Journal of Materials Science

, Volume 51, Issue 2, pp 958–968 | Cite as

Topotaxial reactions during oxidation of ilmenite single crystal

  • Nadežda Stanković
  • Aleksander Rečnik
  • Nina Daneu
Original Paper


The mechanism of ilmenite–rutile transformation during oxidation of natural ilmenite crystal was studied at elevated temperatures in air. The progress of oxidation with annealing time was studied in the temperature range between 600 and 900 °C. 2.5 mm cubes were cut from the single Mn-ilmenite crystal in two special orientations, [001]ILM and \( \left[ {1\bar{1}0} \right]_{\text{ILM}} \), that allowed determination of crystallographic relations among the reaction products. Using X-ray diffractometry, energy-dispersive spectroscopy, and electron microscopy (SEM, TEM) techniques, we determined that the ilmenite to rutile and hematite transformation is triggered by surface oxidation of divalent cations (Fe, Mn) from the starting ilmenite and their crystallization in the form of hematite and bixbyite on the surface of the single crystal. Surface oxidation and out-diffusion of Fe2+ and Mn2+ ions opens paths for exsolution of rutile within the pseudo-hexagonal oxygen sublattice of the parent ilmenite, following simple topotaxial orientation relationship \( {\langle{001}\rangle}_{\text{RUT}} \;\left\{ {010} \right\}_{\text{RUT}} \;||\;{\langle{210}\rangle}_{\text{ILM}} \;\left\{ {001} \right\}_{\text{ILM}} \). With this transformation, new channels for fast out-diffusion of divalent cations to the oxidation surface are opened along the c-axis of the rutile structure. The volume difference of the reaction products causes cracking of the single crystal, which opens additional free surfaces for accelerated oxidation. The results of this study contribute to better understanding of the recrystallization processes during pre-oxidation of ilmenite.


Rutile Hematite Ilmenite Divalent Cation Orientation Relationship 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



This work was supported by the Slovenian Research Agency under the Project No. J1-6742 »Atomic-scale studies of initial stages of phase transformations in minerals« and PhD Grant No. 1000-11-310225. The research leading to these results has received funding from the European Union Seventh Framework Programme [FP7] under Grant agreement no. 312483 (ESTEEM2).


