O objetivo desta pesquisa foi contribuir para o entendimento sobre a suscetibilidade ao dano por umidade de misturas asfálticas densas à luz dos ensaios da ASTM D 4867 e AASHTO T 283. Para isso, foi desenvolvido um programa experimental completo que considerou a variação, em dois níveis, dos seguintes fatores: tipo de asfalto (CAP 50/70 e CAP 50/70+SBS), presença de aditivo (sem e com cal) e modo de preparo (envelhecimentos em curto e em longo prazos). O programa experimental resultou em 8 tipos de misturas asfálticas (condições experimentais) que foram caracterizadas em suas propriedades originais e após um condicionamento térmico composto de uma fase de congelamento (-18º C por 16 horas) e uma fase de descongelamento (60º C por 24 horas). A partir das análises dos resultados foi possível constatar que (i) nenhuma mistura testada foi considerada suscetível ao dano por umidade, mas a relação de resistência à tração das misturas com CAP 50/70 de ambos os métodos se encontraram no limiar dos valores limites; (ii) as misturas com asfalto modificado, em geral, apresentaram maiores valores de módulo de resiliência e resistência à tração e foram mais resistentes à ação da água; (iii) a adição de cal não promoveu mudanças notáveis nas propriedades originais, no entanto contribuiu para a manutenção ou para o aumento da resistência ao dano por umidade; (iv) os envelhecimentos em curto e longo prazos dos métodos da ASTM e da AASHTO não provocaram mudanças importantes nas propriedades originais e após o condicionamento as misturas testadas exibiram tendências de comportamentos similares. / This research presents a contribution to understanding hot mix asphalt (HMA) moisture damage susceptibility according to ASTM D 4867 and AASHTO T 283 tests. A full factorial experiment design was carried out considering the factor variations, on two levels: asphalt type (CAP 50/70 and CAP 50/70+SBS), additive presence (with or without hydrated lime) and mixture procedure (short and long term aging). The experimental program resulted in 8 types of asphalt mixes (experimental conditions) which were characterized by the original properties and after a thermal conditioning wich consisted of a freezing phase (-18 °C for 16 hours) and a thawing phase (60 °C for 24 hours). Findings indicate that (i) no one mix was considered susceptible to moisture damage, however the ITR (indirect tensile ratio) of the CAP 50/70 mixes resulted ITR near to protocol admissible values; (ii) in general, CAP 50/70+SBS mixes presented higher resilient modulus, indirect tensile strength and indirect tensile ratio values, (iii) the addition of hydrated lime did not show remarkable changes in original properties, nevertheless it contributed for maintaining or increasing the moisture damage resistance; (iv) short and long term aging procedures (ASTM and AASHTO) did not cause important changes in original properties and after conditioning the mixes showed similar behavior tendencies.

O presente trabalho foi realizado em cafeeiros (Coffea arabica L.) cv. Icatu Vermelho IAC 4045, cultivados a pleno sol e consorciados com banana ‘Prata An㒠(Musa AAB), em Mococa - SP (Latitude 21º 28’ S, Longitude 47º 01’ W, altitude 665m). Foi realizada a caracterização microclimática, entre outubro de 2001 e setembro de 2002, onde foram medidos a radiação solar global, saldo de radiação, velocidade do vento e temperatura e umidade relativa do ar nos dois sistemas de cultivo. No período do inverno de 2002 e 2003, foi realizado um estudo da influência das bananeiras na variabilidade espacial da temperatura do ar e folha, além do saldo de radiação, em episódios de resfriamento noturno. Realizou-se também uma caracterização aerodinâmica e energética dos cultivos, entre dezembro de 2002 e novembro de 2003, onde foram obtidos os perfis dos bulbos seco e úmido, além da velocidade do vento em sete níveis de medida. Entre julho de 2001 a junho de 2004 foram atribuídas notas de desenvolvimento fenológico dos cultivos, além de se avaliar, o crescimento das plantas em altura e diâmetro da copa. Nas safras de 2002, 2003 e 2004 foram avaliados os parâmetros de produção nos dois sistemas de cultivo, além da variabilidade desses nas parcelas do cultivo consorciado. Houve uma atenuação dos valores de radiação solar global (21%) no cultivo de café consorciado e uma redução de 16% e 48% nos valores do saldo de radiação e velocidade do vento, em relação ao cultivo a pleno sol. Com relação à temperatura e umidade do ar, foram encontradas diferenças apenas na temperatura máxima no ponto central da parcela do cultivo consorciado, que apresentou médias superiores em relação ao cultivo a pleno sol no verão e outono, e em relação ao ponto situado próximo as bananeiras na primavera, verão e outono. Nos episódios de resfriamento do ar no período noturno, apesar do cultivo consorciado apresentar menor perda radiativa, ocorreu apenas um acréscimo de 0,3ºC na temperatura do ar nos episódios amostrados, sendo que para a temperatura das folhas esses valores atingiram até 0,5ºC. Foi verificado ainda que a ação de quebra-vento das bananeiras no cultivo consorciado, promoveu alterações nos perfis de temperatura e umidade do ar, apresentando gradientes reduzidos, em relação ao cultivo a pleno sol, acima do dossel dos cafeeiros. Os valores médios dos componentes do balanço de energia nos sistemas de cultivos de café a pleno sol e consorciado não apresentaram diferenças. Nos sistemas de cultivo avaliados, o crescimento vegetativo em altura e diâmetro apresentou maior atividade vegetativa no período primavera-verão em relação ao período outono-inverno, não tendo sido encontradas diferenças significativas das taxas de crescimento, de desenvolvimento fenológico e dos índices de produção entre os cultivos. No cultivo consorciado, o ponto amostral próximo às bananeiras apresentou diferenças em