The slag found in Hengdong Jiangxian County, Shanxi Province has been recognized by archaeologists as the earliest evidence of bloomery ironmaking in China. The slag was characterized and analyzed by chemical titration, inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), scanning electron microscopy coupled with energy dispersive spectrometer (SEM-EDS), and tescan integrated mineral analysis (TIMA). The smelting technology in ancient China was explored, combined with thermodynamic theory. The results of chemical titration shown that the total Fe was as high as 64.18%, which means that it was very difficult to produce iron on a large scale with the ancient bloomery ironmaking technology, consuming a lot of iron ore while producing very little iron. The distribution of FeO was relatively dispersed, while that of Fe2O3 particles was concentrated and large. The source of Fe2O3 in the slag can be roughly identified as the oxidized metallic iron, which could not be separated in the slag in the past. Tescan integrated mineral analysis (TIMA) images show that Fayalite and Wustite are the main phase forms in smelting slag. The existence of fayalite proves that the temperature of a slag system should reach the condition of liquid phase formation during the smelting process. Based on the characterization results, the metallurgical conditions of the slag at that time are inferred by FactSage7.1. The theoretical smelting temperature was between 1150 °C and 1200 °C. The fayalite and aluminosilicate in the slag had obvious displacement and inhomogeneity, which pointed to the forging temperature ranging from 1050 °C to 1100 °C.
To explore the source of Pb in Bronze Age artefacts from the Central Plains (Zhongyuan) in China, we investigated non-ferrous minerals from the Qingyuan archaeological site in Yuanqu County near the Zhongtiao Mountains. Fragments of smelting slag from the Erlitou cultural layer were collected. The smelting slag was investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and lead isotope analysis. The SEM and EDS results confirmed that the slag contained Pb, Pb–As, and Cu–Pb–Sn inclusions and non-metal impurities such as low-Zn spinels. The XRD results signified that the bulk of the slag comprised Fe–Mn–Si phases. The chemical state of Pb was mainly Pb–O with some metallic Pb, as identified by XPS. The theoretical melting point was calculated using FactSage7.1 based on the composition and phase characterisation. The calculated temperature was 1100–1200 °C, which agreed well with the actual melting point of 1114–1354 °C. The slag composition and inclusion phases indicated that Pb–Zn–O ores with Mn and As were added during reduction smelting in Qingyuan. The raw materials of smelting included crude Pb with minor amounts of Cu, As, and Sn. Lead isotope analysis revealed that the lead materials produced in Qingyuan were likely transferred to Yanshi City in the Shang Dynasty. The findings of this study provide significant clues for exploring lead mineral production in the Central Plains during the Early Bronze Age.
The current research on metallurgical remains from scientific excavations in northeast Yunnan from the Bronze Age period is insufficient. In order to study the smelting technology of the Bronze Age in north-eastern Yunnan, samples of slag and mineral excavated from the Yubei Di site in Dongchuan were examined. Based on the outcome of the characterization analysis, a simulation was executed utilizing the software Factsage 7.1 in order to generate a phase diagram that accurately portrays the melting procedure. This simulation aimed to produce the most credible representation of the phase transition by employing computational methods. Characterisation methods included Metallographic Microscopy, Scanning Electron Microscopy Energy Dispersive Spectromicropy (SEM-EDS), X-ray diffraction (XRD), and Radiocarbon Date (14C dating). The results showed that there was much copper ore left in the slag of the site. Most of these copper ores were in the form of copper ferrite or cuprous oxide. The copper ore was copper oxide ore, and metal copper particles appeared in a small amount of the slag. Most of the slags unearthed from the site of the Yubeidi site were products of sulfur-containing oxide reduction and smelting into copper. Based on the outcomes of the simulations, it was established that the slag excavated from the Yubeidi site was mainly from the reduction and smelting process of sulphur-containing copper oxide minerals into copper, without consciously adding fluxes, not having mastered the slag-making techniques for different types of copper ores, and with primitive techniques. The carbon 14 dating results show that the age of the slag was during the Spring and Autumn Period and the Warring States Period.