The results of this investigation may serve as the basis for some conclusions with regard to the curing of Portland cement concrete. Some of the more important conclusions are as follows l. A concrete, if it may be classed as such, consisting of fine aggregate, cement, and water, is not subject to the extreme effects of freezing as is a true concrete containing a coarse aggregate. 2. Maximum loss of strength, which is evidently long-enduring is suffered by concrete frozen in an extremely green stage when frost enters mortar paste. 3. Freezing may be harmful at any time within the first week. However, in most cases a recovery is indicated. 4. Steam curing, if not carefully controlled at optimum conditions, will result in loss of strength in a concrete. 5. The expansion and drying which occur at the temperatures in the steam chamber apparently are the cause of harmful results in steam.curing. It must be borne in mind that the limitations of data gathered make these conclusions more indicative than conclusive. There is still much room.for further research at this institution along the line of both problems presented herein. / Master of Science

Based on the results of this investigation certain conclusions were arrived at relative to Portland cement concrete using Dolomitic limestone sand as the fine aggregate. The most important of these are as follows: 1. Fresh concrete continues to gain strength while in the frozen state. 2. Freezing and then thawing of fresh concrete does not have an appreciable effect on the twenty-eight day ultimate strength, and the concrete, if given time to recover, will compare favorably with concrete cured under normal conditions. 3. Freezing of concrete immediately after pouring has a greater effect on the twenty-eight day ultimate strength of the concrete than has freezing for the same period at a more advanced age within the twenty-eight days. 4. Concrete cured at 65°C. tends to increase its twenty-eight day ultimate strength, providing the water lost through evaporation is replaced. 5. High early strength concrete can be obtained by curing ordinary Portland cement concrete at high temperatures. Based on the results of compression tests performed in this investigation, Dolomitic limestone sand has been found to be satisfactory as the fine aggregate for Portland cement concrete; verifying what Messrs. Broyles and Brown had said in 1936 and 1937 respectively. What has been done in the way of concrete research at Virginia Polytechnic Institute is satisfactory for relatively new concrete using Dolomitic limestone sand as the fine aggregate; but it is wondered how this concrete will stand up over a long period of time. Professor Hartman and Dr. Holden have inaugurated some long time studies at the Institution, but there is still much room for further investigation. Dolomitic limestone rock has proven itself worthy when used as the coarse aggregate for Portland cement concrete. It is up to time and future research to prove the worth of its sand used as the fine aggregate. / Master of Science

University of Stellenbosch Business School / The objective of this study is to determine whether brands create value for shareholders and the extent to which such value can be quantified. The research methodology is based on a case study of Pretoria Portland Cement, South Africa’s leading cement producer, and seeks to demonstrate how a commodity like cement can be successfully differentiated and branded. Primary data was gathered by conducting unstructured interviews with business leaders and key personnel involved with the development and execution of the company’s brand vision. Secondary data is based on the results of a customer loyalty survey by IPSOS Markinor as well as on customer perceptions from Millward Brown’s BrandDynamics™ model. The results of both these surveys, together with historic market share data and the company’s financial performance over a 15-year period, is analysed and interpreted before conclusions are made about the brand’s contribution to value creation. The study concludes by attempting to make generally applicable findings about the value of brands and their overall contribution to shareholder value. One of the major limitations of the study is the inability to assign a definitive value to the PPC brand because of the vast number of credible brand valuation models available and the lack of consensus among academics and industry experts regarding the determination of brand value.

