<p>Jedno od specijalnih jestivih ulja koje se proizvodi isključivo mehaničkim postupkom i koje se može uvrstiti u grupu funkcionalnih prehrambenih proizvoda je ulje semena tikve. Ovo ulje je veoma atraktivno za potro&scaron;ace, pre svega zbog svoje karakteristične arome, visoke nutritivne vrednosti i dokazanog blagotvornog delovanja na zdravlje. Cilj istraživanja u okviru ove teze je bio da se izvr&scaron;i karakterizacija senzorsko nutritivnog kvaliteta i oksidativne stabilnosti hladno presovanih i devičanskih ulja tikve sa trži&scaron;ta, ispita uticaj termičke obrade semena na kvalitet, nutritivnu vrednost i održivost devičanskog tikvinog ulja i da se defini&scaron;u senzorska svojstva i održivost hladno presovanog ulja semena tikve. U cilju karakterizacije ulja ispitivanja su sprovedena na većem broju uzoraka hladno presovanih i devičanskih ulja semena<br />tikve nabavljenih neposredno, slučajnim izborom sa domaćeg i inostranog trži&scaron;ta. Definisana su osnovna svojstva i najbitnije kvalitativne razlike između ove dve kategorije ulja proizvedenih različitom tehnologijom. Iako se proizvode iz iste sirovine tikvina ulja se međusobno bitno razlikuju po brojnim kvalitativnim, a naročito senzorskim svojstvima (ukus, miris, aroma i boja) &scaron;to može da stvori zabune kod<br />potro&scaron;aca. Ispitivanjima uticaja različite termičke obrade semena utvrđeno je da proces pečenja mlevenog materijala neposredno pre presovanja bitno utiče na kvalitativna svojstva i održivost devičanskog ulja. Termička obrada mlevenog semena pri temperaturi u interval od 90 do 130 ^oC i vremenu od 30 do 70 min pokazala je različit uticaj na senzorski kvalitet, sadržaj bioaktivnih komponenata i oksidativnu stabilnost ulja ispoljavajući kako negativan, tako i pozitivan efekat. U delu istraživanja vezanih za definisanje senzorskih svojstava i određivanje održivosti ulja izdvojenog postupkom hladnog presovanja osu&scaron;enog semena tikve na pužnoj presi, ustanovljeno je da se najkvalitetnije ulje dobije pri prvom presovanju, buduci da je aroma ulja najbolja, pri tom su kiselinski i peroksidni broj najmanji, a indukcioni period najduži. Ovo se potvrdilo, kako pri presovanju samo semena golice, tako i pri presovanju golice sa dodatkom semena sa ljuskom. Promene najbitnijih pokazatelja u cilju odredivanja održivosti ulja praćene su periodično u trajanju od 2 godine. U<br />tom periodu do&scaron;lo je do izvesnog pogor&scaron;anja senzorskog kvaliteta ulja, određenog porasta kiselinskog i peroksidnog broja, kao i do smanjenja indukcionog perioda. Medutim, bez obzira na intenzitet nastalih promena, ulja su odgovarala svim zakonskim normama kvaliteta i nakon dve godine čuvanja. Ipak, radi obezbeđenja vrhunskog kvaliteta za rok trajanja hladno presovanih ulja semena tikve golice može se preporuciti period najvi&scaron;e do godinu dana.</p> / <p> Pumpkin seed oil is one of the specialty oils produced only by mechanical procedure and can be classified in the group of functional food products. This oil is very attractive (interesting) for the consumers first of all for its characteristic flavour, high nutritive value and proved beneficial effect on health. The aim of the investigations in the scope of this thesis was to characterize the sensoric-nutritive quality and oxidative<br /> stability of cold pressed and virgin pumpkin seed oils from the market, to investigate the effect (influence) of heat treatment of seed on quality, nutritive value and stability of virgin pumpkin seed oil and to define the sensory characteristics and stability of cold pressed pumpkin seed oil. Aiming to characterize the oil, a number of cold pressed and virgin pumpkin seed oil samples, randomly taken from the domestic and foreign market, were investigated (analyzed). The basic characteristics and most important qualitative differences between these two categories of oils produced applying different technologies were defined. Both types of pumpkin seed oils are produced from the same raw material, however, they differ significantly regarding a number of<br /> quality, and expecially sensory proterties (taste, odour, flavour and colour), so the consumers may become embarrassed. Investigating the influence of different heat treatment of seed, it was found that the roasting of ground material before the pressing affects significantly the quality characteristics and stability of virgin oil. The heat treatment of ground seed at temperatures 90 to 130 &deg;C, for 30 to 70 min, showed different influence on sensory quality, content of bioactive components and oxidative stability of oil, exhibiting both negative and positive effect. In the part dealing with the defining of sensory characteristics and stability determination of oil obtained by cold pressure of dried pumpkin seed on screw press, it was found that most quality oil was obtained by the first pressing process, the oil flavur is the best, with lowest acid and peroxide value, and the induction period is the longest. This was confirmed by pressing both hull-less pumpkin and hull-less with the addition<br /> of pumpkin seed with hull. The most important characteristics for oil stability were<br /> followed for two years. In this period a certain deterioration of sensory quality was found, the acid and peroxide value increased, and the induction period decreased. However, disregarding the intensity of changes, the oil samples are in accordance with all legal quality normatives even after two years from the production date. However, in order to maintain the high (first-class) quality of cold pressed oil of hull-less pumpkin seed, the recomended period for the shelf-life of oil is one year.</p>

