Hematite colour revisited: Particle size and electronic transitions.

Hematite has been used as a pigment since ancient times, due to its natural abundance and colour that ranges from vivid red to purple. Caput mortuum is a purple α-Fe2O3 whose colour has been ascribed as originating from particle size. In this work, submicrometric synthetic, natural and commercial hematites were investigated by diffuse reflectance spectroscopy (DRS), scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and Raman microscopy aiming to clarify the origin of the purple colour. From the results it was concluded that the purple colour is associated with crystallinity, that promotes a significant decrease in absorption below 500 nm and, simultaneously, an increase in the 6A1(6S) → 4T1(4G) d-d transition at ca. 880 nm. The behaviour of the ca. 880 nm band can be explained by the more extensive magnetic interaction between adjacent Fe3+ ions in crystalline samples but cannot explain the spectral behaviour in the green-blue region considering only the d-d transitions. A plausible explanation is that in the distorted FeO6 octahedra, both the Fe-O distances and the Fe-O-Fe angles area are affected, thus interfering in the low energy oxygen-to-iron charge transfer transition, whose tail span the 400 nm - 500 nm region and is more intense than the d-d transitions in hematite nanoparticles, nanofilms and defective (red) Fe2O3 samples. The decrease in the intensity of the charge transfer band as a consequence of the FeO6 octahedral distortion is yet to be confirmed by further experiments, but the experimental results clearly show that the purple colour of hematite is due to a decrease in optical absorption below 500 nm.

Investigation on the hazing of a Brazilian contemporary painting.

A whitish crystalline-like coating was observed on the surface of the painting "Incêndio", 1990, produced by Emmanuel Nassar and awarded at the 6th Biennial of Cuenca. This work belongs to the Contemporary Art Museum of the University of São Paulo (MAC-USP) and such coating modified the artwork characteristics, causing an unpleasant effect and compromising its exhibition. The choice of the proper conservation and restoration strategies involves the understanding of the degradation process, demanding the identification of the chemical compounds formed on the painting surface, as well as of the other components in the painting. The results here obtained from Raman and optical microscopies, FTIR-ATR, SEM-EDS and GC-MS, revealed that the efflorescence chemical composition is almost only palmitic acid, with minor contents of stearic acid and their methyl esters, and that the paints are composed by chrome yellow, amorphous carbon and toluidine red pigment; an aluminum silicate filler in the black paint applied on the aluminum ground was also detected. Hierarchical Cluster Analyses (HCA) of the Raman spectra also revealed that the concentration of the efflorescence minor components depends on the paint composition. It was suggested, therefore, that the degradation process resulted from segregation and migration of mainly palmitic acid from the dried paints. Restoration methodologies used in similar cases, as well as factors that contribute to this process, were discussed.