Made available in DSpace on 2014-12-17T14:48:13Z (GMT). No. of bitstreams: 1 KievLAP_DISSERT.pdf: 5028363 bytes, checksum: de436550c722f471b673e76a33619bd0 (MD5) Previous issue date: 2012-12-27 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Este trabalho apresenta um estudo da estabiliza??o qu?mica de um solo com cimento e a avalia??o do uso de cinza de lodo como aditivo estabilizante, investigando o comportamento mec?nico das misturas solo-cimento e solo-cimentocinza para uso em base e sub-base de pavimentos rodovi?rios. Os materiais envolvidos no estudo foram: solo silte-areno argiloso, cimento Portland comum e lodo esgoto calcinado de uma lagoa anaer?bia. A metodologia envolveu o estudo dos materiais, com ensaios de caracteriza??o geot?cnica do solo e mec?nica das misturas solo-cimento e solo-cimento-cinza de lodo (SCCLE). As moldagens dos corpos de prova para o ensaio de compacta??o do solo e solo-cimento foram nas energias normal, intermedi?ria e modificada e os teores de cimento adicionados ao solo foram 0%, 3%, 6% e 9%, no qual para cada tra?o/energia foram moldados 3 cp?s, sendo nesta etapa confeccionados 36 cp?s. A adi??o em percentual do cimento ao solo foi feita em rela??o massa do solo seco. Com os pontos da umidade retirados da curva de compacta??o do solo na energia normal, foram moldados 5 cp?s para o ensaio de CBR. O melhor resultado foi o do cp com umidade pr?xima a da umidade ?tima. Seu valor foi de 6,13% e obteve-se expans?o de 0,02%. Foi verificado a partir dos resultados do ensaio de CBR do solo a necessidade de sua estabiliza??o tendo em vista que para o uso em camadas de vi sub-base e base s?o exigidos valores m?nimos de 20% e 80% respectivamente segundo a especifica??o do DNER ES 301/97. No estudo da estabiliza??o do solo foi utilizada como refer?ncia a resist?ncia m?nima ? compress?o simples para base e sub-base que ? de 21 kgf/cm? de acordo com a especifica??o de servi?o ES 305/97 do DNER. O tra?o T4I foi o escolhido para adi??o de cinza, composto por 91% de solo + 9% de cimento na energia intermedi?ria, cuja resist?ncia foi de 22,61 kgf/cm? e este valor lhe credenciou aos padr?es de camadas de base e sub-base. A adi??o cinza de lodo foi feita nos percentuais de 5%, 10%, 20% e 30% e o percentual de cinza foi calculado em rela??o ? massa do solo seco, tendo sido nesta fase moldados 12 cp?s. Foi observado incremento da RCS em todos os tra?os contendo a cinza, sendo mais satisfat?rio o tra?o T7I com um ganho de 25,87% de resist?ncia em rela??o ao tra?o T4I de refer?ncia contendo solo-cimento. A partir do estudo de estabiliza??o podemos inferir que o solo n?o ? expansivo podendo ser usado em camadas de pavimentos ap?s a estabiliza??o com cimento e a cinza de lodo pode ser usada como aditivo estabilizante, visando reduzir os custos com o cimento e diminuir a polui??o com o descarte do res?duo no meio ambiente

Orientador: Jorge Luís Akasaki / Resumo: A indústria cimenteira tem passado por pressões cada vez mais constantes, referentes aos impactos ambientais causados pela emissão de gases na produção de cimento Portland e, atualmente, pela crise econômica que o setor da construção civil vem passando. Estes acontecimentos têm levado pesquisadores a investigarem novas formas de se obter aglomerantes alternativos, de maneira mais sustentável e econômica. Aliada a este problema, está a geração de resíduos de biomassa provenientes da atividade agroindustrial. Uma das alternativas criadas para a redução da emissão de CO2 e do consumo de cimento Portland é a produção de novos aglomerantes à base de argilas calcinadas. Além de reduzir significativamente o teor de cimento em matrizes cimentantes, a utilização destes aglomerantes proporciona economia de energia e menor temperatura de queima, liberando menos CO2 que o cimento durante sua produção. Assim, o objetivo desta pesquisa foi produzir e caracterizar um novo aglomerante formado pela mistura da cinza do bagaço da cana-de-açúcar e argila calcinada, denominada de CBA. A proporções entre bagaço, argila e água foram de 1,000:0,150:0,125, em massa, respectivamente. Após a calcinação, a cinza passou por processo de peneiramento e moagem. O estudo foi divido em três principais etapas: produção e caracterização da CBA; estudo da reatividade da CBA em pastas e; análise do comportamento mecânico de argamassas produzidas com substituição parcial de cimento por CBA. Inicialmente, a cinza p... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Cement industry has been suffering pressure increasing, related to environments impacts due gas emission promoted by Portland cement production and, furthermore, due the currently crisis in civil construction sector that has been passing through. These events have lad researchers to investigate new forms of obtaining alternative binders more sustainable and economic. Allied to this problem, there is to biomass residues generation from agro-industry activity. One of the alternatives created to reduce the CO2 emissions and Portland cement consumption is the manufacturing of new binders based on thermally calcined clay. Besides it to reduce significantly cement content in cementitious matrix, these binders provides energy saving and lower calcination temperature, realizing less CO2 than Portland cement related to its production. Thus, the main of this objective of this study was to produce and characterize a new binder, composed by sugar-cane bagasse ash and calcined clay (SCA). The content of sugarcane bagasse, clay and water in mixture was 1/0.15/0.125, by mass, respectively. After calcination procedure, SCA passed through sieving and mill process. The study was separated in three stages: characterization of SCA; SCA reactivity study in pastes and; mechanical behavior analysis in cement mortars produced with partial cement replacement by SCA. Initially, SCA was characterized by physicochemical tests, being X-ray diffraction, thermogravimetric analysis, scanning electron micros... (Complete abstract click electronic access below) / Mestre

Submitted by Alan Henrique Vicentini (vicentini.alanh@gmail.com) on 2018-07-19T12:54:56Z No. of bitstreams: 1 ALAN HENRIQUE VICENTINI - DISSERTAÇÃO - ENGENHARIA CIVIL.pdf: 4878364 bytes, checksum: 78fb1552972193124495e015f63d3b91 (MD5) / Approved for entry into archive by Cristina Alexandra de Godoy null (cristina@adm.feis.unesp.br) on 2018-07-19T13:49:52Z (GMT) No. of bitstreams: 1 vicentini_ah_me_ilha.pdf: 4878364 bytes, checksum: 78fb1552972193124495e015f63d3b91 (MD5) / Made available in DSpace on 2018-07-19T13:49:52Z (GMT). No. of bitstreams: 1 vicentini_ah_me_ilha.pdf: 4878364 bytes, checksum: 78fb1552972193124495e015f63d3b91 (MD5) Previous issue date: 2018-06-04 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / A indústria cimenteira tem passado por pressões cada vez mais constantes, referentes aos impactos ambientais causados pela emissão de gases na produção de cimento Portland e, atualmente, pela crise econômica que o setor da construção civil vem passando. Estes acontecimentos têm levado pesquisadores a investigarem novas formas de se obter aglomerantes alternativos, de maneira mais sustentável e econômica. Aliada a este problema, está a geração de resíduos de biomassa provenientes da atividade agroindustrial. Uma das alternativas criadas para a redução da emissão de CO2 e do consumo de cimento Portland é a produção de novos aglomerantes à base de argilas calcinadas. Além de reduzir significativamente o teor de cimento em matrizes cimentantes, a utilização destes aglomerantes proporciona economia de energia e menor temperatura de queima, liberando menos CO2 que o cimento durante sua produção. Assim, o objetivo desta pesquisa foi produzir e caracterizar um novo aglomerante formado pela mistura da cinza do bagaço da cana-de-açúcar e argila calcinada, denominada de CBA. A proporções entre bagaço, argila e água foram de 1,000:0,150:0,125, em massa, respectivamente. Após a calcinação, a cinza passou por processo de peneiramento e moagem. O estudo foi divido em três principais etapas: produção e caracterização da CBA; estudo da reatividade da CBA em pastas e; análise do comportamento mecânico de argamassas produzidas com substituição parcial de cimento por CBA. Inicialmente, a cinza passou por ensaios de caracterização físico-química, sendo realizados os ensaios de difração de raios-X, termogravimetria, microscopia eletrônica de varredura, espectroscopia de infravermelho por transformada de Fourier, fluorescência de raios-X e granulometria a laser. A segunda etapa consistiu em avaliar a ação da cinza em pastas de cal e de cimento, através dos ensaios de espectroscopia de infravermelho por transformada de Fourier, microscopia eletrônica de varredura e termogravimetria. A última etapa baseou-se em avaliar a consistência e o comportamento mecânico de resistência à compressão de argamassas produzidas com substituição de cimento por CBA nos teores de 10%, 20%, 30% 40% e 50%. Foi possível substituir cimento por CBA em até 50% em massa, mostrando que o material possui grande potencial de ser utilizado na produção de aglomerantes, além de ser energeticamente viável, devido à geração de calor durante sua produção. / Cement industry has been suffering pressure increasing, related to environments impacts due gas emission promoted by Portland cement production and, furthermore, due the currently crisis in civil construction sector that has been passing through. These events have lad researchers to investigate new forms of obtaining alternative binders more sustainable and economic. Allied to this problem, there is to biomass residues generation from agro-industry