published_or_final_version / Civil Engineering / Doctoral / Doctor of Philosophy

Os finos de resíduos cimentícios (previamente hidratados) podem ser reciclados através de tratamento térmico, tornando-se um ligante alternativo. Quando tratados termicamente em temperaturas inferiores a 550ºC, o processo não gera emissões de CO2 relativas à descarbonatação do calcário. Esta pesquisa teve como objetivo reativar o cimento Portland de alto forno (CP III) previamente hidratado, desidratando-o em temperatura de 500°C com patamar de 2h e reidratando-o com teores de água e de dispersante variados. Inicialmente foram realizadas caracterizações a fim de comparar as características físico-químicas do cimento desidratado com o cimento anidro. Posteriormente, foram analisadas as transformações de fases observadas com a hidratação, desidratação e reidratação do cimento. A segunda parte do estudo foi de otimização das pastas reidratadas e hidratadas, onde foram definidas condições ideais de dispersão, com a saturação ideal de dispersantes e teores mínimos de água resultado em pastas com volume de poros menores e consequentemente resistências mais elevadas. Os resultados obtidos comprovaram que o cimento desidratado se reidrata e forma fases similares às fases formadas na hidratação, como C-S-H, portlandita, hidrotalcita, etc. O cimento de alto forno carbonata mais do que o cimento Portland (CP V). Devido à área superficial elevada (14 vezes superior ao do cimento anidro), o cimento desidratado libera calor de molhagem elevado, consequencia da recombinação da água com as fases desidratadas. Observou-se ainda que, é possível controlar a resistência à compressão da pasta reidratada, otimizando o volume de poros presentes nas pastas. As resistências das pastas reidratadas com dispersante aos 28 dias foram 2,37 vezes maiores quando comparados com sistemas aglomerados. Com relação a porosidade, há indícios que é possível obter níveis de porosidade para as pastas reidratadas semelhantes com a pasta hidratada. / The fines of cementitious wastes (previously hydrated) can be recycled through heat treatment, becoming an alternative binder. When heat treated at temperatures below 550°C, the process does not generate CO2 emissions relative to limestone decarbonation. The objective of this research was to reactivate the previously hydrated Portland cement (CP III), dehydrating it at a temperature of 500°C with a 2-hours plateau and rehydrating it with varying water and dispersant contents. Characterization was initially performed to compare the physicochemical characteristics of dehydrated cement (DC) with anhydrous cement (AC). Subsequently, the AC-HP phase transformations for DC-RP were analyzed. The second part of the study was the optimization of rehydrated (RP) and hydrated (HP) pastes, where ideal dispersion conditions were defined, with optimum dispersant and water minimum contents, resulting in pastes with smaller pore volumes and consequently more compressive strength high. The results confirm that the DC rehydrates and forms phases similar to the phases formed in the hydration, such as C-S-H, portlandite, hydrotalcite, etc. The blast furnace cement carbonate more than Portland cement (no additions). Due to the high surface area (14 times higher than that of the AC), the DC releases high wetting heat, due to the recombination of the water with the dehydrated phases. It was also observed that it is possible to control the compressive strength of the rehydrated paste by optimizing the pore volume present in the pastes. The strengths of dispersed pastes with additives at 28 days were 2.37 times higher when compared to agglomerated systems. With respect to porosity, there are indications that it is possible to obtain porosity levels for the similar rehydrated pastes with the hydrated paste.

Actualmente los materiales cementicios suplementarios como el metacaolín, son comúnmente empleados en la industria cementera y de la construcción, debido a factores ambientales, económicos y técnicos. La mayoría de estudios que evalúan la influencia del metacaolín en sistemas cementicios, se enfocan en aspectos de desempeño y de resistencia mecánica, en edades avanzadas. Existen pocos estudios que evalúan la etapa inicial de hidratación. Por tanto, este trabajo tiene como propósito entender mejor la influencia que tiene la sustitución parcial de metacaolín en pastas de cemento Portland, durante las primeras 72 horas de hidratación. Normalmente para evaluar la cinética de hidratación se analiza el calor liberado, usando un calorímetro de conducción isotérmico. Sin embargo, otra técnica relativamente nueva usada en este estudio, es medir la retracción química en forma continua; en Brasil son raros los estudios que usen retracción química para obtener la cinética de hidratación. Para tal fin se elaboraron pastas utilizando reemplazos de metacaolín de 5, 10 y 20% en masa, además de una pasta de referencia, usando una relación constante agua/sólido de 0.5. La retracción química fue medida en forma continua automatizando el método de la dilatometría, también se evaluó la cinética de hidratación usando un calorímetro isotérmico. Adicionalmente, el desarrollo de los productos hidratados fue estudiado por análisis termogravimétrico y difracción de rayos X. Los resultados obtenidos muestran que existe una excelente relación entre la retracción química y la calorimetría y que la adición de metacaolín produce cambios en la cinética de hidratación, que también afectan a la retracción química. / Currently the supplementary cementitious materials such as metakaolin are commonly used in the cement and construction industry, due to environmental, economic and technical factors. Most studies evaluating the influence of metakaolin in cementitious systems focus on aspects of performance and mechanical strength at older ages. There are few studies evaluating the initial stage of hydration. Therefore, this paper aims to better understand the influence of the partial replacement of metakaolin in Portland cement pastes during the first 72 hours of hydration. Normally to evaluate the kinetics of hydration heat released is analyzed using an isothermal calorimeter. Nevertheless, another relatively new technique used in this study is to measure the chemical shrinkage continuously; in Brazil are rare studies using chemical shrinkage to obtain hydration kinetics. This study shows the influence of partial replacement of Portland cement by metakaolin in the hydration reactions and chemical shrinkage of cementitious pastes. For this, pastes were prepared using metakaolin replacements of 5, 10 and 20% by mass, and a reference paste, using a constant water/solid ratio of 0.5. Chemical shrinkage was measured continuously automating the method of dilatometry, hydration kinetics was evaluated using an isothermal conduction calorimetry. Additionally, the development of hydrated products was studied by thermogravimetric analysis and X-ray diffraction. The results show that there is an excellent relationship between chemical shrinkage and calorimetry and the addition of metakaolin leads to changes of the hydration kinetics, which also affect the chemical shrinkage.