relação aos demais pontos amostrados no crescimento vegetativo e desenvolvimento fenológico para algumas épocas do ano, além de apresentar menor produção por planta e maior massa de 100 sementes. / A study was carried out in coffee crop (Coffea arabica L.) cv. Icatu Vermelho IAC 4045, unshade and shaded by banana ‘Prata An㒠(Musa AAB), in Mococa, São Paulo State, Brazil (Latitude South 21º 28 ', Longitude West 47º 01 ', altitude 665m). The microclimatic measurements (solar radiation, net radiation, wind speed, air temperature and air moisture) were taken from October, 2001 to September, 2002 under different crops conditions. During the winter of 2002 and 2003, a study of the influence of the banana plants was done on space variability of air and leaf temperature, besides net radiation, for cold nights. The aerodynamic and energy characterization were done from December, 2002 to November,2003, by obtining the profiles of the bulb wet and dry air temperature, also measurements the wind speed in seven different levels. From July, 2001 to June, 2004 phenological data for the coffee crops were taken. The growth of the plants concerning height and diameter was also evaluated. The harvests of 2002, 2003 and 2004 were appraised by the production parameters, and their variability for different positions in shaded coffee crop. The banana trees reduced the incoming solar radiation to the coffee crop by 21%, and by 16% and 48% in the values of the net radiation and wind speed, respectively. Concerning on air temperature and air mosture, differences were found just for the maximum air temperature at the central point of the shaded crop, showing higher averages in relation to the unshaded crop during the summer and autumn, and also in relation to the nearest point to the banana plants during the spring, summer and autumn. During cold nights, spite the shaded coffee crop showing smaller radiation loss, an increment of 0.3ºC in the air temperature was observed and for the leaves the values reached 0.5ºC. It was verified an windbreak action of fanlight of the banana trees in the shaded crop, promoting deviation in air temperature and humidity profiles, showing reduced gradients, in relation to the unshaded crop, above the coffee plants canopy. The mean values of the energy balance components for the different systems of cultivation did not show difference. In the cultivation systems evaluated, the vegetative growth in height and diameter showed higher vegetative activity during the spring-summer period in relation to the autumn-winter period. No significant differences of the growth taxes, of phenological development and of the yield indexes were found. In coffee crop shaded, the nearest point to the banana plants showed differences in relation to the other amostral points in vegetative growth and phenological development for some seasons of the year, besides showing smaller plant yield and higher weight of 100 seeds.

A ensilagem de grãos de milho reidratados é uma estratégia de armazenamento vantajosa, economicamente viável e que melhora a digestibilidade do amido. Este estudo foi dividido em dois experimentos - Experimento 1: Utilização de aditivos químicos e microbianos sobre aspectos fermentativos e estabilidade aeróbia de silagens de milho reidratado. Os tratamentos consistiram em silagens de milho tratadas com Lactobacillus buchneri (LB - 5×105 ufc/g da matéria natural); Bactérias homoláticas (Homo - 5×105 ufc/g MN); Lactobacillus buchneri + homoláticas (Combo - 1×106 ufc/g MN); Lactobacillus buchneri + nitrito de sódio (LB - 5×105 ufc/g MN + 1,5 g/kg MN de nitrito) e benzoato de sódio (Benz - 2,0 g/kg MN). Foi utilizado o delineamento experimental inteiramente casualizado com 6 tratamentos e 4 repetições. Experimento 2: Utilização de silagem de grãos de milho reidratados com ou sem a adição de benzoato de sódio sobre a digestibilidade e desempenho de vacas leiteiras. Foram utilizadas 18 vacas Holandês, alocadas em três quadrados latinos para avaliação dos tratamentos: Controle (silagem de milho reidratado); Benz (silagem de milho reidratado + benzoato de sódio - 2,0 g/kg MN) e MiS (milho seco moído). Em todas as dietas o nível de inclusão do milho foi de 17,3%. No primeiro experimento, a composição química das silagens foi adequada e as perdas fermentativas foram baixas (<1,6%) para todos os tratamentos. A presença de aditivos microbianos resultou em silagens bem fermentadas, enquanto silagens Benz preservaram carboidratos solúveis e resultaram em menor concentração de produtos de fermentação. A estabilidade aeróbia foi máxima para LB, Combo e Benz (240h) e intermediária para LBNit (151h). A silagem inoculada com bactérias homoláticas foi menos efetiva em promover estabilidade aeróbia (74,7h), comparada à controle (53,5h). Os melhores parâmetros de degradabilidade ruminal da MS foram obtidos para a silagens LB e Combo. Silagem Benz e Homo foram semelhantes à Controle e o LBNIT piorou a degrabilidade ruminal da MS. No segundo experimento, O CMS foi similar entre os tratamentos, com média de 21,1 kg/dia, ao passo que a digestibilidade do amido e CNF foi maior para os grãos fermentados. O maior aporte energético das silagens gerou tendência de aumento na produção de leite corrigido para 3,5% de gordura. Ao relacionar essa produção com o CMS, os animais alimentados com silagens de grãos reidratados tenderam a uma maior eficiência alimentar. Vacas leiteiras alimentadas com silagens apresentaram menor excreção de nitrogênio ureico no leite (11,9 vs 13 mg/dL), o que sugere um melhor uso de nitrogênio para produção de proteína microbiana. O uso dos aditivos benzoato de sódio, L. buchneri e L. buchneri combinado com bactérias homoláticas é aconselhável para promover a fermentação, estabilidade aeróbia e valor nutritivo de silagens de grãos de milho reidratados. / Rehydrated corn grain silage