activity. One of the alternatives created to reduce the CO2 emissions and Portland cement consumption is the manufacturing of new binders based on thermally calcined clay. Besides it to reduce significantly cement content in cementitious matrix, these binders provides energy saving and lower calcination temperature, realizing less CO2 than Portland cement related to its production. Thus, the main of this objective of this study was to produce and characterize a new binder, composed by sugar-cane bagasse ash and calcined clay (SCA). The content of sugarcane bagasse, clay and water in mixture was 1/0.15/0.125, by mass, respectively. After calcination procedure, SCA passed through sieving and mill process. The study was separated in three stages: characterization of SCA; SCA reactivity study in pastes and; mechanical behavior analysis in cement mortars produced with partial cement replacement by SCA. Initially, SCA was characterized by physicochemical tests, being X-ray diffraction, thermogravimetric analysis, scanning electron microscope, Fourier transform infrared spectroscopy analysis, X-ray fluorescence spectroscopy and laser granulometry analysis. The second stage consisted of to evaluate SCA behavior in lime/SCA pastes and Portland cement/SCA pastes systems, through Fourier transform infrared spectroscopy, scanning electron microscope and thermogravimetric analysis. The third and last stage consisted of to evaluate the plastic consistence and mechanical behavior by compressive strength in mortars produced with partial cement replacement by SCA in 10%, 20%, 30%, 40% and 50% contents, by mass. It was possible replace cement by SCA in up to 50% content, showing that this material has potential to be widely utilized in production of binders, besides being energetically viable, due to the heat generation during SCA production. / CNPq: 830017/2001-1

Made available in DSpace on 2016-12-08T17:19:36Z (GMT). No. of bitstreams: 1 PRE-TEXTUAIS.pdf: 48578 bytes, checksum: 21f78cab7ee8f139f12bf814c8bfa87f (MD5) Previous issue date: 2010-07-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work describes the results of an investigation on the possible applications of ground waste calcined clay bricks (WCB) for use as an active partial replacement for Portland cement in mortars. The investigation has been carried out using a full factorial design for experimental design. For the study, the physical and mechanical properties along their durability of mortar produced with WCB were investigated and the results presented. Mortar mixtures were prepared using WCB as the partial replacement of Portland cement at the level 10%, 20% and 30 wt.% with water/cement ratios of 0.45, 0.55 and 0.65. The necessary data for establishing a mix proportion design and a quality control method are obtained. Properties of fresh (consistency index and specific gravity) and hardened (7-day, 28-day and 120-day compressive strength, 28-day water absorption and 28-day alkali content) mortars were evaluated on specimens. Such statistical modeling is discussed against qualitative X-ray diffraction and microstructures of some selected samples were studied using SEM. Several empirical equations, surface and contour plots for the physicalmechanical properties of fresh and hardened recycled mortar with WCB as replacement content were obtained via regression analysis. The influence of level of WCB on the properties has been established, and its suitability for use in a mortar application has been assessed. The consistency decreased in parallel to an increase in the proportion of WCB. Specific gravity of mortars was far lower than that of normal no replacement mortars. A given 28-day compressive strength (21 MPa to 37 MPa) can be achieved at several water/cement ratio and the replacement contents up to 30 wt. %, thus producing na economical mixture mortar with WCB and lower cement Portland content. XRD and SEM analyses results indicated the presence of quartz, calcite, ettringite, portlandite, and silicates in recycled mortars. / Este trabalho apresenta os resultados da investigação do uso de rejeitos particulados de tijolos (RPT) na forma de pó, proveniente de tijolos de cerâmica vermelha, como substituinte parcial do cimento Portland, na produção de argamassas para construção civil. O estudo foi realizado adotando-se o projeto fatorial completo 32 acoplado com técnicas de metodologia de superfícies de resposta. Foram preparadas argamassas usando RPT em níveis de 10%, 20% e 30% (em massa), em substituição ao cimento Portland, com os níveis de relação água/cimento de 0,45, de 0,55 e 0,65. As misturas foram curadas por períodos de 7, 28 e 120 dias. As propriedades das argamassas contendo RPT no estado fresco foram avaliadas: massa específica e índice de consistência. As propriedades