The Grahamstown clay deposits extend in a broad belt from 26°23 to 26°50 East longitude and from 33°15 to 33°22 South latitude along two distinct geomorphological features, the Grahamstown Peneplane (650 m) and the Coastal Plain (520m). The clay deposits traverse four different lithologies including the Bokkeveld Shale, Witteberg Shale, Dwyka Tillite and Ecca Shale. The two planes invariably have a covering of silcrete which is also present over most of the clay deposits except where erosion has taken place. X-ray fluorescence analysis shows that chemically there is a fairly wide variation between and witnin the deposits. The greatest variation is in the Si0₂/Al₂0₃ ratio which appears to be controlled by the parent lithology and to some extent by the amount of leaching. K²0 shows an increase in concentration with depth and therefore indicates the limits of hydrolysis and leaching and of the clay. X-ray diffraction study shows the Peneplane and Coastal Plain deposits to be quite distinct. The Peneplane deposits consist of kaolinite, illite and quartz and the Coastal Plain deposits of kaolinite, illite, quartz and pyrophyllite. The presence of pyrophyllite is not fully understood as there is no indication of major faulting, metamorphism or pyrophyllite in the parent rock. The pyrophyllite most probably represents a transformation product of kaolinite. The kaolinite from the various deposits shows a considerable variation in crystallinity in both the X-ray diffraction traces and electron photomicrographs. The most poorly crystalline kaolinites are from the Coastal Plain deposits and the difference in crystallinity is most probably due to differences in the degree of hydrolysis and the parent rock material in the case of the tillite. Genetically all of the deposits are residual types generated by hydrolysis and subsequent leaching of micas and feldspars. The principal elements leached are silicon, iron and potassium. The hydrolysis and leaching took place over a long period of time in the flat lying areas of the Peneplane and Coastal Plain. The deposits are exploited economically and the clay is used principally in the tile, pottery and whiteware industries with some usage in the paper, refractory and brickmaking industries. The price commanded by raw kaolin is not very high and as a result the clay industry in Grahamstown is not as viable economically as it could be.

