O objetivo deste trabalho é analisar a distribuição das tensões residuais que resultam da combinação das variações volumétricas resultantes dos gradientes térmicos e das transformações de fase que ocorrem durante a têmpera de cilindros de aço AISI/SAE 1045, 4140 e 4340. O modelo matemático usado para este objetivo utiliza o programa AC3 de modelagem de tratamentos térmicos (curvas de transformação, curvas de resfriamento, microestrutura e a dureza do material), para alimentar um modelo de elementos finitos, considerando acoplamento termo-mecânico e comportamento não linear elasto-plástico, para previsão de tensões residuais em cilindros de aço AISI/SAE 1045, 4140 e 4340 temperados em água. São apresentados, também, os resultados de observações metalográficas e perfis de dureza que confirmam qualitativamente as previsões do programa AC3. A verificação do modelo numérico por elementos finitos foi efetuada através da medição das tensões residuais nos cilindros de aço com o emprego da técnica de difração de raios X. A simulação numérica, através do método dos elementos finitos comprova, nos três casos estudados, a existência de tensões residuais de compressão na região superficial após o processo de têmpera e indica de maneira quantitativa e qualitativa que as tensões mais significativas são as tangenciais. Os resultados obtidos a partir do modelo numérico mostraram uma aderência significativa em comparação com os resultados experimentais. / The aim of this work is to analyze the distribution of residual stresses resulting from combination of volumetric changes due to heat gradients and phase changes occurring during the quenching process of AISI/SAE 1045, 4140 and 4340 steel cylinders. The mathematical model used for this objective uses the AC3 program for modeling thermal treatments (transformation curves, cooling curves, microstructure and material hardness), whose results were fed into a finite element model, considering thermal-mechanical coupling and non-linear elastic-plastic behavior for forecasting of residual stresses in AISI/SAE 1045, 4140 and 4340 steel cylinders quenched in water. The observed microstructures and measured hardness confirmed qualitatively the previsions of the AC3 program. The results of finite element modeling were compared to experimental measurements of residual stresses measured at the surface, using X-Ray diffraction techniques. The finite element numerical simulation shows, for the three studied cases, the presence of compressive residual stresses in the surface region after a quenching process and indicates qualitatively and quantitatively that the most significant stresses are the tangential ones. The results obtained from the numerical model showed a significant adherence in comparison with the experimental results.

Orientadores: Marcelo Cristianini, Pilar Rodriguez de Massaguer / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-12T13:04:24Z (GMT). No. of bitstreams: 1 Tribst_AllineArtigianiLima_M.pdf: 3194893 bytes, checksum: 2ef1a8dcf449b5ddd301d699b525063b (MD5) Previous issue date: 2008 / Resumo: O néctar de manga é apreciado por sua cor e aroma. Este produto, pela sua alta acidez, pode ser contaminado por bolores, dentre os quais são de grande relevância aqueles capazes de sobreviver ao processamento térmico. O processamento a alta pressão dinâmica (APD) é um tratamento ¿a frio¿ realizado para inativação de microrganismos visando uma melhor qualidade sensorial e nutricional do produto obtido. Neste estudo, avaliou-se o efeito do processamento a APD isoladamente ou combinado com tratamento térmico (TT) brando na inativação de Aspergillus niger em néctar de manga e, posteriormente, foi realizada a avaliação do efeito dos processos sobre a cor e a concentração de vitamina C do néctar. Paralelamente foi desenvolvida uma metodologia para limpeza e sanificação do equipamento e um processo para a redução de viscosidade do néctar de manga. Foram estudadas pressões entre 100 e 300 MPa para a inativação do Aspergillus niger. A pressão de 300 MPa inativou toda a carga inicial (> 6,24 reduções decimais), 200 MPa provocou uma inativação parcial (aproximadamente 2 ciclos) e, pressões inferiores a 150 MPa não resultaram em inativação significativa do A. niger. Quando o processo de APD foi associado à TT brando (80ºC/15minutos) foi observado um efeito sinérgico entre pré tratamento a APD e posterior TT (aproximadamente 1 ciclo logaritmo); já quando utilizado pré TT seguido de tratamento a APD, foi observado apenas um efeito aditivo. Utilizando-se aplicação de APD seguida de TT, foi realizado um planejamento experimental fixando-se a pressão em 200 MPa e variando-se temperatura e tempo do TT e ratio do néctar de manga (brix/acidez), de forma a obter um modelo que descrevesse o processo. Os resultados indicaram que tempo e temperatura afetaram positivamente a inativação e o ratio do néctar afetou negativamente. A partir do modelo foram estabelecidos que processos a 200 MPa seguido de TT a 73,5ºC/10 minutos ou 61,5ºC/20 