is an advantageous storage method, economically viable and improves starch digestibility. This study was carried out in two experiments - Experiment 1: Use of chemical and microbial additives on fermentation aspects and aerobic stability of rehydrated corn grain silage. The treatments consisted of rehydrated corn silage with different types of additives: control (no additive); Lactobacillus buchneri (LB - 5 × 105 cfu/g of fresh matter); homolactic bacteria (Homo - 5 × 105 cfu/g FM); Lactobacillus buchneri + homolactic bacteria (Combo LB - 5 × 105 cfu/g + LP - 5 × 105 cfu/g FM); Lactobacillus buchneri + sodium nitrite (LB - 5 × 105 cfu/g FM + nitrite - 1.5 g/kg FM) and sodium benzoate (Benz - 2.0 g/kg FM). The experiment was made in a completely randomized design with six treatments and four replications. Experiment 2: Use of rehydrated corn silage with or without sodium benzoate on the digestibility and performance of dairy cows. Eighteen Holstein cows were distributed in a replicated 3×3 latin square design with three periods (22-d) to evaluate the effect of control treatment (rehydrated corn silage); Benz (rehydrated corn silage plus sodium benzoate - 2.0 g/kg FM) and DGC (dry ground corn). In all diets the inclusion of corn was 17.3% in dry matter basis. In the first experiment, the chemical composition of silages was adequate and the fermentative DM losses were low (<1.6%) for all treatments. The presence of microbial additives resulted in well fermented silages, while Benz silages preserved WSC and showed lower concentration of fermentation products. The aerobic stability was highest for LB, Combo and Benz (240h) and intermediate for LBNit (151h). The Homo silages was less effective in promoting aerobic stability (74.7h), compared to the control (53.5h). The best parameters of ruminal DM degradability were obtained for LB and Combo silages. Benz and Homo silages were similar to the control, while LBNIT worsened the ruminal degrability of DM. In the second experiment, dry matter intake was similar across treatments with average of 21.1 kg/day, whereas starch and CNF digestibility was higher for fermented grains. The higher energy of silages tended to increase the production of 3.5 % fat-corrected milk. Therefore, animals fed rehydrated grain silages tended to present increased feed efficiency. Dairy cows fed silages had lower excretion of milk urea nitrogen, suggesting a better use of nitrogen for microbial protein synthesis. The use of additives sodium benzoate, L. buchneri and L. buchneri combined with homolactic bacteria is advisible to improve the fermentation, the aerobic stability and the nutritive value of rehydrated corn grain silages.

Neste trabalho foi investigado o impacto da evolução dos eventos El Niño (EN) de acordo com as fases distintas da Oscilação Decadal do Pacífico (positiva, ODP(+) e negativa, ODP(-)) nas mudanças no transporte de umidade sobre o Sudeste da América do Sul (SEAS) durante o verão austral de 1950-1999. A resposta da variabilidade do Jato de Baixos Níveis a leste do Andes (JBN) e de algumas propriedades dos ciclones extratropicais sobre o cone sul do continente as modificações na circulação associadas aos eventos mencionados acima foi analisada. Foi mostrado que existem poucas mudanças significativas no regime de precipitação sobre a América do Sul ao se considerar a influência dos anos neutros do Pacífico Equatorial durante a ODP(+) quando comparado com os anos da ODP(- ). Entretanto, os eventos EN da ODP(+) indicam diferenças no padrão de anômalo de ondas em altos níveis em resposta as diferentes anomalias de Temperatura de Superfície do Mar (TSM) dos oceanos Pacífico e Atlântico Equatorial quando comparado com os eventos da ODP(-). Como conseqüência foram observadas anomalias positivas de precipitação no SEAS associadas à intensificação do fluxo convergente de umidade em baixos níveis oriundo do Atlântico Equatorial e região Amazônica para esta região durante os eventos EN da ODP(+). Todavia, os eventos da ODP(-) apresentaram anomalias positivas de precipitação apenas ao sul do SEAS e negativas ao norte desta como resposta ao movimento descendente e divergência anômala sobre o centro-leste do Brasil seguido de enfraquecimento do fluxo de umidade transportado pelos ventos alísios em direção aos subtrópicos. Os experimentos numéricos com Community Atmosphere Model versão 3.0 serviram para ajudar na interpretação das análises observacionais onde foi sugerido que o fenômeno EN é mais importante para forçar as anomalias climáticas de verão do continente do que o modo de ODP. A maior freqüência de casos de JBN detectados com o critério 1 de Bonner durante anos de EN da ODP(+) em relação a ODP(-) foi proporcional à quantidade de eventos selecionados em cada categoria. Em geral, os casos de JBN anômalo se deslocaram desde a Amazônia até o Sul do Brasil e Nordeste da Argentina, mas foi na ODP(-) que o sistema foi mais intenso apesar de apresentar menor potencial para o transporte de umidade para o SEAS quando comparado com os casos da ODP(+). Através do esquema numérico de Murray e Simmonds foi observado que, coerentemente com a intensificação do fluxo convergente de ar quente e úmido dos trópicos para o SEAS, os eventos EN da ODP(+) apresentaram ciclones extratropicais mais freqüentes e com pressões centrais mais baixas sobre o extremo Sul do Brasil, Uruguai, Nordeste da Argentina e vizinhanças do Atlântico Sudoeste em comparação com os eventos da ODP(-). / This work investigates the impact of the El Niño (EN) events and their evolution according to the PDO phases (warm, PDO(+) and cold, PDO(-)) focusing on the moisture transport exchanges from the north to the Southeast of the South America (SESA) during the austral summer period of 1950-1999. The variability of the Low Level Jet east of the Andes (LLJ) and some properties of extratropical