A reação álcali-agregado é uma manifestação patológica diretamente ligada à seleção dos materiais (cimento, agregados miúdo e graúdo, água e aditivos) que pode comprometer a durabilidade das estruturas de concreto, uma vez que a interação desses materiais e as condições ambientais é que vão conferir ao concreto determinadas propriedades ligadas à sua vida útil. A reação entre os hidróxidos alcalinos solubilizados na fase líquida dos poros dos concretos e alguns agregados reativos é lenta e resulta em um gel que, ao se acumular em vazios do concreto e na interface pasta-agregado, na presença de água, se expande, exercendo pressão interna no concreto. Ao exceder a resistência à tração do concreto, a pressão interna pode promover fissurações. A reação álcali-agregado requer a atuação conjunta de água, agregado reativo e álcalis. Sua prevenção pode ser feita a partir da eliminação de um dos fatores, ou seja, a partir do emprego de agregados inertes ou de cimentos com baixos teores de álcalis ou isolamento da umidade. Na impossibilidade de eliminar um dos fatores, medidas preventivas devem ser tomadas para o emprego de agregados reativos em obras de construção civil. Entre essas, destacam-se a utilização de cimentos com baixos teores de álcalis ou a de cimentos com adições ativas mitigadoras da reação álcali-agregado: escória de alto-forno, cinza volante, metacaulim e sílica ativa, que foi o objeto de pesquisa do presente trabalho. No programa experimental foram analisados dois tipos de agregado potencialmente reativos com os hidróxidos alcalinos: EDVDOWR e PLORQLWR_ JUDQtWLFR. O primeiro, proveniente de rocha ígnea, tem como constituintes deletérios vidro, clorofeíta, calcedônia (sílica criptocristalina), que dará origem à reação do tipo iOFDOL_VtOLFD. O agregado milonito granítico provém de rocha metamórfica, tem como constituintes deletérios quartzo microgranular, quartzo recristalizado, quartzo com extinção ondulante e quartzo e feldspato deformados, que dará origem ao tipo de reação iOFDOL_VLOLFDWR. Com o objetivo de avaliar a eficiência de adições ativas em mitigar as reações, os agregados foram combinados com 16 cimentos com adições ativas. Escória de alto-forno foi adicionada a 15%, 30%, 45% e 60% e cinza volante, a 10%, 15%, 25% e 35%, teores normalmente encontrados nos cimentos brasileiros. Metacaulim foi adicionada a 5%, 10%, 15% e 20%, e sílica ativa, a 5%, 10% e 15%, teores representativos da faixa normalmente adicionada diretamente a concretos. Todos os materiais utilizados foram caracterizados química, física e mineralogicamente, incluindo a análise petrográfica dos agregados. As barras de argamassa foram analisadas ao MEV, microscópio óptico de luz transmitida, realizaram-se ensaios de porosimetria por intrusão de mercúrio e análises térmicas para quantificar a teor de portlandita residual, e determinou-se o teor de álcalis dentro das barras após a realização dos ensaios para verificar a migração de íons de sódio. Os resultados indicam que a eficiência das adições ativas varia de acordo com a composição química e mineralógica das adições, da proporção desse material no cimento, e do grau de reatividade do agregado. / The alkali-aggregate reaction is a pathologic manifestation that can induce the premature distress and loss in serviceability of concrete structures affected. It is directly associated to the selection of materials (cement, coarse and fine aggregates, water and additives), as the interaction between these materials and environmental condition will grant the concrete some of the properties related to its service life. The slow reaction between alkali hydroxides soluble in the liquid phase within concrete pores and reactive aggregates gives rise to a gel that piles up within concrete voids and the aggregate-paste interface. In presence of water, the gel expands and exerts internal pressure in the concrete. When the internal pressure exceeds the tensile strength, cracking may come up as result. The alkali-aggregate reaction requires the action of water, reactive aggregate and alkalis altogether. Prevention can be carried out by eliminating one of these factors, i.e. employing either inert aggregates or lowalkali cements, or keeping the concrete away from moisture. Otherwise, preventive measures must be taken when reactive aggregates are used in civil construction works, such as the use of low-alkali cements or composite cements bearing alkaliaggregate- reaction mitigating admixtures: blast-furnace slag, fly ash, metakaolin and silica fume, which are the object of the present research. The experimental work