Résumé : Malgré le nombre croissant de capteurs dans les domaines de la chimie et la biologie, il reste encore à étudier en profondeur la complexité des interactions entre les différentes molécules présentes lors d’une détection à l’interface solide-liquide. Dans ce cadre, il est de tout intérêt de croiser différentes méthodes de détection afin d’obtenir des informations complémentaires. Le principal objectif de cette étude est de dimensionner, fabriquer et caractériser un détecteur optique intégré sur verre basé sur la résonance plasmonique de surface, destiné à terme à être combiné avec d’autres techniques de détection, dont un microcalorimètre. La résonance plasmonique de surface est une technique reconnue pour sa sensibilité adaptée à la détection de surface, qui a l’avantage d’être sans marquage et permet de fournir un suivi en temps réel de la cinétique d’une réaction. L’avantage principal de ce capteur est qu’il a été dimensionné pour une large gamme d’indice de réfraction de l’analyte, allant de 1,33 à 1,48. Ces valeurs correspondent à la plupart des entités biologiques associées à leurs couches d’accroche dont les matrices de polymères, présentés dans ce travail. Étant donné que beaucoup d’études biologiques nécessitent la comparaison de la mesure à une référence ou à une autre mesure, le second objectif du projet est d’étudier le potentiel du système SPR intégré sur verre pour la détection multi-analyte. Les trois premiers chapitres se concentrent sur l’objectif principal du projet. Le dimensionnement du dispositif est ainsi présenté, basé sur deux modélisations différentes, associées à plusieurs outils de calcul analytique et numérique. La première modélisation, basée sur l’approximation des interactions faibles, permet d’obtenir la plupart des informations nécessaires au dimensionnement du dispositif. La seconde modélisation, sans approximation, permet de valider le premier modèle approché et de compléter et affiner le dimensionnement. Le procédé de fabrication de la puce optique sur verre est ensuite décrit, ainsi que les instruments et protocoles de caractérisation. Un dispositif est obtenu présentant des sensibilités volumiques entre 1000 nm/RIU et 6000 nm/RIU suivant l’indice de réfraction de l’analyte. L’intégration 3D du guide grâce à son enterrage sélectif dans le verre confère au dispositif une grande compacité, le rendant adapté à la cointégration avec un microcalorimètre en particulier. Le dernier chapitre de la thèse présente l’étude de plusieurs techniques de multiplexage spectral adaptées à un système SPR intégré, exploitant en particulier la technologie sur verre. L’objectif est de fournir au moins deux détections simultanées. Dans ce cadre, plusieurs solutions sont proposées et les dispositifs associés sont dimensionnés, fabriqués et testés. / Abstract : In spite of the growing number of available biosensors, many biochemical reactions and biological components have not yet been studied in detail. Among them, some require the combination of several detection techniques in order to retrieve enough information to characterize them fully. An unknown reaction based, for example, on DNA hybridization could be characterized with an electrochemical sensor, a mechanical sensor and an optical sensor, each giving a different type of information. The main objective of the work presented here is to design, fabricate and characterize a flexible integrated optical biosensor based on surface plasmon resonance, intended to be then combined with other detection techniques, and in particular, a microcalorimeter. Surface Plasmon Resonance (SPR) is well known to be a sensitive technique for surface-based biochemical detection. It has the advantage to be an unlabeled method and provides real time information on the kinetics of a reaction. The flexibility of the proposed SPR biosensor comes from the fact that it is designed for a large range of analyte refractive indices, from 1.33 to 1.48. These values are suitable for most biological entities and their ligand layers, and especially for hydrophilic polymer matrices used to trap DNA or protein entities and introduced in this work. As several biochemical studies require the simultaneous comparison of measurements to a reference or to another measurement, the second objective of this project is to study the potential of multi-analyte detection in an integrated SPR device on glass. The first three chapters of the thesis are focused on the main objective. The design based on two different models is presented, at the same time as the related simulation tools. The first model is based on the weak coupling approximation and permits to obtain most of the information for the device’s design. The second model, having no approximation, is used to validate the first model and complete and refine the design. The fabrication process of the glass chip is then introduced, as well as the characterization instruments and protocols. A device is obtained, with a volumetric sensitivity between 1000 nm/RIU and 6000 nm/RIU depending on the analyte refractive index. The 3D integration of the waveguide within the glass substrate makes the device extremely compact and adapted to the integration with the microcalorimeter in particular. The last chapter describes the study of several spectral multiplexing techniques adapted to an integrated SPR system using the glass technology. The goal is to provide at least two simultaneous measurements. Several detection techniques are examined and the related devices are designed, fabricated and characterized.