minutos eram suficientes para obter 5 reduções decimais do bolor. A avaliação desses processos combinados, do processo térmico tradicional (100ºC/10 minutos) e do processo utilizando apenas pressão (300 MPa) sobre o conteúdo de vitamina C e cor do néctar demonstrou uma inativação de vitamina C muito similar para todos os processos (perdas de aproximadamente 45%) e uma melhor retenção de cor para os produtos processados à APD. O desenho do processo de limpeza e sanificação para o equipamento foi considerado eficaz uma vez que reduziu para < 1 UFC.mL-1 a contaminação de A.niger inicial de aproximadamente 106 UFC.mL-1 na água de enxágüe. Foi utilizada concentração de 0,05% de ácido peracético e 2,5% de detergente comercial cujos princípios ativos eram o toluenosulfonato de sódio e cloreto de didecilmetilamônio. O processo de redução de viscosidade do néctar também foi efetivo através de seu pré tratamento com enzimas pectinolíticas e celulases, que reduziram a viscosidade inicial do néctar em 50%. Pelos resultados obtidos no presente trabalho, observa-se que a APD isoladamente ou aplicada junto com TT brando é uma alternativa viável para a inativação de A. niger termorresistente em néctar de manga. O processo teve efeito negativo sobre a vitamina C do néctar de manga, o que pode ser atribuído tanto à presença de oxigênio na amostra quanto à presença de selos metálicos no equipamento (selos de berílio-cobre) que promovem a passagem de íons metálicos para o suco, os quais atuam como pró-oxidantes de vitamina C, agravando a oxidação da vitamina / Abstract: Mango nectar is appreciated by its color and flavor. Due to its high acidity, this nectar can be contaminated by molds and the most important molds are those able to survive to the heating process. The dynamic high pressure (DHP) is a cold treatment used to inactivate microorganisms with better nutritional and sensory retention in food. In this study, the DHP process isolated or combined with mild thermal treatment (TT) was used to inactivate Aspergillus niger in mango nectar. The effects of these processes were evaluated on color and vitamin C retention. In parallel, a methodology was developed to clean in place (CIP) the DHP equipment. A process to reduce the viscosity of mango nectar was also developed. Pressures between 100 and 300 MPa were studied to Aspergillus niger inactivation. Pressure of 300 MPa completely inactivated the initial load (> 6.24 decimal reduction), 200 MPa caused a partial inactivation (2 log cycles) and pressures up to 150 MPa did not inactivate the mold. A synergistic effect was observed when pre treatment of DHP was associated to mild TT (80ºC/ 15 minutes) with increase of 1 log cycle on mold inactivation. However, only an additive effect was observed when pre TT was associated to DHP. An experimental design was carried out using fixed pressure of 200 Mpa followed by mild TT. Temperature and time of thermal treatment and ratio of mango nectar (brix/acidity) was select as experimental design variables. The results indicated that time and temperature affected positively and nectar ratio affected negatively the mold inactivation. By the mathematical model, process of 200 MPa followed by 73.5ºC/10 minutes or by 61.5ºC/20 minutes was able to promote 5 decimal reduction of A. niger. The effect of these processes, the conventional heat and DHP at 300 MPa on vitamin C concentration and nectar color retention was evaluated. The vitamin C losses were around 45% for all processes studied but better color retention was observed on the nectar processed by DHP. The CIP design was considered efficient once it was able to reduce the initial load of A. niger from ~106 CFU.mL-1 to <1 CFU.mL-1. 2.5% of a commercial detergent (active agents: sodium toluenosulfonate and didecylmethilamonium chlorine) and peracetic acid at 0.05% were used in this process. The nectar viscosity reduction was effective by using pectic enzymes and celullase, being able to reduce natural mango nectar viscosity by 50%. The results obtained indicated that DHP isolated or combined with mild thermal treatment are a viable alternative to inactivate A. niger in mango nectar. The process has a negative effect on vitamin C retention. It can be attributed to the oxygen dissolved in mango nectar and also to metals seals of equipment (Be-Cu) which can had promoted an increase in metallic ions concentration in nectar. These ions are pro oxidant of vitamin C, resulting in intense vitamin oxidation / Mestrado / Mestre em Tecnologia de Alimentos

