A sequence of 3250 m of the Rustenburg Layered Suite and its associated mineralization south of Potgietersrus was investigated. Four episodes of faulting have deformed the area. This resulted in very early differentiates, not seen elsewhere in the Bushveld Complex, to outcrop together with economic concentrations of the best metallurgical grade chromite presently being mined in the Republic. The Mg:Fe:Ca ratio of theCa-poor pyroxenes varies from 89,5:8,8:1,6 in the lower zone to 44,2:52,3:3,37 in the upper zone. The latter composition demarcates the Fe-rich end of the two pyroxene limit. Textural evidence implies that there is a peritectic reaction between the ironrich Ca-poor pyroxene and the melt and that this may account for the termination of the two pyroxene field. A significantly higher mean Ko~~~F~p; for the study area (0,822) than for the other sectors of the Bushveld Complex (0,782) suggests that the pyroxenes of similar composition crystallized at higher temperatures in the Potgietersrus limb. Examination of the Al :Si ratio in Ca-rich pyroxenes from a variety of magmatic environments confirms that this variable can be used to monitor relative changes in the a ~~~t. Chemical data of the Ca-rich pyroxenes suggest that this phase define~ an Fe enrichment - Ca depletion trend during differentiation uhlike that for most other tholeiitic intrusions. The V205 content of the main magnetitite layer and the cr203 and the Cr/Fe2++Fe3+ values in the upper and lower chromitite layers in the study area are the highest encountered in the Bushveld Complex. Textural evidence in these layers show that they have been up-graded to dense monomineralic layers by postcumulus sintering. Calculated intensive parameters for the Potgietersrus magma suggest that it crystallized over a temperature interval from 1276°C in the lower zone to 1022°C in the basal portion of the upper zone. Oxygen fugacity conditions for the lower zone ranged from 10-6,21 to 10-4,98 atm whereas lower values of 1o-11 to 1o-9 atm were operative in the upper zone. The study area contains abundant concentrations of sulfides at several levels in the sequence. The separation of the sulfide liquid is related in most cases to new influxes of metal-rich magma and mixing with the residual magma in the chamber. Several definite sulfide facies occur in the layered sequence. Sulfur isotope investigations indicate that all the sulfur in the study area is mantle derived and that the isotopic composition of the sulfur was controlled by the prevailing fo2, which in turn controlled the partitioning of S02 and HzS between sulfide melt and magma. / Thesis (PhD)--University of Pretoria, 1983. / gm2014 / Materials Science and Metallurgical Engineering / Unrestricted

Fatty acid intercalated layered double hydroxides were used as additives for Jojoba oil and polymer matrices. The first phase of the study was to intercalate carboxylic acids (C14 to C22). These were successfully intercalated into layered double hydroxides (LDHs), with the formula [Mg0.7Al0.3 (OH) 2](CO3)0. 15•0.5H2O. The one-pot synthesis consistently yielded a bilayer intercalated product for the range of acids employed. The intercalated anions had an orientation tilt angle of 55–63°, depending on the length of the fatty acid chain. However, there is an indication that the anion exchange process employed in this study is accompanied by probable dissolution and recrystallisation of the LDH. This is supported by the different growth habits and sizes of platelets observed through scanning electron microscopy (SEM). Moreover, the organo-LDH platelets were found to have varying MII/MIII compositions, ranging from 1.65 to 6, indicating that the one-pot synthesis yields an array of mixed metal hydroxides. Polymer composites, containing 5% and 10 wt.% of stearate intercalated layered double hydroxides (LDH-stearate) and neat layered double hydroxides (LDH-CO3), were prepared via melt-compounding to explore the use of LDHs as an additive. The stearate modified starting material was bilayer-intercalated clay. During melt compounding, excess stearates were released and the clay reverted to a monolayer-intercalated form. Comprehensive characterisation and study of the fatty acid-intercalated LDH showed that these organoclay hybrids exhibit thermotropic behaviour. This behaviour ultimately leads to the exudation of excess fatty acid. The exuded stearates were found to have lubricating and plasticising effects on the poly(ethylene-co-vinyl acetate) (EVA) and linear low density polyethylene (LLDPE) matrices. Strong hydrogen bond interactions between the chains of poly(ethyleneco- vinyl alcohol) (EVAL) and the clay platelet surfaces overwhelmed the lubrication effect and caused an increase in the melt viscosity of this matrix. The notched Charpy impact strength of this composite was almost double that of the neat polymer. It appears that this can be attributed to the ability of the highly dispersed and randomly oriented nanosized clay platelets to promote extensive internal microcavitation during impact loading. The creation of a large internal surface area provided the requisite energy dissipation mechanism. The study also considered fatty acid-intercalated LDH as an argillaceous mineral for potential use as a rheological additive in Jojoba oil. A minimum of 20 wt.% LDH in Jojoba oil formulation was found to be stable, i.e. it did not form separate layers on standing. The viscosity of the neat Jojoba oil demonstrated Newtonian behaviour, whereas the modified LDH/Jojoba oil formulation shear thinned, which is a typical non-Newtonian behaviour. Viscosity as a function of temperature showed complex rheological behaviour for the long chain fatty acids C16 to C22. The viscosity increase is assumed to be due to a combination of three events, which include the formation and changes of LDH microstructures within the oil, the loss of excess fatty acids into the oil matrix, and the formation of fatty acid crystal networks. Shear action also induced some delamination of the clay platelets. / Thesis (PhD(Eng))--University of Pretoria, 2012. / Chemical Engineering / unrestricted

Since 2016 there are world-wide more mobile phone contracts than people on the planet, and in all these devices critical raw materials (CRMs) are incorporated.[1] For instance, commonly used silicon-based transistors are limited in their chemical modularity. Inorganic materials for solar cells and photocatalysis suffer from critical raw elements content, low apparent quantum efficiencies and photodegradation. Hence, considerable research interest in recent years is focused on development of new high-performance devices for optical and electronic applications that avoid CRMs entirely. To address all these problems materials chemists are exploring for new pathways towards making more sustainable and reliable materials. In that respect, porous organic π- conjugated polymers (POPs) are among the most promising candidates and have gained tremendous attention in materials research over the last decade, especially in the fields of photocatalysis, opto- and electrochemical sensorics, and microelectronics. Synthetic diversity, chemical and physical stability, as well as comparatively low production costs and scalability enable POPs to overcome the drawbacks of inorganic materials. Moreover, the absence of rare earth elements in the purely organic structure of POPs makes these materials more environmentally...