Um dos sistemas de proteção de substratos metálicos mais comumente empregado na indústria é o de tintas. Os fatores favoráveis à utilização das tintas em pó incluem a não utilização de solventes, facilidades de processamento/aplicação e possibilidade de reaproveitamento do material que não aderiu na superfície da peça. As características térmicas, mecânicas e químicas da tinta são influenciadas principalmente pelo tipo de resina utilizada. As tintas em pó híbridas (epóxi/poliéster) visam conciliar a característica de resistência ao intemperismo e ação dos raios UV com as características de resistência química e mecânica. Nas tintas em pó podem ser adicionados nanocargas que tem por finalidade melhorar as propriedades térmicas, mecânicas e químicas dos revestimentos. Outra característica das nanocargas é o baixo custo financeiro, decorrente da utilização de uma menor quantidade de carga, com elevado nível de desempenho. Dentre as nanocargas utilizadas, pode-se citar a mica muscovita e a montmorilonita 30B (MMT 30B) que, quando incorporadas às tintas, mesmo em baixas concentrações, apresentam propriedades de barreira superiores que às cargas convencionais. Este trabalho tem por objetivo desenvolver e caracterizar uma tinta em pó híbrida contendo diferentes teores de mica muscovita e MMT 30B. Os argilominerais foram incorporados numa formulação padrão de tinta em pó híbrida nas proporções de 2, 4 e 6% (m/m), separadamente. Antes da aplicação da tinta, os substratos metálicos foram submetidos a um pré-tratamento de fosfatização com fosfato de zinco. Após isso, a tinta em pó foi aplicada em painéis com dimensões de 70 x 120 x 0,65 mm de aço carbono AISI 1010 através de pulverização eletrostática. Os argilominerais, a tinta em pó e o revestimento foram analisados empregando diferentes técnicas de caracterização, tais como análise granulométrica, análise termogravimétrica (TGA), calorimetria exploratória diferencial (DSC), espectroscopia de infravermelho por transformada de Fourier (FTIR) e microscopia eletrônica de varredura por emissão de campo (MEVFEG). O efeito da incorporação dos argilominerais nas propriedades físicas e de proteção à corrosão das tintas foi avaliado com ensaios de medida de brilho, aderência, flexibilidade, resistência ao impacto, impedância eletroquímica (EIE), exposição à névoa salina (NS) e ensaio de chama. Para todas as tintas contendo argilominerais foi constatado o aumento da dureza superficial e a redução de brilho com o aumento do teor do argilomineral, sendo este efeito mais pronunciado com a adição de 6% (m/m) de MMT 30B. A aderência da tinta ao substrato não foi alterada pela presença dos argilominerais. As tintas contendo mica muscovita apresentaram melhores resultados nos ensaios de resistência ao impacto e de flexibilidade quando comparados as tintas contendo MMT 30B, nas concentrações testadas. A amostra TH/6/MICA apresentou melhor resultado no ensaio de impedância eletroquímica em relação aos outros sistemas estudados. No ensaio de névoa salina todas as amostras apresentaram elevada proteção à corrosão. Não foram observados bolhas ou pontos de corrosão na superfície de nenhuma das amostras. Porém, no ensaio subsequente de migração subcutânea, a amostra TH/2/MMT 30B foi a que apresentou maior desplacamento. No ensaio de chama, as tintas com incorporação de mica muscovita apresentaram melhores resultados que as tintas com MMT 30B. Após a análise de todos os ensaios, conclui-se que a adição de mica muscovita na proporção de 4% resultou em uma tinta com melhores propriedades térmicas, mecânicas e químicas. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior. / One of metallic substrates protection systems most commonly used in the industry is the paint. Factors favorable to the use of powder coatings include non-use of solvents, processing facilities/application and the possibility of reuse of material that did not adhere to the surface of the pieces. The thermal, mechanical and chemical characteristics of the obtained paint are influenced principally by the type of resin used. Hybrid (epoxy/polyester) powder coatings aimed at reconciling the weathering resistance characteristic and action of UV rays with the chemical resistance and mechanical characteristics. In the powder coatings can be added nanofillers which aims to improve the thermal, mechanical and chemical coatings. Another feature of nanofillers is the low financial cost resulting from the use of a lesser amount of filler, with a high level of performance. Among the nanofiller used, it can be cited muscovite mica and montmorillonite 30B (MMT 30B) that, when incorporated into the coatings, even at low concentrations, have higher barrier properties than conventional fillers. This work aims to develop and characterize a hybrid powder coating containing different amounts of muscovite mica and MMT 30B. Clayminerals have been incorporated in a standard formulation hybrid powder coatings in proportions of 2, 4 and 6% (w/w). Before applying the coating, the metal substrates were subjected to a pretreatment phosphating with zinc phosphate. After this, the powder paint was applied to panels with dimensions 70 x 120 x 0.65 mm carbon steel AISI 1010 through electrostatic spraying. The clayminerals, the powder paint and coating were analyzed using various characterization techniques, such as particle size analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), infrared spectroscopy in Fourier transform (FTIR) and scanning electron microscopy for field emission (SEM-FEG). The effect of the incorporation of clayminerals in the physical properties and corrosion protection of coatings was evaluated with brightness measurement tests, adhesion, flexibility, impact resistance, electrochemical impedance spectroscopy (EIS), exposure to fog saline (NS) and flame test. For all coatings containing clayminerals was found to increase the surface hardness of the coating and reduced gloss with increasing clay content, this being more pronounced effect with the addition of 6% (w/w) of MMT 30B. The adhesion of the coating to the substrate was not altered by the presence of clayminerals. The coatings containing mica muscovite showed better results in impact resistance tests and flexibility when compared to coatings containing MMT 30B. The sample TH/6/MICA showed better results in the electrochemical impedance test in relation to other systems studied. In the salt spray test all samples showed high corrosion protection. There were no blistering or corrosion spots on the surface of any of the samples. However, in the subsequent test of subcutaneous migration, the sample TH/2/MMT 30B showed the greatest peeling. In the flame test, coatings with incorporation of muscovite mica showed better results than coatings with MMT 30B. After analyzing all the tests, it is concluded that the addition of muscovite mica in the proportion of 4% resulted in an paint with improved thermal, mechanical and chemical properties.

