Home Physical Sciences Temperature dependences of the hyperfine parameters of Fe2+ in FeTiO3 as determined by 57Fe-Mössbauer spectroscopy
Article
Licensed
Unlicensed Requires Authentication

Temperature dependences of the hyperfine parameters of Fe2+ in FeTiO3 as determined by 57Fe-Mössbauer spectroscopy

  • Antoine Van Alboom EMAIL logo and Eddy De Gravave
Published/Copyright: March 4, 2016
Become an author with De Gruyter Brill

Abstract

The temperature variations of the ferrous Mössbauer parameters for a synthetic ilmenite (FeTiO3) have been determined and interpreted over a very wide temperature range (5–900 K). The Debye model of the lattice vibrations was used in interpreting the temperature dependence of the center shift, yielding a characteristic Mössbauer temperature of 350 ± 20 K and a zero-Kelvin intrinsic isomer shift of 1.30 ± 0.01 mm/s. The temperature dependence of the ferrous Mössbauer quadrupole splitting was interpreted using crystal feld theory. A most adequate description of the experimental ∆EQ(T) curve was obtained assuming an energy shift of at the most ca. 500 ± 50 cm–1 for the highest orbital T2g level relative to the lowest level within this T2g triplet. The temperature dependence of the hyperfine field was interpreted within the molecular field theory of magnetism assuming the magnetic exchange energy being a function of interatomic spacing, indicating a first-order magnetic transition at the magnetic-paramagnetic transition temperature of 59.0 ± 0.5 K.

This detailed presentation of Mössbauer parameters as a function of temperature can serve as a basis for easily detecting ilmenite ore at, for example, the lunar surface and for monitoring by means of Mössbauer spectroscopy the reduction process of the mined mineral, for the purpose of supplying a future Moon base site with oxygen and water.

Acknowledgments

This work was funded by the Fund for Scientific Research, Flanders, Belgium.

References

Balazic, M., Kopac, J., Jackson, M.J., and Ahmed, W. (2007) Review: titanium and titanium alloy applications in medicine. International Journal of Nano and Biomaterials, 1, 3–34.10.1504/IJNBM.2007.016517Search in Google Scholar

Ballhausen, C.J. (1962) Introduction to Ligand Field Theory. McGraw-Hill, New York.Search in Google Scholar

Barth, T.F.M., and Posnjak, E. (1934) The crystal structure of ilmenite. Zeitschrift für Krystallographie, 88, 265–270.10.1524/zkri.1934.88.1.265Search in Google Scholar

Bean, C.P., and Rodbell, D.S. (1962) Magnetic disorder as a first-order phase transformation. Physical Review, 126, 104–115.10.1103/PhysRev.126.104Search in Google Scholar

Bowles, J.F.W. (2011) Ilmenite. In J.F.W. Bowles, D.J. Vaughan, R.A. Howie, and J. Zussman, Eds., Rock-Forming Minerals: Non-Silicates: Oxides, Hydroxides and Sulphides, vol. 5A (2nd ed.), 265–294. The Geological Society of London.Search in Google Scholar

Choudhury, R.N.P., Pati, B., Das, P.R., Dash, R.R., and Paul, A. (2013) Development of Electronic and Electrical Materials from Indian Ilmenite. Journal of Electronic Materials, 42, 769–782.10.1007/s11664-012-2465-zSearch in Google Scholar

De Grave, E., and Van Alboom, A. (1991) Evaluation of ferrous and ferric Mössbauer fractions. Physics and Chemistry of Minerals, 18, 337–342.10.1007/BF00200191Search in Google Scholar

Dyar, M.D., Klima, R.L., Lindsley, D., and Pieters, C.M. (2007) Effects of differential recoil-free fraction on ordering and site occupancies in Mössbauer spectroscopy of orthopyroxenes. American Mineralogist, 92, 424–428.10.2138/am.2007.2441Search in Google Scholar

Dyar, M.D., Schaefer, M.W., Sklute, E.C., and Bishop, J.L. (2008) Mössbauer spectroscopy of phyllosilicates: Effects of fitting models on recoil-free fractions and redox ratios. Clay Minerals, 43, 3–33.10.1180/claymin.2008.043.1.02Search in Google Scholar

Dyar, M.D., Klima, R.E., Fleagle, A., and Peel, S.E. (2013) Fundamental Mössbauer parameters of synthetic Ca-Fe-Mg pyroxenes. American Mineralogist, 98, 1172–1186.10.2138/am.2013.4333Search in Google Scholar

Eeckhout, S.G., and De Grave, E. (2003a) Evaluation of ferrous and ferric Mossbauer fractions. Part II. Physics and Chemistry of Minerals, 30, 142–146.10.1007/s00269-003-0300-zSearch in Google Scholar

Eeckhout, S.G., and De Grave, E. (2003b) Fe-57 Mossbauer-effect studies of Ca-rich, Fe-bearing clinopyroxenes: Part I. Paramagnetic spectra of magnesian hedenbergite. American Mineralogist, 88, 1129–1137.10.2138/am-2003-0721Search in Google Scholar