A fim de garantir a inocuidade, alguns alimentos industrializados são termicamente tratados por um processo contínuo denominado pasteurização, o qual visa inativar os micro-organismos patogênicos, mantendo, ao mesmo tempo, a sua qualidade sensorial e nutricional. Essa operação é aplicada a produtos como sucos, leite, cervejas, polpas, entre outros. A modelagem matemática deste processo tem como intuito auxiliar no entendimento, controle e posterior otimização desta operação. O principal objetivo deste trabalho foi o desenvolvimento da modelagem do processo contínuo da pasteurização HTST do leite e a validação experimental do modelo empírico da incrustação do produto nas placas do trocador de calor, em malha aberta (sem PID). A modelagem fenomenológica foi composta por balanços diferenciais de energia, para temperatura, e de material, para letalidade, nos canais, nas placas, no tubo de retenção e nas conexões do pasteurizador. Também foi realizada a modelagem empírica da incrustação do leite na seção de aquecimento. Os modelos desenvolvidos representam um conjunto de equações diferenciais ordinárias de primeira e segunda ordem, o qual foi resolvido pelo método das diferenças finitas, pelo uso do software gPROMS. O modelo foi aplicado para representar o comportamento de um pasteurizador a placas de escala laboratorial, com e sem incrustação, com e sem perturbações no sistema e durante a partida do equipamento, através de estudo de caso. Os dados simulados foram apresentados pela distribuição unidimensional e temporal de temperatura e da letalidade do tratamento, ao longo do processo, e do perfil do coeficiente global de troca térmica na seção de aquecimento. Para a validação do modelo de incrustação foi realizado um ensaio experimental da pasteurização de solução proteica (similar ao leite). Inseriu-se termopares em diversos pontos do equipamento e as temperaturas foram registradas ao longo do tempo. As placas do trocador foram pesadas e fotografadas antes e depois do teste para controle da quantidade de material depositado. A partir dos resultados laboratoriais, fez-se o ajuste dos parâmetros do modelo de incrustação, simulando novamente. Esses resultados foram comparados aos experimentais, sendo, então, o modelo validado. / In order to guarantee harmlessness, some processed foods are thermally treated in a continuous process named pasteurization, in which the purpose is to eliminate pathogenic microorganisms, while avoiding sensorial and quality losses. This operation is used in products such as juice, beers, milk and dairy food, pulp, and so on. Mathematical modeling of this process seeks to help its understanding, controlling, and optimization. Thus, the aim of this work was to develop and simulate a model of a continuous process pasteurization, and to conduct the experimental validation of a fouling model in the plates of the heat exchanger plates, without a process controller (PID). The phenomenological modeling was composed by differential energy and material balances, for temperature and lethality, respectively, in the channels, plates, holding tube and its connections of the pasteurizer. It was also developed an empirical fouling model for the product in the heating section. All these models represent a set of first and second order differential equations which were solved by a finite difference method through the gPROMS software. This modeling was used to express the behavior of a laboratory scale plate pasteurizer, with and without fouling, with and without system disturbances and during the equipment startup, in a case study. The simulated data was presented by the unidimensional spatial and temporal distribution of temperature and lethality along the process, and overall heat transfer coefficient profile in the heating section. To validate the fouling model, an experimental test by using a protein solution (similar to cow milk) was conducted. The temperature logging over time was done by various thermocouples inserted in the pasteurizer. All the plates were weighed and photographed before and after the tests to quantify the amount of deposits. From laboratory results, fouling model parameters were adjusted and simulation was performed again. These results were compared to the experiments, being the model validated adequately.