avaliadas das argamassas com RPT no estado endurecido foram: resistência à compressão (7, 28 e 120 dias), absorção de água aos 28 dias e teor de álcalis (CaCO3) aos 28 dias. Os resultados obtidos através da metodologia estatística foram confrontados com as análises de difração de raios X (DRX) e microscopia eletrônica de varredura (MEV) de amostras selecionadas. Foram obtidas equações empíricas, gráficos de superfície de resposta e de contorno para as propriedades físico-mecânicas das argamassas com RPT no estado fresco e endurecido, por meio de análise de regressão. A consistência diminuiu linearmente com o aumento da quantidade de RPT incorporado em substituição ao cimento Portland. A massa específica das argamassas contendo RPT foi menor do que na argamassa sem RPT. Foi possível obter argamassas com resistências à compressão aos 28 dias de 21 MPa a 37 MPa para vários níveis de relação água/cimento em até 30 % de substituição de cimento Portland por RPT. Dessa forma, é possível produzir argamassas econômica e ambientalmente viáveis, a partir da substituição parcial de cimento Portland por RPT, nas dosagens estudadas. As análises de DRX e de MEV indicaram a presença do quartzo, da calcita, da etringita, da portlandita, silicatos e porosidade em amostras de argamassas selecionadas, de modo que foi possível relacionar as mesmas com a resistência à compressão das argamassas.

Este trabalho tem por objetivo o estudo de concretos leves com agregados inovadores de argila vermelha calcinada e subprodutos agroindustriais. A argila utilizada na pesquisa foi caracterizada por meio das técnicas de limites de liquidez (LL) e plasticidade (LP), análise granulométrica, análise química e difração de raios X (DRX). Foram confeccionados corpos de prova de argila vermelha calcinada com incorporações de serragem de madeira, cinza do bagaço da cana-de-açúcar e silicato de sódio. Os corpos de prova de argila vermelha calcinada, queimados à temperatura de 900 °C, foram caracterizados por meio da avaliação da retração linear, absorção de água, porosidade aparente, massa específica aparente, expansão por umidade e resistência à compressão. Após a caracterização dos corpos de prova de argila vermelha calcinada, foram produzidos dois tipos de agregados, sendo o primeiro composto por 57% de argila e 43% de cinza do bagaço de cana-de-açúcar, conformados com água e silicato de sódio (proporção 1:1), e o segundo composto por 70% de argila e 30% de serragem de madeira. Os corpos de prova de concreto leve foram caracterizados pelos ensaios de slump, massa específica fresca, resistência à compressão, módulo de deformação, retração por secagem, absorção de água, índice de vazios e massa específica aparente e condutividade térmica. Os resultados desta pesquisa indicam a viabilidade da produção de agregados leves de argila vermelha calcinada com incorporações de subprodutos agroindustriais para utilização em concretos, uma vez que, mesmo com grande quantidade de utilização de subprodutos agroindustriais na produção dos agregados leves, os concretos produzidos com esses agregados apresentaram características similares aos concretos produzidos com agregados comerciais, apresentando um ganho econômico e energético significativo. / This paper aims to study lightweight concrete with innovative calcined clay lightweight aggregates made with agro-industrial by-products. The clay used in this research was characterized by techniques of liquid and plastic limits, particle size analysis, chemical analysis and X-ray diffraction (XRD). Calcined clay specimens were made with incorporations of wood sawdust, sugar cane ash and sodium silicate. These specimens, burned at a temperature of 900°C, were characterized by evaluating of linear shrinkage, water absorption, apparent porosity, specific mass, moisture expansion and compressive strength. After characterization of calcined clay specimens, two types of calcined clay lightweight aggregates with agro-industrial by-products were produced, wherein the first made with 57% of clay and 43% of sugar cane ash, mixed with water and sodium silicate (proportion 1:1) and the second made with 70% clay and 30% wood sawdust, mixed with water and burned at 900 °C. Specimens of lightweight concrete were characterized by slump test, fresh specific mass, compressive strength, modulus of elasticity, water absorption, voids and bulk density and thermal conductivity. Results of this research indicates the viability to produce calcined clay lightweight aggregates made with agro-industrial by-products to use in concrete, even using large amount of agro-industrial by-products, once concretes made with lightweight aggregates with agro-industrial by-products presented similar characteristics than those made with commercial aggregates, presenting significant energetic gain.