cyclones over the southern cone of the continent in response to the modifications in the atmosphere circulation due to above mentioned events is analyzed. It is shown that on the South America continent there are not any significant changes in precipitation distribution during the neutral years in the Equatorial Pacific for PDO(+) when compared to the years of PDO(-). However, the EN events during PDO(+) indicate some differences in the anomalous wave pattern at high levels due to the variability of the Sea Surface Temperature (SST) anomalies on the Equatorial Pacific and Atlantic oceans when compared with the events for PDO(-). This implies in positive precipitation anomalies over the SESA which is associated to the enhancement of convergent moisture flux in this region. However, the events for PDO(-) showed positive precipitation anomalies only over the southern part of the SEAS and negative to the north which is associated to the downward motion and anomalous divergence over the centraleastern Brazil. This pattern may have contributed for weakening the moisture flux transported by the trade winds towards the subtropics. Numerical experiments with the Community Atmosphere Model version 3.0 also helped on the interpretation of the observational analysis where was suggested that EN events are more important to force the climate anomalies in the summer season over the continent than the PDO mode. The frequency of LLJ cases detected with the Bonner criterion 1 during the years of EN for PDO(+) is bigger than for PDO(-). The spatial position pattern for both categories of the anomalous LLJ is from the Amazon to Southern Brazil and Northeastern Argentina. During the PDO(-) the jet is more intense, however it seems to transport less moisture towards the SEAS region when compared to the PDO(+) cases. The extratropical cyclones tracked through a numerical scheme showed higher frequency and lower central pressures on the extreme of Southern Brazil, Uruguay, Northeastern Argentina and around the Southwest Atlantic during the EN events of PDO(+) when compared to the events of PDO(-). This is in agreement with the largest flux convergence of warm and humid air from the tropics to these areas.

No description available.

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No. of bitstreams: 2 Dissertação - Marília Cândido Fideles - 2018.pdf: 3128955 bytes, checksum: 7c96987d4cfb19f05d0952999fb570df (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2019-12-20 / Arrowroot is a plant that has abundant starch content and does not present gluten in its composition, arousing the interest of its use in the production of pasta. However, gluten substitution must be provided through the use of techniques, such as the arrowroot flour modification through physical processes. Starch is the highest percentage of arrowroot composition, so enrichment of the dough is an interesting alternative, and a fortification with agroindustrial coproducts sources of fiber and protein, such as passion fruit peel and bovine rumen, may be viable. The objective of this study is to produce flours from agroindustrial coproducts, to modify by different methods (ultrassonic and heat-moisture treatment) the starch of arrowroot obtained and determine the viability technological and nutritional aspects of the use of modified flours and agroindustrial coproducts, source of fiber and protein, in the production of different types of pasta. The hydration, paste and thermal properties of raw and modified flours were evaluated. The results of the ultrasound treatments vary with the temperature between 35.83 and 62% with time between 5 and 15 minutes. For heat-moisture treatment, the best results were those using the lowest temperature (105 ° C) and shorter times (15 and 30 minutes). Taking into account the use of modified flours in the production of pasta, ultrasonic treatments with parameters of intensity of 43.5% and time of 15 min and heat-moisture treatment with 105 ° C for 15 min were selected. With the technological techniques of the pasta produced, it was possible to analyze and choose the best parameters to obtain a pasta with less cooking time, loss of solids, intermediate increase of pasta, and small values of firmness, angle Hue and C* chromaticity. The proximal composition of the pasta was satisfactory, being able to be characterized as a food with high protein content and high fiber content. The pastas with the greatest desirability are a good sensory acceptance. The results obtained have the possibility to develop and improve the pasta formulated with raw and modified arrowroot flour and agroindustrial coproducts. / A araruta é uma planta que apresenta conteúdo abundante de amido e não glúten em sua composição, despertando o interesse da sua utilização na produção de massas alimentícias. Porém a substituição do glúten deve ser suprida através da utilização de diferentes técnicas, como, por exemplo, a modificação da farinha por meio de processos físicos. O amido é o maior percentual da composição da araruta, portanto o enriquecimento da massa é uma alternativa interessante, e a fortificação com coprodutos agroindustriais fontes de fibra e proteína, como a casca de maracujá e o rúmen bovino, pode ser viável. O objetivo deste trabalho é produzir farinhas a partir de coprodutos agroindustriais, modificar por métodos distintos (ultrassom e tratamento térmico em baixa umidade - TTBU) o amido da farinha de araruta obtida e determinar a viabilidade tecnológica e nutricional da utilização das farinhas de araruta modificadas e de coprodutos agroindustriais na produção de diferentes tipos de massas alimentícias. Foram avaliadas as propriedades de hidratação, de pasta e térmicas das farinhas cruas e modificadas. Os melhores resultados dos tratamentos com ultrassom são os com intensidade variando entre 35,83 e 62% com tempo