included the analysis of two potentially reactive aggregates to alkali hydroxides: basalt and granite milonite. The igneous basalt carries deleterious constituents such as glass, chloropheite (cryptocrystalline silica), that will give rise to the DONDOL_VLOLFD type reaction while the metamorphic granite milonite carries micro granular, recrystallized, undulate-extinction-bearing quartz and deformed feldspar grains, that give rise to DONDOL_VLOLFDWH type reaction. Aiming at evaluating how efficient in mitigating these reactions the active admixtures are, these aggregates were mixed with 16 composite cements. The contents of admixtures followed those usually found in Brazilian industrial cements for blast-furnace slag (15%, 30%, 45%, 60%) and fly ash (10%, 15%, 25%, 35%), and those generally added directly to concrete for metakaolin (5%, 10%, 15%, 20%) and silica fume (5%, 10%, 15%). All materials were characterized for their chemical composition, physical properties and mineralogy. Petrography was carried out on the aggregates. The mortar bars were analyzed at the scanning electronic and transmitted-light optical microscopes. Mercury-intrusion porosimetry and thermal analyses were carried out to quantify residual portlandite. The alkali content within the bars was determined in order to verify migration of Na+ ions. The results show that the efficiency of active admixtures varies according to their chemical and mineralogical composition and proportioning in cement, and to the aggregate reactivity.

Submitted by Mariana Dornelles Vargas (marianadv) on 2015-05-15T13:16:30Z No. of bitstreams: 1 concreto_polimero.pdf: 4719718 bytes, checksum: 2d7016e7eb764275fea0249db0eb55eb (MD5) / Made available in DSpace on 2015-05-15T13:16:30Z (GMT). No. of bitstreams: 1 concreto_polimero.pdf: 4719718 bytes, checksum: 2d7016e7eb764275fea0249db0eb55eb (MD5) Previous issue date: 2009 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A reciclagem e a reincorporação de um rejeito em um processo produtivo são as soluções mais indicadas para o manejo da grande maioria dos resíduos, reduzindo assim custos, além de preservar recursos naturais não renováveis. A construção civil tem absorvido parte destes resíduos, transformando-os em subprodutos importantes, os quais podem ser igualmente eficientes, além de ecologicamente corretos. Dentre as aplicações mais comuns, destacam-se a incorporação de rejeitos em matrizes cimentícias e poliméricas. O concreto polímero, o qual tem como aglomerante uma resina polimérica, tornou-se uma boa opção para construção civil em aplicações onde são solicitados alto desempenho mecânico, durabilidade e cura rápida, propriedades importantes para materiais que visam a sustentabilidade das edificações. Apesar dos já comprovados elevados valores mecânicos encontrados nestes compósitos, torna-se necessário estimar e adequar as propriedades de combustibilidade com os tipos de demandas do mercado, pois tal propriedade pode comprometer sua aplicação. Para tanto, esta pesquisa tem como objetivo produzir compósitos de concreto polímero de elevada resistência mecânica, durabilidade e resistentes à ação do fogo. Os compósitos serão produzidos com uma resina poliéster insaturada reciclada a partir do PET, com incorporação de resíduos industriais, comparando-os com componentes comerciais. Para tanto, as propriedades dos compósitos serão estudadas através de ensaios de caracterização mecânica, durabilidade e microestrutura, compreendendo: resistência à compressão, resistência à tração na flexão, porosimetria por intrusão de mercúrio e MEV. Além disso, os corpos-de-prova foram submetidos a ensaios de análise térmica, com a finalidade de avaliar o comportamento das adições frente à ação do fogo e sua contribuição para a redução da flamabilidade destes compósitos. Os resultados obtidos mostraram que, as composições com 60% de adição de retardante de chamas resíduo apresentaram uma redução de 85% em relação ao tempo de propagação da chama dos compósitos sem adição de retardantes, bem como um acréscimo na sua resistência mecânica em comparação aos mesmos. / Recycling and the reincorporation of a waste in a production process are the most indicated for the management of the vast majority of waste, thus reducing costs, and, of course, preserving non-renewable natural resources. The civil construction has absorbed these wastes, turning them into important products, which can also be efficient, and environmentally correct. Among the most common applications, it can emphasize the incorporation of tailings in cementations and polymer matrices. The polymer