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The Ni-S System and Related Minerals
Authors:KULLERUD  G; YUND  R A
Institution:Geophysical Laboratory, Carnegie Institution of Washington Washington, D.C., U.S.A.
Abstract:The system Ni-S has been studied systematically from 200{cularr}? to1, 030{cularr}? C by means of evacuated, sealed silica-glass tube experimentsand differential thermal analyses. Compounds in the system areNi3S2 (and a high temperature, non-quenchable Ni3{cularr}?{cularr}{alpha}S2 phase),Ni7S6, Ni1{cularr}–S4 Ni3S4, and NiS2. The geologic occurrenceof the minerals heazlewoodite (Ni2S2), millerite ({cularr}ßSNi1-2S),polydymite (Ni3S4), and vaesite (NiS2) can now be describedin terms of the stability ranges of their synthetic equivalents. Hexagonal heazlewoodite, which is stoichiometric within thelimit of error of the experiments, inverts on heating to a tetragonalor pseudotetragonal phase at 556{cularr}? C. This high-temperature phase(Ni3 has a wide field of stability, from 23.5 to 30.5 wt percent sulfur at 600{cularr}? C, and melts incongruently at 806{cularr}?{cularr}?3{cularr}? C.The {cularr}ßNi7S6 phase inverts to {cularr}{alpha}Ni78 at 397{cularr}? C6 when inequilibrium with Ni3S2, and at 400{cularr}? C when in equilibrium with{cularr}{alpha}NiS. Crystals of {cularr}{alpha}Ni7S6 break down to Ni3-{cularr}{alpha}S2{cularr}+{cularr}{alpha}NiS at 573{cularr}?{cularr}?3{cularr}?C.The low-temperature form of Ni1-S1 corresponding to the mineralmillerite, is rhombohedral, and the high-temperature form hasthe hexagonal NiAs structure. Stoichiometric NiS inverts at379{cularr}?{cularr}?3{cularr}?C, whereas Ni1-{cularr}{alpha}S with the maximum nickel deficiency invertsat 282{cularr}?{cularr}?5OC. The Ni1-{cularr}alphS-NiS2 solvus was determined to 985{cularr}?{cularr}?3{cularr}?C,the eutectic temperature of these phases. Stoichiometric NiSis stable at 600{cularr}?C but breaks down to Ni2-{cularr}{alpha}S2 and {cularr}{alpha}Ni1-S below797{cularr}?C, whereas {cularr}{alpha}Ni1-S with 38.2 wt per cent sulfur melts congruentlyat 992{cularr}?{cularr}?3{cularr}?C. Vaesite does not vary measurably from stoichiometricNiS2 composition, and melts congruently at 1.007{cularr}?5{cularr}?C. Polydymitebreaks down to aNi-{cularr}{alpha}S{cularr}? vaesite at 356{cularr}?{cularr}?3{cularr}?C. Differential thermalanalyses showed the existence of a two-liquid field in the sulfur-richportion of the system above 991{cularr}?C and over a wide compositionalrange.
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