Mechanisms of adsorption of alkaline copper quat (ACQ) components in wood were investigated with emphasis on: copper chemisorption, copper physisorption, and quat adsorption. Various factors were investigated that could affect the adsorption of individual ACQ components in red pine wood. Copper chemisorption in wood was affected by ligand types coordinating with Cu and the stability of the Cu-ligand complexes in solution. For Cu-monoethanolamine (Cu-Mea) system, the prevailing active solvent species at the solution pH, [Cu(Mea)2-H]+ complexes with wood acid sites and loses one Mea molecule through a ligand exchange reaction. The amount of adsorbed Cu was closely related to the cation exchange capacity of wood. An increase in Mea/Cu ratio increased the proportion of the uncharged Cu-Mea complex and resulted in decreased Cu chemisorption in wood. Copper precipitation is also an important Cu fixation mechanisms of Cu-amine treated wood. X-ray diffraction analysis revealed that in vitro precipitated Cu was a mixture of copper carbonates (azurite and malachite) and possibly Cu2O. Higher concentration Cu-amine solutions retarded the Cu precipitation to a lower pH because of higher free amine in the preservative-wood system. The changes in zeta potential of wood in relationship to the quaternary ammonium (alkyldimethylbenzylammonium chloride: ADBAC) adsorption isotherm showed two different adsorption mechanisms for quat in wood: ion exchange reaction at low concentration and additional aggregation form of adsorption by hydrophobic interaction at high concentration. Because of the aggregation effect, when wood was treated with ACQ, high amounts of ADBAC were concentrated near the surface creating a steep gradient with depth. This aggregated ADBAC was easily leached out while the ion exchanged ADBAC had high leaching resistance. Free Mea and Cu of ACQ components appeared to compete with ADBAC for the same bonding sites in wood.

Une étude comparative des caractéristiques statiques, dynamiques et structurale a été menée sur 8 membranes échangeuses d'ions (MEIs), 4 neuves (MEIN) et les mêmes usagées (MEIU) après 2 ans de fonctionnement en ED dans l'industrie agroalimentaire. L'objectif essentiel était de mieux connaître les mécanismes de vieillissement in situ. Nous avons donc mesuré pour chacune de ces MEIs la capacité d'échange, la teneur en eau, la perméabilité ionique, la conductivité électrique, le nombre de transport, l'angle de contact, le courant limite, le module d'Young et la résistance à la traction. Aussi, nous avons effectué des analyses d'IRTF, de MEB et d'EDX. Cette étude nous a permis de conclure que (i) la MEC2 est restée presque stable après les 2 ans d'ED, alors que la MEA1 s'est très fortement dégradée. D'une manière générale, les MEAs sont plus sensibles au vieillissement que les MECs, (ii) les sites fonctionnels sulfoniques s'éliminent de la MEC. Nous ne pouvons pas affirmer ce mécanisme dans le cas des MEAs, mais nous soupçonnons un phénomène d'empoisonnement des sites fonctionnels, (iii) les MEAs se colmatent en surfaces avec des ampleurs différentes entre la MEA1 et la MEA2 / A comparative study of static characteristics, dynamic and structural was conducted on 8 ion-exchange membranes (MEIS), 4 new (IEMN) and the same used (IEMU) after two years of ED operation in the food industry. The main objective was to better understand the mechanisms of in situ ageing. We therefore measured for each IEMs exchange capacity, water content, ionic permeability, electrical conductivity, transport number, contact angle, current limit, Young's modulus and tensile strength. Therefore, we performed analysis of FTIR, SEM and EDX. This study concluded that (i) CEM2 remained almost stable after 2 years of ED, while AEM1 has sharply deteriorated. In general, the AEMs are more susceptible to ageing than CEMs, (ii) the sulfonic functional sites are eliminated from the CEMs. We cannot confirm this mechanism in the case of AEMs, but we suspect a poisoning phenomenon of functional sites, (iii) the AEMs fouled in surfaces with different degrees between AEM1 and AEM2

L’eau des circuits d’une centrale nucléaire est purifiée à l’aide de résines échangeuses d’ions. La prédiction de leurs performances constitue une aide importante pour l’exploitation de ces réacteurs. Les méthodes du transport réactif sont particulièrement adaptées pour cela et constituent la base du code OPTIPUR, dédié à la modélisation de ces résines. Le travail présenté comporte trois axes principaux. Le premier est l’intégration d’une limitation au transfert de masse dans une colonne de résines échangeuses d’ions, avec une mobilité spécifique à chaque espèce chimique, dans le cadre d’un découplage des calculs de chimie et de transport. Ce modèle permet, sans paramètre ajustable, de reproduire assez fidèlement une série d’expériences réalisées précédemment par le CEA. Le second axe concerne les aspects numériques du transport réactif, avec l’utilisation de la méthode d’Anderson pour accélérer la convergence du couplage chimie-transport dans un schéma itératif. En utilisant les informations issues des itérations précédentes et sans modification majeure du code, la robustesse et les temps de calcul ont pu être nettement améliorés. La troisième thématique abordée est celle de l’équilibre d’échange d’ions. Les bases d’un modèle prenant en considération l’évolution de l’humidité de la résine, ainsi que son élasticité sont proposées ; les interactions entre groupes fonctionnels, contre-ions et eau sont considérées comme des équilibres chimiques. Les constantes d’équilibre sont ajustées à partir de mesures de la teneur en eau de la résine à différentes pressions de vapeur d’eau. Finalement, des coefficients de sélectivité apparents peuvent être calculés et comparés aux mesures disponibles. / In nuclear power plants, the water contained in different circuits is purified by passing through ion exchange resins. Prediction of the performance of these resins is an important help to the plant operators. To this end, the method of reactive transport modeling are well suited and is the basis of the OPTIPUR code that was designed to model the resins. The work presented in this manuscript covers three main aspects. The first one is the integration of a limitation to mass transfer in a ion exchange deep bed, taking into account a specific mobility for each chemical species, in the context of separated calculations for chemistry and transport. This model was shown to reproduce experimental data, without adjustable parameters. The second part of this work deals with the numerical aspects of reactive transport modelling. A method developped by Anderson was used to accelerate the convergence of the chemistry transport coupling in an iterative scheme. Using the information from previous iterations, and without major changes in the code, calculation times were largely decreased, as well as the number of calculations failures. The third topic is ion exchange equilibrium. The basis of a model that takes into account the change in the water content of the resin and its elasticity are described. The interactions between the fonctional groups, the counterions and water are considered as chemical reactions. The corresponding equilibrium constants are fitted to measurements of the water content of the resin at different relative humidity. Finaly, the selectivity coefficients can be calculated and compared to litterature values.

