La dégradation accélérée des membranes conductrices protoniques en pile est en partie due à une oxydation induite par la production d'H2O2. Cette étude présente une stratégie originale de stabilisation chimique d'une matrice de sPEEK par l'inclusion de nano-charges stabilisantes. Quatre nano-charges ont été préparées par fonctionnalisation de nanoparticules de silice avec des fonctions chimiques organosoufrées (disulfure, tétrasulfure et thiourée). Un protocole spécifique de mise en forme des membranes hybrides a permis d'obtenir des composites présentant des propriétés mécaniques et une conductivité protonique compatibles avec l'application pile. Les fonctions polysulfures permettent de ralentir la dégradation de la matrice de sPEEK durant l'étape de mise en œuvre et d'augmenter sa conductivité au cours d'un vieillissement ex-situ (H2O2). En présence de fonctions tétrasulfures, la membrane sPEEK ne se dégrade pas durant un test de 1200h en OCV à 70°C et 100%HR.

Various aspects of and approaches towards the steric stabilisation of liposomes have been investigated, mainly by use of fluorescence techniques and cryo-transmission electron microscopy (cryo-TEM). It is shown that PEG(2000)-lipids can be incorporated in the liposome membrane up to a critical concentration of 8-10 mol% without any observable structural perturbations. Above 10 mol%, a breakdown of the liposome structure into flat lamellar discs was observed. The sterically stabilised liposomes displayed similar, or even reduced, membrane permeability as compared with conventional liposomes. The presence of PEG-lipids in the EPC membrane was shown to affect the liposome-to-micelle transition in mixtures containing OG. Little or no effects of the PEG-lipids were found on the transition in mixtures containing C12E8. The interactions between a number of PEO-PPO-PEO triblock copolymers and PC or PC/Chol liposomes have been investigated. It is shown that these polymers adsorb rapidly onto the liposome surface and induce a substantial increase in membrane permeability as well as structural perturbations. No evidence of an effective steric stabilisation due to the presence of the polymers at the membrane surface was found. This was shown, by the use of a QCM-technique, to be a consequence of the weak interaction between the polymers and the lipid membrane. Dispersions of reversed lipid phases in mixtures of DOPE and PEG-lipids were characterised using cryo-TEM. Dispersions displaying reasonable colloidal stability were obtained and particles exhibiting a periodic dense inner structure were observed. PEG-lipid micelles were characterised mainly using light scattering techniques. Micelle aggregation numbers and hydrodynamic radii were determined as a function of temperature. It is shown that the inter-micellar interactions are dominated by the steric repulsion. PEG-lipid stabilised liposomes loaded with boronated drugs intended for BNCT have been characterised. The drugs were efficiently encapsulated into the liposomes, resulting in a drug precipitation in the water core of the liposomes.

Neuromuscular control is believed to play an essential role during dynamic knee joint stabilisation. Evaluation of voluntary muscle action can be delineated as support strategies against external loading moments (Lloyd & Buchanan, 2001). The aim of this study was to determine if males and females exhibit differences in knee muscle action and cocontraction during voluntary isometric closed kinetic chain force generation in various directions in the horizontal plane representative of applied loads transverse to the long axis of the shank. Twenty-six healthy young adults (13 male, 13 female) stood with their dominant leg in a boot fixed to a force platform. A force target matching protocol required subjects to position a cursor (projected on a video screen) over a target and maintain the position for one second. To control the cursor, loads were applied against the force platform with their dominant leg to produce various combinations of anterior-posterior, medial-lateral loads while maintaining constant inferior-superior loads. A successful target match required a normalised force magnitude of equal effort for each subject and target location which triggered the recording of electromyography (EMG) for eight muscles crossing the knee joint. EMG was normalised to percent maximum voluntary isometric contraction. A mean magnitude of muscle activation, mean direction of muscle activation and a muscle specificity index was determined using EMG vectors. In addition, cocontraction indices were also computed for antagonist muscle pairs. Based on similar previous research, it was hypothesised that females would have greater quadriceps and hamstrings coactivation, greater muscle activation magnitudes, lower specificity for the quadriceps than males and no difference in hamstring characteristics. In our study, females significantly cocontracted their vastus lateralis and lateral gastrocnemius muscles to a greater degree than males (p=0.001). No significant differences were observed across sexes for the cocontraction of quadriceps and hamstrings or the lateral quadriceps and gastrocnemius muscles. Females displayed significantly lower specificity than males in their semitendinosus (p=0.025) and tensor fascia lata (p=0.012) activity patterns, greater magnitude of muscle activation in their lateral gastrocnemius (p=0.002) and tensor fascia lata (p<0.003) and no statistical difference in the other muscles. Furthermore, the activation patterns in our study grossly differed from previous open kinetic chain force target matching. These findings indicate that healthy young males and females have differences in their knee muscle control strategies and that knee muscle recruitment patterns differ during weight bearing and non-weight bearing tasks.