Os mexilhões são alimentos marinhos freqüentemente ingeridos crus, ou parcialmente cozidos, e o hábito de aferventar estes bivalves somente até que abram as valvas, é insuficiente para eliminar os microrganismos patogênicos eventualmente presentes neste molusco. Após levantamento inicial, e visando melhorar a qualidade do mexilhão Perna perna cultivado e comercializado no município de Ubatuba, SP, esta pesquisa estudou o crescimento de Staphylococcus aureus e Bacillus cereus em mexilhões in natura e pré-cozidos, e a eliminação dos mesmos por meio de tratamentos térmicos, avaliando, posteriormente, as características físico-químicas e sensoriais dos produtos. Em ambos os casos, lotes de 1 kg de mexilhão foram inoculados, individualmente, com cepas de S. aureus e B. cereus e mantidos, por 10 horas, a temperatura ambiente (25ºC±1ºC) e sob refrigeração (7ºC±1ºC). Posteriormente, foram estabelecidos seis tipos de tratamentos térmicos, sendo três sob vapor (5, 10 e 15 min) e três por imersão em água (5, 10 e 15 min), buscando estabelecer o binômio que proporcionasse a eliminação dos mesmos, e avaliando o rendimento, os aspectos físico-químicos e sensoriais. Para ambos microrganismos, ocorreu crescimento durante as 10 horas de estudo, sendo este mais evidente, nos tratamentos mantidos a temperatura ambiente. No mexilhão pré-cozido ocorreram as maiores contagens microbianas, se comparado ao mexilhão in natura. Com relação aos tratamentos térmicos, todos foram eficientes, eliminando os microrganismos da ordem de, pelo menos 2 ciclos logarítmicos, no entanto, os tratamentos térmicos por imersão em água, permitiram melhores resultados do que os tratamentos sob vapor. As análises fisico-químicas e sensoriais, não apresentaram diferença estatística entre os tratamentos térmicos estudados. Com o emprego de altas temperaturas por um determinado período, obteve-se perda de alguns minerais, como Potássio e Boro, tendo outros, não apresentado alteração com relação ao tempo de exposição ao calor. Já, quanto ao rendimento, houve diferença, em nível de 5%, sendo os melhores rendimentos alcançados nos menores tempos de exposição ao calor e, os tratamentos por imersão, apresentaram resultados melhores que os tratamentos sob vapor. Concluiu-se que o tratamento térmico, binômio tempo-temperatura, de 10 min em água à ebulição, é suficiente para reduzir os microrganismos, permitindo a retenção dos nutrientes e um rendimento de 54,36%, podendo, portanto, ser recomendado para os produtores, visando melhorar a qualidade do mexilhão, via adequação do manejo atualmente empregado. / Mussels are seafood frequently ingested raw or partially cooked and the habit of boiling bivalves only to open the valves, is insufficient to eliminate several species of pathogenic bacteria. Seeking to improve the quality of the cultivated and marketed Perna perna mussel in the district of Ubatuba, SP, this research studied the microbiological growth of Staphylococcus aureus and Bacillus cereus in fresh and pre-cooked mussels, and the elimination by thermal treatments, being evaluated its physicochemical and sensorial characteristics. For such, lots of 1 kg of mussel was inoculated individually with strains of S. aureus and B. cereus, and maintained by 10 hours at environmental temperature (25ºC±1ºC) and under refrigeration (7ºC±1ºC). Six thermal treatments were established, 3 in steam (5, 10 and 15 min) and 3 in boiling water (5, 10 and 15 min), being looked in the elimination of B. cereus and S. aureus, and also evaluating the performance, and physical-chemical and sensorial aspects. Microbiological growth was verified after 10 hours for both microorganisms, and this being more evident in the treatments maintained at environmental temperature. Pre-cooked mussel obtained the largest microbial developments, if compared to fresh mussels. About the thermal treatments, everyone was efficient, eliminating at least 2 logarithmic cycles, however, thermal treatments in boiling water obtained better results than the steam treatments. The physical-chemical and sensorial analyses, didn't present statistical difference among the thermal treatments studied. Use of high temperatures for a determinate period, obtained lost in some minerals, like potassium and boron, and others minerals not presented alteration in relation to the heat time exposure. Already in the performance, it was obtained statistical difference, being the best performances reached in the smallest times of heat exposition, and the treatments in boiling water presented better results than the steam treatments. The thermal treatment, binomial time-temperature, of 10 min in boiling water, is enough to reduce the microorganisms, allowing the retention of the nutrients and performance of 54.36%, could be recommended for the producers seeking to improve the traditional handling.

