Diamonds are commonly present in an ore called kimberlite. Kimberlites vary extensively in mineralogy and therefore can complicate the processing and the extraction of diamonds. Weathering of kimberlite was investigated in this study and refers to the rapid physical breakdown of the kimberlite material. Kimberlite weathering by organic molecule adsorption was investigated utilising organic solutions; ethanol, formamide, n-hexane, oxalic acid, urea, pentanoic acid and acetic acid, was investigated. The extent of weathering was measured by XRD, TGA and FTIR analysis as well as by evaluating changes in the particle size distribution. The idea to predict the susceptibility of weathering of kimberlite based on TGA analysis was discredited as it was found that there was no correlation between the smectite content and the % weight loss from TGA analysis.
In XRD analysis studies to relate the d-spacing to the extent of weathering, it was found that the technique was not sensitive enough to enable direct prediction of weathering behaviour. Organic solutions at 0.5 M generally did not significantly alter the d-spacing. In the case of utilising pure organic solutions, it was observed that switching from diluted to pure organic solutions did not increase the d-spacings but rather lowers the space. Cation pretreatment prior to organic weathering resulted in d-spacings up to 2 water layers (12.6 Å being equal to 1 water layer, 15.6 Å equal to 2 layers and 18.6 Å equal to 3 layer). The general trend was that the divalent cations Mg2+ and Ca2+ increased the d-spacings whereas monovalent cations Na+ and K+ decreased the spacing. In the case of pre-organic treatment prior to organic weathering, it was observed that the resulting d-spacing increased to 2 and 3 water layers.
TGA analysis confirmed that the kimberlite structure did absorb organic reagents during weathering. It was observed that the amount of organic reagents adsorbed decrease in the following order: oxalic acid > urea > pentanoic acid > formamide > ethanol > n-hexane > acetic acid, with oxalic acid having been adsorbed the greatest. In addition, it was also shown that the extent of inorganic cation adsorption was more than that of organic solutions. The analysis also showed that organic pretreatments yielded promising results and the order followed was dimethyldioctadecylammonium chloride > cetylpyridium chloride > dodecylamine > pyridine in encouraging subsequent organic adsorption. FTIR analysis results indicated the mechanism by which organic molucules attached onto the mineral surface. It was observed that there was a disturbance of the bond between water in the interlayer and the silicate structure by a stronger H-bond gained through organic molecule attachment. Oxalic acid was observed to cause a structural change due to proton attack of the silicate structure.
It was found that kimberlite weathering, in essence, occurred in the first 24 hours of contact with the solution. Oxalic acid was found to be the most effective weathering agent compared to the rest of the tested organic solutions. The effect of the tested solutions, at 0.5 M concentration, on kimberlite weathering followed the series Cu2+ > oxalic acid > ethanol > acetic acid > formamide > n-hexane > distilled water. This study therefore showed that the accelerated weathering of kimberlite utilising organic solutions was not as efficient as the Cu2+ solution. Comparing Cu2+ and oxalic acid treatments, results showed that 67 % of the particles passed 12 mm screen size due to Cu2+ weathering as opposed to 48 % in oxalic acid.
In investigating the effects of variables, it was found that time of exposure had a small effect in the weathering of kimberlite. Increasing the organic concentration from 0.025 M to 0.5 M saw an increase in the amount of particles passing the 12 mm screen size by~20 %. There was however no improved weathering when the solution temperature was increased from approximately 25 °C to 40 °C.
In the study of kinetics involved during organic weathering utilising oxalic acid and comparing with Cu2+ medium, a high mineral dissolution was observed in the first 24 hours of contact with the weathering solution. However, different weathering mechanisms were observed between Cu2+ and oxalic acid. Inorganic solutions foster weathering by interlayer cation exchange which results in the reduction of the surface energy and this encourages further crack propagation. Oxalic acid weathering mechanism was by proton attack of the structural cations which was then limited thereafter by oxalate salts precipitation. Al3+ and Mg2+ were the dominant cations in solution during weathering (reaching 40 mmol/L) at higher oxalic acid concentration. This indicated that the dissolution of the clay‟s octahedral structure occurred, making oxalic acid a more effective agent than the rest of the tested organic solutions.
An alternative method to transform non-swelling clay minerals to swelling in kimberlites was highlighted. It was observed that cation exchange treatment in conjunction with acid and oxidation treatments on kimberlites containing non-swelling minerals: mica or forsterite that are at least 30 % in quantity may result in the presence of swelling clays after these treatments. Kimberlite that contained serpentine minerals was more resistant to alteration under these conditions.
Dissertation (MEng)--University of Pretoria, 2013.