Valleriite-Containing Ore from Kingash Deposit (Siberia, Russia): Mössbauer and X-ray Photoelectron Spectroscopy Characterization, Thermal and Interfacial Properties

Mikhlin, Y.L., Likhatski, M.N., Romanchenko, A.S., (...), Karacharov, A.A., Borisov, R.V.// Journal of Siberian Federal University: Chemistry, 2022, 15(3), pp. 303-317//

Valleriite, (Cu,Fe)S2n(Mg,Al,Fe)(OH)2, and related layered minerals are of interest due to their unusual two-dimensional structure, formation mechanisms, physical and chemical properties, and potential involvement into mineral processing and materials science applications. Here, we have studied Kingash Cu-Ni ore samples containing 10-25% of valleriite in association with serpentines (lizardite and chrysotile) and magnetite using scanning electron microscopy and electron microprobe analysis, Mössbauer spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal analysis and zeta potential measurement. The data are compared with those for Al-doped valleriite synthesized via a hydrothermal route. It was found that the Kingash valleriite contains excessive iron relative to CuFeS2 stoichiometry, which mainly occurs, leaving aside magnetite, as Fe3+-OH species in hydroxide layers of valleriite and minor Fe centers in serpentines. Thermal dihydroxylation of hydroxide layers of valleriites occurs near 500 oC in inert atmosphere; in air, sulfide sheets oxidize with an exothermal peak at 447 oC, and sulfur oxides don’t volatilize but react with hydroxide groups of valleriite rather than serpentines. Zeta potential measurements of coarse ore particles using the flow potential technique suggested that the surface of valleriite is negatively charged in a wide pH range while the positive values at low pHs for fine particles are inflicted by serpentine. The findings demonstrate close resemblance of the natural and synthetic Al-doped valleriites, and the key role of valleriite, despite its moderate content, for the interfacial characteristics of the valleriite-bearing ores.