Determination of the transition of eutectic to peritectic folding in the Cu(Ni)–Fe–S system by the method of directional crystallization of the melt

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Abstract

Theoretical analysis of the process of quasi-equilibrium directed crystallization of a three-component melt is carried out in this paper. The change in the composition of phases at each of the sample sites and the phase composition transformation for different types of phase reactions are considered. It is shown that at directional crystallization there are possible cases of transition of eutectic reaction to peritectic reaction at lowering of temperature. The directional crystallization of Fe 29.96, Cu 21.55, Ni 2.01, S 46.49 at. % melt was carried out. Since nickel was present in the ingot in the form of impurities dissolved in the phases of the Cu-Fe-S system, it is possible to consider the behavior of the melt belonging to this three-component system when interpreting the data. As a result of which a sample with three zones has been obtained: single-phase from FezS1±d (Poss), two-phase from eutectic mixture of Poss and (Cu,Fe)1+xS (Iss) and single-phase from Iss. During the transition from one zone to the next, the average composition of the solid phase changes discontinuously, while the compositions of the melt and solid solutions present in neighbouring zones change continuously. These results are consistent with theoretical representations.

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About the authors

E. F. Sinyakova

Sobolev Institute of Geology and Mineralogy, Siberian Branch, Russian Academy of Sciences

Author for correspondence.
Email: efsin@igm.nsc.ru
Novosibirsk

I. G. Vasilieva

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: efsin@igm.nsc.ru
Russian Federation, Novosibirsk

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Supplementary files

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2. Fig. 1. Relative location of the monovariant line and the conode triangle during monovariant eutectic (a) and peritectic (b) reactions, c – transition of the eutectic reaction (melt composition L1) to peritectic (L3) through the transition point (L2). Phases  and  of constant composition are in equilibrium with the melt. The arrows show the direction of the temperature decrease. Single and double arrows indicate eutectic and peritectic folds.

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3. Fig. 2. Trajectory of the melt composition (dashed line) during directional crystallization of sample L0 when it hits the peritectic (a) and eutectic (b) folds separating the regions of primary crystallization of phases  and .

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4. Fig. 3. Monovariant line with transition point L on the line between the regions of primary crystallization of phases  and  and the trajectory of the melt composition during directional crystallization; a - peritectic fold transforms into eutectic, b - eutectic fold transforms into peritectic.

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5. Fig. 4. Scheme of the primary zoning of the sample (a) and its microstructure in reflected light (b) and reflected electrons (c). Phases formed from the melt: Poss—pyrrhotite solid solution FezS1±, Iss—intermediate solid solution (Cu,Fe)1+xS. Phases formed during subsolidus reactions: Poss ′ - low-temperature pyrrhotite solid solution, Iss ′ - low-temperature intermediate solid solution, Cbn - cubanite CuFe2S3, Pn - pentlandite (Fe, Ni)9S8, Bn - bornite Cu5FeS4, Hc - heycockite Fe5Cu4S8. Black—cracks in the sample.

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6. Fig. 5. Change in the concentration of copper, iron and sulfur in the sulfide melt (L) and solid phases (Poss, Iss) in three zones of the sample to g = 0.65. Open circles show the average concentrations of components in the melt, closed circles - in solid phases. The dashed horizontal line shows the concentration of the component in the initial melt, the dashed vertical lines separate the Poss || zones. Poss + Iss || Iss.

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