Ao longo dos últimos anos, têm sido expressivo o interesse pelo estudo do Agregado de Trióxido Mineral (MTA) devido às boas propriedades físico-químicas e biológicas que apresenta. Da mesma forma houve um grande interesse no cimento Portland, já que, segundo os trabalhos científicos encontrados na literatura, apresentam composição e desempenho semelhantes. Este trabalho teve como objetivo avaliar o comportamento biológico do Endo-CPM-Sealer e do clínquer do cimento Portland puro e acrescido com sulfato de cálcio (com 2% e 5% do seu peso total) no tecido subcutâneo de ratos, para analisar as possíveis alterações teciduais que possam induzir. Também foi avaliado o tempo de presa dos quatro cimentos. Empregaram-se 24 ratos machos da linhagem Wistar, divididos em três grupos para cada período experimental (15, 30 e 60 dias). Cada animal recebeu quatro tubos de polietileno (preenchidos com os cimentos experimentais e selados numa das extremidades com guta-percha que serviu como controle) no tecido subcutâneo da região dorsal. Decorridos os períodos experimentais, os animais foram mortos e os tubos foram removidos com tecido adjacente suficiente para análise microscópica. Os resultados mostraram que o Endo-CPM-Sealer, produziu a maior resposta inflamatória nos períodos de 15 e 60 dias, sendo estatisticamente significante somente no primeiro período. O clínquer do cimento Portland puro, foi o que produziu a menor resposta tecidual inflamatória, em todos os períodos. Todos os materiais avaliados apresentaram-se semelhantes no período de 60 dias e não apresentaram diferença estatisticamente significante. Com relação ao tempo de presa inicial, o clínquer do cimento Portland puro, foi o que apresentou o menor valor (5min), e o menor valor do tempo de presa final foi dado pelo Endo-CPM-Sealer (22min), seguido pelo clínquer do cimento Portland puro (55min). / During the last years, there has been considerable interest in the investigation of Mineral Trioxide Aggregate (MTA), due to its good physicochemical and biological properties. Similarly, there was great interest in Portland cement, since scientific studies in the literature reveal that these materials present similar composition and performance. This study aimed to evaluate the biological behavior of Endo-CPM-Sealer and clinker of Portland cement, either pure or combined with calcium sulfate (2% and 5% of the total weight), by implantation in subcutaneous tissue of rats, to analyze the possible tissue alterations that may be induced. The setting time of the four cements were also evaluated. The study was conducted on 24 male Wistar rats, divided into 3 groups for each study period (15, 30 and 60 days). Each animal underwent placement of four polyethylene tubes (filled with the experimental materials and sealed with gutta-percha at one end, which served as control) in the subcutaneous tissue at the dorsal region. After the study periods, the animals were killed and the tubes were removed with enough surrounding tissue for microscopic analysis. The results demonstrated that Endo-CPMSealer caused greatest inflammatory response at 15 and 60 days, with a statistically significant difference only on the first period. Pure clinker of Portland cement produced the least inflammatory response at all periods. All materials were similar at 60 days, without statistically significant difference. Concerning the initial setting time, pure clinker of Portland cement exhibited the shortest time (5min); the shortest final setting time was observed for Endo-CPM-Sealer (22min), followed by pure clinker of Portland cement (55min).

