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The high-temperature form of pentlandite (Fe 4.5 Ni 4.5 S 8 ) was found to be stable between 584 ± 3 and 865 ± 3 °C, breaking down into monosulfide solid solution and liquid at the later temperature. The phase is unquenchable and always displays the X-ray pattern of pentlandite (low form) at room temperature. High-temperature X-ray diffraction demonstrated that the high form has a primitive cubic cell with a = 5.189 Å (620 °C) corresponding to a/2 of pentlandite. The high-low inversion is reversible, accompanied by a large latent heat. It is thought to be order-disorder in character. The transition temperature falls with decreasing S content. The high form of pentlandite has a limited solid solution from Fe 5.07 Ni 3.93 S 7.85  to Fe 3.61 Ni 5.39 S 7.85  at 850 °C. However its solid solution extends rapidly toward Ni 3±X S 2  in the Ni-S join with decreasing temperature. High-form pentlandite with Fe = Ni in atomic percent crystallizes first by a pseudoperitectic reaction between monosulfide solid solution and liquid. The high form (Fe = Ni) crystallized from the liquid always has the metal-rich (S-poor) composition in the solid solution at each temperature and coexists with taenite γ (Fe,Ni) below 746 ± 3 °C. This metal-rich high-form Fe 4.5 Ni 4.5 S 7.4  breaks down into pentlandite and g (Fe,Ni) at 584 ± 3 °C (pseudoeutectoid).

High form of pentlandite and its thermal stability