entre 5 e 15 minutos. Já para o TTBU os melhores resultados da modificação são os que utilizaram menor temperatura (105°C) e menores tempos (15 e 30 minutos). Levando em consideração o uso das farinhas modificadas na produção de massas alimentícias, foram selecionados os tratamentos de ultrassom com parâmetros de intensidade 43,5% e tempo 15 min e TTBU com temperatura de 105°C por 15 min. Através das análises tecnológicas das massas alimentícias produzidas foi possível analisar e escolher os melhores parâmetros para se obter uma massa com menor tempo ótimo de cozimento, perda de sólidos, intermediário aumento de massa, e menores valores de firmeza, ângulo Hue e cromaticidade C*. A composição proximal das massas foi satisfatória, podendo ser caracterizada como um alimento com alto teor de proteína e alto teor de fibra, de acordo com a legislação. As massas com maior desejabilidade apresentaram uma boa aceitação sensorial. Os resultados encontrados indicam a possibilidade de se desenvolver e aperfeiçoar massas alimentícias formuladas com farinha de araruta crua e modificadas e coprodutos agroindustriais.

Presently, over 300 proteins or peptide based therapeutic medicines have been approved by the FDA owing to advances in protein engineering and technology. However, majority of these protein-based medications are unstable or have limited shelf life when in aqueous form. During pre-formulation and manufacturing, various technological processes including mixing, dissolving, filling (through pipes) can produce strong mechanical stresses on proteins. These stresses may cause the protein molecule to unfold, denature or aggregate. To improve stability upon formulation, they may be manufactured as freeze dried cakes that requires reconstitution with a buffer or water prior to administration. Although it has been successful in improving the stability of protein-based formulations, the freeze drying process itself also contributes to protein aggregation. This process introduces other stresses such as freezing, thawing and drying. In addition to these stresses, the agitation processes used during reconstitution may also destabilize the protein’s native structure. Two key processes used in preparation of protein based formulations were studied in this work; mechanical agitation and freeze drying. The aim of this project was to explore the aggregation of proteins that occur due to the various technological processes typical in the production of protein based formulations. The project has two parts that relates to liquid and solid formulations. In the first part, the effect of different methods of mechanical agitations on BSA protein was investigated. In the second part, the focus was on the effect of formulation (i.e. the application of amino acids) on aggregation of protein (BSA) in freeze dried formulations. Arginine and lysine were added individually into protein-based freeze-dried formulation to study their potential of improving the stability of the proteins during manufacturing, storage and reconstitution. In the formulation development, additional excipients were added to prevent moisture uptake due to the hygroscopic properties of the amino acids and to provide lyo- and cryo- protection for the protein molecule during freeze drying. Without further purification, BSA solutions prepared by using sonication, low shear rotor mixer or high shear tube/pipe mixing were studied using dynamic light scattering (DLS). Thioflavin T assay and turbidimetry analysis were used as complementary studies. In protein-based freeze dried formulations, at accelerated storage conditions, the presence of aggregates were studied in samples containing arginine or lysine using ThT assay and turbidimetry analysis. Characterisation of the freeze dried cakes was performed relative to their moisture sorption, cake shrinkage, mechanical properties and morphology using various analytical techniques. iv In the BSA solution studies, particle size analysis indicated two distributions for non-agitated BSA solution that corresponds to the average particle sizes of BSA molecules and their aggregates. Under mechanical stresses (all types), the intensity of distribution centered ≈ 7.8 nm reduces and broadens as the agitation time increases, indicating a reduction in the amount of “free” BSA macromolecules. The second distribution, as a result of increasing agitation time or shear intensity, reveals a significant shift towards larger sizes, or even splits into two particle size populations. These particle size growths reflect the formation of aggregates due to intensive collisions and, as a result, partial unfolding followed by hydrophobic interactions of exposed non-polar amino acids. UV spectra showed that aggregation in both low shear and mechanical vibration agitations were lower compared to the high shear stress. When compared to non-agitated BSA solution, ThT assay recorded ≈15 times higher fluorescence emission from the high shear samples, ≈2 times fluorescence emission from low shear and ≈6 times fluorescence emission from mechanical vibrations. Thus all the three agitation methods showed a good correlation between the results. The second part of this project was performed in three stages. In the initial 2 stages, 2- and 3-excipients component system were investigated to develop an optimal preliminary formulations which will be used in the final protein based 4-components formulations. From the 1st stage (ArgHCl/LysHCl + sugar/polyol), among 4 tested excipients (polyol and sugar), mannitol was observed to have resisted moisture uptake by the highly hygroscopic ArgHCl/LysHCl amino acids. However, mannitol is considered a good cryoprotector but has poor lyoprotection properties. Therefore, in the following stage, a 3rd excipient (in a 3-excipients component system) sucrose or trehalose, was introduced into the