A presença de compostos inibidores ao metabolismo de microrganismos é a principal dificuldade encontrada para utilização dos hidrolisados hemicelulósicos para produção de etanol e xilitol. Compostos derivados das degradações da lignina, da celulose e hemicelulose são liberados durante a hidrólise ácida da biomassa. O presente trabalho teve como objetivo avaliar a utilização de diferentes tratamentos de destoxificação de forma combinada, visando a purificação do hidrolisado hemicelulósico de bagaço de cana-de-açúcar para obtenção de etanol e xilitol. Os tratamentos utilizados foram: coagulação/floculação de impurezas coloidais, separação por membranas de microfiltração e ultrafiltração e resinas de troca iônica, sendo o material de partida foi um hidrolisado de bagaço recém-obtido. O tratamento de coagulação/floculação foi otimizado utilizando planejamento de experimentos do tipo fatorial e na melhor condição promoveu reduções de 53,3% em compostos fenólicos, 34,8% de furfural, 3,7% de HMF, 4,2% de ácido acético e 67,6% da área espectral. Na sequência, o hidrolisado tratado na etapa anterior foi submetido a testes de microfiltração e ultrafiltração. Para esta etapa os melhores resultados foram obtidos utilizando membranas de 100 kDa em polietersulfona. Com este tratamento foi possível reduzir em 11,9% os compostos fenólicos, 23,8% de furfural, 21,5% de HMF e 21,4% de área espectral. Após o tratamento com membranas o hidrolisado foi percolado em resinas de caráter catiônico e aniônico utilizadas em série possibilitando a eliminação de 34,8% de compostos fenólicos, 38,5% de furfural, 74,7% de HMF, 55% de ácido acético e 10,3% da área espectral. Ao final, a combinação de todas as tecnologias de separação estudadas possibilitou remoções maiores que 97% para compostos fenólicos, furfural e HMF o que resultou numa redução da área espectral em 99,3%. O hidrolisado purificado foi concentrado e submetido a testes fermentativos preliminares para produção de etanol e xilitol. Estas bioconversões apresentaram rendimentos de 0,58 g/g em xilitol e 0,29 g/g em etanol por D-xilose consumida, que equivalem a 86% e 83% dos rendimentos obtidos a partir dos meios sintéticos, respectivamente. Estes resultados indicaram que a purificação obtida através do uso combinado da coagulação/floculação, separação por membranas e resinas de troca iônica foram bastante satisfatórios principalmente considerando a fermentabilidade obtida a partir deste substrato em comparação ao meio sintético. / The presence of inhibitory compounds in the metabolism of microorganisms is the main difficulty for the use of hemicellulosic hydrolyzate for ethanol and xylitol production. Compounds derived from lignin, cellulose and hemicellulose degradation are released during the biomass acid hydrolysis. This study aimed to evaluate the use of different detoxification treatments in combination, aimed at purifying the hydrolyzed hemicellulosic sugarcane bagasse. The treatments were: coagulation / flocculation of colloidal impurities, separation by microfiltration and ultrafiltration membrane and ion exchange resins, and the starting material was a newly obtained hydrolyzed bagasse. The treatment of coagulation / flocculation was optimized using factorial experiments design of the kind that in the best condition promoted reductions of 53.3%, 34.8%, 3.7%, 4.2% and 67.6% in phenolic compounds, furfural, hydroxymethylfurfural, acid acetic acid and spectral area, respectively. Next, the hydrolyzate treated in the previous step was tested for microfiltration and ultrafiltration. For this step the best results were obtained using a 100 kDa membrane in polyethersulfone. With this treatment were obtaneid reduction of 11.9%, 23.8%, 21.5%, 21.4% in phenolic compunds, furfural, hydroxymethylfurfural and spectral area, respectively. After membrane treatment the hydrolyzate was percolated through resins with anionic and cationic character used in series enabling the elimination of 34.8%, 38.5%, 74.7%, 55% and 10.3% of phenolic compounds, furfural, hydroxymethylfurfural, acetic acid and spectral area, respectively. At the end, the combination of all separation technologies studied was able to remove greater than 97% of phenolic compounds, furfural and hydroxymethylfurfural which resulted in a reduction of 99.3% in spectral area. The purified hydrolyzate was concentrated and subjected to preliminary fermentative testing for the ethanol and xylitol production. These bioconversions had income of 0.58 g/g in xylitol and 0.29 g/g in ethanol by D-xylose consumed, equivalent to 86% and 83% of ethanol and xylitol yield obtained from the synthetic medium, respectively. These results indicated that the purification achieved through the combined use of coagulation/flocculation, membrane separation and íon exchange resins were very satisfactory, especially considering the fermentability obtained from this substrate compared to the synthetic medium.

