Dissertations / Theses on the topic 'Plastic Matter'

Recent studies suggest that a significant proportion of the plastic pollution that enters the sea is disappearing from the surface, despite being less dense than seawater. Observations across size classes show that it is particularly smaller plastics, <5 mm in length, that are susceptible to removal. The dynamics and transport mechanisms that determine the pathways taken by floating marine plastic debris are poorly understood and the processes causing this disappearance of plastic are unknown. A spatial gradient in the size composition of floating litter has also recently been observed by visual at-sea surveys in the South Atlantic Ocean, where smaller plastic litter items are found in greater relative abundance closer to the coast becoming less frequent with increasing distance out to sea. Conversely, larger, more buoyant plastic items were found to be proportionally more abundant at greater distances away from the coastal source. Both the observations of missing microplastic and the apparent spatial gradient evident in the size composition of dispersing litter suggest that size selective mechanisms are removing smaller fragments of plastics from the surface. The nature of these and the whereabouts and ultimate fate of these smaller plastic fragments is unknown. Two studies were conducted. The first was an empirical investigation to confirm how the size and buoyancy of litter items are influenced by dispersal distances from a point source. Beach littler samples were collected from beaches at increasing distances from a major pollution source: Cape Town in the Western Cape province of South Africa. The size and buoyancy compositions of litter at each distance interval were compared. Mean size and buoyancy increased significantly with increased distance from Cape Town. Mean item volume rose from 5.1 ml to 604 ml. Over 90% of the items recovered closer to Cape Town were in the two lowest buoyancy categories, in contrast to the furthest sampling site, where only 20% of the litter recovered occupied these categories and 55% occupied higher bin ranges. The findings from the beach litter samples were comparable to those of the recent at-sea surveys in the same region and confirmed the spatial gradient in size composition shown by that study. The second study was an experimental investigation into marine biofouling as a possible explanation for the size-selective sinking of smaller plastics at sea. . The study was conducted in situ at the False Bay Yacht Club in Simon's Town in the Western Cape. Samples of highdensity and low-density polyethylene plastic of varying thickness were cut into squares of three different sizes, tethered to exposure rails and submerged approximately 10 cm below the surface for a 12-week study period. A subset was removed bi-weekly, their buoyancy observed and change in dry weight measured. My results showed that both fragment size and material thickness were significant determinants of fouling mass accumulated. Exposure times required for sinking varied from 17 days for the smallest thinnest samples to 66 days for the largest, thickest ones. All sample sizes sank within the study period. Sample volume was a close correlate of time to sinking. Refined versions of these estimates could be scaled by factors such as environmental conditions and proximity to litter inputs, and potentially included into numerical models of floating litter abundance and distribution. Both studies showed that high volume debris items persist longer at the ocean surface.

Dois milhões de toneladas por ano de resíduos plásticos são gerados no Brasil. Apenas 16,5% em massa deste resíduo plástico são mecanicamente reciclados, a maior parte restante é levada a aterros ou lixões. Todo este material poderia ser incinerado e, desta forma reduzir em até 90% a massa do volume aterrado, e seu conteúdo energético seria usado para gerar vapor ou energia. Esta investigação foi feita sobre os produtos de combustão incompleta emitidos da pirólise e combustão em estado estacionário do polietileno e poliestireno em um forno vertical de dois estágios, eletricamente aquecido. Separadamente, os polímeros na forma pulverizada foram pirolisados em temperatura constante de 1000°C e, depois da mistura com N2/O2, os produtos de pirólise foram queimados a 900, 1000 e 1100°C. Os testes foram conduzidos com 21% de O2 em volume no forno de oxidação. Diferentes razões de combustível e ar foram usadas no forno de combustão, pela variação da taxa de alimentação de polímero no forno de pirólise. A motivação para a combustão indireta de PE e PS foi obter a combustão nominalmente pré-misturada dos gases de pirólise com ar, assim, obtendo menores emissões dos produtos de combustão incompleta comparativamente à combustão direta do polímero sólido. Este trabalho examinou os efeitos da temperatura de combustão e a razão equivalente de ar e combustível. Os efluentes da pirólise e combustão foram analisados, e as emissões de CO, CO2, O2, hidrocarbonetos leves, hidrocarbonetos policíclicos aromáticos e materiais particulados foram mensurados. Ainda, o material particulado foi caracterizado quanto ao tamanho das partículas. Foi observado que enquanto a quantidade de gás de pirólise diminuiu com o aumento da taxa de alimentação do polímero, sua composição permaneceu praticamente independente da taxa de alimentação. As emissões de CO2 foram máximas perto da razão equivalente 1, enquanto as emissões de CO aumentaram com o aumento da razão equivalente. As emissões totais de hidrocarbonetos leves e PAH na combustão aumentaram tanto com o aumento da razão equivalente, quanto do aumento da temperatura. A maior parte do material particulado teve o tamanho menor que um micrometro. No geral, as emissões de PAH e material particulado da combustão indireta de PE e PS foram uma ordem de grandeza menor que a emissão correspondente da combustão direta e heterogênea do polímero sólido, obtida em outros trabalhos. Como a pirólise destes polímeros requer uma entrada nominal de calor mínima em relação à quantidade de calor gerada na sua combustão, a implantação desta técnica pode ser vantajosa.<br>Two millions tons/year of plastic wastes are generated in Brazil. Only 16.5% of this plastic waste is mechanically recycled, the rest is mostly landfilled. All these material could be incinerated, in a way to reduce by 90% the volume of landfilled waste, and use its energy content to supply energy. This investigation was conducted on pollutants emitted from steady-flow pyrolysis and combustion of polyethylene and polystyrene in a two-stage electrically-heated vertical furnace. Separately, the polymers, in pulverized form, were first pyrolyzed at constant temperature of 1000°C and subsequently their pyrolyzates were burned at 900, 1000 and 1100°C, upon mixing with air. Tests were conducted with 21% of O2 and different fuel to air equivalence ratios in the oxidizer furnace, by keeping the flow of gases and changing the feed rate of polymer in the pyrolyzer furnace. The motivation for this indirect combustion of PE and PS was to attain nominally-premixed combustion of the pyrolyzate gases with air, thereby achieving lower pollutant emissions than those from direct combustion of the solid polymer. This work examined the effects of the combustion temperature, as well as of the polymer feed rate and the resulting fuel to air equivalence ratio. The effluents of pyrolysis and combustion were analyzed for fixed gases (CO, CO2, O2), light hydrocarbons, polycyclic aromatic hydrocarbons and particulate matter. It was found that whereas the amount of pyrolysis gas decreased with increasing polymer feed rate, its composition was nearly independent of the feed rate. CO2 emissions peaked at an equivalence ratio near unity, while the CO emissions increased with increasing equivalence ratio. The total light hydrocarbon and PAH emissions of combustion increased both with increasing equivalence ratio and with temperature. The generated particulates were mostly submicronmeter in size. Overall, PAH and soot emissions from indirect burning of PE and PS were an order of magnitude lower than corresponding emissions from direct heterogeneous burning of the solid polymer, obtained elsewhere. As pyrolysis of these polymers requires a nominal heat input that amounts to a diminutive fraction of the heat released during its combustion, implementation of this technique is deemed advantageous.

