Phase transformations of ternary copper iron sulfide Cu1.1Fe1.9S3.0 under temperature variations: thermodynamic and kinetic aspects
Abstract
The article considers ternary sulfide Cu1.1Fe1.9S3 with a metal/sulfur ratio corresponding to the complete stoichiometry of cubanite CuFe2S3 as an intermediate phase of a solid solution with chemically disordered Cu and Fe cations in the ordered anionic framework. A new approach to determining the nature of the solid solution, its stability and behavior during cooled over a wide temperature and time range is suggested. To synthesize the sample, we used controlled directional solidification of a homogeneous melt with the Cu1.1Fe1.9S3 composition under quasi-equilibrium conditions and obtained a solidified zoned ingot, where the distribution of Cu, Fe, and S elements along its length was quantitatively determined. To detect small-scale structural and chemical changes, we used optical and electron microscopy methods, electron-probe X-ray spectral microanalysis, full-profile X-ray diffraction analysis, and the differential dissolution method, which allowed to determine the phase and chemical states of the samples both at the macro level and with a high spatial resolution. With this approach, we established the following: Cu1.1Fe1.9S3 is an intermediate phase of a system with end-members of cubanite CuFe2S3 and chalcopyrite CuFeS2; a homogeneous solid solution of chalcopyrite with 5 mol. % of cubanite exists near 930 °С with a chaotic distribution of Cu and Fe between the existing crystallographic positions; a solid solution of chalcopyrite with 6 mol. % of cubanite at 900 °С facilitates lattice strain relaxation through the formation of a block nanostructure; there is a solid solution of cubanite with 30 mol. % of chalcopyrite at 900–720 °С, with small-size clusters with a chalcopyrite stoichiometry evenly distributed inside the Cu0.94Fe2S3 matrix. The factors determining the evolution and stability of solid solutions are discussed taking into account the polymorphism of chalcopyrite phase. The newly obtained data is important for the synthesis of magnetic nanosized Cu-Fe sulfide materials and can also be used in the processing of sulfide ores rich in copper
Downloads
References
Lyubutin I. S., Lin C.-R., Starchikov S. S., … Wang S.-C. Synthesis, structural and magnetic properties of self-organized single-crystalline nanobricks of chalcopyrite CuFeS2. Acta Materialia. 2013;61(11): 3956–3962. https://doi.org/10.1016/j.actamat.2013.03.009
Lyubutin I. S., Lin C.-R., Starchikov S. S., Siao Y.-J., Tseng Y.-T. Synthesis, structural and electronic properties of monodispersed self-organized single crystalline nanobricks of isocubanite CuFe2S3. Journal of Solid State Chemistry. 2015;221: 184–190. https://doi.org/10.1016/j.jssc.2014.10.006
Starchikov S. S. Magnetic, structural and electronic properties of nanoparticles of iron sulfides and oxides with different crystal structure*. Cand. of (phys.–math.) sci. diss. Abstr. Moscow: Nauka Publ.; 2015. 18 p. (In Russ.). Available at: https://www.crys.ras.ru/dissertations/Starchikov/Starchikov_avtoref.pdf
Putnis A., McConnel J. D. C. Principle of mineral behavior. Oxford-London-Edinburg-Boston-Melbourne: Blackwell Scientific Publications; 1980, 272 p.
Vaughan D. J., Craig J. R. Mineral chemistry of metal sulfides. Cambridge, UK: Cambridge Earth Science Series; Cambridge University Press: 1978, 493 p.
Sulfide mineralogy and geochemistry. D. J. Vaughan (ed.), Volume 61 in the series Reviews in Mineralogy & Geochemistry. https://doi.org/10.1515/9781501509490
Berger E. L., Keller L. P., Lauretta D. S. An experimental study of the formation of cubanite (CuFe2S3) in primitive meteorites. Meteoritics and Planetary Science. 2015;50: 1–14. https://doi.org/10.1111/maps.12399
Cabri L. J., Hall S. R., Szymanski J. T., Stewart J. M. On the transformation of cubanite. Canadian Mineralogist. 1973;12: 33–38.