Orientador: Rubens Caram Júnior / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-23T05:01:49Z (GMT). No. of bitstreams: 1 Verissimo_NathaliaCarolina_M.pdf: 4539752 bytes, checksum: 5f6eb6507fb9a034b3aca9ed35fdea93 (MD5) Previous issue date: 2013 / Resumo: Ligas de Ti do tipo 'beta' contendo elementos biocompatíveis são potencialmente interessantes em aplicações ortopédicas e odontológicas. Enquanto as propriedades mecânicas dessas ligas podem ser controladas por meio de tratamentos térmicos, suas propriedades de superfície podem ser otimizadas por meio da formação de camada de nanotubos de TiO2 usando processos de anodização. Neste trabalho, amostras de Ti CP e das ligas Ti-35Nb e Ti-35Nb-4Sn, obtidas por fusão a arco voltaico em atmosfera inerte, foram anodizadas sob potencial constante de 20V durante 1 hora, usando uma solução aquosa de HF, a fim de obter uma camada de nanotubos de TiO2 amorfa. Tais camadas amorfas foram tratadas termicamente visando promover transformações de fase amorfo-anatase e anatase-rutilo. As amostras foram caracterizadas por meio de microscopia eletrônica de varredura. Os resultados obtidos indicam que camadas amorfas de nanotubos de TiO2 com espessura superior a 800 nm foram produzidas. Tratamentos térmicos combinados com ensaios de difração de raios-X permitiram identificar a formação de anatase em 225ºC em Ti CP, em 295ºC na liga Ti-35Nb e em 392ºC na liga Ti-35Nb-4Sn. A estrutura cristalina do rutilo foi observada no Ti CP em 398ºC e em 557ºC na liga Ti-35Nb. A formação de cristais de rutilo sobre a liga Ti-35Nb-4Sn ocorreu em 605ºC. Observou-se que o Nb combinado com Sn tem forte efeito estabilizador da fase anatase. Medidas de molhabilidade indicam que a fase anatase apresenta valores elevados de ângulo de contato, enquanto que a fase rutilo exibe valores menores e com características hidrofílicas. Os resultados obtidos sugerem que a combinação anatase-rutilo é a mais adequada para aplicações biomédicas e crescimento celular por não ser altamente hidrofílica / Abstract: 'beta' type Ti alloys containing biocompatible elements are potentially interesting for orthopedic and dental applications. While the mechanical properties of these alloys can be controlled by means of heat treatments, its surface properties can be optimized by formation of TiO2 nanotube layer using anodizing processes. In this work, samples of CP Ti and Ti-35Nb and Ti-35Nb-4Sn alloys obtained by arc melting under inert atmosphere were anodized using HF-based electrolyte for 1 hour, obtaining amorphous layers of TiO2 nanotubes. These layers were heat treated aiming to promote the amorphous structure and phases like anatase, mixture anatase-rutile and rutile. Samples were characterized by scanning electron microscopy. The results indicate that amorphous layers of TiO2 nanotubes with a thickness exceeding 800 nm were produced. Heat treatments combined with X-ray diffraction experiments allowed identifying the formation of anatase at 225ºC in CP Ti, at 295ºC in the Ti-35Nb alloy and at 392ºC in the Ti-35Nb-4Sn alloy. The crystal structure of rutile was observed in CP Ti at 398ºC and at 557ºC in the alloy Ti-35Nb. The formation of rutile crystals on the alloy Ti-35Nb-4Sn occurred at 605°C. It was observed that Nb combined with Sn shows a strong stabilizing effect of anatase. Wettability measurements indicate that the anatase phase shows high values of contact angle, while the rutile phase exhibits lower values and hydrophilic characteristics. The results suggest that the combination anatase-rutile is the most suitable for biomedical applications and cell growth because they are not highly hydrophilic / Mestrado / Materiais e Processos de Fabricação / Mestra em Engenharia Mecânica

Orientador: Rubens Caram Junior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-23T09:33:56Z (GMT). No. of bitstreams: 1 Lopes_EderSocratesNajar_D.pdf: 9279894 bytes, checksum: a2ed77cd79f48134e7daf5bc705afb0e (MD5) Previous issue date: 2013 / Resumo: Ligas de Ti do tipo ? metaestável exibem comportamento singular no tocante à possibilidade de manipulação de seu comportamento mecânico. Nessas ligas, a rigidez pode ser alterada por meio do controle das fases presentes, o que permite que esses materiais sejam incluídos no seleto grupo dos materiais com gradientes funcionais (functionally graded materials - FGM). Neste trabalho, objetivou-se projetar, produzir, processar, caracterizar e aplicar ligas Ti-Nb com adições do elemento ? estabilizador de baixo custo Fe. As ligas foram produzidas por fusão a arco voltaico e submetidas a diversas condições de tratamento térmico, incluindo solubilização acima da temperatura ?-transus, resfriamento rápido até a temperatura ambiente e tratamentos térmicos de envelhecimento entre 260 °C e 400 °C. A caracterização envolveu calorimetria diferencial de varredura, difração de raios-X e dureza Vickers em alta temperatura, análises metalográficas e de módulo de elasticidade por técnicas acústicas, ensaios de tração e mapeamento de rigidez por meio de nanoindentação. Os resultados obtidos mostram a retenção completa da fase ? para a liga Ti-30Nb-3Fe solubilizada e resfriada rapidamente e permitem também, compreender a decomposição da fase martensita ?" e a nucleação das fases ? e ?. A adição do elemento Fe tornou a cinética de transformação de fases bem mais lenta, propiciando, sob algumas condições, a supressão da fase ?, que é conhecida por aumentar a dureza em detrimento da ductilidade. Tais resultados foram utilizados no