concrete, which binder is a polymeric resin, has become a good option for construction where are required applications with high mechanical performance, durability and rapid healing, important properties for materials aimed at the sustainability of buildings. Despite the already proven high mechanical values found in these composites, it is necessary to estimate and adjust the properties of combustibility to the kinds of demands of the market, once this property may jeopardize your application. Thus, this research aims to produce polymer concrete composites of high mechanical strength, durability and resistance to the action of fire. The composites were produced with an unsaturated polyester resin from recycled PET, with the addition of industrial waste in comparison to commercial items, making them more attractive economically, and environmentally sustainable. Thus, the properties of the composites were studied by mechanical tests durability, including: compressive strength test, tensile strength, mercury intrusion porosimetry and SEM. Moreover, the samples were tested for thermal analysis in order to know the behavior of the action items with the fire and its contribution to reducing the flammability of these composites. The results obtained in the tests described above showed that, the composites with 60% in addition of waste had a reduction of 85% in the time of spread of flame, and an increase in its mechanical resistance in comparison to composite reference, with no addition of retardants.

Assunto cada vez mais em pauta nos foros nacionais e internacionais e nas comunidades ao redor do mundo, a questão ambiental tem sido a grande responsável pela geração de produtos novos. A construção de obras de infraestrutura é um dos maiores consumidores de recursos naturais, gerando uma enorme quantidade de resíduos, acaba também por ser um setor causador do impacto ambiental. Tais resíduos, se descartados de maneira incorreta geram problemas ambientais, em contraponto o descarte em aterros sanitários tem um custo bastante elevado. Partindo dessas premissas, buscar a utilização de resíduos como matéria prima para a indústria da construção de obras de infraestrutura é o objetivo global desta pesquisa, visando benefícios ambientais e econômicos. Para tal, foram utilizados a cinza volante, obtida através da queima do carvão nas termelétricas e rica em sílica e alumina e a cal de carbureto, oriunda da produção do gás acetileno e que possui grande quantidade de óxido de cálcio. Através de ensaios de laboratório, busca-se nesta pesquisa avaliar a influência da quantidade de cal e da porosidade, isoladamente, na durabilidade, resistência à tração e resistência à compressão e a relação resistência à tração/resistência à compressão, objetiva-se ainda avaliar a utilização do parâmetro porosidade/teor volumétrico de cal na estimativa de resistência e verificar a existência de uma relação única para este parâmetro versus a perda de massa acumulada/número de ciclos. Para isto, foram escolhidos os pesos específicos aparentes secos de 10,6, 11,6 e 12,6 kN/m³ com os respectivos teores de umidade de 36,6%, 31,3% e 25 %, sendo os teores de cal de carbureto adotados de 5, 8 e 11%. Todas as amostras foram curadas por um período de 28 dias em câmara úmida a 23°C. Os resultados apontam que o incremento da quantidade de cal e do peso específico aparente seco provocam aumentos na resistência à tração por compressão diametral, na resistência à compressão simples e na durabilidade da mistura. A utilização de um expoente como ajuste para a relação porosidade/teor volumétrico de cal [η/( ) , ] apresentou-se adequada para a formulação de equações para a previsão da resistência do material cimentado e para a estimativa da perda de massa acumulada/número de ciclos. Além disso, a existência de relações únicas para o controle da resistência à tração na compressão diametral e da resistência à compressão simples em função da porosidade e teor volumétrico de cal mostraram-se úteis para as formulações de dosagem. / The environmental issue is increasingly been responsible for the generation of new products. Infrastructure construction is one of the largest consumers of natural resources. Looking for the use of industrial residues as material for the construction industry is the overall objective of this research, aiming at environmental and economic benefits. For this, present study has used fly ash (obtained by burning coal in thermoelectric power plants) and carbide lime (originated from the production of acetylene gas) to fabricate a novel material. Through laboratory