Minerals and clay minerals in continental sedimentary successions are valuable tools for reconstructing past environmental conditions. Given the state of preservation of clays minerals, it is possible to identify how they were formed, providing clues about continental weathering conditions (inherited minerals) and geochemical conditions in the water column (neoformed or transformed). This study presents new mineralogical data from the Baskil section, a highly preserved middle Eocene succession in the Neo-Tethys (central Turkey). A gradual shift from a well-crystalline illite and chlorite interval (subsection I) to a detrital smectite dominant interval (subsection II) characterizes a change in source area from metamorphic to igneous rocks and changes from physical to chemical weathering conditions on land. This period coincides with the Middle Eocene Climatic Optimum (MECO), indicating a mineralogical signature of the event. Higher content of terrigenous input being deposited from 40.5 to 40 Ma caused a dilution effect of the carbonate materials as calcite and dolomite significantly decreases. Authigenic palygorskite showed an increasing trend from the middle to the uppermost portion of the section, indicating favorable conditions in the water column for its formation. We assume that conditions in the ocean circulation changed after 40 Ma, forming a stratified water column with warmer and saline conditions at greater depths, favoring palygorskite and possibly authigenic dolomite precipitation. The mineralogical evolution of the Baskil section reflects how sources and weathering regimes changed through time, and how these changes can be related to global (i.e. MECO) and/or local to regional processes. / Minerais e argilominerais em sucessões sedimentares são excelente ferramentas para a reconstrução de condições ambientais. Dado o estado de preservação dos argilominerais, é possível identificar como eles foram formados, fornecendo informação sobre as condições de intemperismo no continente e sobre condições geoquímicas na coluna d\'água. Este estudo apresenta novos dados mineralógicos da seção de Baskil, uma sucessão do Eoceno médio altamente preservada no Neo-Tethys (Turquia central). Uma mudança na assembléia mineralógica com maiores concentrações de ilita e clorita (subseção I) para um intervalo dominante de esmectita detrítica (subseção II) caracteriza uma mudança na área de fonte de rochas metamórficas para rochas ígneas e mudanças de condições de intemperismo físico para intemperismo químico. Este período coincide com o Ótimo Climático do Eoceno Médio (MECO), indicando uma assinatura mineralógica do evento. A paligorsquita autigênica teve um aumento na porção media e superior da seção, indicando condições favoráveis na coluna de água para a sua formação. Possívelmente as condições na circulação do oceano naquela região mudaram após 40 Ma, formando uma coluna de água estratificada com condições mais quentes e salinas em profundidades maiores, favorecendo precipitação de paligorsquita e dolomita. A evolução mineralógica da seção de Baskil reflete como as fontes e os regimes de intemperismo mudaram ao longo do tempo, e como essas mudanças podem estar relacionadas aos processos globais (e.g. MECO) e /ou a processos locais e regionais.

Available instruments for viscosity and rheologic measurements necessitate disruption of the system under test prior to observations. Generally, the gel structure of a thixotropic clay must be disturbed by shaking, pouring into a container for testing, and again upon insertion into the sample of the bob, spindle or paddle of the instrument. Also, these instruments yield a single point reading which is only a final or average value, depending upon the instrument. The occurrences during the test itself cannot be observed. Accordingly? it seemed feasible to determine, if possible, what other rheologic factors are involved in the breakdown of ·the gel structure of a thixotropic clay dispersion. The objective of the study was to design and test an instrument which would not require disturbing the sample before testing, which would give minimal destruction of the sample upon entry of the test probe into the sample, and which would give complete permanent recordings throughout the time of testing.

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

Once similarities between Earth and other terrestrial bodies were discovered, determining the conditions that contributed to the evolution of surface processes on these planets, particularly Mars, is of great interest. More importantly, such research and exploration can provide proof of previous existent life within these near-surface environments. As the past environmental conditions at Mars’ surface are mostly unknown, studies of comparable environments on Earth have been crucial toward deciphering the overall geological understanding of Mars. As the discovery of past conditions on Mars become more absolute, researchers can search for more constrained bio-signatures of life that may have been present. Using the geological similarities between Earth and Mars, analogues can be used to compare the conditions on Mars and Earth and how they evolved over time, further providing more precise understanding of our own environment as it relates to the future. In this study, acid mine drainage (AMD) systems, which are one of the most acidic environments on Earth, were compared to the surface of Mars as a potential analogue to the past conditions of the planet when such acid-impacted environments were widespread at the surface of the planet.