estabelecimento de condições ideais de processamento que permitem obter componentes ortopédicos com rigidez gradual. Finalmente, o conhecimento adquiro foi usado na fabricação de placas e parafusos de osteossíntese a partir da liga Ti-30Nb-3Fe com gradientes de funcionalidade / Abstract: Metastable ? Ti alloys exhibit singular behavior regarding the possibility of manipulating their mechanical behavior. In these alloys, the stiffness can be changed by controlling phases, which allows these materials to be included in the select group of functionally graded materials (FGM). This study aimed to design, produce, process, characterize and apply Ti-Nb alloys with addition of Fe, an inexpensive ? stabilizing element. These alloys were produced by arc melting and subjected to different heat treatment conditions, including solution above the ?- transus temperature, quenching to room temperature and aging heat treatments between 260 °C and 400 °C. Characterization involved differential scanning calorimetry, X-ray diffraction and Vickers hardness at high temperature, metallographic analyzes, elastic modulus by acoustic techniques, tensile test and stiffness mapping via nanoindentation. The results obtained show complete retention of the ? phase in the Ti-30Nb-3Fe alloy after solution in the ? field and rapid cooling to room temperature and also allow understanding martensite ?" decomposition and nucleation of the ? and ? phases. It was found that Fe additions make the phase transformation kinetics much slower, providing, for some conditions, suppression of the ? phase precipitation, which is known to increase the hardness at the expense of ductility. These results were used to establish optimal processing conditions, resulting in orthopedic component with graded stiffness. Finally, the knowledge acquired was used in the manufacturing of osteosynthesis plates and screws with functionality graded from the Ti-30Nb-3Fe / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Rubens Caram Junior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-21T09:06:40Z (GMT). No. of bitstreams: 1 Cremasco_Alessandra_D.pdf: 50106196 bytes, checksum: 2a7da86acd168979590189fcdb26056f (MD5) Previous issue date: 2012 / Resumo: Ligas de titânio com altos teores de elementos _ estabilizadores, solubilizadas em altas temperaturas e resfriadas rapidamente exibem limitada resistência mecânica e boa ductilidade, o que e resultado da formação de martensita ortorrômbica ou da manutenção da fase _ metaestável. Tal resistência pode ser significativamente aumentada por meio da aplicação de tratamentos térmicos de envelhecimento, que promovem a precipitação de novas fases, combinados com encruamento produzido por deformação plástica a frio. Este trabalho teve como objetivo o desenvolvimento de ligas do sistema Ti-Nb-Sn com propriedades mecânicas otimizadas visando sua utilização como biomaterial. Inicialmente, ligas de titânio com diferentes elementos de liga foram submetidas a ensaios de citocompatibilidade in vitro. Os resultados obtidos sugerem que ligas Ti-Nb-Sn sao biocompativeis. Na sequencia, amostras de ligas Ti-Nb-Sn preparadas em forno de fusao a arco foram tratadas termicamente objetivando homogeneizacao quimica e microestrutural, solubilizadas em alta temperatura, resfriadas rapidamente e deformadas plasticamente a frio. Tais amostras foram tratadas termicamente para promover a recuperacao, a recristalizacao e o envelhecimento da microestrutura. Os resultados obtidos indicam que a aplicacao de deformacao plastica e recozimento produz o refinamento da microestrutura. A aplicacao de tratamentos termicos de envelhecimento a 350 °C resultou na decomposicao da fase martensita ortorrombica e na formacao das fases _, w e a. Constatou-se que o comportamento mecanico das amostras envelhecidas reflete a combinacao das fases e suas respectivas fracoes volumetricas. O refino microestrutural e a precipitação da fase a resultaram em expressivo aumento da dureza, modulo de elasticidade e resistencia mecanica, bem como na queda da ductilidade. Finalmente, a aplicacao de condicoes de processamento otimizadas resultou em amostras com elevada resistencia mecanica e razoavel ductilidade. A liga Ti-35Nb-4Sn apresentou reduzido modulo de elasticidade e alta resistencia a tracao, condicao ideal para aplicacao biomedica / Abstract: Titanium alloys with high _ stabilizing elements content, solution heat treated at high temperatures and rapidly cooled to room temperature, exhibit limited mechanical strength and good ductility as a result of orthorhombic martensite formation or maintenance of the _ metastable phase. However, mechanical strength may be significantly improved by applying aging heat treatment, which leads to precipitation of new phases, combined with hardening provided by cold plastic deformation. The aim of this work is the development of alloys in the Ti-Nb-Sn system with optimized mechanical properties to be applied as biomaterial. Initially, titanium alloys with different alloying elements