Um sistema de análises químicas por injeção em fluxo foi desenvolvido e aplicado à determinação espectrofotométrica de baixas concentrações de sulfato em águas de chuva. O método explora a reação de deslocamento entre o ânion sulfato e o complexo dimetilsulfonazo (III) de bário, Ba-DMSA, com consequente formação do sal pouco solúvel BaSO4. A solução com o complexo Ba-DMSA apresenta alta absortividade molar a 656 nm, e uma diminuição pronunciada na absorbância ocorre na presença de sulfato. Desta forma, o sinal analítico é registrado como pico invertido proporcional à concentração de sulfato na amostra. A presença de altas concentrações de dimetilsulfóxido, DMSO, no reagente favorece a intensidade do sinal analítico, por coordenar as moléculas de água, melhorando a sensibilidade do método. A utilização do tensoativo dodecilsulfato de sódio, SDS, determina também uma melhoria considerável na sensibilidade analítica, pois sua presença no ambiente reacional altera as condições de supersaturação. A sensibilidade e seletividade do procedimento são melhoradas incluindo-se uma etapa de troca iônica em linha, com resina aniônica Dowex 1-X8, para concentração do sulfato e separação dos íons interferentes em potencial. O sistema proposto é robusto e fornece resultados precisos (d.p.r. < 0,01) com frequência analítica de 30 determinações por hora. O consumo de DMSA é de 0,17 \'mü\'mol por determinação. A curva analítica se apresenta linear até 2,0 mg L-1 SO42- e os limites de detecção e de quantificação foram estimados em 0,01 mg L-1 SO42- e 0,04 mg L-1 SO42-. / A flow injection system was developed and applied to the spectrophotometric determination of low concentrations of sulphate in rain waters. The method exploits the displacement reaction involving the sulphate anion and the barium dimethylsulfonazo (III) complex, Ba-DMSA, with consequent formation of the slightly soluble BaSO4 salt. As the Ba-DMSA solution is characterized by a high molar absorptivity at 656 nm, a pronounced absorbance lessening is observed in the presence of sulphate. The analytical signal is then recorded as an inverted peak proportional to the sulphate content in the sample. Presence of dimethylsulphoxide, DMSO, at high concentrations in the reaction medium leads to an enhancement of the analytical signals, coordinating water molecules, thus improving the sensitivity of the method. Addition of the surfactant sodium dodecylsulphate, SDS, results also in a pronounced improvement in sensitivity, as its presence in the reaction medium alters the supersaturation conditions. The sensitivity and selectivity of the method were improved by including an in-line ion exchange mini-column with the anionic resin Dowex 1-X8 into the manifold, for sulphate concentration and separation from potential interfering ions. The proposed system is robust and provides accurate results (R.S.D. <0.01) at an analytical frequency of 30 determinations per hour. About 0.17 \'mü\'mol DMSA are consumed per determination. The analytical curve is linear up to 2.0 mg L-1 SO42- and the detection and quantification limits were estimated as 0.01 mg L-1 SO42- and 0.04 mg L-1 SO42-.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A drenagem ácida de mina no Complexo Mínero Industrial de Poços de Caldas - CIPC, das Indústrias Nucleares do Brasil, INB, tem origem nas grandes quantidades de rejeitos constituídos de minério sulfetado de baixo teor de U (<200ppm) e o estéril dispostos em grandes áreas circunvizinhas da região mineradora. Essas áreas tornaram uma fonte de drenagem ácida, gerando águas ácidas com pH em torno de 2,6, contendo radionuclídeos e metais pesados em níveis de concentração acima dos valores permitidos pela legislação para o lançamento direto ao ambiente. Nesse contexto, o presente estudo foi realizado visando a recuperação de urânio e a remoção de manganês presentes nas águas ácidas do CIPC através da utilização de