Thermally-induced color transformation of hematite: insight into the prehistoric natural pigment preparation.

Since the prehistoric era, hematite has been known as a reddish color pigment on rock art, body paint, and decorating substances for objects discovered almost worldwide. Recently, studies about purple hematite used in prehistoric pigment have been done vigorously to investigate the origin of the purple pigment itself. These previous studies indicate that the differentiation of crystallinity, crystal size, morphology, and electronic structure can cause the color shift, resulting in purple hematite. In this study, we conducted a detailed study of the sintering temperature effects on the formation of hematite minerals. This study aims to reveal the structural, crystallography, and electronic transformation in hematite due to heating treatment at various temperatures. The hematite was synthesized using precipitation to imitate the primary method of hematite formation in nature. The sintering process was carried out with temperature variations from 600 °C to 1100 °C and then characterized by crystallographic and structural properties (XRD, Raman Spectroscopy, FTIR), particle size (TEM), as well as electronic properties (DRS, XANES). The crystallinity and particle size of hematite tend to increase along with higher sintering temperatures. Moreover, we noted that the octahedral distortion underwent an intensification with the increase in sintering temperature, which affected the electronic structure of hematite. Specifically, the → transition exhibited lower energy for hematite produced at a higher temperature. This induced a shift in the absorbed energy of the polychromatic light that led to a color shift within hematite, from red to purple. Our finding emphasizes the importance of electronic structure in explaining hematite pigment's color change rather than relying on simple reasons, such as particle size and crystallinity. In addition, this might strengthen the hypothesis that the prehistoric human created a purple hematite pigment through heating.