Thesis (Ph. D.)--University of Wisconsin--Madison, 1958. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 71-76).

It was been reported that untreated wastes from ferrochrome plants release heavy metals including lead, chromium, copper, cadmium, zinc and nickel in the environment. Some of these metals such as hexavalent chromium are potentially toxic and carcinogenic, and can cause a serious threat to human health. The contamination of terrestrial and aquatic ecosystems by hexavalent chromium is worldwide of major environmental concern, especially in South Africa which is the largest producer of chromite and ferrochrome. Therefore, the pre-treatment of these wastes before landfill is of great importance to prevent the contamination of the ecosystems. In the present study, vermiculite, a natural occurring mineral, has been tested for its adsorption effectiveness in removing Cr(VI) from ferrochrome dust leachate. Batch adsorption studies have been carried out to determine the effect of pH, contact time and adsorbent dose on the removal of Cr(VI). The process was found to be highly pH dependent. The optimum conditions for the removal were found to be at pH 1.5, contact time 2 hours and adsorbent dose 10 g.L-1. According to kinetic and isotherm studies, the process is best fitted by the pseudo-second order kinetic model, and to both Langmuir and Freundlich isotherms. The maximum adsorption capacity was found to be 23.25 mg.g-1. Thermodynamic parameters show the spontaneous and endothermic nature of Cr(VI) adsorption onto vermiculite. / Dissertation (MSc)--University of Pretoria, 2011. / Materials Science and Metallurgical Engineering / unrestricted

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Weathering of biotite supplies nutrients such as K+ and weathers into vermiculite/montmorillonite or kaolinite, which have varying influences on soil properties and characteristics. This study was conducted to determine if the weathering mechanisms of biotite are controlled by temperature, or if other factors, such as vegetation or leaching intensity dominantly influence the weathering process. A column study investigation was conducted to assess the influence of different acids, simulated rainfall rates, surface horizons, and temperature on the weathering and cation release of biotite. A field investigation was also conducted on the clay mineral fraction of soils in Grayson County, VA formed above biotite granite. Selected acid leachates did show a greater Al+3, Fe+2, and Si+4 release with organic acids (ascorbic, citric, and fulvic) than that with hydrochloric acid treatment at high leachate rates. Loss of K+ is greater with ascorbic acid than all other acids at high leachate rates. Leachate rate interaction with low temperature was an influencing factor in cation release. Field investigations revealed a greater weathering intensity at high elevations evidenced by; (i) higher clay content, (ii) a dominance of 2:1 minerals, (iii) greater surface area in the upper horizons, (iv) minerals indicative of later stages in the biotite weathering mechanism, and (v) precipitation of halloysite in the C horizon at the high elevation site where temperature is lower and a suspected higher leaching intensity occur. / Master of Science

Les travaux de recherche portent sur un procédé d’élaboration par pressage de joints en vermiculite et sur l’étude de la structure multiéchelle et les propriétés d’étanchéité des joints. La vermiculite a été traitée aux ultrasons pour obtenir des poudres. Des joints ont été élaborés à partir des poudres de vermiculite. Les pores interparticulaires du joint sont connectés et orientés préférentiellement d’après les observations par MEB. Leur dimension mesurée par porosimétrie mercure diminue avec l’augmentation de pression.Les propriétés d’étanchéité ont été étudiées aux températures inférieures à 800°C en mesurant les taux de fuites à l’hélium, ainsi que les taux d’écrasement et de décompression. La fuite comprend deux composantes : la fuite de contact déterminée par l’interface entre les joints et la bride, et la fuite de perméabilité liée à la porosité des joints. / Vermiculite gasket materials were obtained from powders obtained by sonication of vermiculite. The materials were formed of oriented stacked vermiculites platelets. The porous structure characterized by mercury porosimetry, SEM observations, was described. Vermiculite gaskets obtained by pressing powders, were studied for their sealing properties: leak rate and elastic resiliency.

