Reactivity towards oxygen and cation distribution of manganese iron spinel Mn_3-xFe_xO₄ (0≤x≤3) fine powders studied by thermogravimetry and IR spectroscopy

Abstract

The thermal behaviour in oxygen and the cation distribution of manganese iron spinels Mn_3-xFe_x O₄ (0≤x≤3) obtained by a soft chemistry method have been determined by thermogravimetry and IR spectroscopy . The existence of two different cation distributions as function of composition x is established from a quantitative analysis by derivative thermogravimetry. For x>1.50, the IR spectroscopy clearly distinguished the presence of Fe²⁺ and Mn²⁺ ions located in octahedral and tetrahedral sites, respectively. For x<1.50, this method is also efficient for the differentiation of the Mn²⁺ ions located in both types of site of the spinel structure. Kinetic studies on the oxidation process of Mn²⁺ ions show that the oxidation proceeds by way of a diffusion-controlled reaction or by a nucleation–growth mechanism. The difference in the kinetic behaviour is interpreted with regard to a structural change from the cation-deficient spinel to multi-phase oxides initiated by the oxidation temperature.

References

1. K. Naito, H. Inaba and H. Yagi, J. Solid State Chem., 1981, 36, 28.
2. M. Petrera, A. Gennero and N. Burriesci, J. Mater. Sci., 1982, 17, 429.
3. Ph. Tailhades, A. Rousset, R. Bendaoud, A. Fert and B. Gillot, Mater. Chem. Phys., 1987, 17, 521.
4. M. O'Keeffe, J. Phys. Chem. Solids, 1961, 21, 172.
5. J. Töpfer, L. Neupert, D. Schütze and P. Wartewig, J. Alloys Compd., 1994, 215, 97.
6. T. Battault, R. Legros and A. Rousset, J. Eur. Ceram. Soc., 1995, 15, 1141.
7. G. C. Maiti, R. Malessa, U. Lochner, H. Papp and M. Baerns, Appl. Catal., 1985, 16, 215.
8. I. R. Leith and M. G. Howden, Appl. Catal., 1988, 37, 75.
9. K. Kleinstück, E. Wieser, P. Kleinert and R. Perthel, Phys. Status Solidi, 1965, 8, 271.
10. D. G. Wickham, J. Inorg. Nucl. Chem., 1969, 31, 313.
11. S. Krupicka and K. Zaveta, Czech. J. Phys., 1959, 9, 324.
12. B. Gillot, M. El Guendouzi, P. Tailhades and A. Rousset, React. Solids, 1986, 1, 139.
13. B. Gillot, M. El Guendouzi and A. Rousset, J. Solid State Chem., 1987, 68, 285.
14. J. M. Jimenez Mateos, W. Jones, J. Morales and J. L. Tirado, J. Solid State Chem., 1991, 93, 443.
15. J. M. Hastings and L. M. Corliss, Phys. Rev., 1956, 104, 328.
16. G. D. Rieck and F. C. M. Dtiessens, Acta Crystallogr., 1966, 20, 521.
17. A. D. Pelton, H. Schmalzried and J. Sticher, Ber. Bunsen-Ges. Phys. Chem., 1979, 83, 241.
18. B. Gillot, J. Solid State Chem., 1994, 113, 163.
19. B. Gillot, M. Laarj, S. Kacim, T. Battault, R. Legros and A. Rousset, Solid State Ionics, 1996, 83, 215.
20. R. Bendaoud, Ph. Tailhades, A. R. Fert, D. Bertrand, J. P. Redoulès and A. Rousset, IEEE Trans. Magn., 1987, 23, 3869.
21. B. Gillot, A. Rousset and G. Dupré, J. Solid State Chem., 1978, 25, 263.
22. B. Gillot, Vibr. Spectrosc., 1994, 6, 127.
23. M. Ishii, M. Nakahira and T. Yamanaka, Solid State Commun., 1972, 11, 209.
24. K. Siratori, J. Phys. Soc. Jpn., 1967, 23, 948.
25. B. Gillot, M. El Guendouzi and M. Kharroubi, Mater. Chem. Phys., 1989, 24, 199.
26. K. Terayama and M. Ikeda, Trans. Jpn. Inst. Met., 1983, 24, 754.
27. M. El Guendouzi and B. Gillot, Mater. Chem. Phys., 1985, 13, 179.
28. P. Barret, Cinétique Hétérogène, Gauthier-Villard, Paris, 1973.
29. B. Gillot, D. Delafosse and P. Barret, Mater. Res. Bull., 1973, 8, 1431.
30. K. L. Mampel, Z. Phys. Chem. A, 1940, 187, 43.