The diploma thesis focuses on new possibilities to reduce raw materials costs in production of heat-resistant cordierite ceramics. Cordierite is very often used as furnace wagon lining and for production of blazing utilities for its high resistance against temperature changes. The thesis gives complete overview of cordierite material. It includes description of different production technologies for form-pieces preparation, raw materials for their production and their applications. The goal of performed laboratory measuring in an experimental part was to verify and prove a possibility of reducing raw-material costs in production of cordierite ceramics by using cheaper preferably secondary raw materials.

MENVSC / Department of Ecology and Resource Management / In this study, the efficacy of bentonite clay, pre-treated magnesite and their nanocomposite on the removal of Congo red dye from aqueous solution was explored. Batch experimental approach was a technique used to fulfil the goals of this study. A number of operational parameters were optimised, and they include effects of shaking time, adsorbent dosage, initial CR dye concentration, initial solution pH and temperature. Findings of the study revealed that the optimum conditions that are suitable for the removal of CR dye are 20 minutes, 0.5 g of dosage, 120 mg/L, 250 rpm, and pH = 7. This has achieved > 99% removal efficacy of CR dye for the nanocomposite and reduced it to below the South African National Standard (SANS) 241 water quality specifications. Furthermore, kinetic studies revealed that bentonite clay, pre-treated magnesite, and their nanocomposite fitted very well to pseudo-second-order kinetics than pseudo-first-order kinetics. The regression analysis was observed to be 1, 0.9, and 0.9 for bentonite clay, pre-treated magnesite, and their nanocomposite respectively. Adsorption isotherms indicated that CR removal by bentonite clay, pre-treated magnesite, and their nanocomposite fitted well to Langmuir adsorption isotherm than the Freundlich adsorption isotherm hence indicating mono-layer adsorption. Thermodynamic values for CR removal were observed to be: ΔH0 (kJ mol-1) = 43.86, 30.67, and 24.88 for bentonite clay, pre-treated magnesite, and their nanocomposite respectively. This indicates that the reaction is endothermic. The positive ΔS0 (kJ mol-1 K-1) values for bentonite clay and 25 °C for pre-treated magnesite confirms that there is an increase in the degree of randomness at solid/solution interface during the removal of CR ions from aqueous solution. The negative values of ΔG0 (kJ mol-1) for 40 – 70 °C on bentonite and the entire range for the nanocomposite suggest the spontaneity and feasibility of CR adsorption whereas the positive ΔG0 (kJ mol-1) for bentonite clay suggest a non-spontaneous nature of adsorption. As such, pre-treated magnesite/bentonite clay nanocomposite demonstrated superior adsorption capacity in relation to individual materials and other materials reported in literature. / NRF

Made available in DSpace on 2014-07-29T15:03:31Z (GMT). No. of bitstreams: 1 adriano mendes.pdf: 4708776 bytes, checksum: 4bc099a31f3941241f5dd5294da28bba (MD5) Previous issue date: 2010-09-28 / The rolled compacted concrete (RCC) is a still relatively new technique, but with growing volume of use, a fact generated by its technical and economical advantages, requiring more studies in order to use with greater efficiency, safety and economy. This work deals with the RCC with high levels of replacement and addition of part of the Portland cement by calcined clay pozzolan, aiming to analyze and quantify the improvements of the concrete properties and reach a satisfactory level of use, which allows for improvement or maintenance of the properties with a lower consumption of cement per cubic meter. So its impacts on the properties of RCC for this type of mineral addition were studied for the substitution levels adopted, checking the influence on the properties of the fresh concrete in the consistency and the density. For the hardened concrete some mechanical properties and durability were evaluated by compressive and tensile strength, capillarity and immersion by water absorption, test of permeability by water and ultrasound test. The use of calcined clay come together with the needs of the cement production for the construction of dams in the north of the country, as the case of Santo Antônio / RO, because its place is far removed from major industries and cement production slag, fly ash and silica fume, requiring the study of materials to enhance the production of cement. As an important result obtained with this research, it was found that substitution ranging from 27% to 50% achieved the best results, regarding the applicability of this material on the surveyed properties. / O Concreto Compactado com Rolo (CCR) é uma técnica ainda relativamente nova, porém com volume de utilização crescente, fato gerado pelas suas vantagens econômicas e técnicas, requerendo assim mais estudos para embasar o seu uso com maior eficiência, segurança e economia. O presente trabalho trata do CCR com elevados teores de substituição e de adição de parte do volume de cimento Portland por pozolana de argila calcinada, objetivando analisar e quantificar as melhorias das suas propriedades e chegar a um teor satisfatório de utilização, o qual possibilite melhoria ou manutenção das propriedades avaliadas com um menor consumo de cimento por metro cúbico. Desta forma foram avaliados os impactos nas propriedades do CCR para este tipo de adição mineral, nos teores adotados, aferindo a influencia nas propriedades do concreto no estado fresco quanto à consistência e massa específica. No estado endurecido algumas propriedades mecânicas e de durabilidade foram analisadas através da resistência à compressão e à tração por compressão diametral, a absorção de água por capilaridade e por imersão, a permeabilidade à água e ensaio de ultrassom. O uso da argila calcinada vem ao encontro das necessidades da produção de cimento para as usinas em construção na Região Norte do país, como é o caso de Santo Antônio / RO, pois se trata de uma obra muito distante das grandes indústrias cimenteiras e da produção de escória, cinza volante e sílica ativa, o que requer a investigação de materiais para aperfeiçoar a produção de cimento. Como resultado importante obtido na pesquisa em questão, verificou-se que a substituição oscilando entre 27% a 50% atingiu os melhores resultados quanto à aplicabilidade desse material nas propriedades pesquisadas.