vários materiais adsorventes e trocadores iônicos. Foi realizado um levantamento dos principais locais de drenagem ácida, sob ponto de vista da proteção do meio ambiente e selecionada uma amostra de água ácida para o estudo. A amostra de água, denominada de BIA, neste trabalho, foi selecionada para os ensaios de adsorção pois apresentou o maior teor de urânio (12 - 15mg/L) e manganês (173mg/L), além teor de ferro muito elevado (180mg/L). A partir das isotermas de adsorção e dos ensaios contínuos em coluna, foi possível obter a capacidade de carregamento dos adsorventes e trocadores iônicos mais eficientes em relação ao urânio e manganês, além de uma melhor definição das variáveis operacionais como o pH, influência dos íons sulfato e fluoreto. A resina aniônica IRA-910U do fabricante Rohm&Haas foi o material, dentre os doze materiais testados, que se mostrou como o melhor removedor de urânio por ter apresentado o mais elevado carregamento deste metal. O carregamento máximo de urânio atingiu valores próximos de 79mg de urânio por grama de resina, em pH ajustado para 3,9, contendo 12mg/L de urânio. A presença do íon sulfato foi deletéria para o carregamento do urânio pois, o sulfato competiu com os sítios da resina. Já o fluoreto não influenciou o processo de troca iônica. A remoção mais efetiva de manganês do efluente, só ocorreu em pH 7,0 utilizando a levedura Saccharomyces cerevisiae, isolada da Destilaria José Cruz, Salinas/MG. Este material bioadsorvente atingiu carregamento máximo próximo de 65,0mg de manganês por grama de levedura. Os resultados mostram, portanto, que as águas ácidas podem ser tratadas por técnicas de troca iônica/adsorção para a recuperação de urânio e a remoção do manganês. / The Acid Mine Drainage that occurs in the Mineral Industrial Complex of Poços de Caldas (CIPC), which belongs to the Nuclear Industries of Brazil, (INB), is due to the great amount of sulfide waste and tailings with low uranium content (200ppm) disposed in the surrounding areas near the mining region. These areas represent a source of acid waters with pH around 2.6, containing radionuclideos and metals in concentration above the permissible level for discharging in the environment according to Brazilian legislation. In this context, the present study was carried out aiming at the recovery of uranium and removal of manganese present in acid waters of the CIPC by using ionic adsorbents and exchang materials. First, a survey of the main places of acid drainage was carried out, according to environmental protection guidelines. The acid water sample BIA which presented the highest uranium (12 - 15mg/L) and manganese content (173mg/L) along with a very high content of iron (180mg/L), was used in the adsorption assays. From the adsorption isotherms and the continuous column experiments, it was possible to determine the uranium and manganese loading capacity of the most efficient adsorbents and ions exchangers. The optimum pH as well as the influence of ions such as sulphate and chloride was also determined. The anion exchange resin IRA-910U from Rohm&Haas was selected amongst the twelve materials tested, for its best removal of uranium. This resin presented the highest loading capacity around 79mg per gram of IRA 910U resin in acid waters, pH 3.9, with 12mg/L of uranium. The presence of sulphate had a deleterious effect on the uranium removal due to the competition of these species for the resin sites. Fluoride, on the other hand, did not influence the ionic process. Manganese was effectively removed from the effluent, in pH 7.0 by using the Saccharomyces cerevisiae, yeast isolated from white rum at the Distillery Jose Cruz, Salinas/MG. This biosorvent material was able to load around 65.0mg of manganese per gram of yeast. The results showed, therefore, that ionic xchange/adsorption techniques can be used for the uranium recovery and the removal of manganese present in acid waters.