tests, one aim in this research was to evaluate the influence of the amount of lime and porosity of the blend on durability, splitting tensile strength and unconfined compressive strength, as well as on tensile/compressive ratio. Another objective was to further evaluate the use of the porosity/lime index in the estimation of strength and checking for a unique relationship for this parameter versus accumulated loss of mass/number of cycles. For such study were chosen dry unit weights of 10.6 kN/m³, 11.6 kN/m³ and 12.6 kN/m³ with the respective moisture contents of 36.6%, 31.3% and 25.0% and carbide lime contents of 5%, 8% and 11%. All samples were cured for a period 28 days in a moist chamber at 23°C. The results show that increasing dry unit weight and the amount of carbide lime cause increases in durability and splitting tensile and unconfined compressive strength of the studied blends. The use of an exponent as an adjustment to the porosity/lime index [η/( ) . ] showed to be appropriate for formulating equations for predicting the strength of cemented material and to estimate the accumulated loss of mass/number of cycles. Furthermore, the existence of unique relationships for the control of splitting tensile tests and unconfined compression strength as a function of porosity and volumetric lime content proved useful for the dosage formulations.

Cinza leve de carvão, resíduo gerado em usina termelétrica, foi usada para sintetizar zeólita por meio de tratamento hidrotérmico com solução de NaOH. A cinza leve (CL-2) e a zeólita sintética (ZM-2) que foi predominantemente identificada como hidroxi-sodalita foram utilizadas como adsorventes dos corantes aniônicos índigo carmina (IC) e reativo laranja 16 (RL16) de soluções aquosas. Nos processos de adsorção, os efeitos de tempo de contato, concentração inicial de corantes, pH, massa de adsorventes e temperatura foram avaliados. O estudo cinético de adsorção demonstrou que os resultados apresentaram melhor ajuste ao modelo de pseudo-segunda ordem e que adsorção de superfície e difusão intrapartícula participaram no mecanismo de adsorção. Os parâmetros termodinâmicos demonstraram que a adsorção foi espontânea em todos os processos de adsorção. Os processos de adsorção foram de natureza endotérmica para todos os sistemas, com exceção do sistema IC/ZM-2, em que foi exotérmico. Os dados de entropia mostraram a ocorrência do aumento da desordem na interface sólido/solução durante a adsorção em todos os sistemas, exceto novamente no IC/ZM-2, no qual se verificou a diminuição da desordem na interface. As isotermas de adsorção ajustaram-se à equação linear de Langmuir. As capacidades máximas de adsorção foram 1,48 mg/g para o sistema IC/CL-2; 1,13 mg/g para IC/ZM-2; 0,96 mg/g para RL16/CL-2 e 1,14 mg/g para RL16/ZM-2 à temperatura ambiente. O estudo de dessorção realizado com água, com soluções aquosas ácidas e com solução aquosa básica demonstrou ser ineficiente tanto para a recuperação dos corantes quanto para a regeneração dos adsorventes. / Coal fly ash, a waste generated in coal-fired electric power plant, was used to synthesize zeolite by hydrothermal treatment with NaOH solution. The fly ash (CL-2) and this synthesized zeolite (ZM-2) that was characterized as hydroxy-sodalite were used as adsorbents for anionic dyes indigo carmine (IC), and reactive orange 16 (RO16) from aqueous solutions. Effects of contact time, initial dye concentration, pH, adsorbent mass, and temperature were evaluated in the adsorption processes. The kinetics studies indicated that the adsorption followed the pseudo-second order kinetics and that surface adsorption and intraparticle diffusion were involved in the adsorption mechanism. The thermodynamics parameters demonstrated that the adsorption was spontaneous for all adsorption processes. The enthalpy data confirmed the endothermic nature for all adsorption processes except for IC/ZM-2 system which was exothermic. The entropy data showed an increased disorder at the solid/solution interface during the adsorption for all systems except for IC/ZM-2 whose negative entropy value indicated a decreased disorder at the interface. The adsorption isotherms were closely fitted to the Langmuir linear equation. The maximum adsorption capacities were 1.48 mg/g for the IC/CL-2 system; 1.13 mg/g for IC/ZM-2; 0.96 mg/g for RO16/CL-2, and 1.14 mg/g for RO16/ZM-2 at room temperature. The desorption study carried out with water, with acid aqueous solutions, and with an alkali aqueous solution showed to be inefficient both for recovering the dyes and regenerating the adsorbents.