Neuromuscular control is believed to play an essential role during dynamic knee joint stabilisation. Evaluation of voluntary muscle action can be delineated as support strategies against external loading moments (Lloyd & Buchanan, 2001). The aim of this study was to determine if males and females exhibit differences in knee muscle action and cocontraction during voluntary isometric closed kinetic chain force generation in various directions in the horizontal plane representative of applied loads transverse to the long axis of the shank. Twenty-six healthy young adults (13 male, 13 female) stood with their dominant leg in a boot fixed to a force platform. A force target matching protocol required subjects to position a cursor (projected on a video screen) over a target and maintain the position for one second. To control the cursor, loads were applied against the force platform with their dominant leg to produce various combinations of anterior-posterior, medial-lateral loads while maintaining constant inferior-superior loads. A successful target match required a normalised force magnitude of equal effort for each subject and target location which triggered the recording of electromyography (EMG) for eight muscles crossing the knee joint. EMG was normalised to percent maximum voluntary isometric contraction. A mean magnitude of muscle activation, mean direction of muscle activation and a muscle specificity index was determined using EMG vectors. In addition, cocontraction indices were also computed for antagonist muscle pairs. Based on similar previous research, it was hypothesised that females would have greater quadriceps and hamstrings coactivation, greater muscle activation magnitudes, lower specificity for the quadriceps than males and no difference in hamstring characteristics. In our study, females significantly cocontracted their vastus lateralis and lateral gastrocnemius muscles to a greater degree than males (p=0.001). No significant differences were observed across sexes for the cocontraction of quadriceps and hamstrings or the lateral quadriceps and gastrocnemius muscles. Females displayed significantly lower specificity than males in their semitendinosus (p=0.025) and tensor fascia lata (p=0.012) activity patterns, greater magnitude of muscle activation in their lateral gastrocnemius (p=0.002) and tensor fascia lata (p<0.003) and no statistical difference in the other muscles. Furthermore, the activation patterns in our study grossly differed from previous open kinetic chain force target matching. These findings indicate that healthy young males and females have differences in their knee muscle control strategies and that knee muscle recruitment patterns differ during weight bearing and non-weight bearing tasks.

Dans le contexte des réseaux à grande échelle, la prise en compte des pannes est une nécessité évidente. Ce document s'intéresse à l'approche auto-stabilisante qui vise à concevoir des algorithmes se ''réparant d'eux-même ' en cas de fautes transitoires, c'est-à-dire de pannes impliquant la modification arbitraire de l'état des processus. Il se focalise sur deux contextes différents, couvrant la majeure partie de mes travaux de recherche ces dernières années. La première partie du document est consacrée à l'algorithmique auto-stabilisante pour les réseaux de processus. La seconde partie du document est consacrée quant à elle à l'algorithmique auto-stabilisante pour des entités autonomes (agents logiciels, robots, etc.) se déplaçant dans un réseau.

Cette thèse s'intéresse au problème de préparation et de stabilisation de systèmes quantiques. Nous considérons des modèles correspondant à des expériences actuelles en électrodynamique quantique en cavité, circuits Josephson, et de contrôle quantique cohérent par laser femtoseconde. Nous posons les problèmes dans le contexte de la théorie du contrôle et nous proposons des lois de commande qui préparent ou stabilisent des états cibles. En particulier, nous nous intéressons à des états cibles qui n'ont pas d'analogue classique: des états superpositions et intriqués. De plus, nous proposons une commande pour la stabilisation d'un sous-espace de l'espace des états, contribuant ainsi au domaine de la correction d'erreur quantique. Ces résultats ont été obtenu en étroite collaboration avec des expérimentateurs. Des mesures expérimentales préliminaires sont en bon accord avec certaines prédictions théoriques de cette thèse.

