Abstract
Members of the solid solution series Zn1-x Fe x Al2O4 (x = 0.2, 0.4, 0.6 and 1.0) with spinel structure were synthesized by direct solid-state reaction of the simple metal oxides and metallic iron in evacuated silica ampoules at 1175°C. Two aliquots of the single-phase spinels obtained for each composition were annealed under vacuum at 1075° C and 725° C for 48 hours and then quenched in liquid nitrogen.
The cation distributions of all the quenched samples were determined by X-ray powder diffraction, using the Rietveld method of structural refinement. The degree of inversion increases with iron content and for spinels with the same chemical composition with quenching temperature. The relative areas estimated for the contributions to the Mössbauer spectra of tetrahedrally and octahedrally-coordinated Fe2+ suggest that most of Zn2+ cations remain at the tetrahedral site, as expected from the relative cation site preferences.
Failure to quench the equilibrium cation distributions, suggested by deviations between the observed composition dependence of the cation distribution and that expected from the thermodynamic model of O'Neill and Navrotsky (1983,1984), may be explained by an enhancement of cation diffusion rates in the Zn1-x Fe x Al2O4 (0 < x ≦ 1) spinels caused by the presence of cation vacanies. Fe3+/vacancy defects are easily formed in these spinels due to partial oxidation of Fe2+ at high temperature.
Similar content being viewed by others
References
Basso R, Carbonin S, Delia Giusta A (1991) Cation and vacancy distribution in a synthetic defect spinel. Z Kristallogr 194:111–119
Brun E (1964) 27Al-Nuclear Magnetic Resonance in Zinc Spinels. Helv Phys Acta 37:626
Choudhary SN, Sinha TP, Srivastava KKP (1986) Orbit-lattice interaction and Mössbauer quadrupole splitting of 57Fe2+ in GeFe2O4. Phys Status Solidi (b) 137:255–258
Cromer DT (1976) Anomalous scattering factors for CoKα1 radiation. Acta Cryst 32:339
Cromer DT, Liberman DA (1981) Anomalous dispersion calculations near to and on the long-wavelength side of an absorption edge. Acta Cryst 37:267–268
Dickson BL, Smith G (1976) Low-temperature optical absorption and Mössbauer spectra of Staurolite and Spinel. Can Mineral 14:206–215
Evans BJ, Hafner SS, Weber HP (1971) Electric Field Gradients at 57Fe in ZnFe2O4 and CdFe2O4. J Chem Phys 55:5282–5288
Figueiredo MO, Penna-Costa A, Waerenborgh JC (1987) Cation reordering in gahnite by thermal treatment. (in Portuguese) Garcia de Orta, Sér Geol, 10:27–33
Finger WL, Hazen RM, Yagi T (1979) Crystal structures and electron densities of nickel and iron silicate spinels at elevated temperature or pressure. Am Mineral 64:1002–1009
Hill RJ (1984) X-ray powder diffraction profile refinement of synthetic hercynite. Am Mineral 69:937–942
Hovestreydt E (1983) On the atomic scattering factor for O2-. Acta Cryst A39:268
Hudson A, Whitfield HJ (1967) Electric field gradients in normal spinels. Mol Phys 12:165–172
Ingalls R (1964) Electric Field Gradient Tensor in Ferrous Compounds. Phys Rev A 133:787–795
International Tables for Crystallography vol A space-group symmetry (1983) Hahn T (ed.), D. Reidel Dordrecht The Netherlands
International Tables for X-ray Crystallography Vol 4: Revised and supplementary tables (1974) Ibers JA, Hamilton WC (eds.), Kynoch Press, Birmingham England
Larsson L, O'Neill HStC, Annersten H (1994) Crystal chemistry of synthetic hercynite (FeAl2O4) from XRD structural refinements and Mössbauer spectroscsopy. Eur J Mineral 6:39–51