O objetivo deste estudo foi avaliar o efeito da temperatura de troca iônica (TI) nas propriedades mecânicas da porcelana Ultrapaline ST e o efeito da TI nos parâmetros de crescimento subcrítico de trincas (SCG) (coeficiente de SCG - n, parâmetro escalar - ?f0), de Weibull (resistência característica - ?0, módulo de Weibull - m) e no comportamento de curva R desta porcelana. 250 discos (12 mm diâmetro x 1 mm espessura) foram fabricados de acordo com as instruções do fabricante, usinados em retificadora plana e polidos até 1 ?m. Para determinar o efeito da temperatura de TI na resistência à flexão biaxial (?), dureza (H) e tenacidade à fratura (KIc), 40 discos foram divididos em 4 grupos (n=10): GI (controle) - sem TI; e GII, GIII e GIV submetidos a TI com KNO3 por 15 min a 450°C; 470°C e 490°C, respectivamente. A ? foi determinada por \"pistão sobre três esferas\" em saliva artificial a 37°C a 10 MPa/s. Para dureza e tenacidade à fratura, foram feitas 3 indentações Vickers em cada espécime (2kg, 30s) e as diagonais e trincas radiais foram medidas e os valores de H e KIc calculados. As médias e desvios-padrão para ? (MPa), H (GPa) e KIc (MPa.m1/2) foram: GI: 57,95 ± 8.97, 7,24 ± 0,79 e 1,14 ± 0,14; GII: 125,04 ± 23,58, 5,80 ± 0,14, 2,62 ± 0,14; GIII: 133,00 ± 11,00, 5,88 ± 0,45, 2,54 ± 0,22; GIV: 137,67 ± 12,05, 5,88 ± 0,17, 2,57 ± 0,10, respectivamente. Para determinação dos parâmetros de SCG e de Weibull, 140 espécimes foram divididos em 2 grupos: GC (controle) e GT (submetidos à TI por 15 min a 470°C). Para determinação de n e de ?f0, 50 espécimes de cada grupo foram testados em saliva artificial a 37°C em flexão biaxial em uma das seguintes taxas de tensão: 10-2, 10-1, 100, 101 e 102 MPa/s. Para determinação dos parâmetros de Weibull, mais 20 espécimes de cada grupo foram ensaiados na taxa de 100 MPa/s. Os valores de n, ?f0, m e ?0 foram, respectivamente (valores entre parênteses representam intervalos de confiança de 95%): 24,1 ± 2,5; 58,1 ± 0,01; 13,8 (10,0 a 18,8) e 60,4 (62,2 a 58,5) para GC e 36,7 ± 7,3; 127,9 ± 0,01; 7,4 (5,3 a 10,1) e 136,8 (129,1 a 144,7) para GT. Para determinação do efeito da TI no curva R, 7 espécimes de cada grupo receberam uma indentação Vickers em uma das seguintes cargas de indentação (kg): 0,18; 0,32; 0,56; 1,0; 3,2. Após armazenados ao ar por 24 h os espécimes foram ensaiados a 10 MPa/s em saliva artificial a 37°C. Os parâmetros ?, ?, q foram, respectivamente: 62,57; 0,12 e 0,2857 para GC e 161,50; 0,34 e -0,0074 para GT. Os valores de k variaram de 0,371 a 0,515 para GC e de 1,240 a 0,804 para GT. Não houve diferença nas propriedades mecânicas entre as três temperaturas de TI testadas. A TI promoveu aumento significativo do valor de n, ?f0 e ?0, entretanto resultou em diminuição do valor de m e também suprimiu o comportamento de curva R, presente no material antes da realização da TI. / The objectives of this study were to determine the influence of different ion exchange (IE) temperatures on mechanical properties of a dental porcelain Ultrapaline ST and the effect of IE on slow crack growth (SCG) (coefficient of SCG - n, scale parameter - ?f0) and Weibull parameters (characteristic strength - ?0; Weibull modulus - m) and R-curve behavior of this porcelain. 250 specimens (12 mm diameter x 1 mm height) were fabricated according to the manufacturer\'s instructions, grounded with a surface-grinding device and polished up to 1?m. To determine the effect of IE temperature on biaxial flexural strength (?), hardness (H) and fracture toughness (KIc), 40 specimens were divided in four groups (n=10) as follow: GI - control (no ion exchange); GII, GIII and GIV submitted to IE with KNO3 for 15 min at 450°C; 470°C e 490°C, respectively. The ? was determined using a piston-on-three-balls device, in artificial saliva at 37°C and constant loading rate of 10 MPa/s. For hardness and fracture toughness, 3 Vickers indentations (2kg, 30s) were made on each specimen. The diagonals and radial cracks were measured in order to calculate H and KIc. Mean and standard deviations values of ? (MPa), H (GPa) and KIc (MPa.m1/2) were: I: 57.95 ± 8.97; 7.24 ± 0.79; 1.14 ± 0.14; II: 125.04 ± 23.58; 5.80 ± 0.14; 2.62 ± 0.14; III: 133.00 ± 11.00; 5.88 ± 0.45; 2.54 ± 0.22; IV: 137.67 ± 12.05; 5.88 ± 0.17; 2.57 ± 0.10, respectively. To determine the effect of IE on SCG and Weibull parameters, 140 specimens were divided in 2 groups: GC (control) and GIE (submitted to IE at 470°C for 15 min). To determine the SCG parameters, 10 specimens of each group were tested in biaxial flexural strength in each one of five constant stress rates: 10-2, 10-1, 100, 101 e 102 MPa/s. To determine the Weibull parameters, 20 specimens of each group were tested in the stress rate of 100 MPa/s. The n, ?f0, m and ?0 (values in parenthesis represent the confidence interval) were: 24.1 ± 2.5; 58.1 ± 0.01; 13.8 (10.0 to 18.8) and 60.4 (62.2 to 58.5) for GC and: 36.7 ± 7.3; 127.9 ± 0.01; 7.4 (5.3 to 10.1) and 136.8 (129.1 to 144.7) for GIE, respectively. To determine the effect of IE on R-curve behavior, 7 specimens of each group received a Vickers indentation in one of the following indentation loads (kg): 0.18; 0.32; 0.56; 1.0; 3.2. After stored on air for 24 h, the specimens were tested biaxial flexure strength in artificial saliva at 37°C in a stress rate of 10 MPa/s. The ?, ?, q parameters were, respectively: 62.57; 0.12 and 0.2857 for GC and 161.50; 0.34 and -0.0074 for GIE. The values of k varied from 0.371 to 0.515 for GC and from 0.34 to 0.0074 for GIE. There are no differences on mechanical properties among the three IE temperatures tested. The IE promoted significantly increase of n, ?f0 and ?0 however, decreased the m value and suppressed the R-curve behavior originally present on material before the IE.

