Skip to main content
SpringerLink
Log in

Structural properties of (Mn1-x Fe x )Nb2O6 columbites from X-ray diffraction and IR spectroscopy

  • Original Paper
  • Published:
Physics and Chemistry of Minerals Aims and scope Submit manuscript

Abstract

A suite of (Mn1-x Fe x )Nb2O6 (x=0, 0.05, 0.25, 0.50, 0.75, 1) columbite samples has been prepared by solid-state reaction from oxides. X-ray diffraction and spectroscopic investigations have been carried out in order to gain different perspectives on how the solid solution adapts at different length scales to cation mixing. X-ray powder diffraction and powder absorption IR spectroscopy data are presented. The powder diffraction data show that there is no significant excess volume of mixing on the Fe–Mn columbite join. All the unit-cell parameters decrease linearly as a function of increasing Fe content. Substitution of Fe2+ for the larger Mn2+ cation causes a decrease in the volume of the A polyhedron, which also becomes more regular with respect to both bond-length and edge-length distortion parameters. No significant variation of the B site has been observed. Wavenumber shifts of the IR peaks nearly all vary linearly with composition, consistent with linear variations of the lattice parameters. Line broadening has been quantified by autocorrelation analysis of the IR spectra. This is interpreted as suggesting that there is some element of local strain or positional disorder at the length scale of second or third nearest neighbours around sites occupied by Fe.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Betteridge PW, Carruthers JR, Cooper RI, Prout K, Watkin DJ (2003) CRYSTALS version 12: software for guided crystal structure analysis. J Appl Crystall 36:1487

    Article  Google Scholar 

  • Bordet P, McHale A, Santoro A, Roth RS (1986) Powder neutron diffraction study of ZrTiO4, Zr5Ti7O24 and FeNb2O6. J Solid State Chem 64:30–46

    Article  Google Scholar 

  • Bosenick A, Dove MT, and Geiger CA (2000) Simulation studies on the pyrope—grossular garnet solid solution. Phys Chem Miner 27:398–419

    Article  Google Scholar 

  • Carpenter MA (1992) Thermodynamics of phase transitions in minerals: a macroscopic approach. In: Price GD, Ross NL (eds) The stability of minerals, mineral. soc. series, 3. Chapman and Hall, London, pp 172–215

  • Carpenter MA (2002) Microscopic strain, macroscopic strain and the thermodynamics of phase transitions in minerals. In: Gramaccioli CM (ed) EMU Notes in Mineralogy, vol 4. Eötvös University Press, Budapest, pp 311–346

  • Carpenter MA, Boffa Ballaran T (2001) Solid solution in silicate and oxide systems. In: Gaiger CA (ed) EMU Notes in mineralogy, vol 3. Eötvös University Press, Budapest, pp 155–178

  • Carpenter MA, Boffa Ballaran T, Atkinson AJ (1999) Microscropic strain, local structural heterogeneity and the energetic of solid solutions. Phase Trans 69:95–109

    Article  Google Scholar 

  • Carruthers JR, Watkin DJ (1979) Chebychev weighting. Acta Cryst A35:698–699

    Article  Google Scholar 

  • Chang IF, Mitra SS (1968) Application of a modified random-element-isodisplacement model to long-wavelength optic phonons of mixed crystals. Phys Rev 172:924–933

    Article  Google Scholar 

  • Donovan JD, Rivers ML (1990) PRSUPR—a PC-based automation and analysis software package for wavelength-dispersive electron-beam microanalysis. In: Michael JR, Ingram P (eds) Microbeam analysis, San Francisco Press, San Francisco, pp 66–68

  • Geiger CA, Kolesov BA (2002) Microscopic–macroscopic relationships in silicates: examples from IR and Raman spectroscopy and heat capacity measurements. In: Gramaccioli CM (ed) EMU notes in mineralogy, vol 4. Eötvös University Press, Budapest, pp 347–387

  • Hayward SA, Salje EKH (1996) Displacive phase transition in anorthoclase: the “plateau effect" and the effect of T1-T2 ordering on the transition temperature. Am Mineral 81:1332–1336

    Google Scholar 

  • Ibers JA, Hamilton WC (1974) In: International tables for X-ray crystallography, vol 4. Kynoch Press, Birmingham, pp 99–101

  • Larson AC (1970) In: Ahmed FR, Hall SR, Huber CP (eds) Crystallographic computing. Munsksgaard, Copenhagen, pp 291–294

  • Novák M, Černý P (2000) Highly ordered, homogeneous ferrocolumbite from an anorogenic granitic pegmatite at Ivittuut (Ivigtut), SW Greenland. N Jb Miner Mh 10:433–443

    Google Scholar 

  • Pagola S, Carbonio RE, Alonso JA, Fernández-Díaz MT (1997) Crystal structure refinement of MgNb2O6 columbite from neutron powder diffraction data and study of the ternary system MgO–Nb2O5–NbO, with evidence of formation of new reduced pseudobrookite Mg5-xNb4+x O15-δ (1.14 ≤ x ≤ 1.60) phases. J Solid State Chem 134:76–84