This thesis describes research carried out to investigate techniques for (i) rapidly assessing the reactivity of fly ash; and (ii) evaluating its interaction with air-entraining admixtures (AEAs), both with regard to use in concrete. The materials considered for the project included, 54 fly ashes from 8 UK sources, and an additional three materials from Bangladesh, covering a range of fineness, loss-on-ignition (LOI) and production conditions (run-of-station, carbon removed, air-classified, co-combustion, oxy-fuel technology); Portland Cements (PCs) from five UK sources with various properties (strength classes 32.5 R, 42.5 N and 52.5 N); laboratory grade hydrated and quick limes; and three commercial AEAs and a standard laboratory grade reagent (surfactant). The research examining fly ash reactivity considered activity index tests to BS EN 450 (BSI, 2005c) as the reference and investigated tests covering fly ash properties/providing measures of fly ash behaviour to rapidly assess this. These included (i) fly ash fineness (45 µm sieve residue, or LASER particle size distribution (PSD) parameters), LOI and flow properties; (ii) accelerated curing of PC and lime-based mortars (iii) lime consumption by fly ash when combined with PC in paste or suspension (Frattini) or from a saturated lime solution; (iv) various measures of fly ash chemical composition (based on oxide/mineralogical analysis); and (v) a quicklime slaking test. The test results were validated by strength tests with 100 mm concrete cube. Results of the above indicated good correlations between fly ash fineness, mortar flow/water requirement and (pozzolanic) activity index (standard or accelerated curing). However, fly ash reactivity and fresh properties appeared to be influenced by the properties of the test PC (e.g. chemical composition and fineness) and there is a need to take this into account during assessment. Generally, finer fly ashes gave better flow; however, there is an optimum fineness (d90 ~40 µm) for best performance, and which is similar to the fineness of the test PC. Strong correlations between the accelerated and standard cured PC-based mortar indicate the latter can be used to estimate the former taking account of the fly ash properties. In view of eliminating the effect of PC properties on reactivity, mortar tests with laboratory grade hydrated lime suggested potential for this. However, for better assessment, this approach requires further work to address issues relating to slower rates of strength gain and increased time requirements, although high temperature conditions were used for curing. Measuring Ca(OH)2 consumption from fly ash/PC paste or suspension agreed with the behaviour in mortar, but needs special instruments (e.g. TGA or XRF). A similar approach with saturated lime did not work well, despite several measures being taken to try and improve this. The oxide and mineralogical analysis results of fly ash did not give good correlations with activity index, but improved when a factor combining them with fineness was considered. The test results were validated in concrete and with air-classified fly ashes from single sources which gave clear trend/behaviour. The lime slaking test was found to be ineffective for identifying fly ash reactivity. The reactivity assessment results were validated by carrying out concrete strength tests. In general, more consistent trends were obtained for fly ash from single source as noted with mortar earlier. Methods adopted/developed to assess the interaction of fly ash with AEA included (i) the foam index test; (ii) acid blue 80 (AB80) dye adsorption test (spectroscopic method); and (iii) methylene blue test. High variability in foam index test results between different operators were noted, which reflected differences in the degree of shaking applied and difficulties in identification of the test end point. Adoption of an automatic shaker and determination of suitable test conditions reduced this by more than 50%. Reliable test procedures were also established for the AB80 dye adsorption method. The results obtained from these tests gave very good correlations with fly ash specific surface area and the AEA dose required (both with commercial AEAs