O objetivo principal do presente estudo foi avaliar o efeito do tratamento térmico das partículas strand (pré-tratamento) e dos painéis (pós-tratamento) sobre as propriedades físicomecânicas dos painéis, visando principalmente à melhoria de sua estabilidade dimensional. O delineamento experimental se constituiu de sete tratamentos, com a avaliação de: Duas temperaturas de tratamento das partículas (200 e 240°C) por um período de 60 minutos; do póstratamento térmico dos painéis produzidos com e sem a aplicação de parafina na temperatura de 220°C e por um período de 12 minutos; e do aumento do teor de adesivo e a aplicação de parafina em painéis sem tratamento térmico. Para cada tratamento foram produzidos três painéis com densidade nominal de 0,65 g/cm³, colados com adesivo à base de fenol-formaldeído. O ciclo de prensagem dos painéis foi o seguinte: pressão de 35 kgf/cm², temperatura de 160ºC e tempo de 8 minutos. A partir dos painéis produzidos, corpos-de-prova foram obtidos para a realização de ensaios físicos (Teor de umidade, densidade aparente, absorção de água e inchamento em espessura) e mecânicos (Módulo de ruptura, Módulo de elasticidade e Ligação interna), conduzidos conforme as normas ASTM D 1037 (2006) e DIN 52362 (1982). Mediante à análise dos resultados dos ensaios foi possível extrair as seguintes conclusões: Os painéis produzidos com as partículas tratadas termicamente a 240°C apresentaram-se superiores aos outros tratamentos em todas as propriedades físicas avaliadas, sendo portanto o tratamento com a melhor estabilidade dimensional. O pós-tratamento térmico promoveu melhora significativa das propriedades físicas dos painéis sem comprometer as propriedades mecânicas. O pré-tratamento térmico teve efeito mais pronunciado sobre as propriedades dos painéis do que o pós-tratamento térmico, proporcionando a melhoria das propriedades físicas e a diminuição das propriedades mecânicas. O aumento do teor de adesivo e a aplicação de parafina não se mostraram tão eficientes na estabilidade dimensional dos painéis OSB quanto o tratamento térmico aplicado nas partículas na temperatura de 240°C. / The main objective of this study was to evaluate the effect of thermal treatment of strand particles (pre treatment) and panels (post-treatment) on the physical and mechanical properties of the panels, aiming primarily to improve the dimensional stability. The experimental design was consisted of seven treatments, with the evaluation of: two temperatures of particle treatment (200 and 240 °C) during 60 minutes; thermal post-treatment of the panels produced with and without the application of paraffin at 220 ° C during 12 minutes; and the increase in adhesive content and application of paraffin on the panels without thermal treatment. Three panels were produced for each treatment with nominal density of 0.65 g/cm ³, bonded with phenol-formaldehyde adhesive. The pressing cycle of the panels was as follows: 8- minute press time, pressure of 35 kgf/cm ², and temperature of 160 °C. From the panels produced, specimens were obtained to conduct physical tests (moisture content, bulk density, water absorption and thickness swelling) and mechanical (Modulus of Rupture, Modulus of elasticity and internal bonding), tests according to ASTM D 1037 (2006) and DIN 52 362 (1982) standard. Through the analysis of test results it was possible to conclude: The panels produced with the particles thermally treated at 240°C were superior to the others for all physical properties evaluated, and therefore it was treatment with better dimensional stability. The post-thermal treatment caused a significant improvement of the physical properties of the panels without compromising the mechanical properties. The prethermal treatment had an effect on the properties of the panels that was more pronounced than the post-heat treatment, providing improved physical properties and lower mechanical properties. The increase in adhesive content and the application of paraffin were not as efficient in the dimensional stability of OSB as the thermal treatment applied on the particles at 240 ° C.