PhDENV / Department of Ecology and Resource Management / Some industries such as textiles, ceramics, paper and printing are known to use significant amounts of dye to colour their products and during the colouring process, certain quantities of dyes are absorbed by the products, and some of them end up in wastewater. Depending on their application, some synthetic dyes are designed to be chemically or biologically resistant and their presence in the environment can cause severe environmental problems because of their colour impartation to water bodies. Therefore, proper treatment is required to remove these pollutants from wastewater before discharge into the environment. In this thesis, the potential of dye removal from wastewater by calcined magnesite, halloysite nanoclay and calcined magnesite - halloysite nanoclay composite was evaluated. To this end, the study was subdivided to four segments. The first segment of the study focused on evaluating the efficiency of using calcined magnesite to remove Methylene Blue (MB), Direct Red 81 (DR81), Methyl Orange (MO) and Crystal Violet (CV) dyes from aqueous systems using a batch study. To achieve that, several operational factors like residence time, adsorbent dosage, dye concentration and temperature were appraised. The adsorbent was subjected to different kinds of physicochemical characterization to determine the various characteristics that would assist in the dye uptake process. Characterization results showed that the adsorbent material was highly crystalline with magnesite, periclase, dolomite, and quartz as some of the crystalline phases. The batch study proved that calcined magnesite is effective in the treatment of dye contaminated water and moreover it performed well in terms of colour removal, though exceptional results were recorded for CV removal with complete decolourisation occurring in first few minutes of contact. In terms of experimental adsorption capacity, the performance of calcined magnesite was in the order CV (14.99 mg/g) > DR81 (12.56 mg/g) > MO (0.64 mg/g) > MB (0.39 mg/g). Mechanisms of adsorption where explained by fitting the experimental data into adsorption isotherms, kinetics, and thermodynamic parameters. Neither, the Langmuir, nor the Freundlich nor the Dubinin Radushkevich, nor the Temkin model could perfectly describe the adsorption of the four dyes onto calcined magnesite, however adsorption kinetics obeyed the pseudo second order model, implying that, the dye removal process was primarily a chemical process. In accordance with the results of this study, it can be concluded that calcined magnesite can be used effectively for the removal of dyes in aqueous solution and thus can be applied to treat wastewater containing dyes. The second segment of the study focused on the removal of MB, DR81, MO and CV dyes by halloysite nanoclay. Physicochemical characterisation revealed that the nanoclay has a surface area of 42 m²/g and its ABSTRACT iv morphology is predominated by tubular structures, which exhibit some hollow rod like structures. Various important parameters namely contact time, initial concentration of dyes, dosage, solution temperature and solution pH were optimized to achieve maximum adsorption capacity and it was observed that the effect of initial pH and temperature of the aqueous solution was neglibible on removal of the four dyes. The experimental adsorption capacities towards 40 mg/L of MB, DR81, MO and CV dyes were 17.51, 14.11, 0.38, and 4.75 mg/g respectively. The results indicate that natural halloysite nanoclay is an efficient material for the removal of the selected dyes. Due to its low cost and non-toxicity, halloysite nanoclay can be considered a good replacement option of other high cost materials used to treat coloured wastewater especially in developing countries like South Africa. Having observed the performance of calcined magnesite and halloysite nanoclay individually in the removal of selected dyes, a third study was designed with the aim of preparing a nanocomposite adsorbent from the aforementioned adsorbent materials and then evaluating the synergistic influence of the mechanochemical modification by a ball miller on the removal of MB, DR81, MO and CV dyes. Physicochemical characterization was carried out to get an insight of pre- and -post adsorption characteristics of the nanocomposite material and results showed major changes which could be an indication of dye uptake by the nanocomposite material. According to the results, the nanocomposite material outcompeted its component individual constituent materials i.e (calcined magnesite and halloysite nanoclay material) in the removal of DR81, which in turn was the highest removal efficiency observed for the whole batch adsorption study recording a maximum adsorption capacity and percentage