Abstract

The firing of traditional gray pottery relies on complex physicochemical reactions governing its color, dimensional accuracy, and structural stability. Unclear kiln-transformation mechanisms restrict standardized and digital production of this Chinese intangible cultural heritage. Herein, direct ink writing (DIW) was used to fabricate Hejin gray pottery green bodies from local ternary raw materials. Thermodynamic calculations, TG–DTG/DSC, XRD, XRF, and atmosphere-controlled firing tests were combined to reveal coupled phase evolution and reduction color-forming mechanisms during sintering. Two interrelated kiln-transformation processes were identified. First, sequential mineral reconstruction occurs at four critical temperatures: free water loss at 119.8 °C, two-stage dehydroxylation of hydrous silicates at 270.5 °C and 767.9 °C, and CaCO3 decomposition at 547.9 °C. Uneven shrinkage and gas release at these temperatures induce cracking, blistering, and deformation of printed bodies. Micron-sized CaCO3 (equivalent radius ≈ 1.31 μm) exhibits high surface energy and significantly reduces its decomposition temperature, consistent with experimental observations. Second, reducing atmospheres trigger competitive phase formation. Distinct from the conventional Fe2O3 → Fe3O4 → FeO reduction pathway, Fe oxides preferentially react with abundant Al2O3 to form thermodynamically stable FeAl2O4 spinel, yielding uniform celadon-gray tones. The final color is nearly independent of 20–90 vol% CO, and air-isolated cooling below 600 °C is mandatory to prevent secondary oxidation and reddening. This work establishes a thermodynamic framework for DIW-printed Hejin gray pottery kiln transformation, clarifies microscale defect and color-evolution mechanisms, and offers theoretical guidance for atmosphere-controlled firing and digital mass production of heritage ceramics.

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