Advertisement

Physics and Chemistry of Minerals

, Volume 32, Issue 3, pp 155–164 | Cite as

The distribution of Cu(II) and the magnetic properties of the synthetic analogue of tetrahedrite: Cu12Sb4S13

  • F. Di BenedettoEmail author
  • G. P. Bernardini
  • C. Cipriani
  • C. Emiliani
  • D. Gatteschi
  • M. Romanelli
Original papers

Abstract

A wide investigation of the synthetic analogue of tetrahedrite, Cu12Sb4S13, has been performed by a combination of several techniques, magnetisation and differential scanning calorimetric measurements, cw, and pulsed EPR spectroscopy, to obtain complementary information about the presence and the distribution of Cu(II). The high temperature susceptibility of the sample accounts for two Cu(II) per formula unit, in agreement with the charge balance. However, strong antiferromagnetic interactions, observed even at room temperature, are associated with a transition at 83(3) K. At lower temperatures a residual susceptibility is observed. At 4.2 K ESEEM experiments enabled observation of the chemical environment of the residual paramagnetic species. Cu(II) was found randomly distributed in the M(1) site. The statistical presence of nearest neighbouring Cu(II) ions justify the observed antiferromagnetic interactions and transition. Nevertheless, isolated paramagnetic ions have been determined below the Néel temperature: they are mainly located near the surface of the grains. A colour centre, previously observed in natural samples, has been also identified.

Keywords

EPR SQUID ESE Cu(II) distribution Antiferromagnetic transition 

Notes

Acknowledgements

The authors are indebted to M. Brustolon and A. Zoleo of the University of Padova for the ESE measurements, to F. Olmi of the IGG/CNR, for the microprobe analyses, and to M. Affronte of the University of Modena, for the low temperature DSC measurements. An anonymous referee and Professor Makovicky are also sincerely acknowledged for their punctual and stimulating revision of this manuscript. This work was partially financed by the MIUR COFIN2001 and COFIN2003 funds to C. Cipriani.