were tested in terms of cytocompatibility. The results suggest that Ti-Nb-Sn alloys are biocompatible. Following, Ti-Nb-Sn samples were prepared in arc furnace, heat treated aiming chemical and microstructural homogeneity, solution heat treated at high temperature, rapidly cooled to room temperature and cold plastically deformed. These samples were heat treated to promote recovery, recrystallization and aging of the microstructure. The results indicate that application of plastic deformation and annealing produces very refined microstructure. Application of aging heat treatments at 350 ° C resulted in decomposition of orthorhombic martensite phase and formation of _, w and a phases. It was found that mechanical properties of aged samples reflect the combination of such phases and their volume fractions. Microstructural refinement and a phase precipitation resulted in significant increase in hardness, elastic modulus and mechanical strength, as well as a decrease in ductility. Finally, application of optimal processing conditions resulted in samples with high mechanical strength and reasonable ductility. The Ti-35Nb-4Sn alloy showed lower elastic modulus and superior tensile strength. These results consist in ideal conditions for biomedical applications / Doutorado / Materiais e Processos de Fabricação / Doutora em Engenharia Mecânica

Les superalliages à base de nickel sont très utilisés pour la réalisation des parties chaudes des turbomoteurs aéronautiques. Ainsi le superalliage Inconel 718 est utilisé pour la fabrication de pièces telles que les disques de turbines. Ce superalliage est fortement utilisé car il associe de bonnes propriétés mécaniques jusqu’à 650°C à un coût raisonnable. Au début des années 2000, ATI Allvac a développé un nouveau superalliage à base de nickel dans le but de concurrencer l’Inconel 718. Ce nouvel alliage, nommé ATI 718Plus, promet des propriétés mécaniques supérieures que celles de l’Inconel 718 pour une utilisation pouvant aller jusqu’à 700°C. Pour obtenir de bonnes propriétés mécaniques jusqu’à 700°C, la composition chimique de l’alliage ATI 718Plus a été établi par ATI Allvac, de façon à obtenir la phase intragranulaire !’ comme phase durcissante, et la phase intergranulaire " comme dans l’Inconel 718. L’objectif de l’étude a été dans un premier temps de comprendre la microstructure de l’alliage. Pour cela des analyses en MEB et en MET ont été menées sur un grand nombre d’échantillons, traités à diverses températures et pour divers temps, de façon à identifier la nature cristallographique et chimique et la cinétique de précipitation des phases présentes dans l’alliage. Dans un second temps l’étude a consisté à caractériser la microstructure et les propriétés mécaniques en traction et en fluage de l’alliage ATI 718Plus traité selon neuf gammes de traitements thermomécaniques différentes. Ensuite l’étude a permis de tester trois gammes de traitements thermomécaniques dont nous avons défini les paramètres grâce aux résultats précédents de manière à optimiser la microstructure dans l’objectif d’améliorer les propriétés mécaniques de l’alliage. Les essais de traction réalisés sur une grande varieté de microstructures et pour différentes températures ont également permis de caractériser la sensibilité de l’alliage ATI 718Plus au phénomène de Portevin - Le Chatelier. / Nickel base superalloys are used to manufacture many high temperature parts of aeronautical turboengines like turbine disks. The Inconel 718 superalloy is commonly used because it associates good mechanical properties until 650°C with a moderate cost. In the beginning of the 2000’s, ATI Allvac has developed a new nickel base superalloy to compete with the Inconel 718. This new superalloy, called ATI 718Plus, promises better mechanical properties than those of Inconel 718 for a use up to 700°C. To obtain such good mechanical properties, the chemical composition of the alloy ATI 718Plus has been designed by ATI Allvac to obtain the !’ intragranular phase as the strengthening phase, and the " intergranular phase like in the Inconel 718. The objective of the study is first to understand the microstructure of the alloy. For that reason, SEM and TEM analyses were performed on a large number of samples, treated at various temperatures and for different times, to identify the crystallographic and chemical nature and the precipitation kinetic of the phases present in the alloy. In a second time, the study has consisted in characterizing the microstructure and the mechanical properties of the alloy ATI 718Plus, forged according to nine different thermomechanical treatments. Then, the study has permitted to test three thermomechanical treatments, wich parameters we have determined according to the previous results, to optimize the microstructure in order to improve alloy mechanical properties. Strength tests performed on various microstructures and several temperatures also permitted to characterize the alloy ATI 718Plus sensitivity to Portevin-Le Chatelier effect.

