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Structure of the αFexAl1:xOOH solid solution

I. Evidence by polarized EXAFS for an epitaxial growth of hematite-like clusters in Fe-diaspore

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Abstract

The three-dimensional local organisation around Fe atoms in a natural diaspore (αAl0.9955Fe0.0045OOH) has been investigated by angular measurements of X-ray absorption spectra. It is demonstrated that in a single crystal of diaspore, the absorption cross-section exhibits the special case of trichroism where three independent measurements are needed to determine the absorption cross-section for any direction of polarization. Extended X-ray absorption fine structure (EXAFS) spectra were thus recorded at the following orientations of the polarization vector: \(\), \(\), and \(\). The incoming white beam was monochromatized using two Si(331) crystals, which deliver at the Fe K-edge a completely linearly polarized X-ray beam. The reliability of our measurements was checked by comparing the isotropic EXAFS spectrum calculated from the three orthogonal measurements to the one of the diaspore powder recorded at the magic angle. It is shown that Fe3+ ions are not randomly distributed within the diaspore framework. Furthermore, only part of the Fe3+ ions substitutes Al, the others being located in the channels of the structure. The 3D local structure of the Fe domains has been modeled assuming hematite-like clusters of three Fe octahedra topotactically grafted to aluminous chains. These Fe clusters are thought to represent ancient multinuclear Fe surface complexes having formed at the time of the diaspore growth, and being sealed in its bulk structure. The whole crystal of diaspore is then thought to have kept the memory of the heterogeneous nucleation mechanism of these hematite nuclei. In addition to the well-known examples of atom segregations, ion vacancies, and intergrowths of discrete phases, this new type of crystal defect represents another evidence of non-equilibrium crystallization process under the thermodynamic and kinetic conditions that prevail at the earth's surface.

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Hazemann, J.L., Manceau, A., Sainctavit, P. et al. Structure of the αFexAl1:xOOH solid solution. Phys Chem Minerals 19, 25–38 (1992). https://doi.org/10.1007/BF00206797

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Keywords

  • Hematite
  • Nucleation Mechanism
  • Discrete Phasis
  • Orthogonal Measurement
  • White Beam