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In this work, the chloride transport related properties of slag concrete have been studied. For this, traditional experiments and an innovative computational method were applied to novel mixes with a low carbon footprint. In part 1 combination of Ground Granulated Blast Furnace Slag and Steel Basic Oxygen Slag activated using ordinary Portland cement, waste cement industrial residues and recycled Plasterboard Gypsum were studied. In order to characterize these blended binders, the compressive strength, the volume stability, the mineralogical changes due to hydration and the setting times were measured. In part 2 the chloride penetration was simulated to study the transport properties using a multi-species model. In this, the ionic species flow is given by the Nernst– Planck equation; however, due to ion–ion interactions there are ionic fields that affect the final flux producing an additional voltage known as the membrane potential. In order to calculate the inputs of the model a neural network methodology was developed to find the fundamental properties of concrete including the diffusion coefficients In part 3 a range of traditional transport chloride related experimental tests were carried out on concrete mixtures developed in part 1. These tests were workability, compressive strength, open porosity, initial water absorption capacity (sorptivity), carbonation, chloride migration and self diffusion, electrical resistivity, water permeability, and corrosion. Additionally, the methods developed in part 2 were used to calculate the chloride transport related properties of those mixes.

No description available.

No description available.

Routes to novel heterocyclic azo compounds and components of use as potential inkjet dyes were investigated. A new route to fluorenones from biphenyl acid chlorides using FVP (Flash Vacuum Pyrolysis) has been discovered. Fluorenone and 4-methylfluoren-9-one were prepared by FVP of 2-phenylbenzoyl chloride and 2-methylbiphenyl-2-carbonyl chloride respectively. Xanthen-9-one and thioxanthen-9-one were also prepared by FVP from the corresponding acid chlorides. 9-Phenanthrol could also be prepared via the FVP of biphenylacetyl choride and the application of this method to a heterocylic thiophene system afforded naphtho[1,2-b]thiophen-4-ol. Naphtho[2,1-b]thiophen-4-ol and naphtho[1,2-b]furan- 4-ol could be obtained in low yields by the FVP of (2-thiophen-3-ylphenyl)acetic acid methyl ester and (2-furan-2-ylphenyl) acetic acid methyl ester over a tungsten trioxide catalyst. Coupling of these systems with the diazonium salt of Acid Yellow 9 afforded the corresponding azo compounds. New heterocyclic dyes were also prepared from the condensation of heterocyclic hydrazines with 4,9-disulfophenanthrenequinone. Pyridine, pyridazine, phthalazine, isoquinoline and 2-quinoline disulfophenanthrene quinone metallised 2:1 nickel complexed magenta dyes were prepared. Industrial tests by standard methods revealed the pyridazine dye has a particularly impressive balance of light and ozone fastness over similar magenta dyes. The reaction of an arylnitro compound with 2-aminopyridine appeared to be an attractive and high yielding route to 2-(phenylazo)pyridine. However, application of this reaction to substituted and naphthalene systems failed. This afforded byproducts due to nucleophilic substitution of groups such as methoxy and the relatively uncommon nucleophilic substitution of hydrogen with none of the required azo products obtained. Therefore it appeared that the reaction of a nitro and amine was not a robust and versatile route to heterocyclic azo compounds. An alternate route to heterocyclic azo compounds involved the use of the Mills reaction by the condensation o-anisidine, p-chloroaniline, 2-aminophenol, 3- aminophenol, naphthylamine, 8-amnioquinoline and 2-acetylamino-5-aminobenzenesulfonic acid with 2-nitrosopyridine afforded the heterocyclic azo products in moderate to high yields. The Mills reaction does appear to be the favored route to heterocyclic azo compounds. Several factors were identified which affect the process of bisazo coupling of chromotropic acid and products obtained. Reaction at the ipso position of monoPACAs (2-phenylazochromotropic acid) leading to increased yields of the ipso substitution monoPACA by-product as opposed to the expected bisazo coupling position was a major problem. Studies indicated reactivity at the ipso position was greatly reduced by the presence of electron withdrawing groups around the phenyl ring of the monoPACA. Further study indicated reaction at the bisazo coupling position increased with the strength of the diazonium salt used in bisazo coupling. Therefore the electronic nature of the monoPACA starting material and the diazonium salt used in bisazo coupling greatly affected the products obtained. Reaction pH studies also revealed attack at the bisazo coupling position increases with pH and at lower pH (5.0 – 8.0) attack at the ipso position dominated. Reactivity of the monoPACA starting material also increased with pH. The influence of steric effects upon bisazo coupling revealed, in the cases where ortho sulfonic acid groups were present in the monoPACA, a reduction in attack at the ipso position. Hence the reaction appeared to be directed towards the required bisazo coupling position.

No description available.