Neste trabalho foi avaliado o efeito do termotratamento na composição química de madeiras utilizadas na confecção de tonéis e o impacto no aroma de uma solução modelo de cachaça, que apresentasse características físico-químicas desta bebida. As madeiras foram avaliadas quanto à composição química em suas formas original e termotratada. Extratos hidroalcoólicos foram obtidos em cada madeira representando a solução modelo de cachaça e em seguida, foram analisados instrumental e sensorialmente, para comprovar o efeito do termotratamento. As espécies Amburana cearensis Fr. Allem. (amburana) e Myroxylon balsamum (L.) Harms. (bálsamo) foram selecionadas, de acordo com pesquisa junto a produtores de cachaça e fabricantes de tonéis, como fornecedoras das madeiras mais utilizadas para envelhecimento de cachaça, mas ainda, sem a prática sistemática do termotratamento, durante a confecção do barril. O carvalho (Quercus sp.) foi selecionado como padrão de referência no envelhecimento de bebidas. Em relação à anatomia da madeira, a principal distinção encontrada foi a maior presença de tilos nos vasos do carvalho e a melhor distinção das zonas dos anéis de crescimento da madeira, por ser uma espécie de clima temperado. As densidades das madeiras apresentaram valores próximos para a amburana e carvalho, sendo o bálsamo uma madeira mais densa. As análises químicas efetuadas nas madeiras nativas mostraram um comportamento esperado próximo ao do carvalho (Quercus sp.). Os teores de lignina solúvel diminuíram, e os de lignina insolúvel aumentaram proporcionalmente à massa total da madeira. Os extrativos totais diminuíram em todas as madeiras termotratadas. A cromatografia em fase gasosa mostrou a formação de alguns compostos e a degradação de outros durante o termotratamento da madeira. Na análise sensorial houve diferença significativa entre as amostras termotratadas e não termotratadas, para as três madeiras, em relação ao aroma das soluções. No teste de preferência olfativo, carvalho, amburana e bálsamo termotratados e carvalho sem termotratamento foram os mais preferidos, sem diferenças significativas entre si. / On this work the effect of the termotreatment was evaluated in the chemical composition of wood that have already been used in the making of barrels and its impact in the aroma of a solution model that represents the main physiochemical conditions of this drink. The woods were appraised, as the chemical composition in their termotreated or not forms. The hydroalcoholic extracts obtained in each wood were analyzed instrumental and sensorially to prove the effect of the termotreatment on the wood. The s Amburana cearensis species Fr. Allem. (amburana) and Myroxylon balsamum (L.) Harms. (bálsamo) were selected, as a research according to producers of white rum and manufacturers of barrels, as being suppliers of the wood often used for cachaça´s aging, and still, without the systematic practice of the termotreatment, during the making of a barrel. The Oak (Quercus sp.) was selected as a refference standard in drinks aging. Due to the wood´s anatomy, the main found distinction was that there were lots of larger thilos presence in the vases Oak´s vases Neverthless the best distinction of the growing ring zones of Oaks due to temperate climate. The wood´s density showed close values for the amburana and oak, being the bálsamo a denser wood. The chemical analyses showed a next behavior to the of the oak (Quercus sp.). The values of soluble lignin decreased, and the one of insoluble lignin, proportionally increased. The totals extractive decreased in all of the termotreated wood. It could be noticed decrease in the holocellulose tenors for all of the wood explained by the hemicellulose degradation. The chromatography in gaseous phase showed the formation of some composed and the degradation of others during the termotreatment of the wood. In the sensorial analysis for the three woods there was significant difference among the termotreated samples and no termotreated in relation to the aroma of the solutions. On the preferably smell test, the oak, amburana, and bálsamo termotreated and oak without it burns were the most favorite ones, with no significant differences amongst themselves.

O aumento da população, o crescimento das grandes cidades, da industrialização e do consumo, tem trazido preocupação com relação a sustentabilidade quanto à disponibilidade energética e quanto à destinação dos resíduos sólidos urbanos gerados. Dessa forma, é fundamental realizarem-se os estudos visando novas formas de reutilização dos resíduos gerados pelas atividades industriais. Os resíduos sólidos urbanos e os pneus inservíveis gerados trazem conseqüências ao meio ambiente e às populações quando destinados inadequadamente. A destinação final dos resíduos sólidos urbanos é complexa, sendo sempre um grande desafio para as administrações públicas. Com a Política Nacional de Resíduos Sólidos (instituída pela Lei n 12.305/2010), tem-se um marco da preservação ambiental, coma a gestão e gerenciamento de resíduos sólidos, com a ordem de prioridade: não geração, redução, reutilização, reciclagem, tratamento