Carbonation is a naturally-occurring process whereby Ca-containing cement phases lose their hydration water and are converted to carbonate minerals by reaction with atmospheric CO&#8322;. As these secondary minerals develop in the microstructure of hydrated cement, porosity, pore-size distribution and permeability are decreased. These are all considered desirable properties in a wasteform. The objective of this study was to examine the effect of carbonation and different pozzolans on the leach performance and mechanical strength of ordinary Portland cement (OPC) wasteforms. Two methods of accelerated cement carbonation were used: <ol> <li>A vacuum carbonation method, where wasteforms are placed in an evacuated, sealed cell and subjected to small additions of CO&#8322; over several days at near vacuum conditions; and <li>A one-step carbonation method, where CO&#8322; gas is added to the wasteform paste as it is being mixed. </ol> Thirteen elemental constituents of interest to the safety assessments of long-term management of Ontario Power Generation's radioactive waste (Cl, N, S, Se, 13C, Th, Pb, Co, Ni, Cu, Sr, Ba and Cs) were stabilised/solidified via cement mix water. Wasteforms were produced with only OPC, OPC and fly ash, or OPC and silica fume. Most wasteforms were carbonated using one of the carbonation methods. Some wasteforms were not carbonated and served as controls. Wasteforms were subjected to either standard leach tests or compressive strength tests. The extent of carbonation was found to be about 20% for vacuum carbonation method, substantially higher than that for one-step treatment (up to about 10%). For vacuum carbonated wasteforms, carbonation occurred at the outer selvages of the wasteforms, whereas one-step treatment resulted in homogenous carbonation. Generally, compared to uncarbonated OPC wasteforms, vacuum carbonation increased leaching of elements that are anionic in cementitious conditions (Cl, N, S, Se, 13C, Th), decreased leaching of large metal cations (Sr, Ba, Cs, Pb) and had negligible effect on the leaching of the elements that form hydroxyl complexes (Co, Ni, Cu). 13C was the only anionic element whose leachability was reduced by vacuum carbonation, as it may be precipitated in the form CO32- in the large quantity of secondary carbonate minerals produced during the vacuum carbonation process. One-step carbonation did not result in substantial reductions in leachability, compared to uncarbonated OPC wasteforms. However, it had an interesting inverse effect on large metal cation leachability from fly ash- and silica fume-containing wasteforms. A model is presented that proposes that porewater pH changes can have an effect on waste element leachability because 1) the C-S-H Ca/Si ratio is dependent on the equilibrating porewater pH and 2) the degree of ion sorption on C-S-H is dependent on the C-S-H Ca/Si ratio. This model should be tested experimentally as it has important implications on wasteform design. Because of this inverse behaviour, overall neither pozzolan outperformed the other with respect to leachability. Generally, for uncarbonated wasteforms, OPC retained the elements more effectively than OPC with pozzolans. For pozzolans, the leachability of these elements from OPC with fly ash was lower than that of OPC with silica fume. Leaching of Cs was anomalously low from uncarbonated OPC wasteforms, but follow-up experimentation did not corroborate this anomaly. Further testing of these wasteforms to determine how the mineralogical fate of Cs can differ between wasteforms is recommended. All wasteforms tested were of acceptable strength (<0. 689 MPa). Fly ash, and, to a greater degree, silica fume, improved wasteform strength when compared to OPC wasteforms. Carbonation treatments had little effect on wasteform strength. This study has provided much information about the leaching characteristics of a representative set of waste elements from several cement-based wasteform treatments. Although it has not indicated a wasteform design that is ideal for all elements studied, it does suggest that some treatments may be effective for certain groups of elements. Most notably, vacuum carbonation shows promise in improving the immobilisation of isotopes of large metal cations such as Sr, Ba, Cs and Pb as well as 14C (as suggested by 13C here) in cement-based wasteforms.

Carbonation is a naturally-occurring process whereby Ca-containing cement phases lose their hydration water and are converted to carbonate minerals by reaction with atmospheric CO&#8322;. As these secondary minerals develop in the microstructure of hydrated cement, porosity, pore-size distribution and permeability are decreased. These are all considered desirable properties in a wasteform. The objective of this study was to examine the effect of carbonation and different pozzolans on the leach performance and mechanical strength of ordinary Portland cement (OPC) wasteforms. Two methods of accelerated cement carbonation were used: <ol> <li>A vacuum carbonation method, where wasteforms are placed in an evacuated, sealed cell and subjected to small additions of CO&#8322; over several days at near vacuum conditions; and <li>A one-step carbonation method, where CO&#8322; gas is added to the wasteform paste as it is being mixed. </ol> Thirteen elemental constituents of interest to the safety assessments of long-term management of Ontario Power Generation's radioactive waste (Cl, N, S, Se, 13C, Th, Pb, Co, Ni, Cu, Sr, Ba and Cs) were stabilised/solidified via cement mix water. Wasteforms were produced with only OPC, OPC and fly ash, or OPC and silica fume. Most wasteforms were carbonated using one of the carbonation methods. Some wasteforms were not carbonated and served as controls. Wasteforms were subjected to either standard leach tests or compressive strength tests. The extent of carbonation was found to be about 20% for vacuum carbonation method, substantially higher than that for one-step treatment (up to about 10%). For vacuum carbonated wasteforms, carbonation occurred at the outer selvages of the wasteforms, whereas one-step treatment resulted in homogenous carbonation. Generally, compared to uncarbonated OPC wasteforms, vacuum carbonation increased leaching of elements that are anionic in cementitious conditions (Cl, N, S, Se, 13C, Th), decreased leaching of large metal cations (Sr, Ba, Cs, Pb) and had negligible effect on the leaching of the elements that form hydroxyl complexes (Co, Ni, Cu). 13C was the only anionic element whose leachability was reduced by vacuum carbonation, as it may be precipitated in the form CO32- in the large quantity of secondary carbonate minerals produced during the vacuum carbonation process. One-step carbonation did not result in substantial reductions in leachability, compared to uncarbonated OPC wasteforms. However, it had an interesting inverse effect on large metal cation leachability from fly ash- and silica fume-containing wasteforms. A model is presented that proposes that porewater pH changes can have an effect on waste element leachability because 1) the C-S-H Ca/Si ratio is dependent on the equilibrating porewater pH and 2) the degree of ion sorption on C-S-H is dependent on the C-S-H Ca/Si ratio. This model should be tested experimentally as it has important implications on wasteform design. Because of this inverse behaviour, overall neither pozzolan outperformed the other with respect to leachability. Generally, for uncarbonated wasteforms, OPC retained the elements more effectively than OPC with pozzolans. For pozzolans, the leachability of these elements from OPC with fly ash was lower than that of OPC with silica fume. Leaching of Cs was anomalously low from uncarbonated OPC wasteforms, but follow-up experimentation did not corroborate this anomaly. Further testing of these wasteforms to determine how the mineralogical fate of Cs can differ between wasteforms is recommended. All wasteforms tested were of acceptable strength (<0. 689 MPa). Fly ash, and, to a greater degree, silica fume, improved wasteform strength when compared to OPC wasteforms. Carbonation treatments had little effect on wasteform strength. This study has provided much information about the leaching characteristics of a representative set of waste elements from several cement-based wasteform treatments. Although it has not indicated a wasteform design that is ideal for all elements studied, it does suggest that some treatments may be effective for certain groups of elements. Most notably, vacuum carbonation shows promise in improving the immobilisation of isotopes of large metal cations such as Sr, Ba, Cs and Pb as well as 14C (as suggested by 13C here) in cement-based wasteforms.