References

  1. Barbon A, Brustolon M, Maniero AL, Romanelli M, Brunel LC (1999) Dynamics and spin relaxation of tempone in a host crystal. An ENDOR, high field EPR and spin echo study. Phys Chem Chem Phys 1:4015–4023Google Scholar
  2. Belov NV, Pobedimskaya EA (1969) Covelline (klockmannite), chalcocite (acanthite, stromeyerite, bornite), fahlerz. Soviet Phys Crystall 13:843–847Google Scholar
  3. Bernardini GP, Borrini D, Caneschi A, Di Benedetto F, Gatteschi D, Ristori S, Romanelli M (2000) EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite). Phys Chem Miner 27:453–461Google Scholar
  4. Birgenau RJ (1998) Random fields and phase transitions in model magnetic systems. J Magn Magn Mater 177-181:1–11Google Scholar
  5. Caneschi A, Cipriani C, Di Benedetto F, Sessoli R (2004) Characterisation of the antiferromagnetic transition of Cu2FeSnS4, the synthetic analogue of stannite. Phys Chem Miner 31:190–193Google Scholar
  6. Ciani L, Branciamore S, Romanelli M, Martini G (2003) Nucleoside–copper(II) system in water and on 13X-Zeolite studied by continuous-wave and pulsed-wave EPR. Appl Magn Reson 24:55–71Google Scholar
  7. Cipriani C, Di Benedetto F (2004) Nuovo riesame delle “calcosine” del Museo di Mineralogia di Firenze. Museol Sci (in press)Google Scholar
  8. Di Benedetto F, Bernardini GP, Borrini D, Emiliani C, Cipriani C, Danti C, Caneschi A, Gatteschi D, Romanelli M (2002a) Mineral chemistry of tetrahedrite s.s.: EPR and magnetic investigations. Can Miner 40:837–847Google Scholar
  9. Di Benedetto F, Bernardini GP, Caneschi A, Cipriani C, Danti C, Pardi L, Romanelli M (2002b) EPR and magnetic investigations on sulfides and sulfosalts. Eur J Mineral 14:1053–1060Google Scholar
  10. Eivazov EA, Safarov AF, Atakishiev SM, Abasov Ya M (1990): The EPR spectrum of the Co0.7Cu0.3Cr2S4-xSex system. Phys Stat Sol a 117:K147–K151Google Scholar
  11. Foit FF Jr, Ulbricht ME (2001) Compositional variation in mercurian tetrahedrite-tennantite from epithermal deposits of the Steens and Pueblo Mountains, Harney County, Oregon. Can Mineral 39:819–830Google Scholar
  12. Furdyna JK (1988) Diluted magnetic semiconductors. J Appl Phys 64:R29–R64Google Scholar
  13. Johnson NE, Craig JR, Rimstidt JD (1986) Compositional trends in tetrahedrites. Can Mineral 24:385–397Google Scholar
  14. Johnson NE, Craig JR, Rimstidt JD (1988) Crystal chemistry of tetrahedrite. Am Miner 73:389–397Google Scholar
  15. Lind IL, Makovicky E (1982) Phase relations in the system Cu–Sb–S at 200°C, 108 Pa by hydrothermal synthesis. Microprobe analyses of tetrahedrite—a warning. N Jb Miner Abh 145:134–156Google Scholar
  16. Makovicky E, Karup Møller S (1994) Exploratory studies on substitution of minor elements in synthetic tetrahedrite. Part I: Substitution by Fe, Zn, Co, Ni, Mn, Cr, V and Pb. Unit-cell parameter changes on substitution and the structural role of Cu2+. Neues Jahrb Mineral Abh 167:89–123Google Scholar
  17. Makovicky E, Skinner BJ (1979) Studies of the sulfosalts of Copper. VII. Crystal structures of the exsolution products Cu12.3Sb4S13 and Cu13.8Sb4S13 of unsubstituted synthetic tetrahedrite. Can Mineral 17:619–634Google Scholar
  18. Pauling L, Neumann EW (1934) The crystal structure of binnite, (Cu,Fe)12As4S13 and the chemical composition and structure of the tetrahedrite group. Z Kristallogr 88:54–62Google Scholar
  19. Pfitzner A, Evain M, Petricek V (1997) Cu12Sb4S13: a temperature-dependent structure investigation. Acta Crystallogr B 53:337–345Google Scholar
  20. Romanelli M, Kevan L (1997) Evaluation and interpretation of Electron Spin-Echo decay. Part I: Rigid samples. Concept Magn Reson 9:403–430Google Scholar
  21. Sansonetti JE, Mullin DP, Dixon JR, Furdyna JK (1979) Electron paramagnetic resonance in powdered semiconductors and semimetals. J Appl Phys 50(8):5431–5441Google Scholar
  22. Schosseler PM, Wehrli B, Schweiger A (1999) Uptake of Cu2+ by the calcium carbonates vaterite and calcite as studied by continuous wave (CW) and pulse electron paramagnetic resonance. Geochim Cosmochim Acta 63:1955–1967Google Scholar
  23. Scott SD (1974) Experimental methods in sulfide synthesis. In: Ribbe (ed) Sulfide mineralogy. Short course notes, vol 1, Mineralogical Society of America, WashingtonGoogle Scholar
  24. Spalek J, Lewicki A, Tarnawski Z, Furdyna JK, Galazka RR, Obuszko Z (1986) Magnetic susceptibility of semimagnetic semiconductors: the high temperature regime and the role of superexchange. Phys Rev B 33(5):3407–3418Google Scholar
  25. Sykes MF, Gaunt DS, Glen M (1976) Percolation processes in three dimension. J Phys A Math Gen 9(10):1705–1712Google Scholar
  26. Twardowski A (1990) Magnetic properties of Fe-based diluted magnetic semiconductors. J Appl Phys 67(9):5108–5113Google Scholar
  27. Twardowski A, Lewicki A, Arciszewska M, de Jonge WJM, Swagten HJM, Demianiuk M (1988) Magnetic susceptibility of iron-based semimagnetic semiconductors: high-temperature regime. Phys Rev B 38(15):10749–10754Google Scholar
  28. Twardowski A, Swagten HJM, de Jonge WJM, Demianiuk M (1991) Magnetic properties of the diluted magnetic semiconductor Zn1-xFexS. Phys Rev B 44(5):2220–2226Google Scholar
  29. Wuench BJ (1964) The crystal structure of tetrahedrite, Cu12Sb4S13. Z Kristallogr 119:437–453Google Scholar

Copyright information

© Springer-Verlag 2005

Authors and Affiliations

  • F. Di Benedetto
    • 1
    Email author
  • G. P. Bernardini
    • 2
  • C. Cipriani
    • 1
  • C. Emiliani
    • 2
  • D. Gatteschi
    • 3
  • M. Romanelli
    • 3
  1. 1.Museo di Storia NaturaleUniversità di FirenzeFirenzeItaly
  2. 2.Dipartimento di Scienze della TerraUniversità di FirenzeFirenzeItaly
  3. 3.Dipartimento di ChimicaUniversità di Firenze(Firenze) Sesto FiorentinoItaly

Personalised recommendations