The aim of this study was to arrive at a fundamental understanding of kimberlite weathering and of factors which affect the rate and extent of weathering. Weathering was evaluated by measuring the change in size distribution after immersing crushed kimberlite in solutions of various compositions. Reproducibility of the measurements was found to be good, with the cumulative mass passing a given size differing by 7% or less, as tested for various weathering conditions. Kimberlite mineralogy, specifically the swelling clay content, was found to play a central role: kimberlite ores containing no swelling clay were not prone to weathering under any of the conditions tested. The cation exchange capacity (CEC) correlates well with the swelling clay content and with the weathering behaviour. The cation exchange capacity may be used in conjunction with the swelling clay content, as a predictor of possible kimberlite behaviour; however, given the relative complexity and cost of measuring swelling clay content (by X-ray diffraction), the CEC is the preferred parameter for practical use. Cations in the weathering solution have a strong effect on kimberlite weathering; the strength of the effect followed the series Cu2+ > Li+ > Fe2+ > Ca2+ > Fe3+ > Mg2+, whereas K+ and NH4+ stabilised the kimberlite somewhat against weathering. This sequence was in reasonable correlation with the ionic potential (ratio of valency to ionic radius), but with exceptionally strong weathering effects of Cu2+, and (to a lesser extent) of Li+ and Fe2+. The strong effect of the latter group of cations may be related to their tendency to adsorb onto other crystal sites in addition to the interlayer – the associated change in surface energy can change the fracture behaviour of the kimberlite. Measurement of the layer spacing of the swelling clay (by X-ray diffraction) showed no correlation between the weathering effect of a cation and the associated thickness of the interlayer. For solutions of cupric ions, the identity of the anion (chloride or sulphate) has little effect on weathering. The size of the crushed kimberlite ore similarly has little effect on the relative extent of size degradation by weathering. The concentration of cupric ions affects weathering, as does the weathering time – although 85% of the weathering caused by 30 days' exposure was found to occur within the first 24 hours. Increasing the temperature to 40°C (in a magnesium chloride solution) also increased weathering strongly. The kinetics of exchange of cuprous and potassium ions was measured (for two different kimberlites); the apparent reaction order (with respect to the concentration of exchanging cations in solution) varied between 1 and 3.5, and exchange of potassium was more rapid. This work has practical implications for in-plant processing of kimberlite, possible alternative kimberlite processing routes which eliminate one or more crushing steps, and for the stability of mine tunnels which pass through kimberlite. / Thesis (PhD (Metallurgical Engineering))--University of Pretoria, 2006. / Materials Science and Metallurgical Engineering / PhD / unrestricted

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20390号 / 工博第4327号 / 新制||工||1671(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 作花 哲夫, 教授 安部 武志, 教授 佐藤 啓文 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Phyllosilicates are widespread on Noachian to Early Hesperian terrains on Mars and can help constrain the planet’s geologic and environmental history, particularly its aqueous and redox history, which in turn can provide clues about past habitability. A range of ferrous and mixed-valence smectites were synthesized and then exposed to varying O2 fluxes under dry conditions to determine if Fe/Mg trioctahedral smectites can be oxidized without an aqueous medium to form dioctahedral smectites like those observed on the surface of Mars. The appearance of a secondary peak in some unaltered samples indicates a separate phase formed during synthesis, which remained throughout the oxidation process. Partial oxidation was achieved by all samples, but only those with the highest starting Fe3+ content reached almost complete oxidation. Rapid initial oxidation was observed for all samples, but seemed to subside before oxidation was complete, indicating the process becomes unfavorable after a certain point. All three O2 fluxes used in this study were successful in partially oxidizing the smectite samples but no correlation was observed between O2 flux and actual amount of oxidation, i.e., a higher O2 flux does not necessarily result in higher production of ferric iron. The process of oxidation did cause octahedral sheet contraction in some cases; however, in some samples octahedral sheet expansion was observed with oxidation. No additional phases were formed upon oxidation and no Fe ejection was observed. Overall, the amount of oxidation observed for all samples indicates that O2 alteration of trioctahedral smectites into dioctahedral smectites can proceed under dry conditions, meaning oxidation could have continued on Mars after surface water dried up. / Geology

Several recent studies that have proposed MUSIC models for gibbsite surfaces have purported to achieve a very good fit with potentiometric titration data. However, in order to achieve such results, several significant parameters, such as the number of surface sites, site densities, and pKa values were sometimes re-introduced in the model as fitted parameters, and physically unrealistic modeling assumptions were sometimes used. In addition, recent evidence supports the idea that some of the gibbsite potentiometric titration data from these studies may be unreliable. In order to re-interpret the potentiometric titration data, we used several recently published methods. In order to detect possible problems with estimates of gibbsite basal and edge surface area, we synthesized two gibbsite samples with different aspect ratios and characterized their surface areas using BET, AFM, and computerized image analysis routines. We also estimated pKa values for acid/base reactions at gibbsite surfaces by applying a new bond-valence method to gibbsite (001)-type and (100)-type surface structures based on ab initio calculations. The resulting pKa estimates are not to be taken as precise values due to difficulties and assumptions associated with calculating reasonable ab initio surface structures. Instead, we believe they represent a more reasonable range than has been previously estimated. Using these estimates, we propose an improved MUSIC model for gibbsite, which seems to predict surface adsorption, not perfectly, but within a reasonable range for a number of titration data sets without re-introducing any of our estimated parameters as adjustable parameters. Discrepancies that exist between model predictions and various potentiometric titration data sets are likely due to error associated with potentiometric titrations and pKa predictions.