Spectral and other physicochemical properties of submicron powders of hematite (α‐Fe2O3), maghemite (γ‐Fe2O3), magnetite (Fe3O4), goethite (α‐FeOOH), and lepidocrocite (γ‐FeOOH)

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Abstract
Spectral and other physicochemical properties were determined for a suite of submicron powders of hematite (α‐Fe2O3), maghemite (γ‐Fe2O3), magnetite (Fe3O4), goethite (α‐FeOOH), and lepidocrocite (γ‐FeOOH). The spectral reflectivity measurements were made between 0.35 and 2.20 μm over the temperature interval between about −110° and 20°C. Other physicochemical properties determined were mean particle diameter, particle shape, chemical composition, crystallographic phase, magnetic properties, and Mössbauer properties. Only the magnetite powders have significant departures from the stoichiometric phase; they are actually cation‐deficient magnetites having down to about 18.0 wt % FeO as compared with 31.0 wt % FeO for stoichiometric magnetite. A structured absorption edge due to crystal field transitions and extending from weak absorption in the near‐IR to intense absorption in the near‐UV is characteristic of the ferric oxides and oxyhydroxides and is responsible for their intense color. Particularly for hematite, the number and position of the spectral features are consistent with significant splitting of the degenerate cubic levels by noncubic components of the crystal field. The position of the crystal‐field band at lowest energy, assigned to the envelope of the components of the split cubic 4T1 level, is near 0.86, 0.91, 0.92, and 0.98 μm at room temperature for hematite, goethite, maghemite, and lepidocrocite, respectively. Comparison with Mössbauer data suggests covalent character increases sequentially through the aforementioned series. The positions of the spectra features are relatively independent of temperature down to about −110°C. The maximum shifts observed were on the order of about 0.02 μm shortward for the ferric oxyhydroxides. Variations in the magnitude of the reflectivity of the hematite powders as a function of mean particle diameter are consistent with scattering theory. The absorption strength of the crystal‐field bands increases with increasing mean particle diameter over the range 0.1–0.8 μm; visually this corresponds to a change in color from orange to deep purple. The position of the split cubic 4T1 band shifts longward by about 0.02 μm with decreasing mean particle diameter over the same range; this trend is consistent with wavelength‐dependent scattering. The cation‐deficient magnetite powders are very strong absorbers throughout the near‐UV, visible and near‐IR; their spectral properties are independent of temperature between about −110 and 20°C.