dos resíduos sólidos e disposição final ambientalmente adequada dos rejeitos e prevê, de forma inteligente, a atribuição aos fabricantes de responsabilidade pelo retorno de produtos descartados pelos consumidores. Uma alternativa para minimizar estes aspectos e impactos ambientais é o tratamento térmico com aproveitamento energético. Este processo contribui para mais uma solução de destinação dos resíduos, proporcionado uma redução das áreas a serem utilizadas nos aterros sanitários e contribuindo como uma fonte de geração de energia elétrica / The increase in population, the growth of big cities, industrialization and consumption, have brought with them a kind of awareness about sustainability towards availability of energy and toward the destination of generated municipal solid waste. This way, it is primordial to carry out studies aiming to find new ways to reutilize the waste generated by industrial activities. The municipal solid waste and unusable tires produced cause serious consequences to the environment and to the population when these issues are improperly addressed. The final destination of the municipal solid waste is complex and it is always a big challenge to public management. With our National Policy of solid waste (established by the law number 12.305/2010).It consists of the administration and management of solid waste with the following order of priority: non-generation, reduction, reuse, recycling, treatment of solid waste and final environmentally appropriate disposal. With this we can foresee, in an intelligent way, a responsible plan for the return of goods discarded by consumers to the original manufacturers. An alternative to minimize these aspects and the negative environmental impacts caused is the usage of the thermal treatment with the good use of energy. This process contributes to another solution to the problem of the aforementioned waste, providing a reduction of landfill spaces and contributing to a new source of electrical energy generation

Les phosphures de métaux de transition nanométriques trouvent de nombreuses applications, notamment en catalyse hétérogène. Les silices mésoporeuses organisées (SMO) de type SBA-15, grâce à leurs paramètres physico-chimiques ajustables (surface spécifique, taille de pores, épaisseur de parois, etc.) et la reproductibilité de leurs synthèses, sont des supports de nanoparticules (NPs) de choix. Dans ce contexte, l'objectif de cette thèse est de synthétiser des NPs de phosphure de cobalt dans les pores de matrices de type SBA-15 à partir de clusters organométalliques comme uniques précurseurs. Dans une première partie, nous étudions le comportement de trois clusters contenant un ou plusieurs ligands phosphorés à haute température. Ceux-ci présentent des rapports Co/P différents, ce qui a un impact direct sur la phase phosphure obtenue après activation. Nous suivons également l'influence de l'atmosphère et de la température sur les phases formées lors du traitement thermique. Pour contrôler la taille et la polydispersité des NPs étudiées, nous avons imprégné le cluster précurseur [Co4(CO)10(µ-NH(PPh2)2)] dans des SMO de type SBA-15. L'atmosphère et la température choisies pour le traitement thermique influent sur la phase obtenue, comme précédemment, mais les conditions ne sont pas identiques. De plus, des phases parasites ferromagnétiques sont formées et des lavages à l'acide chlorhydrique concentré sont nécessaires pour s'en affranchir. Enfin, la préparation de grandes quantités de produit (transfert d'échelle) requiert l'utilisation d'un volume contrôlé lors du traitement thermique, pour assurer une homogénéité dans l'échantillon. / Nanosized transition metal phosphides find applications in various fields, including heterogeneous catalysis. Ordered mesoporous silica (OMS) such as SBA-15 are supports of choice for nanoparticles (NPs), since they feature adjustable microstructural parameters (specific surface area, pore size, wall thickness, etc.) and reproducible synthesis conditions. In this context, the goal of this PhD work is to synthesize cobalt phosphide NPs within the pores of SBA-15-type OMS, starting from organometallic clusters as single-source precursors. First, we study the behavior of three organometallic clusters bearing one or more phosphine-based ligands at high temperatures. Depending on the initial Co/P ratio, those clusters afford different phosphide phases. We also monitored the influence of the atmosphere and the temperature during the thermal treatment on the phases obtained. To control size and polydispersity of the NPs, we impregnated the cluster precursor [Co4(CO)10(µ-NH(PPh2)2)] in SBA-15-type OMS. As in the previous case, atmosphere and temperature influence the obtained phase, but the conditions are different. Moreover, ferromagnetic impurities are formed and it is necessary to wash the samples with concentrated hydrochloric acid to remove them. Finally, larger quantities of product can be prepared (scale-up) but the volume of sample thermally treated at once needs to be controlled precisely to ensure homogeneity of the final product.