Neste trabalho estudou-se o efeito de três diferentes tratamentos químicos utilizando- se soluções aquosas de LiCl, NaCl, e HCl sobre o inchamento, a distribuição de tamanho de partículas e a capacidade de troca catiônica (CTC) de uma vermiculita proveniente da jazida de Paulistana, localizada no Estado do Piauí, visando seu uso em compósitos de matriz polimérica. Para os tratamentos com sais inorgânicos foram utilizadas várias concentrações de LiCl e NaCl a 90°C por 144 horas, permitindo a secagem da solução de tratamento. Para o tratamento ácido foram utilizadas soluções 2M de HCl à temperatura ambiente, utilizando tempos de tratamento de 2 a 10 horas. Após os tratamentos, as amostras foram submetidas a agitação mecânica intensa em dispersor de alta energia de cisalhamento (24000 RPM). Todos os tratamentos empregados resultaram em aumentos nos índices de inchamento e reduçães nos tamanhos de partícula em diferentes graus. Os maiores inchamentos antes da agitação mecânica foram observados nas amostras tratadas com soluções 0,8M de LiCl sem lavagem (4 a 5 vezes a da prova em branco). Após agitação mecânica, os maiores inchamentos foram observados nas amostras tratadas com soluções 2M de HCl por 5 horas (11 vezes a da prova em branco). No entanto, após o processo de secagem não foi possível atingir-se os mesmos valores de inchamento. A diminuição mais importante no tamanho de partícula foi observada nas amostras tratadas com soluções 2M de HCl durante 5 horas, enquanto que as quedas mais significativas nos valores de CTC foram obtidas com as amostras tratadas com soluções 2M de HCl (CTC crescentes com o aumento do tempo de tratamento). Foi analisado o efeito da incorporação de vermiculita tratada acidamente em uma matriz polimérica de polipropileno (PP). A presençaa dessa vermiculita provocou um alto nível de degradação na matriz de PP, com a consequentemente perda de propriedades mecânicas. Esta degradação pode ser atribuída à formação de sítios ácidos nas partículas de vermiculita gerados pelo ataque do HCl, bem como à presença de HCl residual da solução de tratamento. / In the present work, the effect of three different chemical treatments using inorganic solutions of LiCl, NaCl, and HCl on the swelling, particle size distribution, and cation exchange capacity (CEC) of a vermiculite clay was studied. The clay is originary from Paulistana mine, located in the State of Piauí, Northeastern Brazil, and the final purpose of the treatment of the clay was its use in polymer-matrix composites. For the inorganic salts treatments, several solutions of NaCl and LiCl at different concentrations were used, at 90°C for 144 hours, allowing the treatment solution to dry out. For the acid treatment, 2M HCl solutions at room temperature were used, using treatment times of 2 to 10 hours. After the treatments, all the samples were subjected to intense mechanical stirring in the high shear energy disperser (24000 RPM). The results showed that all treatments resulted in increases in the rates of swelling and reduction in the mean particle sizes, in different degrees. The largest swelling before mechanical stirring was observed in samples treated with solutions of 0.8M LiCl without washing (4 to 5 times that of the untreated sample). After mechanical desagglomeration, the highest swelling was observed in samples treated with solutions 2M HCl for 5 hours (11 times that of the untreated sample). However, after drying, it was no longer possible to achieve the same values of swelling. The most significant decrease in particle size was observed in samples treated with solutions 2M HCl for 5 hours, whereas the most significant reduction in the CEC values were also obtained with the samples treated with solutions 2M HCl (CEC increasing with the time of treatment). Finally, the effect of the addition of the acid treated vermiculite to a polymeric matrix of polypropylene (PP) was examined. The evaluation of the resultant composite specimens indicated that the presence of vermiculite caused a high level of degradation of the PP matrix, with the consequent loss of mechanical properties. This degradation can be attributed to the formation of acidic sites on the vermiculite particles, generated by the direct attack of HCl, and the presence of residual HCl from the treatment solution.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Nos últimos 20-30 anos polímeros biodegradáveis vêm sendo estudados e desenvolvidos e atualmente já são comercializados. Contudo, o custo, a processabilidade e algumas propriedades ainda dificultam a penetração desses polímeros no mercado e a competição com as chamadas commodities. Não são poucos os autores que se dedicam a desenvolver aditivos e formulações para superar essas limitações. Desta forma, esta Tese se dedicou ao desenvolvimento de compósitos de Ecobras, fabricado pela Basf e comercializado pela Corn Products, utilizando como carga mineral resíduo da extração da bauxita, no município de Santa Luzia/PB, o qual consiste em sua totalidade de vermiculita. Esta vermiculita foi quimicamente modificada com sais de alquil fosfônio para melhorar a compatibilidade com a matriz polimérica e também espaçar as camadas de aluminossilicato. De fato, a modificação com o brometo de hexadecil tributil fosfônio resultou na esfoliação da vermiculita tornando-a potencialmente apropriada para a obtenção de nanocompósitos. A preparação dos compósitos foi realizada pelo método de intercalação no estado fundido e foram comparadas a utilização da câmara interna de mistura e da mini extrusora