and standard reagent) for achieving target air contents in mortar and concrete. The methylene blue dye test also gave good correlations with these parameters, but was less effective for low LOI fly ashes. Between laboratory tests were carried out at three UKQAA members and considered, LOI, fineness (45 µm sieve and LASER PSD), and activity index. The results gave good agreement with those obtained at the Concrete Technology Unit for this work and again emphasized the role of fly ash fineness on its reactivity. Overall, fly ash fineness was found to be the best means of rapidly assessing its reactivity. Some of the other methods considered gave promising behaviour but require further refinements. Therefore, it is suggested that in addition to 45 µm sieve residue, other types of fineness measurement (e.g. sub 10 µm quantities, d50 and d90) can be considered suitable alternatives to activity index. Similarly, foam index tests with the automatic shaker or the AB80 test method could both be used as fly ash physical requirement tests, or in production control for air-entrained concrete.

<p>Thallium is a highly toxic element that humans are exposed to mainly by consumption of drinking water and vegetables grown in soil with high thallium content but also through inhalation of particles in the air. Thallium is also present in fossil fuels, alloys, and in electronic utilities. The increasing use of the element and emissions from notably energy production has lead to a higher load on the surface of the Earth. This study aims at increasing the knowledge about the behaviour of thallium in aquatic environments. Focus has been on the redox chemistry of thallium in relation to its mobility, which is of great importance because Tl(I) and Tl(III) have very different properties in this respect.</p><p>The relationship between Tl(I) and Tl(III) in surface waters from contaminated and uncontaminated environments was examined by ion chromatography connected on line to ICP-MS (inductively coupled plasma mass spectrometry). It was found in controlled systems that even though Tl(III) is thermodynamically unstable under fresh water conditions Tl(I) was oxidised in the presence of light and iron(III). This was also confirmed in field studies. When lake water samples were exposed to light, Tl(I) was oxidised and thallium was lost from the solution. The most likely explanation for this was adsorption of thallium to particle surfaces.</p><p>The concentration of thallium in Swedish lakes and soil were measured. In unpolluted lakes the concentration ranges between 4.5-12 ng/l, the sediment concentration was 0.07-1.46 mg/kg. The anthropogenic load was found to have increased since the end of the Second World War although concentrations above background were found since the early industrialisation. In contaminated areas the concentration in soil ranges from 0.64-88 mg/kg, high concentrations were found in systems with alum shale and in soil exposed to runoff from a lead and zinc enrichment plant.</p><p>The mobilisation of thallium from solid phases in contaminated areas was dependent on pH and about 50% of the leachable content was mobilised already at pH 5-6. Once it had been released to water it was highly mobile. These conditions suggest that in a large part of the Swedish environment a high mobility of thallium can be expected.</p>

Polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs), two groups of struc-turally related chlorinated aromatic hydrocarbons, generally referred to as “dioxins” are of great concern due to their extreme toxicity and presence in all compartments of the environment. Since they occur at very low levels, their analysis is complex and challenging, and there is a need for cost-efficient, reliable and rapid analytical alternatives to the expensive methods in-volving use of gas chromatography high-resolution mass spectrometry (GC-HRMS). It is im-portant to routinely monitor food and feed items to detect contaminations at an early stage. For the regulation of dioxins and dioxin-like PCBs in food and feed according to current legis-lation, large numbers of samples have to be analysed. Furthermore, soils at many industrial sites are also contaminated with dioxins and need