Les aciers Dual-Phase (DP) sont des aciers à très haute résistance mécanique (AHSS) fortement utilisés pour des applications automobiles en raison de leur très bon compromis résistance mécanique/ductilité ainsi que par leur habilité à répondre aux multiples exigences industrielles (bas prix, assemblage, revêtement etc.). A l'heure actuelle, le développement d'aciers DP apparait durable pour la caisse-en-blanc des structures automobiles. La microstructure ferrite-martensite, caractéristique des aciers DP, est obtenue par un traitement thermique complexe composé de différentes étapes au cours desquelles différents mécanismes métallurgiques entrent en jeux. Les principales difficultés de production sont liées au fait (i)que les évolutions microstructurales sont influencées par les différents paramètres de traitement thermique (vitesse de chauffe, température ...), (ii) que les différentes étapes de traitement sont interconnectées et que (iii) les évolutions microstructurales peuvent se chevaucher et, part conséquent, interagir entre elles. Ces travaux de thèse ont pour objectif d'améliorer la compréhension des évolutions métallurgiques entrant en jeux lors des traitements thermiques des aciers DP, et notamment d'améliorer la compréhension de l'influence des paramètres de traitement. Les différentes évolutions métallurgiques ont été, dans un premier temps, caractérisées en couplant un ensemble de techniques expérimentales (dilatométrie, dureté, TPE ...) et grâce à un protocole assurant de décorréler les mécanismes se superposant et interconnectés. A titre d'exemple, les deux principaux mécanismes entrant en jeux lors de l'étape de recuit intercritique ont été, dans un premier temps, étudiés séparément ((1) la recristallisation a été étudié en dessous de la température de formation d'austénite et (2) la formation d'austénite a été étudié sur un acier pré-recristallisé) avant de se concentrer sur le cas des aciers laminés à froid où la recristallisation et formation d'austénite se superposent. Le projet avait également pour objectif de développer des outils de prédictions permettant de décrire les évolutions microstructurales basés sur des approches empiriques (loi de JMAK) ainsi que vers des modèles à base plus physique (mixed-mode modèle et modèle diffusif). Une attention particulière a été dédié à discuter de la fiabilité, l'adaptabilité, des forces et limitations des différentes approches développées. / Dual-Phase steels (DP) are one of the most used Advanced High Strength Steels (AHSS) for automotive applications because they present good strength/ductility compromise and they adapt to number of industrial constraints (low price, shaping, welding, coating etc.). Nowadays, the development of DP steels seems to be promising and sustainable for the body-in-white structure. The typical ferrite-martensite microstructure, characteristic of DP steels, are obtained by a thermal treatment composed of different stages during which metallurgical evolutions occur. Major difficulties of their processing are due to the fact that (i) microstructural evolution kinetics are influenced by cycle parameters (heating rate, annealing temperature etc.), (ii) different stages are interconnected and (iii) some microstructural evolutions may overlap and, therefore, interact. This PhD-work aimed at getting a better understanding of microstructural evolutions during the thermal cycle of DP steel and, namely, the influence of cycle parameters. Different microstructural evolutions occurring during the thermal cycle were first characterized coupling different experimental techniques (dilatometry, hardness, TPE etc.) and with a particular protocol in order to decorrelate overlapping and interconnected phenomena. As example, two major evolutions occurring during the intercritical annealing were first studied individually ((1) recrystallization was investigated below austenite formation temperature and (2) austenite formation was investigated on prior recrystallized steels) before investigated cold-rolled steel case where recrystallization and austenite formation overlap. The study was then attached to develop some predictive tools to describe microstructural evolutions based on phenomenological approaches (JMAK law) towards more physical based models (mixed-mode, diffusive models). A particular care was attached to discuss on model reliability, versatility, strengths and limitations.

Ligas de titânio do tipo ??compostas de elementos não tóxicos são materiais com potencial para aplicações biomédicas por apresentarem baixo módulo de elasticidade, efeito de memória de forma, biocompatibilidade satisfatória e boa conformabilidade. Para os biomateriais, o conhecimento das propriedades de fadiga é essencial para garantir uma alta confiabilidade para implantes ortopédicos e odontológicos. As propriedades mecânicas dependem diretamente do processamento termomecânico, da taxa de resfriamento imposta à liga e da composição química, que são fatores responsáveis pela determinação de sua microestrutura. Neste contexto, neste trabalho foi avaliado o comportamento em fadiga da liga Ti-35Nb-7Zr (% em p.) para aplicações biomédicas. Trata-se de uma liga de titânio do tipo ??e a motivação desse estudo baseou-se em complementar resultados de suas propriedades microestruturais e mecânicas obtidos em estudos anteriores realizados no DEMAR - EEL/USP. A liga foi produzida por fusão a arco a partir de materiais (Ti, Nb, Zr) de pureza comercial. A rota de processamento termomecânico envolveu as etapas de tratamento térmico de solubilização, forjamento rotativo a frio, tratamento térmico de recristalização. Um tratamento térmico ultrarrápido (Flash) foi adicionado para promover o refino de grãos e aumento da resistência mecânica. A caracterização microestrutural foi realizada por técnicas de microscopia óptica, microscopia eletrônica de varredura, microscopia eletrônica de transmissão, difratometria de raios X e medidas de dureza Vickers. As propriedades mecânicas foram investigadas por ensaios de tração uniaxial e ensaios de fadiga de alto ciclo por flexão rotativa de corpos de prova lisos e entalhados. Com relação ao conjunto de propriedades, os melhores resultados podem ser considerados para a condição recristalizada à 1000ºC/2h + flash. Os resultados obtidos neste trabalho confirmam a possibilidade de uso da liga Ti-35Nb-7Zr para aplicações biomédicas. / ?