mineral of Galena, Anglesite, Pyrite etc. From the result about lead isotope ratio analysis, we found out most samples are classified as the Western Gyeonggi massif in South Korea. Especially three of raw materials and slag samples which collected in the Seosan Doseongri was presumed to be the provenance. We figure out that slags we analyzed were made in non-ferrous metal smelting process and especially that were more likely to smelt from Seosan Doseongri. If various slags in this area are analysed by someone, It will contribute understanding non-ferrous metal refining process as well as metal refining which are composed.

• Korean Journal of Heritage: History & Science
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• v.50 no.1
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• pp.4-17
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• 2017

In this research, the chemical composition of the iron artifacts from the late 6th-century to early 7thcentury Baekje remains in Gwanbuk-ri, Buyeo, specifically of the nine iron artifacts including slags, furnace walls and ingot iron excavated in the District "Na", were examined by observing their chemical compounds and microstructures. As a result, GB1 and GB6 were determined to be proto-reduction lumps whereas GB2, GB3, GB4 and GB5 were determined to be tempered slags, respectively. Also, he furnace wall GB7 were containing mullite and cristobalite, which are high temperature index minerals, The extrusion temperature was found out to be about $1200{\sim}1300^{\circ}C$, and it is most likely that the smelting temperature in the furnace was in that temperature range. GB8 ingot iron was determined to be a forged ironware. This ingot iron was an intermediary product for making ironware and its nonmetallic inclusions displayed similar microstructure and contents compared to the forged iron. Because of the existence of proto-reduction lumps and forged iron, the iron making facility located in District "Na" most likely had a small-scale iron making facility that handled iron bloom smelting and refining processes.

• Journal of Conservation Science
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• v.36 no.2
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• pp.143-151
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• 2020

In the present article, we have analyzed five slags excavated from the Unified Silla period iron smelting site, i.e., location 4-2 of the Inje Bupyeong-ri site, to investigate the iron smelting process. The total Fe content of the slag excavated from the Inje Bupyeong-ri site ranged between 3.65 and 23.78 wt%, lower than that of typical slag, and deoxidation agent of the slag ranged between 65.92 and 88.96 wt%, higher than that of typical slag. These results suggest that the recovery rate of iron was significantly high. Furthermore, cristobalite was detected in most of the samples, and the furnace temperature, estimated by substituting the analyzed data into the FAS and FCS state diagrams, was confirmed as 1,600℃ or more. These results suggest that the operation at the Inje Bupyeong-ri site was performed at a temperature capable of producing cast iron by completely melting the carbon-containing iron. Observation of the microstructure showed that the iron fragments excavated at the Inje Bupyeong-ri site were identified as white cast iron. Steadite from the ternary iron-carbon-phosphorus system was observed in the white cast iron structure. These results show that indirect smelting was performed when the iron smelting by-products were produced. Based on the analysis results, it was confirmed that the Inje Bupyeong-ri site was the indirect smelting site in the Unified Silla period.

• Journal of Conservation Science
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• v.36 no.3
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• pp.162-177
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• 2020

Research was conducted to characterize the copper production and smelting process with 11 copper smelting by-products (copper slag and copper crucible) excavated from the NA and LA areas at the Gwanbuk-ri archeological site in Buyeo. Scanning electron microscopy-energy dispersive spectroscopy, wavelength dispersive X-ray fluorescence, X-ray diffraction, and Raman microspectroscopy were employed in the analysis. The research results reveal that the copper slag from Gwanbuk-ri contained silicate oxide, magnetite, fayalite, and delafossite, which are typical characteristics of crucible slag and refined slag. The outward appearance and microstructure of the slag were grouped as follows: 1. glassy matrix + Cu prill, 2. glassy matrix + Cu prill + magnetite, 3. silicate mineral matrix + Cu prill, 4. crystalline (delafossite and magnetite) + amorphous (Cu prill), 5. magnetite + fayalite, and 6. slag from slag. The copper slags from Guanbuk-ri were found to contain residues of impurities such as SiO₂, Al₂O₃, CaO, SO₄, P₂O₅, Ag₂O, and Sb₂O₃ in their microstructure, and, in some cases, it was confirmed that copper, tin and lead are alloys. These results indicate that refining of intermediate copper(including impurities) and refining of alloys of copper(including impurities) - tin and refining of copper(including impurities) - tin - lead took place during the copper production process at Gwanbuk-ri, Buyeo.

• Journal of Conservation Science
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• v.26 no.2
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• pp.171-182
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• 2010

The slag excavated from Gyesil-ri in Gongju, Yeonje-ri in Cheongwon and Beopcheonsaji (temple) site in Wonju are analyzed by X-ray Fluorescence Analyzer, metallurgical microscope, SEM-EDS etc., for chemical composition and microstructure to figure out the raw material and the iron manufacturing technique. First of all, as a result of principal component analysis, the total Fe-content of slag from Gyesil-ri is 39 to 44% and the modified rate is 15 to 21%, which is common in ancient iron slag. Yeonje-ri site is found the ancient iron-smelting furnace. The total Fe-content of slag from Yeonje-ri is 41 to 43% and modified rate is 18~30%, which is also the general value in the ancient slag. However only slag is excavated in the residential area at Beopcheonsaji site and there is no iron making relic. In addition, the result of principal component analysis contains that the total Fe-content of Beopcheonsaji site is 52 to 57%, and modified rate is 8 to 14%. It shows that the total Fe-content of Beopcheonsaji site is higher than relic from Gyesil-ri and Yeonje-ri and the modified rate is lower than other sites. This results mean that recollecting rate of Fe in Beopcheonsaji site is lower than other sites. Also, as a result of minor elements analysis, the slag from Gyesil-ri has the higher level of Ti, V and Zr than other sites and the microstructure are observed as magnetite and ulvospinel, so that the raw material of slag is iron sand. But the slag from Yeonje-ri and Beopcheonsaji site are identified to use iron ore. As a result of microstructure observation, fayalite, gray-columnar crystal, is found in the slag from Yeonje-ri and big wustite as main phase is observed in the slag from Beopcheonsaji site. This study show that the slag from Yeonje-ri is made of smelt ash produced during smelting works and the slag from Beopcheonsaji site is made of forging ash produced during forging work concerning the excavated location and the microstructure.