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A revised phase diagram for the bornite-digenite join from in situ neutron diffraction and DSC experiments

B. A. Grguric^1,, R. J. Harrison² and A. Putnis^2,*

¹ Department of Earth Sciences, University of Cambridge, Downing Street, Cambridge CB2 3EQ, UK
² Institut für Mineralogie, Universität Münster, Corrensstrasse 24, D-48149 Münster, Germany

^* E-mail: putnis{at}nwz.uni-muenster.de

Phase relations along the join bornite (Cu₅FeS₄)-digenite (Cu_8.52Fe_0.12S_4.88) have been redefined using a combination of in situ high-resolution neutron diffraction and differential scanning calorimetry (DSC). Time-of-flight neutron diffraction patterns were collected on a synthetic sample of bn90 at 16 temperatures between 35 and 350°C. This data is compared with data from a natural end-member bornite sample obtained in an earlier study under identical conditions. Phase relations along the bornite–digenite join are inferred from the temperature evolution of the lattice parameters and the intensity of subcell and supercell reflections of coexisting phases.

The DSC scans over the temperature range 50–300°C were performed on a natural digenite sample and samples synthesized at 5 mol.% intervals along the join Cu₅FeS₄-Cu₉S₅. The thermal anomalies are correlated with structural phase transitions in component phases and the solvus temperature for each bulk composition. A phase diagram topology is defined, which was consistent with both diffraction and calorimetric data, but in marked contrast to previous diagrams, shows a consolute point at X = Cu₅FeS₄ and T = 265°C. This temperature corresponds to that of the tricritical intermediate–high transition in bornite. Isothermal annealing experiments carried out on synthetic starting materials for up to 7 months showed coarsening behaviour consistent with the revised phase diagram topology.

KEYWORDS: bornite, digenite, differential scanning calorimetry, neutron diffraction, exsolution

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