Abstract

A correlated ESR and Mössbauer spectroscopic study of the glass system 2Ca O3B 2 O 3.Al 2 O 3.xFe 2 O 3 (0.1⩽ x⩽1) is reported. At low Fe contents ( x⩽0.1) Fe 3+ ions are found only in tetrahedral environments, giving a single, sharp ESR peak at g=4.13. For higher x, occupation by Fe 3+ of other-symmetry sites become possible, as seen by the evolution of g=2.0 and g=6.0 ESR features. A careful examination of Mössbauer isomer shift data has yielded an average value of 1.96 Å for the Fe 3+−O 2− distance, besides confirming the tetrahedral site symmetry. Using this value, and quadrupole splitting data the extent of angular distortion (α) from perfect tetrahedral symmetry has been deduced as 30° from a calculation based on Newman's superposition model.

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