-type titanium alloys composed of non-toxic elements are materials with potential for biomedical applications because they have low elastic modulus, shape memory effect, satisfactory biocompatibility and good workability. For biomaterials, knowledge of fatigue properties is essential to ensure high reliability for orthopedic and dental implants. The mechanical properties depend directly on thermomechanical processing, alloy cooling rate and chemical composition, which are responsible for the determination of its microstructure. In this context, this work was evaluated the fatigue behavior of the Ti- 35Nb-7Zr alloy (wt. %) for biomedical applications. It is a ?-type alloy and the motivation of this study was based on complementing the results of its microstructural and mechanical properties previously obtained at DEMAR-EEL/USP. The alloy was produced from materials of commercial purity (Ti, Nb and Zr) by arc meling. The thermomechanical processing route consisted the steps of solubilization heat treatment, cold rotary forging, recrystallization heat treatment. A ultrafast thermal treatment (Flash) was additioned to promote the grain refinement and to increase mechanical strength. The microstructural characterization was done by optical microscopy, scanning electron microscopy, transmission electron microscopy, X ray diffraction techniques and Vickers microhardness tests. The mechanical properties was investigated by uniaxial tensile tests and rotary bending high cycle fatigue tests of smooth and notched specimens. With respect to the set of properties, the best results can be considered for recrystalized condition at 1000ºC/2h + flash. The results obtained in this work confirm the possibility of using the Ti-35Nb-7Zr alloy for biomedical applications.

Ultra-high performance concrete (UHPC) is relatively a new generation of concretes optimized at the nano and micro-scales to provide superior mechanical and durability properties compared to conventional and high performance concretes. Improvements in UHPC are achieved through: limiting the water-to-cementitious materials ratio (i.e., w/cm < 0.20), optimizing particle packing, eliminating coarse aggregate, using specialized materials, and implementing high temperature and high pressure curing regimes. In addition, and randomly dispersed and short fibers are typically added to enhance the material¡¦s tensile and flexural strength, ductility, and toughness. There is a specific interest in using UHPC for precast prestressed bridge girders because it has the potential to reduce maintenance costs associated with steel and conventional concrete girders, replace functionally obsolete or structurally deficient steel girders without increasing the weight or the depth of the girder, and increase bridge durability to between 75 and 100 years. UHPC girder construction differs from that of conventional reinforced concrete in that UHPC may not need transverse reinforcement due to the high tensile and shear strengths of the material. Before bridge designers specify such girders without using shear reinforcement, the long-term tensile performance of the material must be characterized. This multi-scale study provided new data and understanding of the long-term tensile performance of UHPC by assessing the effect of thermal treatment, fiber content, and stress level on the tensile creep in a large-scale study, and by characterizing the fiber-cementitious matrix interface at different curing regimes through nanoindentation and scanning electron microscopy (SEM) in a nano/micro-scale study. Tensile creep of UHPC was more sensitive to investigated parameters than tensile strength. Thermal treatment decreased tensile creep by about 60% after 1 year. Results suggested the possibility of achieving satisfactory microstructural refinement at the same temperature input despite the maximum temperature applied. For the first time, the presence of a 10 Ým (394 micro inch) wide porous fiber-cementitious matrix interface was demonstrated by nanoindentation and SEM for non-thermally treated UHPC only. Tensile creep at 90 days increased by 64% and 46% upon eliminating fibers for thermally and non-thermally treated UHPC, respectively. Increases in creep upon reducing the fiber content suggested that fibers carry part of the sustained load and thus reduce creep. Tensile creep strain was proportional to the stress applied up to 60% of the ultimate strength. No tensile creep failure occurred for a period of 1 year for pre-cracked UHPC under stress level of 40%. Also, no tensile creep failure occurred for a period of 90 days under stress level of 60%. Tensile creep failure occurred at stress levels of 70% and 80%. This study showed that fibers cannot be accounted for as shear reinforcement in lieu of stirrups unless micro-defect-free fiber-matrix interface is achieved.