Concretos com baixo consumo de cimento Portland se justificam por motivos técnicos (menor calor de hidratação, retração e fissuração) e de sustentabilidade (menores consumos de energia e matérias-primas, emissão de CO2 e demanda por transporte). A variabilidade nas matérias-primas, nas condições ambientais e no processo de confecção de um concreto resultam em variabilidade de diversas propriedades no estado fresco e endurecido. A viabilidade da aplicação de concretos com baixo consumo de cimento, em escala no campo, depende da sensibilidade que estes apresentam diante das variabilidades presentes. Concretos com robustez adequada, ou seja, suficientemente tolerantes às variações, são desejáveis. Esta pesquisa teve como objetivo avaliar a robustez de concretos com baixo consumo de cimento, com foco principal em desvios no proporcionamento e variabilidade granulométrica e morfológica dos agregados. Aplicando conceitos de empacotamento e dispersão de partículas, uso de fílers calcários, escolha adequada dos materiais e aplicação de métodos reológicos para desenvolvimento da composição, desenvolveu-se um concreto com efetivo baixo consumo de ligantes (3,66 kg/m3/MPa). Os resultados obtidos indicam que as mudanças granulométricas são as mais impactantes, em especial devido à variabilidade no teor de pó fino nos agregados britados. Mudanças morfológicas, em especial na fração de tamanho que mais impacta no empacotamento (fração dominante), também são relevantes. O cenário de desvios de pesagem proporcionou o menor impacto dentre os três avaliados. Estas conclusões são específicas do concreto analisado e das particularidades dos cenários de variabilidade considerados. Por este motivo esta pesquisa buscou explicar de modo mais geral a influência das diversas variáveis. A distância que separa as partículas (IPS e MPT), a área específica dos materiais granulares e as concentrações de sólidos são alguns dos parâmetros que se correlacionam com o comportamento reológico nos diversos cenários avaliados. Com base no processo experimental e de análise dos resultados aplicados, propôs-se uma metodologia para avaliação de robustez e um índice numérico para avaliação quantitativa da robustez. Foram ainda propostas algumas ferramentas que visam atribuir mecanismos robustos ao processo de produção de concreto: sistema computacional para previsão de propriedades baseado em caracterização fundamental dos constituintes, uso de reômetro de concreto como instrumento de controle de qualidade e medida no campo da robustez e instrumentação de misturador como mecanismo de detecção de mudanças na etapa de mistura. / The use of concretes with low Portland cement content is justified by technical reasons (lower hydration heat, shrinkage and cracking) and sustainability (lower energy and raw materials consumptions, CO2 emissions and demand for transport). Variability in raw materials, environmental conditions and production process result in variability of various concrete properties in the fresh and hardened states. The feasibility of applying low cement concretes in large production scale depends on the sensitivity that these concretes show, given the existing variability. Concretes with adequate robustness, that is, sufficiently tolerant to variations are desirable. This research evaluated the robustness of concretes with low cement consumption, with focus on deviations in proportioning and particle size and morphological variability of the aggregates. Applying particle packing and dispersion concepts, rheological control, use of limestone fillers and appropriate of material choice a concrete with effective low binder consumption (3.66 kg/m3/MPa) was developed. The obtained results indicate that among the considered scenarios, the particle size changes are the most impactful, especially due to the presence of fine dust in the crushed aggregates. Morphological changes, especially in the size fraction that most impacts the packing (dominant fraction), are also relevant. Weighing deviations provided the smallest impact among the three evaluated scenarios. These findings, however, are specific to the analyzed concrete and the considered variability scenarios. For this reason, this research aimed to explain more generally the influence of several variables. The distance between the particles (IPS and MPT), the specific area of the granular material and the solids concentrations are some of the parameters that explain the rheological behavior. Based on the experimental process and the analysis of the applied results, a methodology was proposed for robustness evaluation and a numerical index for the quantitative evaluation of the robustness. Some additional tools to confer robust mechanisms to the concrete production process were proposed: a computer system for forecasting concrete properties, based on fundamental characterization of the constituents, use of a mobile rheometer as a quality control instrument and mixer instrumentation as change detection mechanism during the mixing process.