Au cours des procédés d’appertisation, qui impliquent des traitements thermiques généralement pratiqués à hautes températures, la qualité nutritionnelle des produits alimentaires est souvent altérée. En effet, certaines vitamines, telles que la vitamine C, sont très thermolabiles.L’objectif du projet PREDINUT était de proposer un outil d’aide à la décision afin de prévoir la quantité de vitamine C (marqueur de qualité nutritionnelle) détruite dans des conditions données de durée/température, afin de pouvoir optimiser les procédés.Un thermorésistomètre Mastia®, a été utilisé pour établir des conditions de température et pression représentatives des procédés d‘appertisation. L’impact de la variation de paramètres physico-chimiques tels que le pH, la concentration initiale en acide ascorbique ou encore la pression partielle en oxygène dans l’espace de tête, sur la dégradation de l’acide ascorbique a été étudié en solution modèle. Des études ont également été menées dans des produits alimentaires (purée de pomme, purée de carotte et jus de carotte) afin d’établir un profil de destruction de la vitamine C dans des aliments concrets. Dans ce projet, la plage de température étudiée est de 95 à 125 °C, le pH fixé en solution modèle est de 2,5 à 5,5 en conditions d’anaérobiose stricte, et de 3,5 en conditions d’aérobiose (3,5 étant la valeur de pH de la majorité des fruits), les concentrations initiales en acide ascorbique varient de 15 à 90 mg/100mL, et la pression partielle en oxygène de 30000 à 100000 Pa. Dans les produits alimentaires, les expériences ont été réalisées par enrichissement en acide ascorbique à hauteur de 450 mg/L, la valeur du pH ne subissant pas d’ajustement.Des modèles ont été établis pour décrire le profil cinétique de la dégradation de la vitamine C en aérobiose et en anaérobiose. En l’absence d’oxygène la dégradation de la vitamine C suit une cinétique d’ordre 1 (sauf à pH = 4,5). En présence d’oxygène (conditions aérobies) la vitesse de dégradation croit avec la pression partielle d’oxygène, mais très peu avec la température. Des ordres apparents variant de 0,5 à 0,75 en fonction de la pression partielle en oxygène dans l’espace de tête, s’avèrent mieux ajuster les données que l’ordre 1.Dans les aliments, le mécanisme de dégradation de la vitamine C apparaît beaucoup plus complexe, et la vitesse de réaction n’évolue pas de façon continue avec le temps, avec des phases de plateau suivies de réaccélérations. Une connaissance fine des mécanismes et des espèces chimiques impliquées sera nécessaire pour comprendre cette évolution. / Canning involves thermal treatments performed at high temperatures, which may alter nutrional quality of food products. Indeed, some vitamins, like vitamin C, are very heat sensitive.The aim of the project PREDINUT was to propose a decision support tool that predicts vitamin C (as indicator of nutritional quality) degradation in given conditions of time/temperature, in order to optimise processes.A thermoresistometer Mastia® was used to reach the temperature and pressure conditions encountered during canning. The impact of the variation pH, initial concentration of ascorbic acid or again partial pressure of oxygen in headspace, on ascorbic acid degradation was studied in model solution. Studies were also performed in apple puree, carrot puree and carrot juice in order to obtain a destruction profile of vitamin C in real foods. . The temperature range studied was from 95 to 125 °C, the fixed pH in model solution was from 2.5 to 5.5 in strict anaerobic conditions, and 3.5 in aerobic conditions (3.5 being the pH value of common fruits), initial concentrations of ascorbic acid varied from 150 to 900 mg/100mL, and the partial pressure of oxygen from 30000 to 100000 Pa. Foods were enriched in ascorbic acid (up to 450 mg/mL), and the pH value was not adjusted.Models were established to describe the kinetics of vitamin C degradation in aerobiosis and anaerobiosis. En absence of oxygen ascorbic acid degradation was well described by a first order kinetics (except at pH = 4.5). In presence of oxygen the degradation speed increased with head-space oxygen’s partial pressure but very little with temperature. Apparent reaction orders varying from 0.5 to 0.75, depending on the partial pressure of oxygen in the headspace, fitted the data better than first-order.In foods, degradation kinetics of vitamin C appeared more complex, with eventual presence of plateaus followed by acceleration of the reaction. Definitely more knowledge on mechanisms is needed to predict ascorbic acid degradation in real foods.