de dupla rosca, sendo esta última mais eficaz na dispersão da vermiculita, conforme revelado pela microscopia eletrônica de varredura, difração de raios-X e reometria de placas. O grau de dispersão também foi influenciado pela estrutura química do modificador da vermiculita e pelo teor dessa carga incorporada à matriz. Teores mais elevados levaram a formação de aglomerados, enquanto a modificação da carga implicou na formação de micro e nanocompósitos. Ainda houve alterações das propriedades térmicas com aumento dos valores da temperatura de transição vítrea, de cristalização e fusão, embora o grau de cristalinidade tenha sido mantido. Nitidamente, foram obtidos materiais mais rígidos, com maior módulo e menor capacidade de deformação. Cerca de 58% de perda de massa foi observada para os micro e nanocompósitos obtidos após 17 semanas de enterro em solo simulado para avaliação da biodegradabilidade, valor bem próximo ao Ecobras puro. De modo geral, a incorporação das diferentes vermiculitas retardou nas primeiras semanas a biodegradação, provavelmente em função de modificações na estrutura cristalina, conforme sugerido pelos maiores valores de temperatura de fusão observados durante o acompanhamento do processo de biodegradação. No entanto, após 7 semanas os perfis de biodegradação dos micro e nanocompósitos se aproximaram bastante do Ecobras puro. Desta forma, foi possível nesta Tese obter um nanocompósito de Ecobras com vermiculita modificada com brometo de hexadecil fosfônio utilizando ferramentas comuns de processamento no estado fundido com biodegradabilidade próxima ao polímero de partida, porém mais rígido e menos deformável / In the last 20-30 years biodegradable polymers have been studied and developed and currently are already commercialized. However, cost, processability and some properties still avoid the penetration of such polymers on the market and the competition with the so-called commodity. There are few authors who are dedicated to developing additives and formulations to overcome these limitations. Thus, this thesis is devoted to the development of Ecobras composites, blend of PBAT and starch manufactured by BASF and commercialized by Corn Products, using as mineral filler a residue of bauxite extraction from Santa Luzia / PB, which consists entirely of vermiculite. The vermiculite was chemically modified with alkyl phosphonium salts to improve compatibility with the polymer matrix, and also to increase the space between aluminosilicate layers. In fact, its modification with hexadecyl tributyl phosphonium bromide promoted the exfoliation of vermiculite making it potentially suitable for obtaining a nanocomposite. The preparation of the composites was performed by the melt intercalation technique. Internal mixing chamber and a twin screw mini-extruder were compared as processing tool, the latter was more effective in dispersing the vermiculite, as revealed by scanning electron microscopy, X-ray diffraction and plate rheometry. The degree of dispersion was also influenced by the amount and chemical structure of the vermiculite. Higher filler levels led to formation of agglomerates, while filler modification led to formation of micro and nanocomposites. There were changes in the thermal properties with increasing temperature values of glass transition, crystallization and melting, although the degree of crystallinity has been retained. Clearly, stiffer materials were obtained, with a higher modulus and low strain capacity. About 58% of weight loss was observed for micro and nanocomposites after 17 weeks of burial in simulated soil for evaluation of biodegradability, very close to pure Ecobras value. Generally, the incorporation of different vermiculite delayed biodegradation in the first weeks, probably due to changes in crystalline structure as suggested by the higher melting temperature values observed during the monitoring of the biodegradation process. However, after seven weeks of the micro and nanocomposites biodegradation profiles approached quite to pure Ecobras. Thus, it was possible in this work obtain a Ecobras nanocomposite with hexadecyl tetrabutyl phosphonium bromide modified vermiculite prepared by melt intercalation technique using common processing tools and with biodegradability close the starting polymer, but more rigid and less deformable

Understanding how natural Cs, Rb, and K have been redistributed in Savannah River Site (SRS) soils during pedogenesis is important to understanding how radiocesium released to the soils will behave over the long term. In this effort, it is important to distinguish K that has participated in mineral-water reactions from that still residing in primary silicate structures, particularly in the clay fraction. The impact of different degrees of acid extraction on K and radiogenic Ar in bulk soil and in clay from five SRS soil samples has been determined. Strong treatment (50% HNO3, three hours, 100°C) releases K from primary minerals, as shown also by a concomitant release of radiogenic Ar, but a more moderate treatment (6% HNO3, three hours, 80°C) does not release K. K in the clay fraction is mostly nonexchangeable K in remnants of primary mica, and clay K-Ar age values near 300 Ma indicate the mica originated in the Appalachian mountain belt.

Bibliography: leaves 178-186 / 186 leaves, [9] leaves of plates : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1989

Thesis (Ph. D.)--University of Adelaide, Dept. of Physical and Inorganic Chemistry, 1989. / Includes bibliographical references (leaves 178-186).