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After cooking, kraft pulps always contain not only residual lignin but also significant amounts of hexenuronic acid and other non-lignin structures oxidizable by permanganate under the standard kappa number determination conditions. These here referred to as false lignin. Like ordinary lignin, the false lignin also consumes bleaching chemicals, thus increasing both the production costs and the environmental impact of bleach plant effluents. The false lignin also has an effect on pulp properties such as brightness stability. This necessitates the development of efficient experimental routines for the determination of false lignin in different types of unbleached and bleached kraft pulps, together with studies of its formation, chemical behaviour, and ultimate fate. The main aim of this work has been to establish a method for the quantification of various types of oxidizable structures in bleached kraft pulps and to study their impact on pulp quality, particularly, on the brightness stability of pulps bleached in elemental-chlorine-free (ECF) and a totally-chlorine-free (TCF) processes. Part of this research deals with the relationship between the kappa number and the lignin content in the case of partly oxidized lignins. Spruce and birch kraft pulps processed according to the ODEQP and OQ(OP)Q(PO) bleaching sequences, respectively, have been analyzed. It has been found that the oxidation equivalent of the residual lignin decreases with increasing degree of oxidation along each bleaching sequence. This finding has been further supported by experiments with a number of model compounds. The Ox-Dem kappa number method has been shown to be an accurate means of determining the residual lignin content and of monitoring the efficiency of lignin removal along different bleaching sequences. It has been demonstrated that the kappa number can always be fractioned into partial contributions, the first of which comes from the residual lignin and is measured by the Ox-Dem kappa number, and the second from the false lignin and is given by the difference between the standard kappa number and the Ox-Dem kappa number. The effect of false lignin on the pulp kappa number is most pronounced in unbleached and oxygen-delignified kraft pulps. The extractability of residual and false lignin in different solvents has been investigated. The changes that occurred in the kappa number following different extraction steps have been compared with corresponding changes in the chemical composition and the conclusion has been drawn that the hemicellulose component of a kraft pulp is a major sourse of non-lignin structures contributing to the kappa number. The influence on the brightness stability of various oxidizable structures, viz.: residual lignin, hexenuronic acid and other non-lignin structures, in spruce, birch and eucalyptus kraft pulps bleached in ECF and TCF type processes was studied. It was demonstrated that the selective removal of all false lignin structures significantly improves the brightness stability. The degree of yellowing was found to be proportional to the content of HexA groups in pulps. It has been shown that 2-furancarboxylic acid, 5-formyl-2furancarboxylic acid and reductic acid are formed during the course of thermal yellowing. The influence of two bleaching sequences, D0(EP)D1 (ECF-type) and Q1(OP)Q2(PO) (TCF)-type, on the content of different oxidizable structures in eucalyptus kraft pulp was studied in relation to the brightness stability of the pulp. It was shown by kappa number fractionation that pulp bleached to full brightness with ECF- and TCF-type sequences contains different amounts of HexA. The most significant discoloration was observed in the case of TCF-bleached pulp having an especially high content of HexA. The mechanism of the moist (8 % moisture) thermal yellowing of fully bleached kraft pulps was further studied using dissolving pulp impregnated with a set of model compounds representing the most likely HexA degradation products, viz. as 2-furancarboxylic acid (FA), 5-formyl-2-furancarboxylic acid (FFA) and reductic acid (RA), either alone or in combination with Fe(II) or Fe(III) ions. It was found that the latter two acids take part in reactions leading to colour formation whereas 2-furancarboxylic acid does not. The effect of iron ions on the colour formation appears to vary with their oxidation state. The brightness loss caused by either FFA or RA, present in an amounts similar to the content of HexA in industrial pulps, was of the same order of magnitude as that observed in industrial pulps aged under the same conditions. Based on these findings, it is suggested that the overall mechanism of moist thermal yellowing involves several stages, including the degradation of hexenuronic acid and the formation of reactive precursors, such as 5-formyl-2-furancarboxylic acid and reductic acid. The presence of ferrous ions further enhances the discoloration. / QC 20101005

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Orientador: Prof. Dr. Emery Cleiton Cabral Correia Lins / Dissertação (mestrado) - Universidade Federal do ABC. Programa de Pós-Graduação em Engenharia Biomédica, 2016. / A polpa dental, considerada um tecido mole, é o tecido mais interno do dente. Sua função principal é garantir a formação de dentina (dentinogênese) durante toda a vida do indivíduo. Sendo assim,a informação sobre sua saúde é de extrema relevância no ambiente clínico odontológico. Uma vez que a polpa do dente é diagnosticada não saudável por consequência de infecções e/ou traumas, o procedimento clínico sugere a realização de tratamento com remoção total do tecido degradado. Dessa maneira, a proposta do presente projeto de pesquisa foi a proposição de um novo método diagnóstico utilizando-se da espectroscopia de reflexão com radiações no visível e no infravermelho próximo (VIS/NIR e NIR de 350nm a 1700nm) para discriminação de polpas humanas sadias e polpas patológicas indicadas para procedimento