Surfactant-mediated intercalation of aliphatic fatty acids into a commercial,layered double hydroxide (LDH) with the approximate composition of [Mg0.689Al0.311(OH2)] (CO3)0.1569nH2O was explored. The reactions were conducted at elevated temperatures with the LDH powder suspended in a fatty acid oil-water emulsion. The acidic fatty acid, e.g. stearic acid, reacts with the basic carbonate anions from LDH-CO3. In the process, CO2 is released as a gas and the fatty acids are intercalated as a bilayer. A high concentration of anionic or non-ionic surfactants, i.e. sodium dodecylsulphate or Tween 60, facilitates the intercalation process by emulsifying the molten fatty acids and dispersing the LDH particles. The presence of carboxylate anions in the interlayer region was confirmed by the carboxylate absorption peaks observed in the region 1700–1000 cm-1 on Fouriertransform infrared spectroscopy (FT-IR). Several bands were observed, i.e. ionised and non-ionised. An increase in the d-spacing of the d003 plane of the brucite-like LDH layers was observed on X-ray diffraction (XRD) analysis of all the LDH intercalates. The d-spacing increased linearly with the length of the carboxylic acid chain. Sharp reflection peaks were obtained on XRD, showing the high crystallinity of the LDH intercalates. The thermal decomposition of these materials was explored on thermogravimetric or differential thermogravimetric analysis (TGA/DTA) and temperature-scanned XRD. The mole ratio of Mg to Al was obtained by XRF and the morphology by scanning electron microscopy (SEM). The present method works well with long-chain aliphatic fatty acids at temperatures above or at the melting point of the desired acid. Temperature proved to be the most important parameter to control during the preparation process, i.e. at low temperatures incomplete reactions were obtained. The method is convenient, economical and environmentally friendly. It employs the readily available carbonate form of LDH as a starting reagent, water is used as medium rather than organic solvents, there are no high-temperature calcinations, and an inert atmosphere is not required. Copyright / Dissertation (MSc)--University of Pretoria, 2008. / Chemistry / unrestricted

Hydrotalcite-like compounds are synthetic anionic clays that have outstanding adsorption and catalytic properties. Hydrotalcite nanoclays (Mg–Al layered hydroxides) were synthesized by co-precipitation method. Obtained solids were converted into mixed metal oxides by thermal decomposition at temperatures up to 723 K. High adsorption and reconstructive properties of the mixed metal oxides allowed incorporating metal ions in their structure. Thus, these materials can be used as ion traps from aqueous media. Cesium ions were incorporated into hydrotalcite lamellar structure by impregnation method. Effects of different loads of Cs+ and adsorption times on the material properties were studied. The materials were characterized by X-ray diffraction, surface area analysis, scanning electron microscopy, energy dispersive X-ray spectrometry for obtaining a localized chemical analysis, and temperature-programmed desorption of CO2 for measurement of basic sites density. The amounts of metal incorporated in the structure was high enough due to small size of Cs+ ion. Synthetized materials also demonstrated high concentrations of strong surface basic sites formed through a synergistic effect of Cs and Mg ions. Basic properties of Cs-containing hydrotalcites enable their potential use as catalysts of base-catalyzed reactions.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21119号 / 工博第4483号 / 新制||工||1697(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 阿部 竜, 教授 安部 武志, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Water polluted by metals and phosphates can be hazardous to both the environment and human health. The aim of this study was used to improve understanding of the adsorption properties of low-cost, green adsorbents for removal of pollutants from aqueous solution. Biochar was used as an adsorbent, which was produced from the gasification of pine wood waste and the fast pyrolysis of Douglas fir. Biochar is a bio-renewable product that can easily be modified, and the cost is lower compared to other adsorbents like activated carbon. The gasifier produced biochar was modified by coating the biochar surface with chitosan. Douglas fir biochar, produced by pyrolysis, was used in Mg/Al-layered double hydroxides (LDHs) and magnetization modifications. The Mg/Al-LDHs were prepared by co-precipitation using solutions of Mg and Al salts and NaOH treatment. The magnetization modification of the biochar was prepared by magnetite (Fe3O4) precipitation onto the biochar’s surface from Fe2+/Fe3+ solution upon NaOH treatment. Chapter I provides an introduction into biochar production, uses, and modification methods. Chapter II is a study of the aqueous adsorption Cu2+ and Cd2+ metals using chitosan coated and uncoated gasifier biochars. Chapter III focused on the removal of phosphate from aqueous solutions. Different ratios of Mg:Al in the LDHs were used to test the ratio’s affect on the adsorption properties of the modified adsorbents. Chapter IV describes the removal of phosphate from water using LDH modified biochars that are magnetized. This study looks at how the order in which the modifications were done influences the biochars adsorption ability. The surface chemistry and composition of each biochar in chapters II-IV were examined by SEM, SEM-EDX, TEM, PZC, XRD, elemental analysis, and surface area measurements. Each biochar’s adsorption ability was studied by pH effects, kinetics, and maximum capacity for the analyte.

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