removal of 19.89 mg/g and 99.40% respectively. Experimental results fitted the Langmuir and pseudo-second order models perfectly hence demonstrating that adsorption took place on a homogenous adsorbent layer via chemisorption. In overall, the results suggested that the nanocomposite is a suitable adsorbent for decolourising industrial wastewater. Based on the overall performance of the adsorbents in removing the four dyes, it was observed that the nanocomposite material had a high affinity for DR81 dye hence it was chosen as the model dye for further application in column studies. The effect of flow rate, bed height and initial dye concentration on the removal of DR81 was investigated. Maximum bed capacity and equilibrium dye uptake were determined and break through curves were plotted. Percentage dye removal increased with decrease in flow rate and increase in bed height. The maximum capacity of column was found to be about 51.73 mg DR81 per gram of the nanocomposite adsorbent for a flow rate of 3 mL/min, initial concentration of 10 mg/L and 4 cm bed height. Data from column studies was fitted to the Thomas model and Adams-Bohart models. The comparison of the R2 values obtained from both models showed a better fit for the nanocomposite material than the individual halloysite nanoclay and calcined magnesite materials. The study revealed the applicability of calcined magnesite- halloysite nanoclay composite in fixed bed column for the removal of DR81 dye from aqueous solution. v The reuse of an adsorbent is essential in order to make the adsorption process economic and environmentally friendly. To recover the adsorbate and renew the adsorbent for further use, a chemical method of regeneration was applied by using 0.1 M NaOH as the desorbent. Regeneration with 0.1 M NaOH proved very efficient for some dyes and less efficient for others depending on the adsorbent material used at the time. The general observation was that the adsorption capacity of the adsorbent materials decreased with successive adsorption – desorption cycles. Furthermore, regeneration with NaOH, favoured the acidic dyes (DR81 and MO) more than the basic dyes (MB and CV) possibly due to electrostatic interactions between oppositely charged molecules allowing for reversible reactions to take place. The three tested adsorbents namely calcined magnesite, halloysite nanoclay and their nanocomposite thereof were applied for the treatment of real wastewater effluent from a printing and ink industry. The adsorbents performed very well in terms of colour removal as recommended by the South African standards of wastewater discharge, However, in terms of pH, calcined magnesite and the nanocomposite produced a highly alkaline solution hence wastewater neutralisation by an acid is recommended before discharge. These findings show that the two natural clay-based materials (calcined magnesite and halloysite nanoclay) and their nanocomposite thereof have a great potential for application in dye wastewater remediation since the materials used in the process are inexpensive, abundant and require minimal modifications. / NRF

M. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / For centuries the contamination of surface water has been problematic, especially in third world countries whereby socio-economic issues are prevalent. With the development of various technologies for surface water rehabilitation, adsorption has been found to be the most viable due to its lower cost implications. As such the development of innovative adsorbents which are synergistic to the low cost method have been sought. Herein, the use of fossil coral limestone from Mauritius as adsorbents for the removal of Pb(II), Cr(VI) and methylene blue is presented. The pristine material (PCLS) was thermally treated by calcination to temperatures 800°C (CLS-800) and 900°C (CLS-900) and chemically treated by using an acid HCl (ACL) and base NaOH (BCL). The optimum conditions found for chemical and thermal treatment of the pristine material were used for the one pot synthesis of magnetite and maghemite calcium carbonate based nanocomposites. The pristine fossil coral limestones were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDS), X-ray fluorescence XRF), X-ray diffractometer (XRD), Brunauer, Emmett and Teller (BET) and Fourier transformed infrared (FTIR) spectroscopy, UV visible spectrophotometer (UV/vis) and Photolumiscent spectroscopy (PL). Surface morphology of the material was found to contain an interconnected framework of pores, with a surface area of 20.45 m2/g and pore with of 4.04 nm. Thermal treatment of the material was found to increase the surface area of the materials to 64.10 and 63.28 m2/g for CLS-800 and CLS-900. The surface morphology of the calcined materials compared to the pristine were fibrous