Lima-de-Faria J, Figueiredo MO (1976) Classification, notation and ordering on a table of inorganic structure types. J Solid State Chem 16:7–20
Meyers CE, Mason TO, Petuskey WT, Halloran JW, Bown HK (1980) Phase equilibria in the System Fe-Al-O. J Am Ceram Soc 63:659–663
O'Neill HStC (1992) Temperature dependence of the cation distribution in zinc ferrite (ZnFe2O4). Eur J Mineral 4:571–580
O'Neill HStC, Navrotsky A (1983) Simple spinels: crystallographic parameters, cation radii, lattice energies and cation distribution. Am Mineral 68:181–194
O'Neill HStC, Navrotsky A (1984) Cation distribution and thermodynamic properties of binary spinel solid solutions. Am Mineral 69:733–753
O'Neill HStC, Dollase WA, Roth CRII (1991) Temperature dependence of the cation distribution in Nickel aluminate (NiAl2O4) spinel: a powder XRD study. Phys Chem Minerals 18:302–319
O'Neill HStC, Annersten H, Virgo D (1992) The temperature dependence of the cation distribution in magnesioferrite (MgFe2O4) from powder XRD Structural refinements and Mössbauer spectroscopy. Am Mineral 77:725–740
O'Neill HStC, McCammon CA, Canil D, Rubie DC, Roth CR II, Seifert F (1993) Mössbauer spectroscopy of mantle transition zone phases and determination of minimum Fe3+ content. Am Mineral 78:456–460
Osborne MD, Fleet ME, Bancroft GM (1984) Next-Nearest Neighbor Effects in the Mössbauer Spectra of (Cr,Al) Spinels. J Solid State Chem 53:174–183
Ramdani A, Gerardin R, Gleitzer C, Gavoille G, Hubsch J, Cheetham AK (1986) Désordre atomique, magnétique et electronique dans les ferrites Zn1-xGexFe2O4 (x = 0.25–0.5–0.75). J Solid State Chem 65:309–321
Roelofsen JN, Peterson RC, Raudsepp M (1992) Structural variation in nickel aluminate spinel (NiAl2O4) Am Mineral 77:522–528
Schneider J (1987) Rietveld method runs on IBM-AT. Acta Cryst A43, C295
Stone AJ (1967) Least squares fitting of Mössbauer spectra appendix to Bancroft GM, Maddock AG, Ong WK, Prince RH, Stone AJ. J Chem Soc (a) 1966
Waerenborgh JC (1992) Crystal chemistry of spinel solid solutions within the system ZnO-Al2O3-FeO-Fe2O3. (in Portuguese) PhD Dissertation IST, Technical University of Lisbon, Lisboa, Portugal
Waerenborgh JC, Annersten H, Ericsson T, Figueiredo MO, Cabral JMP (1990) A Mössbauer study of natural gahnite spinels showing strongly temperature-dependent quadrupole splitting distributions. Eur J Mineral 2:267–271
Waerenborgh JC, Figueiredo MO, Cabral JMP, Pereira LCJ (1994) Temperature and composition dependence of the cation distribution in synthetic ZnFeyAl2-yO4 (0 ≤y ≤2) spinels. J Solid State Chem (in press)
Wiles DB, Young RA (1981) A new computer program for Rietveld analysis of X-ray powder diffraction patterns. J Appl Cryst 14:149–151
Wiles DB, Young RA (1988) User's guide to DBW3.2S program for Rietveld analysis of X-ray and neutron powder diffraction patterns (version 8804), 24 p
Young RA, Wiles DB (1982) Profile shape functions in Rietveld refinements J Appl Cryst 15:430–438
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Waerenborgh, J.C., Figueiredo, M.O., Cabral, J.M.P. et al. Powder XRD structure refinements and 57Fe Mössbauer effect study of synthetic Zn1-xFexAl2O4 (0 < x ≦ 1) spinels annealed at different temperatures. Phys Chem Minerals 21, 460–468 (1994). https://doi.org/10.1007/BF00202276
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00202276