endodôntico. Para isso, fez-se uso do modelo estatístico da Análise de Componentes Principais (PCA) nas bandas espectrais VIS/NIR e NIR para proposições de modelos matemáticos que diferenciasse os dois grupos de amostras. Os modelos apresentaram que a distinção destes dois grupos é possível com uma taxa de acertos de 94,7% no NIR e 95% no VIS/NIR. Além disso, no VIS/NIR a diferenciação dos grupos também se dava ao analisar o comprimento de onda onde ocorria o pico da emissão: observou-se que os picos do grupo sadio patológico estavam sempre acima de 700nm enquanto que os picos do grupo patológico mantinham abaixo de 700nm. Com tudo, o objetivo do presente projeto de pesquisa foi alcançado: os grupos de polpas sadias e patológicas puderam ser separados ao utilizar radiações VIS/NIR e NIR pela técnica de espectroscopia de reflexão, seja pela análise estatística da PCA por parte dos espectros no NIR ou pela análise colorimétrica do pico de emissão por parte dos espectros no VIS/NIR. / The dental pulp, a soft tissue, is the innermost tissue of the tooth. Its main function is to ensure the formation of dentin (dentinogenesis) throughout the life of the individual. Therefore, the information about their health is extremely relevant in the clinical dental environment. Since the pulp of the tooth is diagnosed unhealthy as a result of infections and/or trauma, the clinical procedure suggests performing treatment with total removal of the degraded tissue. In this way, the proposal of the present research project was the proposal of a new diagnostic method using reflection spectroscopy with visible and near infrared (VIS/NIR and NIR from 350nm to 1700nm) for discrimination of healthy human pulps and pathological pulps indicated for endodontic procedure. For this, we used the statistical model of Principal Component Analysis (PCA) in the spectral bands VIS/NIR and NIR for propositions of mathematical models that differed between the two groups of samples. The models showed that the distinction between these two groups is possible with a success rate of 94.7% in NIR and 95% in VIS/NIR. In addition, in the VIS/NIR group differentiation also occurred when analyzing the wavelength where the emission peak occurred: it was observed that the peaks of the pathological healthy group were always above 700nm whereas the peaks of the pathological group maintained Below 700nm. However, the objective of the present research project was reached: the groups of healthy and pathological pulps could be separated by using VIS/NIR and NIR radiation by the reflection spectroscopy technique, or by the statistical analysis of PCA by the NIR spectra or by the colorimetric analysis of the emission peak by the VIS/NIR spectra.

La présente étude vise à valoriser des résidus agroindustriels comme matériaux pour l’habitat et la construction. Dans ce contexte, les travaux de recherche s’articulent autour de deux axes majeurs : le développement d’un liant alternatif et l’élaboration de matériaux composites à partir de ce liant alternatif et des matériaux végétaux. Deux liants composés utilisant des cendres de bagasse, nommés cendres de bagasse-chaux et ciment-cendres de bagasse ont été étudiés. A partir de ces liants composés, deux types de matériaux composites incluant des matériaux végétaux ont été élaborés : un composite incorporant des granulats de bagasse et de coco et un autre renforcé par des pulpes d’eucalyptus. Les propriétés physiques, chimiques, mécaniques et hydriques de ces matériaux ont été déterminées. Les résultats obtenus montrent que la calcination des cendres de bagasse à 600°C et la sélection des particules de taille inférieure à un diamètre seuil compris entre 45 et 63µm augmentent sa réactivité. Le liant composé cendres de bagasse-chaux est susceptible de développer une résistance à la compression de l’ordre de 39MPa à 28 jours, une valeur supérieure à celle des liants composés matériaux pouzzolaniques-chaux étudiés dans la littérature. Grace à sa faible alcalinité, ce liant composé préserve mieux les matériaux végétaux vis à vis de leur minéralisation et leur fragilisation comparativement au liant à base de ciment. L’incorporation de pulpes cellulosiques dans le liant composé cendres de bagasse-chaux permet d’obtenir des matériaux composites ayant des propriétés à la flexion comparables à celles d’un composite ciment-pulpes cellulosiques. / The present study aims to add value to agroindustrial residues as housing and building materials. In this context, the research works revolve around two main lines: the development of an alternative binder using agroindustrial residues and the production of composite materials from this alternative binder and plant resources. Two composed binder using bagasse ash, named bagasse ash lime and cement-bagasse ash, were optimised and produced. Using these composed binder, two kinds of composite materials including plant resources were produced: one composite developed with vegetable aggregates and another one reinforced with eucalyptus pulps. The physical, chemical, mechanical and hydric properties of these materials were investigated. The results show that the bagasse ash recalcination at 600 °C and the selection of the particles under a diameter limit (between 45 and 63 µm) improve its reactivity. Blended with slaked lime, the composed binder obtained with these parameters is likely to develop a compressive strength higher than 39 MPa at 28 days; this value is higher than the compressive strength of pouzzolanic material and lime based binder studied in the literature. In addition, due to the lower alkalinity of the interstitial solution of this composed binder, related to the lime consumption by the pouzzolanic material, it better protects vegetable materials from mineralization than the binders based on Portland cement. The incorporation of the cellulosic pulps in the composed binder lime-bagasse ash produces composite materials with a similar flexural behaviour as a composite made with cement and cellulosic pulp.