René C., Cervelle B., Cesbron F., Oudin E., Picot P., Pillard F. Isocubanite, a new definition of the cubic polymorph of cubanite CuFe2S3. Mineralogical Magazine. 1988;52: 509–514. https://doi.org/10.1180/minmag.1988.052.367.10
Yund R. A., Kullerud G. Thermal stability of assemblages in the Cu-Fe-S system. Journal of Petrology. 1966;7: 454 – 488. https://doi.org/10.1093/petrology/7.3.454
Pruseth K. L., Mishra B., Bernhardt H. J. An experimental study on cubanite irreversibility: implications for natural chalcopyrite–cubanite intergrowths. European Journal of Mineralogy. 1999;11(3): 471–476. https://doi.org/10.1127/ejm/11/3/0471
Putnis A., McConnel J. D. C. The transformation behavior of metal-enriched chalcopyrite. Contributions of Mineralogy and Petrology. 1976;58: 127–136. https://doi.org/10.1007/bf00382181
Putnis A. Talnakhite and Mooihoekite: the accessibility of ordered structures in the metal-rich region around chalcopyrite. Canadian Mineralogist. 1978;16: 23–30.
Engin T. E., Powel A. B, Hull S. A high temperature diffraction-resistance study of chalcopyrite CuFeS2. Journal of Solid State Chemistry. 2011;184: 2272–2277. https://doi.org/10.1016/j.jssc.2011.06.036
Putnis A. Electron microscope study of phase transformations in cubanite. Physics and Chemistry of Minerals. 1977;1: 335–349. https://doi.org/10.1007/bf00308844
Kosyakov V. I. Possible usage of directional crystallization for solving petrological problems. Russian Geology and Geophysics. 1998;39(9): 1245–1256.
Kosyakov V. I, Sinyakova E. F. Directional crystallization of Fe–Ni sulfide melts within the crystallization field of monosulfide solid solution. Geochemistry International. 2005;43(4): 372–85.
Kosyakov V. I., Sinyakova E.F. Melt crystallization of CuFe2S3 in the Сu–Fe–S system. Journal of Thermal Analysis and Calorimetry.2014;115: 511-516. https://doi.org/10.1007/s10973-013-3206-0
Kosyakov V. I., Sinyakova E. F. A. Study of crystallization of nonstoichiometric isocubanite Cu1.1Fe2.0S3.0 from melt in the system Cu–Fe–S. Journal of Thermal Analysis and Calorimetry. 2017;129(2): 623–628. https://doi.org/10.1007/s10973-017-6215-6
Vasilyeva I. G., Sinyakova E. F., Gromilov S. A. Structural and chemical transformations of isocubanite CuFe2S3 at cooling from melt*. Journal of Structural Chemistry = Zhurnal Strukturnoi Khimii. 2024;65: 127132. (In Russ.). https://doi.org/10.26902/jsc_id127132
Malakhov V. V., Vasilyeva I. G. Stoichiography and chemical methods of phase analysis of multielement multiphase substances and materials. Russian Chemical Reviews. 2008;77(4): 351–372. https://doi.org/10.1070/RC2008v077n04ABEH003737
Malakhov V. V., Vasilyeva I. G. Stoichiography: evolution of solid-phase reactions. New principles of research, preparation and characterization of functional materials*. Novosibirsk: Siberian Branch of Russian Academy of Sciences Publ.; 2023. 251 с. (In Russ.)
Inorganic crystal structure database. D–1754. Eggenstein–Leopoldshafen: Germany. 2022.
Kraus W., Nolze G. POWDER CELL – a program for the representation and manipulation of crystal structures and calculation of the resulting X-ray powder patterns. Journal of Applied Crystallography. 1996;29: 301–303. https://doi.org/10.1107/s0021889895014920
Cabri L. J., Hall S. R., Szymanski J. T., Stewart J. M. On the transformation of cubanite. Canadian Minerologist. 1973;12: 33–38.
Dutrizac J. E. Reactions in cubanite and chalcopyrite. Canadian Minerologist. 1976; 14, 172–18
Copyright (c) 2024 Kondensirovannye sredy i mezhfaznye granitsy = Condensed Matter and Interphases
This work is licensed under a Creative Commons Attribution 4.0 International License.