Les produits alimentaires secs sont courants dans l’industrie agroalimentaire. Cependant, leur innocuité n’est pas toujours assurée et de nombreux cas de toxi-infections alimentaires collectives à travers le monde sont annuellement recensés. Deux bactéries pathogènes sont particulièrement impliquées, l’une correspond à grand nombre de cas, Salmonella enterica, et l’autre est reconnue pour sa capacité à résister aux perturbations environnementales, Cronobacter spp.. Une compréhension plus poussée de l’impact du séchage et traitement thermique à l’état sec peut permettre une optimisation des procédés de de décontamination des produits alimentaires secs et contribuer à réduire le nombre de toxiinfections alimentaires. Dans un premier chapitre, une attention particulière a été portée au procédé de séchage de microorganismes pathogènes qui peut, s’il est conduit de manière rapide, réduire considérablement la cultivabilité microbienne. De cette façon, le séchage peut être considéré comme une étape supplémentaire de décontamination à condition d’en optimiser les conditions d’application. Puis dans un deuxième chapitre, l’impact de la réhydratation, rarement traitée jusqu’à présent, a été étudié afin de proposer des conditions permettant de maximiser l’inactivation bactérienne. Cette étude remet partiellement en cause les dénombrements de bactéries pathogènes dans les aliments qui peuvent être, dans quelque cas, sous estimées du fait de l’utilisation de réhydratation rapide. Dans un troisième chapitre, l’application de différents traitements thermiques sur du lait en poudre, destiné à une population dite sensible, a permis de comprendre le rôle couplé de l’activité de l’eau et de la température sur l’efficacité du traitement thermique à l’état sec mais également de proposer un modèle d’inactivation thermique des pathogènes. Il a été notamment possible de définir un paramètre représentatif de l’effet de l’activité de l’eau (yaw). Les mécanismes de mort cellulaire pour les deux bactéries ont été ensuite étudiés, que ce soit après un séchage ou après un traitement thermique. Il apparait clairement que le séchage induit majoritairement une perméabilisation de la membrane tandis que le traitement thermique des cellules viables séchées dégrade majoritairement l’activité enzymatique en détruisant peu la membrane. Finalement, il a été montré que la virulence des deux pathogènes étudiés est augmentée par le séchage mais que le traitement thermique à l’état sec n’a pas d’impact sur cette virulence. Les connaissances apportées par cette étude peuvent être utiles d’un point de vue industriel, afin d’optimiser au mieux les conditions d’application des différents procédées pour une inactivation bactérienne maximale. / Dried food products are common in food industry. Nevertheless, their safety is not well insured, involving numerous outbreaks every years around the world. Particularly, two pathogenic bacteria are of interest, one of them due to its number of cases, Salmonella enterica, and the other one due to its ability to survive environmental perturbations, Cronobacter spp.. A deeper comprehension of drying and heat treatment in dried state impact could lead to an optimization of drying and heating processes, insuring food safety. In the first instance, drying was considered as a supplementary decontamination step by optimizing its conditions of use. In a second phase, the rehydration impact was studied in order to found optimal conditions of pathogen inactivation. The study questions the rehydration currently puts in practice for food safety analysis. In a third phase, several heat treatments on a dried food product, intended to susceptible population, permitted to understand the specific role of water activity on the efficiency of heat treatment in dried state, and also propose a modelling for bacterial heat inactivation. In addition, it was possible to define two new parameters which represent the effect of temperature (zT) and the effect of water activity (yaw). Fourth, cellular death mechanisms for both studied bacteria, during the drying or during the heat treatment, were considered. It was clear that drying involved mainly membrane damages whereas heat treatment involved mainly enzymatic damages. Finally, in a fifth part, it was shown that virulence properties of both studied bacteria were affected by drying, increasing invasion capacity, but not by heat treatment in dried state. To finish, the knowledges brought by this study are useful for industrial point of view, in the case of drying and heat process optimization and also by proposing biological indicators to valid process efficiency in situ.

Pas de résumé en français / Being compared with oxide glasses, chalcogenide glasses have fine infrared transmissivity and higher optical nonlinearity, and also could be drawn into optical fibers. So chalcogenide glasses and fibers have potential wide applications in the fields of all-optical information processing, infrared lasers, nonlinear optical devices, and so on, the studies of their optical nonlinearity are one of the attractive subjects in the area of optoelectronics at present. The main purpose of this paper is to improve the stability and enhance the intensity of nonlinearity in chalcogenide glasses and fibers by means of exploring new glass compositions, optimizing the external field poling method, designing and fabricating fibers with special structures, all of these will promote their real applications. The main results are concluded as follows . The glass-forming region of GeS2-GA2S3-AgX (X=Cl, Br, I) and GeS2-Ga (In)2S3-CuI systems were determined , the maximal content of the additive halides are 70% and 12% respectively. In both two systems glasses, with the increasing addition of halides, the thermal stability reduce, density and linear refractive index increase, the ultraviolet cut-off edges shift