remediation. In order to optimize the cost-efficiency of reclamation activities it is important to acquire information about the levels and distribution of dioxins in the contaminated areas. The aim of the studies underlying this thesis was to investigate the potential of comprehen-sive two-dimensional gas chromatography with a micro-electron capture detector (GC × GC-µECD) as a cost-effective method for analysing dioxins and dioxin-like PCBs in food, feed, fly ash and contaminated soils. Quantification studies of dioxins and dioxin-like PCBs were con-ducted and results were compared with GC-HRMS reference data. Generally, there was good agreement between both the congener-specific results and data expressed as total toxic equiva-lents (TEQs). The developed GC × GC-µECD method meets the European Community (EC) requirements for screening methods for control of dioxins and dioxin-like PCBs in food and feed. The presented results also indicate that GC × GC-µECD has potential to be used as a routine method for the congener-specific analysis of 2,3,7,8-PCDD/Fs and dioxin-like PCBs in matrices such as food and feed, fly ash and soil. However, to fully exploit the potential of the GC × GC-µECD technique, it should be combined with a fast and cost-efficient sample preparation procedure. Therefore, a number of certified reference materials (CRMs) were extracted using a new shape-selective pressurized liquid extraction technique with integrated carbon fractionation (PLE-C), and the purified extracts were analysed for PCDD/Fs using GC × GC-µECD. The results compared well with the certified values of a fly ash and a sandy soil CRM, but they were much too high for a com-plex clay soil CRM. It was concluded that this combination of techniques was very promising for screening ash and highly permeable soils. Further assessments and method revisions are still required before GC × GC-µECD can be used on a routine basis, and available software packages need to be refined in order to accelerate the data-handling procedures, which currently restrict the sample throughput.

Slurry walls have been widely used for more than 25 years to control the migration of contaminants in the subsurface. In the USA, vertical barriers are mostly constructed of soil-bentonite using the slurry trench method of construction. In this method, sodium bentonite is mixed with water to form a viscous slurry that is pumped into a trench during excavation to maintain the trench stability. The stable trench is then backfilled with a mixture of soil and slurry having a consistency of high slump concrete. These barriers have been designed primarily for low permeability, generally less than 10&minus / 9 m/s. Some investigations have pointed toward improved performance using admixtures that would provide low permeability. In this study, Soma thermal power plant fly ash, granulated blast furnace slag, lime, and steel slag are used as admixture to improve the performance of slurry walls. Permeability, compressive strength, slump, compressibility properties of the mixtures were found and checked for the minimum requirements. According to the findings of this study, granulated blast furnace slag (GGBS), fly ash and steel slag can be used at certain percentages and curing periods as additive in cement-bentonite barrier wall construction. Permeability of specimens having fly ash decreases by increasing fly ash content. Mixtures having 50 % of GGBS type I with 5 % of lime and 9% bentonite content gave acceptable results in 28 days of curing time. Specimens including 50 % of GGBS type II with 5 % of lime and 9% bentonite content gave the higher permeability value in 28 days of curing time with respect to GGBS type I. In addition, most of the mixtures prepared by steel slag gave the acceptable permeability values in 28 days of curing period. Unconfined compressive strength of all mixtures increase by increasing curing time. Cc, Cr, Cv, kcon values were found from consolidation test results. Permeability values found from consolidation tests are 10 times to 100 times higher than flexible wall k results for the same effective stress of 150 kPa. Generally, mv values are decreasing with increasing curing time. As mv decreases, D increases.

