Abstract
The phase relations in the Cu-Zn-S system were studied at temperatures ranging from 100 ° to 1050 °C with emphasis on the 500 ° and 800 °C isotherms. All experiments were performed in closed, evacuated silica tubes in which vapor always is a phase. Ternary phases did not appear in any of these experiments. At 800 °C tie-lines exist between cubic ZnS (sphalerite) and the digenite-chalcoite solid solution, between ZnS and three CuZn alloys (α, β, γ) and between ZnS and ZnCu liquid containing from zero to about 30 wt % Cu. Only the cubic, sphalerite, form of ZnS was encountered in the present study. At 800 °C the solid solution of ZnS in Cu2S is 7.0 ± 1 wt % and the solid solution of Cu2S in ZnS is less than 1.0 wt %. At lower temperatures ZnS coexists with all other phases once they become stable, i.e., ε-CuZn (<598 °C), CuS (<507 °C), and blue-remaining covellite (<157 °C). At 500 °C the solid solution of ZnS in Cu2S is 1.5±0.5 wt % and that of Cu2S in ZnS is less than 0.1 wt %. The presence of ZnS depresses the temperature of the hexagonal ⇄ cubic inversion in Cu2S by about 13 °C, but does not measurably affect the temperature of the monoclinic ⇄ hexagonal inversion in Cu2S nor that of the cubic ⇄ cubic inversion in Cu9S5. The coexistence in nature of sphalerite and copper-sulfides is discussed in light of the low temperature phase relations in the Cu-Zn-S system.
Zusammenfassung
Die Phasengleichgewichtsredaktionen des Dreistoffsystems Cu-Zn-S wurden über einen weiten Temperaturbereich, nämlich von 100 °C bis zu 1050 °C und dabei besonders nachdrücklich die 500 ° und 800 °C-Isothermen, untersucht. Alle Experimente wurden in abgeschmolzenen und vorher evakuierten Quarzglasampullen durchgeführt, in welchen eine Dampfphase (vapor) stets gegenwärtig war. In keinem der Experimente war das Vorhandensein einer ternären Phase zu verzeichnen. Bei 800 °C verlaufen Konodenscharen vom kubischen ZnS (Zinkblende) zur Digenit-Kupferglanz-Mischkristallreihe, ferner Konoden zwischen ZnS und drei Cu-Zu-Legierungen (α, β, γ) und zwischen ZnS und einer Zn-Cu-Schmelze von 0 bis ca. 30 Gew.-% Cu. In der hier vorliegenden Arbeit trat nur kubisches ZnS (Zinkblende) auf. Cu2S vermag bei 800 °C 7,0±1 Gew.-% ZnS in fester Lösung aufzunehmen, während die Löslichkeit von Cu2S in ZnS weniger als 1,0 Gew.-% beträgt. Mit zunehmender Temperaturerniedrigung koexistiert ZnS mit allen übrigen Phasen des Systems, sobald diese stabil werden, z. B. ε-CuZn (<598 °C), CuS (<507 °C) und blaubleibender Covellin (<157 °C). Bei 500 °C beträgt die Löslichkeit von ZnS in Cu2S nur noch 1,5±0,5 Gew.-% und die von Cu2S in ZnS weinger als 0,1 Gew.-%. Die Gegenwart von ZnS erniedright die Inversionstemperatur von hexagonalem ⇄ kubischen Cu2S um etwa 13 °C, hat aber weder einen meßbaren Einfluß auf die Inversionstemperatur des monoklinen ⇄ hexagonalen Cu2S noch auf die kubisch ⇄ kubische Inversion des Cu9S5. Angeischts der im Cu-Zn-S-System ermittelten Phasenbeziehungen bei niedrigen Temperaturen werden die Koexistenz natürlicher Zinkblende mit Kupfersulfiden diskutiert.
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Craig, J.R., Kullerud, G. The Cu-Zn-S system. Mineral. Deposita 8, 81–91 (1973). https://doi.org/10.1007/BF00203352
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DOI: https://doi.org/10.1007/BF00203352