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. / gm2014 / Materials Science and Metallurgical Engineering / UPonly

The mechanisms and kinetics of combustion of waste wood as well as the phases during combustion processes are important to eliminate these wastes without any possible damage to environment. In the present study, combustion mechanisms, activation energy and pre-exponential constants, and phases of combustion were investigated for untreated natural pine and treated Medium Density Fiberboard (MDF), plywood and particleboard samples that involve some chemicals and additives. Waste wood samples were heated in air at 10, 20 and 30oC/min heating rates in a Thermo Gravimetric Analyzer (TGA) from room temperature to 900oC. Thermogravimetry (TG) and Derivative Thermogravimetry (DTG) curves for all samples were obtained. The gases formed during combustion reactions were directly fed to a Fourier Transform Infrared Spectroscopy (FTIR) instrument coupled to TGA. Emission characteristics of the samples were determined in-situ by using the FTIR spectrums. As a result of TG analysis, thermal decomposition of treated samples was observed at lower temperatures as compared to the untreated pine sample because of the catalyzing effects of the chemicals in the treated samples. Therefore, there were less flammable products, lower weight losses in the main oxidation region, decrease in the max. weight loss temperatures and formation of more char for treated samples as compared to untreated pine sample. In other words, chemicals used during production of these samples lead to decrease in the combustibility of the treated samples. Thermal kinetic constants for the samples were calculated by using Coats Redfern and Broido Methods. In order to find out the mechanisms responsible for the oxidation of the waste wood samples in different regions, six solid state mechanisms of Coats Redfern Method were tested. As a result of FTIR analysis of the emitted gases from TG analysis, several chemical groups were detected from pine and treated samples. Combustion of all samples revealed some gases containing aromatics, C-H groups, CO2 and CO. However, there were some toxic and carcinogenic gases like formaldehyde, isocyanate group, ammonia, phenyl group and benzoylbromide among the emissions of treated samples which need utmost attention when recovering energy from treated waste woods.

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