like and irregularly shaped for CLS-800 and CLS-900 respectively. The FTIR revealed the dominant surface groups to be (-C-O) and (-C=O) asymmetric stretch of the in and out of plane bend of carbonate (-CO32-), with the composition of the material being 91.76 % (-CaO) and 3.32% SrO. The thermally treated materials also exhibited vibrations of asymmetric stretch, which are characteristics of the carbonates as with the pristine material. However, EDS of the pristine compared to that of the calcined materials show a decline in the carbon and oxygen content, due to calcination. The XRD analysis confirmed the orthorhombic structure of aragonite, while CLS-800 was rhombohedral calcite with newly developed (-CaO) peaks. CLS-900 showed complete removal of CaCO3 polymorphs with more (-CaO) peaks. The surface morphology of the chemically modified samples show irregularly shaped surface. The XRD analysis confirmed that chemical treatment did convert the materials to a different polymorph. The FTIR of the chemically modified materials compared to the pristine, were found to reveal a removal of the vibrations of the asymmetric stretch associated with carbonates. However, vibrations associated with (-CaO) were observed. The SEM of the nanocomposites was observed to deviate from sphericity with variable size distribution. The materials were both red and blue shifted due to their variable sizes. Their UV/vis revealed absorption bands in the visible region. The adsorption analysis was done by varying parameters such as time, pH, concentration and temperature. The data was such that the highest capacity for the pristine material was found to be 37.24, 39.26 and 69.42 mg/g for MB, Pb(II) and Cr(VI) respectively. The removal of MB and Pb(II) pollutants were due to physical adsorption, as observed from the good fitting to pseudo first order model (PFOM). The removal of Cr(VI) was due chemisorption and the good fit on pseudo second order model (PSOM). The adsorption process was supported on a heterogeneous surface whereby multilayer adsorption could occur. Adsorption was spontaneous and feasible, exothermic for MB and Pb(II) and endothermic for Cr(VI) at all the studied temperatures as observed from thermodynamics. The adsorption of methylene blue was found to be more favourable on adsorption compared to photo-degradation Chemical modification was observed to increase adsorption and the maximum removal capacities for PCLS, ACL and BCL for Cr(VI) ions were 69.42, 65.04, 64.88 mg/g, Pb(II) ions 39.36, 74.11, 78.34 mg/g and methylene blue 37.24, 46.28, 46.39 mg/g, respectively. Uptake of Cr(VI) and methylene blue on ACL and BCL was feasible on a heterogeneous surface whereby multilayer adsorption took place. Monolayer adsorption on a homogenous surface of ACL and BCL was observed for Pb(II) uptake. The uptake of Pb(II) was exothermic on PCLS and ACL while methylene blue only on PCLS. The adsorption of Cr(VI) ions onto PCLS, ACL and BCL and methylene blue dye onto ACL and BCL were endothermic in nature. The adsorption process was spontaneous and feasible at all the studied temperatures. Thermal modification further increased the adsorption uptake of the pollutants. The recorded uptake for Cr(VI) and Pb(II) were 99.12 and 98.42 mg/g onto CLS-800 and CLS-900, respectively. The adsorption process was found to be physisorption, due to the good fit on PFOM. In addition, the adsorption occurred on a heterogeneous surface whereby multilayer adsorption was possible. The removal of Cr(VI) was found to be exothermic for both the materials and Pb(II) was found to be endothermic. The materials were tested for their reusability to up to four cycles, whereby the removal on the fourth cycle were 16.87, 63.60, 73.13 mg/g for Cr(VI), 9.87, 64.19 and 70.95 mg/g for Pb(II) on PCLS, CLS-800 and CLS-900. While the leaching test for PCLS, CLS-800 and CLS-900 for the release of Ca2+ into solution was found to be within the permissible limits of world health organisation (WHO). The as synthesized nanocomposites increase adsorption of the pollutants. Maximum capacities were found to be 345.34, 388.31, 377.92 and 375.35 mg/g for Pb(II) onto magnetite-PCLS, magnetite-CLS, maghemite-PCLS and maghemite-CLS, respectively and 308.01, 335.3, 335.29 and 335.27 mg/g for Cr(VI) onto magnetite-PCLS, magnetite-CLS, maghemite-PCLS and maghemite-CLS, respectively. From the data it was observed that the maghemite samples were much more favourable for the removal of the pollutants. The removal was due to chemical adsorption, as observed from the good fit onto PSOM and intraparticle diffusion (IPD), whereby surface adsorption was the rate limiting step. The adsorption process was heterogeneous and multilayer, while thermodynamic data reveal that adsorption was spontaneous and favourable at the studied temperature.