L’électrodialyse (ED) est principalement basée sur l’action spécifique des membranes échangeuses d’ions (MEIs) et est largement répandue en industrie agroalimentaire pour la stabilisation tartrique des vins, la désacidification et le traitement des jus de fruits, la déminéralisation du lactosérum ou l’élimination et le fractionnement des protéines du lait. Le colmatage organique, accentué par la complexité de composition des effluents alimentaires et leur richesse en composés phénoliques, représente un facteur majeur de limitation de l’efficacité des procédés et des performances des MEIs. Ce phénomène provoque une diminution de la sélectivité de membranes, une augmentation de leur résistance électrique et réduit le rendement énergétique du procédé conduisant à des pertes économiques en industrie. Cette étude consiste principalement à étudier le décolmatage de MEIs par procédés chimiques et biologiques. Des lots de membranes échangeuses de cations (MECs) et d’anions (MEAs) neuves (1 lot de MEC et 1 lot de MEA) et usées (3 lots de MECs et 2 lots de MEAs) à différentes durées d’utilisation en ED dans l’industrie agroalimentaire –application confidentielle- ont été étudiés. L’ensemble des échantillons ont préalablement été caractérisés pour détermination des paramètres physicochimiques (capacité d’échange (CE), épaisseur (Tm), conductivité électrique (km), angle de contact (θ), teneur en eau (WC) ainsi que la fraction volumique de la solution inter-gel (f2) résultant de l’exploitation du modèle microhétérogène), de structure et morphologiques par spectroscopie IR-TF, microscopie optique, microscopie électronique à balayage et mécaniques par essais de traction. Les effets directs et indirects (causés par les opérations de lavage régulières en industrie) du colmatage ainsi que l’anisotropie des propriétés mécaniques de membrane ont été mis en évidence. Des méthodes de nettoyage non agressives et respectueuses de l’environnement ont été expérimentées en mode statique en ex-situ : Solutions salines (NaCl à 35 g.L-1 et eau de mer reconstituée), solution hydro-alcoolique (mélange eau-éthanol 12%, pH=3,5) et solutions biologique utilisant 3 catégories d’agents enzymatiques (Rohalase BX-BXL, β-glucanase / Corolase 7089, endo-peptidase / Tyrosinase, polyphenol-oxydase) dont les conditions opératoires d’activité enzymatiques optimale ont été déterminées. L’évolution de CE, km, θ et f2 ont été suivis en fonction de la durée de nettoyage. Les solutions salines ont un effet négligeable sur le nettoyage en profondeur mais restent efficaces pour le nettoyage de surface. Cependant, l’application de la solution hydro-alcoolique et des solutions d’enzymes se sont avérées être efficaces pour le décolmatage interne et externe et parviennent à rétablir significativement les paramètres suivis. Il a été démontré que les composés phénoliques, principaux constituants des effluents traités, sont en majeure partie responsables du colmatage des MEIs. Ceux-ci forment des nanoparticules colloïdales denses, non perméables aux ions dans les méso- et macropores des MEIs et ne pénètrent pas dans ses micropores. Une modification du modèle microhétérogène selon cette hypothèse a permis de fournir une interprétation adéquate du km et de modéliser la modification structurale de la phase inter-gel engendrée par les mécanismes de colmatages de polyphénols et expliquer les raisons de diminution du facteur f2app. Une méthode d’extraction utilisant un mélange de solvants (25%V/V, acétone/méthanol/isopropanol/eau) a été mise au point et a permis d’extraire certains composés phénoliques de différents lots de MECs et MEAs usées et ont été identifiés par chromatographie liquide à haute performance. Il a été démontré que les interactions entre les composés phénoliques et la matrice polymère étaient principalement régies par l’empilement des cycles aromatiques et des interactions électrostatiques du type CH-pi et pi-pi ainsi que les liaisons hydrogènes / Conventional electrodialysis (ED) is mainly based on the specific action of ion exchange membranes (IEMs) and is widely used in food industry for tartaric stabilization of wines, deacidification and treatment of fruit juices, demineralization of whey or elimination and fractionation of milk proteins. The organic fouling, accentuated by the complex composition of the food effluents and their richness in phenolic compounds, represents a major limitative factor of the process efficiency and the IEMs performance. This phenomenon causes a decrease in the selectivity of membranes, an increase in their electrical resistance and reduces the energy efficiency of the process leading to economic losses in industry. This study mainly consists in studying the IEMs cleaning by chemical and biological methods. Two batches of new membranes (cation- (CEMs) and anion-exchange membranes (AEMs)) and five batches of used ones (3 CEMs and 2 AEM) with different durations of use in ED units in food industry -confidential application- have been studied. All the samples have been previously characterized to determine their physicochemical parameters (ion-exchange capacity (IEC), thickness (Tm), electrical conductivity (km), contact angle (θ), water content (WC) and the volume fraction of the inter-gel