to longer wavelength, while the infrared cut-off edges keep almost the same. 30GeS2 35Ga2S3 35AgCl and 47.5GeS2 17.5Ga2S3 35AgCl surface- and bulk-crystallized glasses that contain AgGaGeS4 nonlinear optical crystallites were prepared. Obvious second harmonic generation (SHG) could be observed in these crystallized glasses, and their intensity relate to the distribution and size of the precipitated AgGaGeS4 crystals, the maximal second-order nonlinearity coefficients is as high as 12.4pm/V. These crystallized glasses have good chemical and SHG stability. For GeS2-Ga (In)2S3-CuI systems glasses, due to their small glass-forming region, they are not suit for the preparation of crystallized glasses that contain CuGaS2 or CuInS2 nonlinear optical crystals. According to the structural studies of two system glasses, the main structural units of theses glasses are [YS4-xXx] (Y=Ge, Ga, In. X=Cl, Br, I) mixed anion tetrahedrons, they form a three-dimensional glassy network through bridging sulphur bonds. When the contents of halides MX(M=Ag, Cu. X=Cl, Br, I) are low, some [XxS3-xGe(Ga)S3-xXx] (X=Cl, Br, I) mixed ethane-like structural units exist in the glass network, and they will gradually transform to [YS4-xXx] (Y=Ge, Ga, In. X=Cl, Br, I) mixed anion tetrahedrons with the increasing content of halides, till totally disappear. Both two system glasses have ultrafast (~150fs) third-order optical nonlinearity and reverse saturation absorption, they belong to self-focusing medium. The third-order optical nonlinearity mainly originate from the distortion of electron cloud of Y-X (Y=Ge, Ga, In, X=Cl, Br, I, S) bonds in the structural units. For GeS2-GA2S3-AgX (X=Cl, Br, I) system glasses, the largest nonlinear susceptibility n2 is 10.50x10-18 m/W, the smallest figure of merit (FOM) is 0.606. In addition, the relation of n2 with n0 do not obey Miller’s rule, but in accordance with the structural variation. Among the glass compositions with different additive halogens, Br-containing glasses have relatively best third-order nonlinearities. For GeS2-Ga (In)2S3-CuI system glasses, the largest nonlinear susceptibility n2 is 9.37x10-18 m/W, the smallest figure of merit (FOM) is 2.237. High purity AS2S3 glass performs and low loss single index fibers with diameter of 100~400µm that drawn form these performs were prepared, the transmission losses between 2~6 µm is only 0.5dB/m. AS2S3 tapered fibers have a uniform diameter of taper wasit, fine surface smoothness, and sharp taper transition part.

Les manilles utilisées pour l'assemblage et l'amarrage des plates-formes pétrolières nécessitent des propriétés mécaniques de plus en plus élevées. Mais les défauts de fabrication de ces manilles, responsables de leur rupture prématurée, engendrent des coûts d'intervention très élevés. Afin de comprendre et d'anticiper ces défauts de fabrication, trois outils numériques ont été développés permettant de simuler (i) le procédé de fabrication, (ii) le traitement thermique et (iii) le chargement mécanique de la manille. Le procédé de fabrication des manilles est constitué d'une succession de différentes étapes de forgeage à chaud et a été caractérisé avec des mesures de température, géométrie et efforts durant toutes les étapes. Un modèle numérique thermo- mécanique du procédé de fabrication a été développé en 3D et permet de prédire tous les paramètres de forge. Une étude numérique d'influence de certains paramètres du procédé a permis de comprendre les différentes causes de mise au rebut. Des mesures de température, des observations métallographiques au microscope et au MEB ainsi que des essais mécaniques ont été effectués sur des lopins après différents cycles de traitement thermique. Un modèle numérique de traitement thermique a été développé en 1D et permet de simuler les changements de phases pendant la normalisation et la trempe, et ainsi d'obtenir la dureté résultante en tout point du lopin. Finalement, une cartographie des propriétés mécaniques d'une manille a été obtenue et les modes de déformation de la manille en condition de chargement ont été évalués par le biais d'un essai de tension sur banc. Le modèle numérique de la manille sous tension a été développé en 3D et permet d'évaluer la charge maximale en service, la charge à rupture ainsi que la zone critique de la manille étudiée / Shackles used for the assembly or the mooring of petroleum platforms require constantly higher mechanical properties. But the manufacturing defects often lead to premature failure which can cost 1M€/day. Thus, in order to understand and anticipate those manufacturing defects, three numerical tools have been developed to simulate (i) the manufacturing process, (ii) the heat treatment and (iii) the mechanical behavior of the shackle. A shackle is manufactured via a sequence of hot forming stages and the manufacturing process has been characterized during all the stages, with measures of temperature, geometry and loads. The numerical thermo-mechanical model has been developed in 3D and gives a very good prediction of each forging parameters. A numerical study of influence of some process parameters has led to a better understanding of scrapping. Temperature measurements, metallographic observations as well as mechanical testing have been carried out on cylindrical rods after various heat treatment cycles. The numerical heat treatment model has been developed in 1D and predicts phase transformations during normalizing and quenching, as well as the hardness at each point of the rod. Finally, the distribution of the mechanical properties over a shackle has been characterized and the deformation modes of the shackle were evaluated via a load test on a dedicated bench. The numerical model of the shackle under tension has been developed in 3D and allows to evaluate the working load limit, the break load as well as the critical zone of the shackle.