The thermal formation of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and naphthalenes (PCNs) is a major problem in waste incineration. Ideally, rather than relying on air cleaning systems and treatment techniques, their formation should be minimized or, if possible eliminated. The work presented in this thesis was conducted to obtain a deeper understanding of the thermal formation of PCDDs, PCDFs, PCBs, and PCNs during incineration using a 5 kW laboratory scale incinerator and two artificial wastes that were designed to reflect regional differences in waste composition. The first part of the thesis focuses on the validation of a recently-developed flue-gas sampling probe with enhanced cooling capabilities. Artifact formation of PCDDs and PCDFs can occur during the sampling of hot flue gases if the cooling is insufficient. The new probe was successfully used to collect samples at 700 °C without biasing the measured POP levels. The thermal formation of PCDDs, PCDFs, PCBs, and PCNs in the post-combustion zone of the incinerator was then studied by collecting flue gas samples at 400 °C, 300 °C, and 200 °C during the incineration of the two artificial wastes. Highly chlorinated POPs were formed in larger quantities when burning the waste with the higher content of metals and chlorine, which suggests that high metal levels in the waste favor the chlorination of less chlorinated POPs or otherwise facilitate the formation of highly chlorinated polyaromatics, possibly via the condensation of highly chlorinated phenols. The concentrations of these pollutants and the abundance of highly chlorinated homologues increased as the flue gas cooled. Fly ash particles play an important role in thermal POP formation by providing essential elements (carbon, chlorine, etc.) and catalytic sites. The chemical and mineralogical properties of fly ash samples were studied by X-ray diffraction (XRD), Fourier Transform Infrared (FTIR), Scanning Electron Microscopy/Energy Dispersive X-ray (SEM/EDX), and X-ray photoelectron spectroscopy (XPS) to determine their impact on thermal POP formation. Orthogonal Partial Least Squares (OPLS) modeling was used to identify correlations between the observed POP distributions and the physicochemical data. This investigation provided new insights into the impact of fly ash chemistry on thermal POP formation. In addition, the POP isomer distribution patterns generated during waste combustion were examined. These patterns are used to “fingerprint” mechanisms of POP formation. It was found that wastes containing large quantities of metals and chlorine favored the formation of highly chlorinated homologues including the very toxic 2,3,7,8-congeners. The data suggest that reducing fly ash emissions might increase the SO2 content of the flue gas and thereby suppress the Deacon process and the formation of harmful highly chlorinated aromatic species.

Self consolidating concrete (SCC) is defined as an innovative concrete that does not require vibration for placing and compaction and it is able to flow under its own weight, completely filling formwork and achieving full compaction. Although significant amount of research has been carried out regarding the fresh properties, mix design, placing methods and strength of various SCC mixes, only a very limited amount of work has been done to assess the durability performance of SCC. Concretes in cold climates are subjected to freeze-thaw cycles which are one of the major durability problems, and if the concrete is in a saturated or nearly saturated condition, those cycles lead to expansion of the water in the capillary pores of concrete causing great internal stresses. For a durable concrete subjected to freeze-thaw cycles, an adequate air void system is obtained by using air-entraining admixtures. The performance of the air void system is characterized by air void parameters that are determined using microscopical examination of the concrete microstructure. In this thesis a software tool, based on image analysis of concrete surface, is developed to evaluate the air void parameters of concrete using both American and European standards. Later on, an experimental program is conducted to evaluate the effect of freezing-thawing on self consolidating concrete that contain different percentages of fly ash (FA) and air entraining agents. For this purpose, a total of ten self consolidating concrete mixtures that contain four different contents of fly ash, and three different levels of air entrainment were prepared. During the casting operation, the workability properties of SCCs were observed through slump flow time and diameter, air content, V-funnel flow time, L-box height ratio, and segregation ratio. Hardened properties were evaluated by compressive strength, permeability tests (water absorption, sorptivity and rapid chloride permeability test), freezing-thawing test, resonant frequency test, ultrasonic pulse velocity test. The developed tool was used to characterize and evaluate the effects of air void parameters of SCC on its resistance to freeze-thaw cycles. At the end of this experimental investigation, it was concluded that the addition of air entraining agent increased the flowability and an increase in the fly ash content decreased the effect of air entraining agent. On the other hand, during image processing, it was observed that the surface preparation procedures have a crucial effect on processing quality. Moreover, spacing factor -which is the most important air void characteristic that is utilized for determination of the resistance to freezing-thawing- should not be restricted to 0.2 mm for SCC, since SCCs with spacing factors smaller than 0.4 mm could still exhibit good freezethaw resistance.