A carbonatação acelerada é um processo químico que têm se tornado muito atrativa para a indústria do fibrocimento, por mitigar a degradação das fibras vegetais utilizadas nos materiais e por melhorar o desempenho físico-mecânico dos compósitos. Nesse contexto, o presente trabalho avaliou a influência da umidade no processo de carbonatação acelerada, em fibrocimentos reforçados com polpas celulósicas de eucalipto. Para o desenvolvimento das atividades experimentais foi realizado primeiramente um estudo da evolução da carbonatação nos compósitos de fibrocimento, considerando diferentes concentrações de umidade relativa (60, 70, 80 e 90%). Posteriormente, foi realizada a caracterização dos compósitos de fibrocimento por meio da avaliação do desempenho físico-mecânico, com ensaio mecânico de flexão em quatro pontos que determinou o módulo de ruptura (MOR), módulo elástico (MOE), limite de proporcionalidade (LOP) e energia específica (EE); e ensaios físicos para obtenção dos valores de absorção de água (AA), densidade aparente (DA) e porosidade aparente (PA). Os compósitos foram também avaliados quanto à durabilidade e microestrutura, através de ensaios de envelhecimento acelerado, composição mineralógica e análise microestrutural. A partir dos resultados obtidos, os compósitos carbonatados com 60% de umidade relativa apresentaram maior formação de carbonato de cálcio, maior densificação da matriz cimentícia e, consequentemente, menor quantidade de espaços vazios logo nas primeiras horas de carbonatação. Em relação ao desempenho dos compósitos de fibrocimento, as umidades de 60 e 70% permitiram que a carbonatação proporcionasse maiores valores de MOR, LOP e MOE, diferindo estatisticamente dos demais compósitos. Os ensaios físicos complementaram os ensaios mecânicos, mostrando que os compósitos carbonatados com 60 e 70% de umidade apresentaram menores valores de AA e PA, junto de maiores valores de DA. O processo de carbonatação acelerada foi favorecido pelas menores concentrações de umidade relativa, como apresentado também pelas análises de TG e DRX, que permitiram que o processo acontecesse de forma mais efetiva, melhorando a interface fibra-matriz. / The accelerated carbonation is a process that can be made very feasible for the fiber cement industry, for mitigating the degradation of the vegetable fibers used in the materials and for improving the physico-mechanical performance of composites. In this context, the present work evaluated the influence of relative humidity in the accelerated carbonation process in fiber cement composites reinforced with eucalyptus cellulosic pulps. For the development of experimental activities, a study of the evolution of carbonation in fiber cement composites was carried out, considering different concentrations of relative humidity (60, 70, 80 e 90%). Subsequently, the characterization of fiber cement composites was evaluated through the physical-mechanical performance evaluation, with a four-point mechanical test that determined the modulus of rupture, modulus of elasticity, limit of proportionality and specific energy; and physical tests to obtain the values of water absorption, bulk density and apparent void volume. The composites were also evaluated for durability and microstructure, through accelerated aging, mineralogical composition and microstructural analysis. From the results obtained, the carbonate composites with 60% relative humidity showed a higher calcium carbonate formation, a higher densification of the cementitious matrix and, consequently, a lower amount of voids in the first few hours of carbonation. In relation of the performance of fiber cement composites, the 60 and 70% humidity allowed the carbonation to provide higher values of mechanical analysis, differing statistically from the other composites. The physical tests complemented the mechanical tests, showing that the carbonated composites with 60 and 70% humidity presented lower values of water absorption and apparent void volume, with a greater filling of the empty spaces of the composites. The accelerated carbonation process was favored by the lower concentrations of relative humidity, as also shown by the TG and XRD analyzes, which allowed the process to happen more effectively, improving the fiber-matrix interface.

