The ruins of the Imperial City of the Minyue Kingdom were an important site of the Minyue Kingdom during the Han Dynasty. Characteristic bronze arrowheads unearthed from the East Gate, with their exquisite craftsmanship, provide important physical evidence for studying ancient bronze casting technology and the military activities of that time. However, there is still a lack of systematic research on the alloy composition, casting process, and chemical stability of these arrowheads in long-term burial environments. The bronze arrowheads that were found in the East Gate warehouse are the subject of this study. Metallographic analysis, scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS) were used to carefully examine their composition and microstructure, as well as the casting process characteristics. The findings reveal the following: (1) The East Gate bronze arrowheads primarily consist of copper–tin binary alloys, and certain samples exhibit a lead (Pb) content of up to 11.19%, potentially due to element addition during casting or element migration in the burial environment. (2) The metallographic structure shows that the sample matrix has a typical α-dendrite structure, indicating that a high-temperature casting process was used, and then a certain surface treatment was performed to enhance corrosion resistance. (3) Under a scanning electron microscope, it was observed that a three-layer structure was formed on the surface of the arrowhead, including a fully mineralized layer, an intermediate transition layer, and the original core tissue. (4) The detection of molybdenum (Mo) in some samples suggests a close relationship between the complexity of the buried soil environment and human activities. (5) By comparing the microstructure and corrosion degree of the longitudinal section and the cross-section, it was found that the longitudinal section has a stronger corrosion resistance due to its denser structure. Comprehensive analysis shows that the technical details of the bronze arrowheads unearthed from the Minyue Imperial City in terms of material selection, casting process, and later use reflect the outstanding achievements of the Minyue Kingdom in the field of bronze manufacturing in the Han Dynasty.
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