THE OXIDATION OF VIOLARITE

A sample of violarite was synthesized from pure components and charact erized. Samples of particle size 45-75 mu m were oxidized in a TG-DTA apparatus at a heating rate of 10 degrees C min(-1) and the products c haracterized at various temperatures by X-ray diffraction (XRD), backs cattered electron (BSE) images obtained on a Scanning Electron Microsc ope (SEM), Fourier transform infrared (FT-IR) spectroscopy and electro nprobe microanalysis (EPMA). Only minor sulfation reactions occurred u p to 405 degrees C, but above this temperature the violarite decompose d to form a monosulfide solid solution (mss, (Fe,Ni)(1-x)S) and sulfur . The first reaction produced a mass loss, and oxidation of the evolve d sulfur produced an exotherm. From 470 degrees C, there was a mass ga in due to the continued formation of sulfate species and an exotherm c aused by the conversion of iron sulfide to hematite. From 585 degrees C, a mass loss occurred as the iron sulfates decomposed. At 670 degree s C decomposition of the mss took place, with the formation of heazlew oodite, (Ni, Fe)(3+/-x)S-2, and sulfur. The first reaction produced a mass loss, and oxidation of the evolved sulfur gave an exotherm. Trevo rite, (Fe, Ni)(3)O-4, was also formed above this temperature, from the oxidation of either mss or heazlewoodite, and this reaction also cont ributed to the mass loss. Above 725 degrees C a mass loss and sulfur d ioxide evolution was associated with the decomposition of nickel sulfa te. This was followed by an endotherm at 785 degrees C caused by the m elting of the heazlewoodite, which immediately oxidized to produce a m ass loss and exotherm. The final product above 860 degrees C contained trevorite, nickel oxide and hematite. Extensive migration of iron occ urred during the oxidation process.