formulation. The formulation was made up of 20% ArgHCl (LysHCl), and various ratios of mannitol and sugar were explored. The criteria for selecting the best systems were based on ideal physicochemical properties i.e. moisture uptake, shrinkage, mechanical properties, matrix structure and appearance, and thermal properties. The final stage was the formulation of a 4-components system comprising the three excipients and combinations selected from the stage 2 studies, and the addition of BSA as the model protein. To study aggregation in this system, a freeze dried 4-components excipient/protein system was reconstituted and incubated at accelerated storage conditions over time. Fluorescence spectroscopy and turbidimetry were used to study aggregation of proteins, moisture uptake kinetics with gravimetric balance, and thermal analytical techniques were used to characterise the freeze dried cakes with and without BSA protein. This study represented a systematic analysis of aggregation of proteins in both liquid and solid formulations. Some of the novel aspects of this study include: v 1. The new experimental results obtained for aggregation of proteins in solution subjected to mechanical agitations. The high shear stress created by syringe agitation, simulated the real situation in post manufacturing process during filling through narrow pipes, and has been shown here to strongly affect the aggregation of protein macromolecules. 2. The development of a methodical approach for optimization of multi component (up to 4 excipients) protein based formulations. 3. The unexpected non-linear behavior of the physicochemical properties of the 3-excipients component system as a function of composition. To the best of my knowledge, this novel aspect has not been previously reported in literature. 4. Application of amino acid in protein based formulations has shown the inhibition of aggregation of BSA, with the highest effect observed with ArgHCl. The results of this study coincide with the conclusions published previously for aggregation of proteins in solution.

Ce travail concerne la modélisation numérique et expérimentale de la variabilité des propriétés thermo-hydriques de matériaux cimentaires en vue de l’évaluation de son impact sur la prédiction du comportement hygrothermique de parois de bâtiments. Une approche probabiliste qui prend en compte la variabilité spatiale des propriétés de matériaux lors des transferts couplés de chaleur et d’humidité a été développée. Elle est basée sur la génération, par la décomposition modale de Karhunen-Loève, de champs aléatoires spatialement corrélés. Une implémentation d’un modèle de transfert hygrothermique dans un code de simulation numérique a été ensuite réalisée en adoptant cette démarche stochastique. Cette dernière, qui considère comme variables d’entrée des champs aléatoires, permet de quantifier l’incidence de cette variabilité sur le comportement hygrothermique d’une paroi de bâtiment. Une étude préalable, dédiée à l’évaluation de l’incidence de la variabilité aléatoire du coefficient de diffusion, a été entreprise en considérant une variabilité de ±30% pour un mortier et de ±20% pour un BHP suivant une loi de distribution normale. Aussi, nous avons relevé un certain nombre d’incertitudes possibles de la teneur en eau à saturation tout en montrant leurs effets sensibles sur le résultat de la prédiction du comportement hygrothermique. Ces études ont permis de mettre en exergue l’importance de la prise en compte des incertitudes sur les données du matériau lors des simulations numériques des transferts hygrothermiques. Sur le plan expérimental, une campagne d’évaluation de la variabilité spatiale des paramètres les plus influents a été menée. Cette campagne a été réalisée sur un voile de dimension 2x1,2 m fabriqué au laboratoire. À l’issue de ce programme expérimental, l’espérance, la variance et la longueur de corrélation des propriétés étudiées (porosité à l’eau, perméabilité à la vapeur, isotherme de sorption et perméabilité au gaz) ont été déterminées. Ces trois paramètres sont indispensables pour la bonne mise en œuvre de la décomposition de Karhunen-Loève. Aussi, une autre campagne de caractérisation expérimentale a été menée sur des pâtes de ciment, mortiers et béton. Elle a été divisée en trois grandes parties selon les propriétés étudiées : (i) Les propriétés microstructurales et d’hydratation où l’on retrouve les mesures des porosités à l’eau et au mercure ainsi que les distributions de la taille des pores et une analyse de l’effet du taux d’hydratation de matériaux cimentaires sur leurs propriétés hygrothermiques. (ii) Les propriétés hydriques : dans cette partie, une analyse sous différents angles (évolution en fonction de l’âge des matériaux, en fonction de la température, effet des constituants des matériaux, etc.) a été réalisée sur les isothermes de sorption et sur la perméabilité à la vapeur d’eau. (iii) Les propriétés thermiques où des mesures de conductivités thermiques et de chaleurs spécifiques ont été effectuées. Les résultats de l’étude ont mis en exergue les limites des approches déterministes suite à leurs confrontations avec les résultats obtenus par l’approche probabiliste, mise en œuvre dans le cadre du présent travail. / This study deals with the experimental and the numerical modeling of the variability properties of cement based materials to evaluate their effects on the prediction of hygrothermal behavior of building envelops. A probabilistic approach taking into account the spatial variability of the materials properties during the coupled heat and mass transfer has been developed. It is based on the generation of spatially correlated random fields by the Karhunen Loève decomposition. The stochastic model’s program has been implemented in a numerical simulation code. Using this tool that considers the input