Eeckhout, S.G., De Grave, E., Vochten, R., and Blaton, N.M. (1999) Mössbauer effect study of anapaite, Ca2Fe2+(PO4)2.4H2O, and of its oxidation products. Physics and Chemistry of Minerals, 26, 506–512.10.1007/s002690050213Search in Google Scholar

Grant, R.W., Housley, R.M., and Geller, S. (1972) Hyperfine interactions of Fe2+ in ilmenite. Physical Review B, 5, 1700–1706.10.1103/PhysRevB.5.1700Search in Google Scholar

Hoy, G.R., and Chandra, S. (1967) Effective field parameters in iron Mössbauer spectroscopy. Journal of Chemical Physics, 47, 961–965.10.1063/1.1712062Search in Google Scholar

Hutchings, M.T. (1964) Point-charge calculations of energy levels of magnetic ions in crystalline electric fields. Solid State Physics, 16, 227–273.10.1016/S0081-1947(08)60517-2Search in Google Scholar

Ingalls, R. (1964) Electric-field gradient tensor in ferrous compounds. Physical Review, 133, 787–795.10.1103/PhysRev.133.A787Search in Google Scholar

Ito, A., Morimoto, S., Someya, Y., and Ikeda, H. (1982) Mössbauer and neutron diffraction studies of competing magnetic orderings in random mixtures: Co1–xFexTiO3. Solid State Communications, 41, 507–510.10.1016/0038-1098(82)90187-9Search in Google Scholar

Kato, H., Yamada, M., Yamauchi, H., Hiroyoshi, H., Takei, H., and Watanabe, H. (1982) Metamagnetic phase transitions in FeTiO3. Journal of the Physical Society of Japan, 51, 1769–1777.10.1143/JPSJ.51.1769Search in Google Scholar

Kato, H., Yamaguchi, Y., Yamada, M., Funahashii, S., Nakagawa, Y., and Takei, H. (1986) Neutron scattering study of magnetic excitations in oblique easy-axis antiferromagnet FeTiO3. Journal of Physics C: Solid State Physics, 19, 6993–7011.10.1088/0022-3719/19/35/013Search in Google Scholar

Klingelhöfer, G. (2012). Extraterrestrial Mössbauer spectroscopy. In M. Kalvius and P. Kienle, Eds., The Rudolf Mössbauer Story, 293–316. Springer-Verlag, Berlin.10.1007/978-3-642-17952-5_15Search in Google Scholar

Li, Y., Li, X., Wang, S., Tang, H., Gan, H., Li, S., Wei, G., Zheng, Y., Tsang, K.T., and Ouyang, Z. (2012) In-situ water production by reducing ilmenite. In V. Badescu, Ed., Moon: Prospective Energy and Material Resources, 189–200. Springer-Verlag, Berlin.10.1007/978-3-642-27969-0_8Search in Google Scholar

Morrish, A.H. (1965) The Physical Principles of Magnetism, Wiley, New York.Search in Google Scholar

Nakatsuka, D., Fujii, T., Nakanishi, M., and Takada, J. (2010) Synthesis of Ge substituted ilmenite and their magnetic and electronic properties. Journal of Physics: Conference Series, 200, 012144.10.1088/1742-6596/200/1/012144Search in Google Scholar

Perkins, H.K., and Hazony, Y. (1972) Temperature-dependent crystal field and charge density: Mossbauer studies of FeF2, KFeF3, FeCl2, and FeF3. Physical Review B, 5, 7–18.10.1103/PhysRevB.5.7Search in Google Scholar

Pound, R.V., and Rebka, G.A. Jr. (1960) Variation with temperature of the energy of recoil free gamma rays from solids. Physical Review Letters, 4, 274–277.10.1103/PhysRevLett.4.274Search in Google Scholar

Raghavender, A.T., Hong, N.H., Lee, K.J., Jung, M., Skoko, Z., Cerqueira, M.F., Samantilleke, A.P., and Vasilevskiy, M. (2013) Nano-ilmenite FeTiO: Synthesis and characterization. Journal of Magnetism and Magnetic Materials, 331, 129–132.10.1016/j.jmmm.2012.11.028Search in Google Scholar

Robinson, M.S., Hapke, B.W., Garvin, J.B., Skillman, D., Bell, J.F. III, Ulmer, M.P., and Pieters, C.M. (2007) High resolution mapping of TiO2 abundances on the Moon using the Hubble Space Telescope. Geophysical Research Letters, 34, L13203.Search in Google Scholar

Schwandt, C., Hamilton, J.A., Fray, D.J., and Crawford, I.A. (2012) Oxygen from Lunar Regolith. In V. Badescu, Ed., Moon: Prospective Energy and Material Resources, 165–187. Springer-Verlag, Berlin.10.1007/978-3-642-27969-0_7Search in Google Scholar

Syono, Y., Ito, A., and Morimoto, S. (1981) Systematics of Mössbauer parameters in 57Fe-doped titanate and germanate ilmenites. Journal of Physical Chemistry, 42, 483–486.Search in Google Scholar

