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An EPR and SQUID magnetometry study of bornite

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Abstract

A magnetic and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence. The combination of magnetic measurements and continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy at different temperatures and frequencies provided information about the distribution and valence states of Cu and Fe in bornite. The studied sample was found to obey the Curie–Weiss law with a transition from a paramagnetic to an antiferromagnetic phase at 64 K; its possible attribution to a disordered spin glass phase was ruled out by ac susceptibility measurements. Q- and X-band cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite: the single EPR line registered in the temperature range from 300 to 65 K can be assigned, in fact, to the Fe(III) single ions. Some Cu(II) signals were revealed in the low temperature EPR spectra and attributed to an early stage of the surface alteration. The width of the Fe(III) EPR spectrum, which hinders any characteristic spectral structure, can be ascribed to the exchange interaction. The pure antiferromagnetic character of the magnetic transition confirms the ordering between Fe and Cu in the bornite structure, at least at low temperature (≤70 K). Moreover, the relatively high Nèel temperature suggests the accepted model of Collins et al.’s (Can J Phys 59:535–539, 1981) to conveniently explain the overall magnetic properties in the range 298–4 K. Despite the increasing of the susceptibility in the paramagnetic range, in fact, the integrated EPR line area decreases by lowering the temperature, thus suggesting a progressive rising of the antiferromagnetic interactions among next-nearest-neighbouring paramagnetic centres.

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Acknowledgments

The authors want to express their warmest thanks to G.P. Bernardini for the useful and stimulating discussion. The authors are also indebted to G. Amthauer of the University of Salzburg for his critical discussion of the present results. An anonymous referee and P. Sainctavit are sincerely acknowledged for their revision of the text and for the stimulating comments. The financial support of MIUR, Ente Cassa di Risparmio di Firenze and CSGI is grateful acknowledged.

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Authors and Affiliations

  1. Dipartimento di Scienze della Terra, Università di Firenze, Via G. La Pira 4, I50121, Firenze, Italy

    M. Borgheresi & G. Pratesi

  2. Museo di Storia Naturale, Università di Firenze, Via G. La Pira 4, I50121, Firenze, Italy

    F. Di Benedetto & G. Pratesi

  3. Dipartimento di Chimica, Università di Firenze, Via della Lastruccia 3, I50019, Sesto Fiorentino, Italy

    A. Caneschi, M. Romanelli & L. Sorace

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  1. M. Borgheresi
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  2. F. Di Benedetto
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  3. A. Caneschi
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  4. G. Pratesi
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  5. M. Romanelli
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  6. L. Sorace
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Correspondence to M. Borgheresi.

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Borgheresi, M., Di Benedetto, F., Caneschi, A. et al. An EPR and SQUID magnetometry study of bornite. Phys Chem Minerals 34, 609–619 (2007). https://doi.org/10.1007/s00269-007-0175-5

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  • DOI: https://doi.org/10.1007/s00269-007-0175-5

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