Nanostructured (Co x Fe1– x )3–y O4 spinel – mechanochemical synthesis

Autor: E. Wu, S. J. Campbell, W. A. Kaczmarek, M. Hofmann, S. J. Kennedy
Rok vydání: 2003
Předmět:
Zdroj: International Journal of Materials Research. 94:1127-1133
ISSN: 2195-8556
1862-5282
DOI: 10.1515/ijmr-2003-0204
Popis: The effects of wet-milling mixtures of α-Fe2O3 and cobalt hydroxide Co(OH)2 over a range of Co/Fe ratios for 215 h have been investigated by neutron diffraction and Mössbauer spectroscopy. The starting materials were mixed according to the stoichiometric formula (Co x Fe1 –x )3O4 for values of x = 0.037, 0.071, 0.133, 0.234 and 0.380 (i. e., from ≈ Co0.1Fe2.9O4 to the cobalt spinel CoFe2O4). These studies reveal the formation of a nanostructured, mixed Co–Fe spinel phase with non-stoichiometric composition (Co x Fe1– x )3 –y O4; the defect spinels have refined values x c = 0.04, 0.08 and 0.14 for the mixtures with the lowest Co content (x = 0.037, 0.071 and 0.133) and defect concentrations in the range y ≈ 0.1 –0.2. Both the spinel phase and un-reacted α-Fe2O3 are found to occur in the neutron diffraction patterns and Mössbauer spectra for the high Co content mixtures x = 0.234 and x = 0.380. Rietveld refinements of the neutron data indicate that the Co atoms predominantly occupy the octahedral B sites with vacancies also found to be located on the octahedral B sites. Analyses of the Mössbauer spectra of the milled samples confirm the existence of vacancy defects in the B sites and reveal that the vacancies cause similar effects to those of the Co ions, leading to a higher average charge state per iron atom.
Databáze: OpenAIRE