<p>Waste Stabilisation Ponds (WSPs) are characterised by low phosphorus (P) removal capacity. Heterotrophic bacteria are principal microbial agents in WSPs in addition to algae. As treatment proceeds in WSPs, algal growth increases and pH rises, this has lead to believe that P removal is mainly through sedimentation as organic P algal biomass and precipitation as inorganic P. In activated sludge treatment plants (AS), microbial P removal has been improved and is termed as enhanced biological phosphorus removal. There was a need to establish whether it was possible to enhance P removal in WSPs. A performance assessment of pond system at the University of Dare s Salaam (UDSM), Tanzania, has shown that 90% of the P removed was in the primary pond (facultative) and the rest in the maturation pond (aerobic).</p><p>In these studies, a pure strain A. hydrophyla was isolated from an activated sludge wastewater treatment plant in Sweden. This plant has a train that functions with enhanced biological phosphorus removal. The strain was tested for P uptake in minimal media supplemented with glucose, succinate or acetate, grown aerobically and anaerobically/aerobically. This strain was able to take up P without having been subjected to the anaerobic phase. It was observed that P uptake was enhanced after the anaerobic phase with media supplemented with glucose, but not with succinate or acetate. Phosphorus uptake repeatedly followed the bacterial growth pattern with correlation coefficients of more than 95%. Therefore P removal has a direct correlation with bacterial growth.</p><p>Two isolates Acinetobacter sp. (isolated from the primary facultative pond) and E .coli (isolated from the maturation pond) were obtained from a tropical WSP treatment system at the UDSM. They were subjected to aerobic P uptake experiment similar to those of A.hydrophyla. The uptake per unit absorbance of bacterial growth was found to be comparable to that of A.hydrophyla, isolated from AS. These results showed that heterotrophic activity is important in WSPs. It is possible to enhance P removal in these systems by designing the primary ponds for maximum heterotrophic activity and probably enrichment.</p>

Dans les applications, on rencontre fréquemment des structures minces de géométrie<br />complexe qui nécessitent l'utilisation de maillages surfaciques comportant des éléments<br />triangulaires. Il faut donc trouver des éléments finis triangulaires de coque qui<br />soient robustes vis-à-vis du verrouillage numérique, mais aussi au défaut de consistance.<br />Nous avons formulé un test numérique qui permet de détecter le verrouillage<br />membranaire, et également l'existence de modes parasites de membrane. L'élément<br />MITC6a (Bathe et Lee) apparaî t comme le meilleur élément à six noeuds, mais il<br />exhibe des modes parasites de membrane qui peuvent considérablement détériorer la<br />solution numérique. Nous proposons une technique de filtrage qui consiste à ajouter<br />un terme de stabilisation de cisaillement non réduit et nous avons défini l'élément<br />MITC6rs avec une interpolation plus riche pour le cisaillement. Après une évaluation<br />numérique détaillée, nous recommandons l'usage de l'élément MITC6a stabilisé.