    Article  Google Scholar 

  • Renner B, Lehmann G (1986) Correlation of angular and bond length distortion in TO4 units in crystals. Z Kristallogr 175:43–59

    Article  Google Scholar 

  • Rodríguez-Carvajal J (1990) FULLPROF: a program for Rietveld refinement and pattern matching analysis. Satellite meeting on powder diffraction of the XV congress of the IUCr (Toulouse), 127p

  • Rodríguez-Carvajal J (1998) Reference Guide for the computer program Fullprof. Laboratoire Léon Brillouin, CEA-CNRS, Saclay, France

  • Roisnel T, Rodríguez-Carvajal J (2001) WinPLOTR: a Windows tool for powder diffraction analysis. In: Materials science forum; proceedings of the 7th European powder diffraction conference

  • Salje EKH (1992) Hard-mode spectroscopy—experimental studies of structural phase-transitions. Phase Transit 37:83–110

    Article  Google Scholar 

  • Salje EKH (1994) Feldspars and their reactions NATO ASI Ser. C. 421. In: Parsons I (ed) Kluwer, Dordrecth, pp 103–160

  • Salje EKH, Carpenter MA, Malcherek T, Boffa Ballaran T (2000) Autocorrelation analysis of infrared spectra from minerals. Eur J Mineral 12:503–519

    Google Scholar 

  • Shannon RD (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Cryst A32:751–767

    Article  Google Scholar 

  • Spinolo G, Maglia F (1999) Cohen’s method revisited. Powder Diffr 14:208–212

    Google Scholar 

  • Sturdivant JH (1930) The crystal structure of columbite. Z Kristallogr 75:88

    Google Scholar 

  • Tarantino SC, Zema M (2005) Mixing and ordering behavior in manganocolumbite-ferrocolumbite solid solution: a single-crystal X-ray diffraction study. Am Mineral 90:1291–1299

    Article  Google Scholar 

  • Tarantino SC, Zema M, Pistorino M, Domeneghetti MC (2003a) High-temperature X-ray investigation of natural columbites. Phys Chem Minerals 30:590–598

    Article  Google Scholar 

  • Tarantino SC, Carpenter MA, Domeneghetti MC (2003b) Strain and local heterogeneity in the forsterite-fayalite solid solution. Phys Chem Minerals 30:495–502

    Article  Google Scholar 

  • Tarantino SC, Ghigna P, McCammon C, Amantea R, Carpenter MA (2005) Local structural properties of (Mn,Fe)Nb2O6 from Mössbauer and X-ray absorption spectroscopy. Acta Cryst B61:250–257

    Article  Google Scholar 

  • Weitzel H (1976) Kristallstrukturverfeinerung von Wolframiten und Columbiten. Z Kristallogr 144:238–258

    Article  Google Scholar 

  • Wise MA, Turnock AC, Černý P (1985) Improved unit cell dimensions for ordered columbite-tantalite end members. N Jb Miner Abh 8:372–378

    Google Scholar 

  • Zhang M, Wruck B, Barber AG, Salje EKH, Carpenter MA (1996) Phonon spectra of alkali feldspars: phase transitions and solid solutions. Am Mineral 81:92–104

    Google Scholar 

Download references

Acknowledgements

We thank Simona Bigi for microprobe analyses, Prof. M. Novák for providing sample MM-13 and F. Cámara for useful discussion. M. Zhang provided invaluable assistance for the IR experiments. Financial support was provided by the Italian MIUR project “Mineral physics and technological applications of columbite-tantalite-tapiolite system”. SCT is thankful for NATO-CNR grant.

Author information

Authors and Affiliations

  1. Department of Earth Sciences, University of Cambridge, Downing Street, CB2 3EQ, Cambridge, UK

    S. C. Tarantino & M. A. Carpenter

  2. Dipartimento di Scienze della Terra, Università di Pavia, Via Ferrata 1, 27100, Pavia, Italy

    S. C. Tarantino, M. Zema & M. C. Domeneghetti

  3. Dipartimento di Chimica Fisica “M. Rolla”, Università di Pavia, V.le Taramelli 16, 27100, Pavia, Italy

    F. Maglia

Authors
  1. S. C. Tarantino
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. Zema
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. F. Maglia
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. M. C. Domeneghetti
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. M. A. Carpenter
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. C. Tarantino.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Tarantino, S.C., Zema, M., Maglia, F. et al. Structural properties of (Mn1-x Fe x )Nb2O6 columbites from X-ray diffraction and IR spectroscopy. Phys Chem Minerals 32, 568–577 (2005). https://doi.org/10.1007/s00269-005-0031-4

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s00269-005-0031-4

Keywords

Search

Navigation