variables as random fields, the impact of this variability on the hygrothermal behavior of building envelops was quantified. A prior study dealing with the assessment of the effect of the diffusion coefficient random variability was carried out by considering a variation of ±30% for mortar and ±20% for high performance concrete (HPC) according to a normal distribution. Also, we have identified some possible uncertainties of the water content at saturation and showed their significant impact on the prediction of hygrothermal behavior of the material. These studies highlight the importance of considering the data uncertainties of building materials during numerical simulation of hygrothermal transfers. At the experimental level, the spatial variability of the most influential parameters was evaluated. It was carried out by manufacturing a concrete wall in lab. At the end of this experimental program, the expected value, standard deviation and the correlation length of the studied properties (water porosity, water vapor permeability, sorption isotherm and gas permeability) were determined. These three parameters are important for the successful implementation of Karhunen Loeve decomposition. Also, another experimental program was conducted on cement pastes, mortars and concrete. It was divided into three parts according to the studied properties:(i) Hydrations and microstructural properties which include the measurement of water and mercury porosity, the pore size distributions and an analysis of some techniques for stopping cement hydration.(ii) Hydric properties: where an analysis of the sorption and the water vapor permeability was performed considering their evolution with materials ages, temperature…(iii) Thermal properties where measurement of specific heat and thermal conductivity were performed. The result of the study highlighted the limits of deterministic approaches after their confrontation with the obtained results using the probabilistic one developed in this work.

La simulation des transferts couplés de chaleur et de masse dans l’enveloppe du bâtiment est une pratique qui se démocratise de plus en plus. Pour les bâtiments construits avec des matériaux très hygroscopiques, l'évaluation correcte des champs de température et d’humidité est importante pour prédire avec précision les flux de chaleur et d'humidité, le confort hygrothermique et la consommation énergétique des bâtiments. En outre, l'humidité peut causer des dommages aux matériaux de construction et a un impact sur la santé des occupants. Pour les matériaux très hygroscopiques, les outils de simulation ont montré des lacunes à modéliser correctement le comportement hygrothermique. Sur ces questions, le projet de recherche HYGRO-BAT est un projet fédérateur. Dans ce contexte, nous avons développé un modèle suffisamment fin de transfert couplé de Chaleur, d’Air et d’Humidité (CAH) qui permet l’analyse des principaux phénomènes physiques mis en jeu. Afin de valider le modèle développé et d’étudier en détail le comportement hygrothermique d’une paroi très hygroscopique, nous avons conçu et réalisé un outil expérimental avec une instrumentation riche et variée permettant de simuler les contraintes rencontrées dans le cas réel. Le choix des sollicitations hygrothermiques retenues permet une compréhension progressive du modèle. De surcroît, pour simplifier l’analyse des mécanismes de transfert couplés au sein de la paroi, une formulation adimensionnée du modèle développé a été proposée, permettant ainsi de mettre en avant des nombres adimensionnels qui simplifient l’analyse du comportement d’une paroi très hygroscopique. Ces nombres permettent une nouvelle caractérisation représentative des mécanismes de transfert qui dépendent de l’état thermodynamique de la paroi / Simulation of Heat, Air and Moisture (HAM) transfers in building envelope is a practice which is becoming increasingly popular. The correct evaluation of temperature and moisture fields is important to predict accurately heat and moisture fluxes, hygrothermal comfort and building energy consumption, especially for highly hygroscopic materials. Additionally, moisture has an impact on the health of occupants and can causes damage to building materials. For highly hygroscopic materials, simulation models show discrepancy to the real hygrothermal behavior. The research project HYGRO-BAT is a unifying project on these issues. In this context, we developed a hygrothermal transfer model sufficiently fine allowing the analysis of the main physical phenomena involved. In order to validate the developed model and to study in detail the coupled heat and mass transfers for highly hygroscopic walls, we designed and realized an experimental tool that allows numerous and various measurement and creating climates encountered for building application. The choice of hygrothermal loading allows progressive understanding of involved physical mechanisms in the envelope. Moreover, to simplify the analysis, a dimensionless hygrothermal formulation was proposed. It allows highlighting dimensionless numbers which are very convenient to study the behavior of a very hygroscopic wall. These numbers allow a new representative characterization of transfer mechanisms that rely on the thermodynamic state of the wall