solution (f2) resulting from the study of the micro heterogeneous model), structure and morphology by FTIR spectroscopy, optical microscopy, scanning electron microscopy and mechanical by tensile strength tests. The direct and indirect effects (caused by the regular cleaning operations in industry) of fouling as well as the anisotropy of the membranes mechanical properties have been highlighted. Non-aggressive and environmentally friendly cleaning methods have been experimentally tested in ex-situ static mode: Saline solutions (35 g.L-1 NaCl and reconstituted seawater), hydro-alcoholic solution (12% water-ethanol mixture, pH = 3,5) and biological solutions using 3 categories of enzymatic agents (Rohalase BX-BXL, β-glucanase / Corolase 7089, endo-peptidase / Tyrosinase, polyphenol oxidase) whose operating conditions of optimal enzymatic activity have been determined. The evolution of IEC, km, θ and f2 were followed in function of the cleaning duration. Saline solutions have a negligible effect on intern cleaning but remain efficient for extern cleaning. However, the application of the hydro-alcoholic solution and enzyme solutions have been found to be efficient for both intern and extern cleaning and led to significant recoveries of the studied parameters. It has been shown that phenolic compounds, the principal constituents of treated effluents, are mainly responsible for MEIs fouling. Apparently, they form dense colloidal nanoparticles not permeable for ions within membrane meso- and macropores, not penetrating into micropores. A modification of the micro heterogeneous model under this assumption allowed an adequate interpretation of km and the modelization of structural modifications of the inter-gel phase generated by the fouling mechanisms by polyphenols and explained the reasons why the f2app decreases. An extraction method using a mixture of solvents (25% V/V, acetone/methanol/ isopropanol/water) was developed and made it possible to extract certain phenolic compounds from different batches of used CEMs and AEMs that were identified by high performance liquid chromatography. It has also been demonstrated that the interactions between the phenolic compounds and the polymer matrix are mainly governed by the stacking of aromatic rings and electrostatic interactions of the CH-pi and pi-pi type as well as the hydrogen bonds

La volonté actuelle de réduire les risques environnementaux et humains amène les chercheurs à trouver de nouvelles solutions de traitement-recyclage poussé des combustibles usés. Dans le but de réduire les volumes d’effluents qu’elle génère, ses temps de réponse et son coût, la miniaturisation de l’analyse chimique en ligne constitue l’un des principaux enjeux de ces recherches. Dans ce contexte, le présent manuscrit traite de la conception, du dimensionnement, de la fabrication et de la caractérisation d’un capteur spectrophotométrique intégré sur verre borosilicate, pour l’analyse des cations radioactifs. Le dispositif, nommé « guide à nanocanal », est réalisé à l’aide des techniques de gravure sèche par plasma et d’échange d’ions. Il contient un coeur ruban surmonté d’un canal de (100 ± 10) nm de profondeur et d’un coeur plan, et permet la propagation d’un mode hybride optimisant ainsi l’interaction fluide/onde guidée sur un large domaine de longueurs d’ondes. Des mesures spectrales d’une solution de nitrate de néodyme en milieu nitrique peu acide (pH 2) et un traitement statistique ont permis de démontrer une limite de détection minimale en terme de coefficient d’absorption de (3,7 ± 0,9) x 10-3 cm-1 sur une longueur de (3,70 ± 0,05) cm et un volume de seulement (7 ± 3) nL. Une structure permettant d’augmenter la longueur d’interaction et donc de diminuer la limite de détection est proposée en perspectives de ce travail, de même qu’une étude préliminaire pour l’utilisation du dispositif en milieu actif. / The current will of reducing environment and human hazards has led the scientists to imagine new solutions for nuclear waste reprocessing. Miniaturized online chemical analysis of industrial processes has in particular an important role to play to reduce effluent volumes, response times and costs. In this context, we present the design, fabrication and characterization of an integrated spectrophotometric sensor on glass for chemical analysis of radioactive cations. The device is called a ―nanochannel waveguide‖ and is fabricated by reactive ion etching and ion exchange on glass. It is made of two borosilicate glass wafers bonded together. The first one contains a strip core and the second one a (100 ±10) nm deep nanochannel and a slab core. It allows the propagation of a hybrid mode, optimizing the fluid/guide wave interaction on a large wavelength range. Spectrometric measurements of a neodymium nitrate in nitric acid (pH 2) followed by statistical treatment have led to a limit of detection in terms of absorption coefficient of (3.7 ± 0.9) x 10-3 cm-1 for a device length of (3.70 ± 0.05) cm and fluid volume as low as (7 ± 3) nL. A structure allowing to increase the interaction length and therefore further decrease the detection limit has been proposed as an outlook of this work, and a preliminary study for use in a nuclear environment has been performed.