O aproveitamento de fibras de origem vegetal, como reforço de matrizes inorgânicas frágeis à base de cimento, é uma alternativa que tem despertado interesse ao redor do mundo pelas suas vantagens a nível econômico, social e ambiental. Porém, seu uso apresenta limitações em relação à baixa durabilidade apresentada por este material de reforço nos compósitos, refletida na perda de resistência das fibras celulósicas degradadas pelo ambiente alcalino da matriz e na instabilidade dimensional-volumétrica. Como alternativa para esse problema, pesquisas têm mostrado que é possível implementar mecanismos que modifiquem certas propriedades das fibras celulósicas antes de serem incorporadas como reforço na matriz cimentícia. Dentro desse contexto, este estudo aplicou e avaliou o efeito do tratamento de hornificação, que consta de quatro ciclos de secagem e umedecimento, sobre polpas celulósicas de eucalipto e pinus branqueadas e não branqueadas, como processo para otimizar as suas características e permitir uma maior durabilidade e desempenho dos compósitos de cimento reforçado. Foram determinadas e analisadas as características químicas, físico-mecânicas, morfológicas e microestruturais das polpas antes e após o processo de hornificação. Posteriormente, em uma segunda etapa do trabalho, foram produzidos compósitos cimentícios reforçados com polpas tratadas e não tratadas e realizada a avaliação de suas propriedades termo-físico-mecânicas, microestruturais e de durabilidade após cura térmica e 200 ciclos de envelhecimento acelerado. Os resultados indicam que o tratamento de hornificação nas fibras provocou a redução dos teores de retenção de água, não gerou diminuição significativa na viscosidade ou índice de cristalinidade e foram observadas mudanças morfológicas em relação ao colapso da fibra e maior rugosidade da sua superfície. Em relação ao desempenho das propriedades físicas dos compósitos com cura térmica ou após envelhecimento acelerado não foi identificada influência significativa das fibras de reforço tratadas, quando comparadas com não tratadas. Considerando as propriedades mecânicas, foram observadas melhorias na energia especifica de compósitos submetidos à cura térmica com fibras tratadas, destacando-se as polpas de eucalipto não branqueado tratadas como a fibra de reforço, com os melhores valores de energia especifica e módulo de ruptura. Após o ensaio de envelhecimento acelerado foi observado uma queda nas propriedades mecânicas de interesse dos compósitos para todos os tipos de fibras tratadas e não tratadas, indicando uma deterioração das polpas e perda da capacidade de reforço ao longo do tempo. Os resultados de condutividade térmica indicam que o fibrocimento com fibras hornificadas apresenta um desempenho térmico que favorece sua aplicação em coberturas de instalações zootécnicas. / The use of vegetable fibers as reinforcement of cement based inorganic matrices, is an alternative that has attracted attention around the world for its economic, social and environmental benefits. However, their use has limitations with respect to low-term reinforcement capacity in composites, reflected in the strength loss of cellulosic fibers which are degraded by the alkaline environment of the matrix and the volumetric-dimensional instability. As an alternative to this problem, several researches have showed that it is possible to implement mechanisms that modify certain properties of cellulosic fibers before their incorporation as cement matrix reinforcement. In this context, this study applied and evaluated the effect of the treatment of hornification, which consists of four drying and wetting cycles on bleached and unbleached eucalyptus and pine pulps, as a process to optimize their characteristics and allow a greater durability and performance of the reinforced cement composites. Chemical, physical-mechanical, morphological and microstructural characteristics of the pulp were determined and analyzed before and after hornification process. Later, in a second stage, cement composites reinforced with treated and untreated pulp were produced and the evaluation of its thermo-physical and mechanical properties, microstructural and durability after thermal curing and 200 cycles of accelerate aging ware assessed. The results indicate that the treatment of hornification on the fibers induced reduction of water retention values, did not cause significant decrease in viscosity or crystallinity index and morphological changes were observed regarding to the collapse of the fiber and its surface roughness increased. In relation to the physical properties of the composites with thermal curing or after accelerated aging not significant influence of treated reinforcing fibers was identified, when compared with untreated. Considering the mechanical properties improvements in specific energy was observed determined for composites subjected to thermal curing with treated fibers, highlighting the treated unbleached eucalyptus as reinforcing fiber, with the best specific energy and modulus of rupture values. After the accelerated aging a decrease in the mechanical properties of the composites was observed for all types of treated and untreated fibers indicating a deterioration of pulp and a loss of its capacity of reinforcement over time. The results of thermal conductivity indicated that the fibercements with hornificated fibers have a thermal performance that would favor its application in livestock roofing facilities.

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