Cette étude vise à contribuer au développement d’un produit de construction à faible impact environnemental utilisant la terre crue. Pour cela, le comportement hygro-mécanique de la terre crue compressée à haute pression par une technique novatrice mise au point dans ce projet a été caractérisé. De plus, plusieurs méthodes de stabilisation ont été évaluées afin d’améliorer la durabilité de ce matériau, notamment vis-à-vis de l’érosion induite par l’eau. Une vaste campagne d’essais expérimentaux a été menée sur ces matériaux stabilisés ou non, à deux échelles différentes : les caractérisations des échantillons cylindriques (petite échelle) ont tout d’abord permis de sélectionner la formulation optimale. Par la suite, les tests menés à grande échelle sur les briques de terre compressée ont contribué à développer un produit pour la construction. Une nouvelle technique de fabrication basée sur l’application d’une contrainte de compactage très élevée (hyper-compactage) a été mise au point. Son objectif principal est d’augmenter la densité du matériau afin d’améliorer ses performances mécaniques. Les échantillons compactés par la méthode proposée présentent une densité sèche d’environ 2320 kg/m3, ce qui représente la valeur la plus élevée jamais enregistrée dans la littérature pour une terre non stabilisée. Les effets de la contrainte de compactage sur la microstructure du matériau ont été analysés par intrusion au mercure et adsorption d’azote liquide. Les résultats montrent que l’augmentation de la contrainte de compactage réduit la porosité du matériau, majoritairement les grands pores inter-agrégats. Cependant, le compactage mécanique influence peu les petits pores intra-agrégats. L'approfondissement de la caractérisation des propriétés microstructurales des échantillons stabilisés constitue un développement intéressant de ce travail. La résistance et la rigidité des échantillons non stabilisés et stabilisés ont été mesurées. Ces essais mécaniques confirment que la méthode d'hyper-compactage permet d’améliorer grandement la réponse mécanique du matériau par rapport aux techniques de fabrication existantes. Ainsi, les briques réalisées présentent une résistance en compression comparable à celle-là des matériaux traditionnels de construction (e.g. terre stabilisée et briques en terre cuite). Pour compléter cette étude, des essais mécaniques à l’échelle paroi sont à mener. Le comportement hygroscopique des échantillons stabilisés et non stabilisés a été analysé par la mesure du paramètre MBV (i.e. Moisture Buffering Value), qui traduit la capacité d’échange avec la vapeur d’eau. Il s'avère que la terre non stabilisée possède une excellente capacité à absorber et relarguer l’humidité ambiante. Cette capacité est, par contre, réduite pour les échantillons stabilisés testés dans le cadre de cette étude. La caractérisation du comportement thermique de la terre compressée à haute pression ainsi que l’analyse expérimentale des transferts thermo-hygroscopiques à l’échelle paroi représentent deux compléments d'étude afin de préciser le comportement hygroscopique d'un mur à base de terre crue. Enfin, la durabilité par rapport à l’érosion induite par l’eau des briques stabilisées et non stabilisées a été estimée à travers les essais d’immersion, de succion et de contact qui sont prévus par la norme DIN 18945 (2013). Les briques stabilisées montrent une meilleure résistance à l’eau par rapport aux briques non stabilisées. Toutefois, des études supplémentaires sont nécessaires pour améliorer les méthodes de stabilisation garantissant la durabilité dans le cas d'applications structurelles exposées aux intempéries, tout en maintenant de bonnes performances hygro-mécaniques et un faible impact environnemental. / The present work explores the hygro-mechanical behaviour of a raw earth material and investigates different stabilisation techniques to improve the durability of the material against water erosion. An extensive campaign of laboratory tests was performed on both unstabilised and stabilised materials at two different scales: small cylindrical samples and large bricks. An innovative manufacturing method based on the application of very high compaction pressures (hypercompaction) was proposed. Also, the compaction load was maintained constant for a sufficient period of time to allow soil consolidation. The main objective was to increase material density, thus improving mechanical performance. Samples compacted with the proposed method exhibited a dry density of about 2320 kg/m3, which is the highest value registered in the literature for an unstabilised earthen material. The effect of the compaction pressure on the material fabric was assessed by means of mercury intrusion porosimetry and nitrogen adsorption tests. Results showed that the increase of compaction pressure reduced material porosity with major effects on large inter-aggregate pores. On the contrary, small intra-aggregate pores were not affected by the mechanical compaction. Mechanical tests were then performed to measure stiffness and strength of both unstabilised and stabilised samples. These tests demonstrated that hypercompaction can largely improve the mechanical response of the material over conventional manufacturing methods. Hypercompacted bricks showed a compressive strength comparable with that of traditional building materials, such as stabilised compressed earth and fired bricks. The hygroscopic behaviour of both unstabilised and stabilised samples was investigated. The capacity of the samples to absorb/release water vapour was assessed by measuring their moisture buffering value (MBV). Results showed that unstabilised earth has an excellent capacity to buffer ambient humidity. This capacity was significantly reduced by the different stabilisation techniques tested in the present work. Finally, the durability against water erosion of both unstabilised and stabilised bricks was assessed by performing different tests prescribed by the norm DIN 18945 (2013). Stabilised bricks exhibited a higher resistance against water erosion compared to unstabilised bricks. Still, these materials cannot be adopted for structural applications exposed to natural weathering as indicated by the norm DIN 18945 (2013). Therefore, further investigation is required to identify novel stabilisation methods that can balance the needs of sustainability, durability, moisture buffering and mechanical performance.