Van Alboom, A., De Grave, E., and Wohlfahrt-Mehrens, M. (2011) Temperature dependence of the Fe2+ Mössbauer parameters in triphylite (LiFePO4). American Mineralogist, 96, 408–416.10.2138/am.2011.3630Search in Google Scholar

Van Alboom, A., de Resende, V.G., da Costa, G.M., and De Grave, E. (2015) Mössbauer spectroscopic study of natural eosphorite, [(Mn,Fe)AlPO4(OH)2H2O]. American Mineralogist, 100, 580–587.10.2138/am-2015-4911Search in Google Scholar

Vandenberghe, R.E., De Grave, E., and de Bakker, P.M.A. (1994) On the methodology of the analysis of Mössbauer spectra. Hyperfine Interactions, 83, 29–49.10.1007/BF02074257Search in Google Scholar

Varret, F. (1976) Mössbauer spectra of paramagnetic powders under applied field: Fe2+ in fluosilicates. Journal of Physics and Chemistry of Solids, 37, 265–271.10.1016/0022-3697(76)90086-XSearch in Google Scholar

Wechsler, B.A., and Prewitt, C.T. (1984) Crystal structure of ilmenite (FeTiO3) at high temperature and at high pressure. American Mineralogist, 69, 176–185.Search in Google Scholar

Yan, S., Ge, S., Qiao, W., and Zuo, Y. (2010) Synthesis of ferromagnetic semiconductor 0.67FeTiO3-0.33Fe2O3 powder by chemical co-precipitation. Journal of Magnetism and Magnetic Materials, 322, 824–826.10.1016/j.jmmm.2009.11.011Search in Google Scholar

  1. Manuscript handled by M. Darby Dyar.

Received: 2014-11-25
Accepted: 2015-10-27
Published Online: 2016-3-4
Published in Print: 2016-3-1

© 2016 by Walter de Gruyter Berlin/Boston

Articles in the same Issue

  1. Editorial
  2. The most-cited journal in mineralogy and petrology (and what scientists can learn from baseball)
  3. Fluids in the Crust
  4. Fluids in the crust during regional metamorphism: Forty years in the Waterville limestone
  5. Research Article
  6. Remanent magnetization, magnetic coupling, and interface ionic configurations of intergrown rhombohedral and cubic Fe-Ti oxides: A short survey
  7. Research Article
  8. Are covalent bonds really directed?
  9. Dana Medal Paper
  10. Constraints on the early delivery and fractionation of Earth’s major volatiles from C/H, C/N, and C/S ratios
  11. Crossroads in Earth and Planetary Materials
  12. Octahedral chemistry of 2:1 clay minerals and hydroxyl band position in the near-infrared: Application to Mars
  13. Special Collection: Advances in Ultrahigh-Pressure Metamorphism
  14. Multi-stage barite crystallization in partially melted UHP eclogite from the Sulu belt, China
  15. Spinels Renaissance: The Past, Present, and Future of those Ubiquitous Minerals and Materials
  16. Crystal chemistry of spinels in the system MgAl2O4-MgV2O4-Mg2VO4
  17. Spinels Renaissance: The Past, Present, and Future of those Ubiquitous Minerals and Materials
  18. Magnetite spherules in pyroclastic iron ore at El Laco, Chile
  19. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  20. Evidence for dissolution-reprecipitation of apatite and preferential LREE mobility in carbonatite-derived late-stage hydrothermal processes
  21. Special Collection: Apatite: A Common Mineral, Uncommonly Versatile
  22. Compositional variation of apatite from rift-related alkaline igneous rocks of the Gardar Province, South Greenland
  23. Special Collection: Perspectives on Origins and Evolution of Crustal Magmas
  24. Dynamics and thermodynamics of magma mixing: Insights from a simple exploratory model
  25. Special Collection: From Magmas to Ore Deposits
  26. Geochemistry, petrologic evolution, and ore deposits of the Miocene Bodie Hills Volcanic Field, California and Nevada
  27. Research Article
  28. Recognizing sulfate and phosphate complexes chemisorbed onto nanophase weathering products on Mars using in-situ and remote observations
  29. Research Article
  30. Crystallographic orientation relationships in host–inclusion systems: New insights from large EBSD data sets
  31. Research Article
  32. In-situ infrared spectroscopic studies of hydroxyl in amphiboles at high pressure
  33. Research Article
  34. Confined water in tunnel nanopores of sepiolite: Insights from molecular simulations
  35. Research Article
  36. Equation of state of the high-pressure Fe3O4 phase and a new structural transition at 70 GPa
  37. Research Article
  38. Reflectance spectroscopy of chromium-bearing spinel with application to recent orbital data from the Moon
  39. Research Article
  40. Temperature dependences of the hyperfine parameters of Fe2+ in FeTiO3 as determined by 57Fe-Mössbauer spectroscopy
  41. Letter
  42. Accurate predictions of iron redox state in silicate glasses: A multivariate approach using X-ray absorption spectroscopy
  43. Research Article
  44. New Mineral Names
Downloaded on 19.1.2026 from https://www.degruyterbrill.com/document/doi/10.2138/am-2016-5262/html
Scroll to top button