O uso de escoria de aciaria, principal subproduto das industrias siderúrgicas do processo de conversão do ferro gusa em aço, como matéria-prima na produção de cimento Portland a partir de substituições de parte da escoria de alto forno, apresenta benefícios econômicos e ecológicos, visto que um resíduo industrial tornar-se-á matéria-prima na fabricação do cimento, reduzindo custo de energia, material e depósitos para estocagem de resíduos. Para tal estudo, a escória de aciaria foi submetida a refusão e a diferentes taxas resfriamento, com o objetivo de formar escorias com diferentes graus de cristalinidade. Após resfriamento foram conformados corpos de prova com adição ao cimento Portland de 0; 1,8; 3,6 e 5,4% em peso de escoria de aciaria. Foram determinados tempo de início e final pega, resistência a compressão após 3, 7, 28 e 91 dias da conformação dos corpos de prova, expansibilidade a quente e a frio. Os resultados confirmam que a escória de aciaria apresenta potencial para ser utilizada na indústria cimenteira. A verificação da influência da adição das escorias dará suporte para a Companhia Siderúrgica Nacional (CSN) decidir quanto a viabilidade da mudança do processo atual de resfriamento e quanto a destinação do resíduo. / The use of steel slag, the main byproduct of the steel industries of the process of converting pig iron into steel as raw material for the production of Portland cement by replacing part of blast furnace slag, offering economic and ecological benefits, as that an industrial - waste becomes the raw material in cement production, reducing energy costs, equipment and tanks for storage of waste. For this study, steel slag was subjected to remelting and cooled at different rates, with the goal of forming slag with different degrees of crystallinity. After cooling, specimens with addition to Portland cement of 0, 1,8; 3,6 and 5,4% steel slag were conformed. Were determined the start time and end handle, compressive strength after 3, 7, 28 and 91 days of conformation, hot and cold expandability. The results confirm that the steel slag has the potential to be used in the cement industry. The verification of the influence of the addition of slag will support the National Steel Company (CSN) on the feasibility of changing the current cooling process and the allocation of the new waste.

Os compósitos reforçados com fibras naturais são uma opção frente a fibrocimentos com amianto, devido à grande disponibilidade de fibras naturais como as de coco, sisal além das fibras de celulose. Aspectos relacionados com a durabilidade precisam ser melhorados, podendo ser citado a diminuição da resistência das fibras quando em meio alcalino causando a perda de propriedades mecânicas dos compósitos. Uma alternativa a esse problema é o uso de pozolana que irá consumir o hidróxido de cálcio proveniente da hidratação do cimento Portland, resultando em fases hidratadas como o C-S-H e aluminatos de cálcio, contribuindo assim, para a redução da alcalinidade e para o aumento da resistência mecânica. A metodologia adotada consistiu da análise do efeito de ciclos de molhagem e secagem quanto à formação de produtos da hidratação do cimento e da reação pozolânica a partir de formulações de cimento, filler dolomito, pozolana (metacaulim ou sílica ativa) e fibras de PVA (polivinil álcool) e celulose. As pozolanas empregadas foram efetivas no consumo de hidróxido de cálcio, porém não se constatou grandes ganhos mecânicos devido à degradação da matriz, observada em 250 ciclos, causada pela formação de hidróxido de magnésio com caráter expansivo. As hipóteses para a causa da formação de brucita consistem da reação de desdolomitização do filler dolomito ou da hidratação do periclásio que compõe o cimento Portland. / Composites reinforced with natural fibers are a good asbestos fibercomposites replacement material, as a result of the great natural fiber avaibility such as coco nut, sisal and cellulose. Durability aspects need to be improved, like the decrease of fiber resistance in alkaline environment causing the loss of mechanical properties of the composites. An alternative way to solve this problem is using pozzolan. It will react with calcium hydroxide formed by Portland cement hydration and will provide hydration phases as C-S-H and calcium aluminate hydrated, which contributes for the alkaline reduction and in an increase of mechanical performance. The methodology analyzes the effect of wet/dry cycles in composites among the hydration of cement and pozzolanic reaction in composite formulation made with cement, dolomite filler, pozzolan (metakaolin or silica fume) and PVA and cellulose fibers. The pozzolans used in this study consumed almost calcium hydroxide, although low mechanical properties were found. The matrix degradation with expansive brucite formation is explained with two hypotheses: dedolomitization reaction from dolomite filler or periclase hydration from Portland cement observed from 250 cycles.