This study systematically analyzes the composition and microstructure of Neolithic pottery unearthed from the Dazhuzhuang, Likou, and Biting Sites in the Yongcheng District using techniques such as X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), infrared spectroscopy (IR), and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS). The results show that although the raw materials for pottery at the three sites were likely sourced from nearby ancient soil layers, significant differences in chemical composition and manufacturing techniques are evident. Pottery from the Dazhuzhuang Site is mainly composed of argillaceous gray pottery, with relatively loose raw material selection and a wide fluctuation in SiO₂ content (64.98–71.07%), reflecting diversity in raw material sources. At the Likou Site, argillaceous black pottery predominates, characterized by higher Al₂O₃ content (17.78%) and significant fluctuations in CaO content (1.46–2.22%), suggesting the addition of calcareous fluxes and the adoption of standardized manufacturing techniques. Pottery from the Biting Site mainly consists of argillaceous gray pottery, showing higher Al₂O₃ content (17.36%), stable SiO₂ content (65.19–69.01%), and the lowest CaO content (0.84–1.81%). The microstructural analysis further reveals that the black pottery (from the Likou Site) displays dense vitrified regions and localized iron enrichment. In contrast, the gray pottery (from the Dazhuzhuang and Biting Sites) shows clay platelet structures and vessel-type-specific differences in porosity. This research provides important scientific evidence for understanding raw material selection, manufacturing techniques, and regional cultural interactions in the Yongcheng area during the Longshan Culture period.

The Dazhuzhuang, Biting, and Likou Sites are located along the Hui River basin in Yongcheng, eastern Henan. These three sites are situated close to each other and all yielded Longshan Culture period (2300–1800 BCE) remains, including large quantities of pottery with similar stylistic characteristics. However, archaeological surveys did not discover kiln sites at any of the three locations. To investigate the sources of Longshan period pottery in this region, its firing technology, and whether pottery circulated between the sites, this study employed a combination of X-ray fluorescence spectroscopy (XRF), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM) to conduct a comprehensive scientific analysis of pottery unearthed from Longshan Culture contexts at the Dazhuzhuang, Likou, and Biting Sites in the Huai River basin, Yongcheng, Henan Province. The results reveal significant differences among the sites in terms of raw material selection, chemical composition, and technological characteristics. Pottery from the Dazhuzhuang Site exhibits with diverse clay sources. The Likou Site is characterized by highly homogeneous compositions derived from relatively high-alumina, low-iron clays, indicating standardized production practices. In contrast, the Biting Site shows greater variability in raw materials and functional differentiation. Thermal and microstructural analyses indicate that the dense glassy phase of black pottery was achieved through reducing firing conditions. In contrast, gray pottery was manufactured with calcareous additives to produce a porous structure.

Ceramic production technology is a key indicator of craft specialization and social differentiation in Late Neolithic societies of the Central Plains. This study investigates Longshan-period pottery excavated from three representative sites, Niumugang, Zhoulonggang, and Shigudui in western Shangqiu, Henan Province. A suite of archaeometric techniques, including X-ray fluorescence (XRF), infrared spectroscopy (IR), X-ray diffraction (XRD), differential thermal analysis (DTA), and scanning electron microscopy coupled with energy-dispersive spectroscopy (SEM–EDS), was employed to systematically examine the chemical composition, mineralogical phases, thermal behavior, and microstructural characteristics of the pottery assemblages. The results reveal statistically significant differences (p < 0.05) in the contents of major ceramic-forming oxides (SiO₂, Al₂O₃, Fe₂O₃, CaO, etc.) among the three sites. Pottery from the Shigudui site exhibits the narrowest range of compositional variation, whereas that from the Zhoulonggang site shows moderate dispersion. In contrast, pottery from the Niumugang site displays the widest compositional range. Mineralogical analyses indicate that pottery from all three sites is primarily composed of quartz, mica, and mullite. Notably, the high degree of mineralogical homogeneity observed in the Shigudui assemblage reflects a well-controlled and technologically mature firing process. Microstructural observations further demonstrate that pottery from the Shigudui site is characterized by uniformly dense fabrics, functionally differentiated vessels from the Zhoulonggang site exhibit clear technological stratification, and black pottery from the Niumugang site shows highly compact microstructures. These technological patterns closely correspond to differences in vessel assemblages and indicate varying levels of craft specialization and production control. Together, the results provide archaeometric evidence for the differentiation of settlement hierarchy and the development of specialized handicraft production during the Longshan period, contributing to a deeper understanding of regional technological interaction and social processes within the Longshan cultural sphere of the Central Plains.