  1. 1.
    Murphy P, Frick L (2006) Titanium. In: Kogel JE et al (eds) Industrial minerals and rocks—commodities, markets and uses. Society for Mining Metallurgy, and Exploration, Inc., Colorado, pp 987–1003Google Scholar
  2. 2.
    Zhang W, Zhu Z, Cheng CY (2011) A literature review of titanium metallurgical processes. Hydrometallurgy 108(3–4):177–188CrossRefGoogle Scholar
  3. 3.
    Xiao W, Lu X, Zou X, Wei X, Ding W (2013) Phase transitions, micro-morphology and its oxidation mechanism in oxidation of ilmenite (FeTiO3) powder. Trans Nonferrous Met Soc China 23(8):2439–2445CrossRefGoogle Scholar
  4. 4.
    Janssen A, Putnis A (2011) Processes of oxidation and HCl-leaching of Tellnes ilmenite. Hydrometallurgy 109(3–4):194–201CrossRefGoogle Scholar
  5. 5.
    Zhang G, Ostrovski O (2002) Effect of preoxidation and sintering on properties of ilmenite concentrates. Int J Miner Process 64(4):201–218CrossRefGoogle Scholar
  6. 6.
    Fu X, Wang Y, Wei F (2010) Phase transitions and reaction mechanism of ilmenite oxidation. Metall Mater Trans A 41(5):1338–1348CrossRefGoogle Scholar
  7. 7.
    Gupta S, Rajakumar V, Grieveson P (1991) Phase transformations during heating of ilmenite concentrates. Metall Trans B 22(5):711–716CrossRefGoogle Scholar
  8. 8.
    Jabłonski M, Przepiera A (2001) Estimation of kinetic parameters of thermal oxidation of ilmenite. J Therm Anal Calorim 66(2):617–622CrossRefGoogle Scholar
  9. 9.
    Karkhanavala MD, Momin AC (1959) The alteration of ilmenite. Econ Geol 54(6):1095–1102CrossRefGoogle Scholar
  10. 10.
    Zhang J, Zhu Q, Xie Z, Lei C, Li H (2013) Morphological changes of panzhihua ilmenite during oxidation treatment. Metall Mater Trans B 44(4):897–905CrossRefGoogle Scholar
  11. 11.
    Bhogeswara Rao D, Rigaud M (1974) Oxidation of ilmenite and the product morphology. High Temp Sci 6:323–341Google Scholar
  12. 12.
    Bhogeswara Rao D, Rigaud M (1975) Kinetics of the oxidation of ilmenite. Oxid Met 9(1):99–116CrossRefGoogle Scholar
  13. 13.
    Briggs R, Sacco A (1993) The oxidation of ilmenite and its relationship to the FeO–Fe2O3–TiO2 phase diagram at 1073 and 1140 K. Metall Trans A 24(6):1257–1264CrossRefGoogle Scholar
  14. 14.
    Grey IE, Reid AF (1972) Shear structure compounds (Cr,Fe)2Tin−2O2n−1 derived from the α-PbO2 structural type. J Solid State Chem 4(2):186–194CrossRefGoogle Scholar
  15. 15.
    Grey IE, Li C (2001) Low temperature roasting of ilmenite—phase chemistry and applications. AusIMM Proc 306(2):35–42Google Scholar
  16. 16.
    Dent Glasser LS, Glasser FP, Taylor HFW (1962) Topotactic reactions in inorganic oxy-compounds. Q Rev Chem Soc 16(4):343–360CrossRefGoogle Scholar
  17. 17.
    Armbruster T (1981) On the origin of sagenites: structural coherency of rutile with hematite and spinel structures types. Neues Jahrb Mineral 7:328–334Google Scholar
  18. 18.
    Force E, Richards P, Scott K, Valentine P, Fishman N (1996) Mineral intergrowths replaced by ‘elbow-twinned’ rutile in altered rocks. Can Miner 34(3):605–614Google Scholar
  19. 19.
    Daneu N, Schmid H, Rečnik A, Mader W (2007) Atomic structure and formation mechanism of (301) rutile twins from Diamantina (Brazil). Am Miner 92:1789–1799CrossRefGoogle Scholar
  20. 20.
    Daneu N, Rečnik A, Mader W (2014) Atomic structure and formation mechanism of (101) rutile twins from Diamantina (Brazil). Am Mineral 99:612–624CrossRefGoogle Scholar
  21. 21.
    Rečnik A, Stanković N, Daneu N (2015) Topotaxial reactions during the genesis of oriented rutile/hematite intergrowths from Mwinilunga (Zambia). Contributions to Mineralogy and Petrology 169(2): 19/1-22Google Scholar
  22. 22.
    Wechsler BA, Prewitt CT (1984) Crystal structure of ilmenite (FeTiO3) at high temperature and at high pressure. Am Miner 69:176–185Google Scholar
  23. 23.
    Kidoh K, Tanaka K, Marumo F (1984) Electron density distribution in ilmenite-type crystals. II. manganese(II) titanium(IV) trioxide. Acta Crystallogr B 40:329–332CrossRefGoogle Scholar
  24. 24.
    Wu X, Qin S, Dubrovinsky L (2010) Structural characterization of the FeTiO3–MnTiO3 solid solution. J Solid State Chem 183:2483–2489CrossRefGoogle Scholar
  25. 25.
    Grant RW, Geller S, Cape JA, Espinosa GP (1968) Magnetic and crystallographic transitions in the α-Mn2O3–Fe2O3 system. Phys Rev 175(2):686–695CrossRefGoogle Scholar
  26. 26.
    Sasaki J, Peterson NL, Hoshino K (1985) Tracer impurity diffusion in single-crystal rutile (TiO2 − x). J Phys Chem Solids 46(11):1267–1283CrossRefGoogle Scholar
  27. 27.
    Putnis A (1978) The mechanism of exsolution of hematite from iron-bearing rutile. Phys Chem Miner 3(2):183–197CrossRefGoogle Scholar
  28. 28.
    Sabioni ACS, Huntz AM, Daniel AMJM, Macedo WAA (2005) Measurement of iron self-diffusion in hematite single crystals by secondary ion-mass spectrometry (SIMS) and comparison with cation self-diffusion in corundum-structure oxides. Phil Mag 85(31):3643–3658CrossRefGoogle Scholar
  29. 29.
    Reece M, Morrell R (1991) Electron microscope study of non-stoichiometric titania. J Mater Sci 26:5566–5574. doi: 10.1007/BF00553660 CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2015

Authors and Affiliations

  • Nadežda Stanković
    • 1
  • Aleksander Rečnik
    • 1
  • Nina Daneu
    • 1
  1. 1.Department for Nanostructured Materials & Jožef Stefan International Postgraduate SchoolJožef Stefan InstituteLjubljanaSlovenia

Personalised recommendations