As estruturas de concreto armado existentes em regiões marítimas são fortemente atacadas por agentes agressivos, sendo os cloretos os causadores dos maiores danos quando atingem níveis críticos, afetando de forma significativa a vida útil do concreto. Nos últimos anos a comunidade científica vem realizando pesquisas relativas à penetração de cloretos e suas conseqüências, sendo a maioria desenvolvida em laboratórios. Em ambiente natural, no Brasil, foram realizadas pesquisas nas regiões Nordeste e Sul, mais especificamente no Rio Grande do Sul na cidade de Rio Grande. O litoral Norte do Rio Grande do Sul possui condições climáticas diversas em relação ao litoral Sul, apresentando municípios com significativo incremento na indústria da construção civil, justificando assim o desenvolvimento do estudo nesta região. Esta pesquisa tem por objetivo estudar a influência do tipo de cimento utilizado, do uso de adições de sílica ativa da relação água/aglomerante em relação à penetração de cloretos nas estruturas de concreto em ambiente natural. Foi analisado, também, o distanciamento da estrutura de concreto em relação ao mar e as condições ambientais do local, tais como direção dos ventos predominantes e umidade relativa. Para fundamentar a pesquisa, foram realizados ensaios químicos para determinar o teor de cloretos nas amostras retiradas dos corpos-de-prova colocados em Tramandaí a três distâncias do mar (50, 150 e 800 m) e junto a Lagoa Tramandaí (1800 m em relação ao mar), em Imbé, a diversas profundidades (superficial, 5, 15 e 25 mm). Os resultados indicam que quanto menor a relação água/aglomerante e maior o distanciamento em relação ao mar, menor o teor de cloretos que ingressam nas estruturas de concreto, sendo que a 800 m da orla marítima essa agressividade não é significativa. Concretos com as faces posicionadas a nordeste foram as que apresentaram maior penetração de cloretos. O uso de cimento CP V-ARI com adição de sílica ativa proporciona uma maior concentração superficial de cloretos no concreto, porém, um menor ingresso em seu interior. Nesta pesquisa, nenhum concreto atingiu o teor crítico de cloretos (0,15%) para o ambiente de atmosfera marítima onde foram expostos. / The reinforced concrete structures existing in maritime regions are heavily attacked by aggressive agents, with chlorides those who cause more damage when they reach critical levels, significantly affecting the life of the concrete. In recent years the scientific community is conducting research on the penetration of chlorides and their consequences, mostly developed in laboratories. In the natural environment, in Brazil, were searched in the Northeast and South, more specifically in Rio Grande do Sul in Rio Grande. The northern coast of Rio Grande do Sul has different climatic conditions over the south coast, with municipalities with a significant increase in the construction industry, thereby justifying the development of the study in this region. This research aims to study the influence of cement type, the use of additions of silica fume of the water / binder for the penetration of chlorides in the concrete structures in the natural environment. We also analyzed the distance of the concrete structure from the sea and the environmental conditions of the site, such as direction of prevailing winds and relative humidity. In support of this research, we conducted chemical tests to determine the chloride content in the samples of soils-proof Tramandaí placed in the three distances from the sea (50, 150 and 800 m) and along the lagoon Tramandaí (1800 m above the sea), in Imbé at various depths (surface, 5, 15 and 25 mm). The results indicate that the lower the water / binder and the greater the distance from the sea, the smaller the amount of chlorides entering the concrete structures, and 800 meters from the seafront this aggression is not significant. Concrete with faces positioned northeast showed the highest penetration of chlorides. The use of cement CP V-ARI with the addition of silica fume provides greater surface concentration of chlorides in concrete, however, a lower entry inside. In this study, no case has reached the critical content of chloride (0.15%) to the environment of maritime atmosphere where they were exposed.

A pesquisa aborda os métodos ASTM C 1152 e ASTM C 114, para determinação de cloretos em concreto. Os ensaios foram realizados em dois laboratórios, o da Escola Politécnica da USP, em São Paulo e o da Universidade de Pernambuco, em Recife. Foram preparados concretos com 5 tipos de cimento Portland. O estudo teve como objetivo fazer um levantamento de trabalhos publicados sobre métodos de determinação de cloretos total e solúvel, em concretos, especificamente, discutir a influência do tipo de cimento no teor de cloreto combinado e livre, em amostras de concreto. Foi também objetivo, determinar como se distribui o íon cloreto, solúvel e combinado ao longo da altura de corpos-de-prova de 10x20 cm de diâmetro e apresentar sugestões ao método proposto visando a sua normalização. Paralelamente foram realizados análises químicas e físicas dos cimentos, pela ABCP. O método proposto apresentou boa reprodutibilidade entre os dois laboratórios, através dos cálculos estatísticos, confirmando sua atualidade e, adequação para outros laboratórios. É importante no entanto dizer que este método é demorado, exige dedicação, equipamentos sensíveis e a resposta é lenta. Os cálculos encontram-se informatizados através de planilha interativa de cálculos, facilitando a sua aplicação. A metodologia pareceu adequada para elaboração de norma técnica nacional. / The aim of this research was the application of ASTM method for determination of chlorides in concrete. The tests were made by two laboratories, the EPUSP in São Paulo and POLI in Recife, on concretes prepared with five types of Portland cement. The purpose of this study was to make a survey of published works about the methods of determination of total and soluble chlorides in Portland cement concrete, to discuss the influence of each kind of cement on chlorides, combined and free, in samples of concrete. The purpose was too, determine how the free and linked chlorides are distributed through the height of the specimens of 10x20 diameter and to present suggestions to the standardization of this method. The method presented good results among the two laboratories, the statistical tests demonstrating the method\'s actuality and, adequate to anothers laboratories. It is important to say that this method is slow, needs dedication and specific facilities. The mix-proportion calculations from chemical analysis were made with a spreadsheet software. The methodology seemed to be adequated for the elaboration of a National Standard.