Astrophysical observations give convincing evidence for a vast non-baryonic component, the so-called dark matter, accounting for over 20% of the overall content of our Universe. Direct dark matter search experiments explore the possibility of interactions of these dark matter particles with ordinary baryonic matter via elastic scattering resulting in single nuclear recoils. The ZEPLIN-III detector operated on the basis of a dualphase (liquid/gas) xenon target, recording events in two separate response channels { scintillation and ionisation. These allow discrimination between electron recoils (from background radiation) and the signal expected from Weakly Interacting Massive Particle (WIMP) elastic scatters. Following a productive first exposure, the detector was upgraded with a new array of ultra-low background photomultiplier tubes, reducing the electron recoil background by over an order of magnitude. A second major upgrade to the detector was the incorporation of a tonne-scale active veto detector system, surrounding the WIMP target. Calibration and science data taken in coincidence with ZEPLIN-III showed rejection of up to 30% of the dominant electron recoil background and over 60% of neutron induced nuclear recoils. Data taking for the second science run finished in May 2011 with a total accrued raw fiducial exposure of 1,344 kg days. With this extensive data set, from over 300 days of run time, a limit on the spin-independent WIMP-nucleon cross-section of 4.8 10-8 pb near 50 GeV/c2 WIMP mass with 90% confidence was set. This result combined with the first science run of ZEPLIN-III excludes the scalar cross-section above 3.9 10-8 pb. Studying the background data taken by the veto detector allowed a calculation of the neutron yield induced by high energy cosmic-ray muons in lead of (5.8 0.2) 10-3 neutrons/muon/(g/cm2) for a mean muon energy of 260 GeV. Measurements of this kind are of great importance for large scale direct dark matter search experiments and future rare event searches in general. Finally, this work includes a comprehensive measurement of the energy dependent quenching factor for low energy nuclear recoils in a plastic scintillator, such as from the ZEPLIN-III veto detector, increasing accuracy for future simulation packages featuring large scale plastic scintillator detector systems.

Le but de l'expérience EDELWEISS est la détection directe de matière noire sousforme de WIMPs, par l'étude de leur diffusion élastique sur les noyaux de germanium des détecteurs bolomètriques. Le plus problématique des bruits de fond provient des neutrons pouvant mimer l'interaction d'un WIMP dans un détecteur. Ces neutrons sont notamment produits par les rares muons cosmiques de haute énergie qui atteignent le laboratoire souterrain malgré les 4800 m w.e. de roche. Les muons résiduels sont détectés par un système veto de 46 modules de scintillateur plastique entourant l'expérience, qui permet de rejeter la plupart du bruit de fond associé. La détermination précise du bruit de fond neutron résiduel induit par ces muons dans EDELWEISS-III, essentielle pour l'identification des WIMPs, est le but de cette thèse. Le taux de bruit de fond dépend de la géométrie de l'expérience ainsi que des matériaux utilisés, qui ont subi d'importantes modifications depuis EDELWEISS-II. Des simulations GEANT4 du passage des muons dans la nouvelle géométrie ont été réalisées afin d'extraire le taux d'événements induits par les muons dans les bolomètres. Ce taux est en bon accord avec le taux mesuré extrait des données du Run308. En parallèle, une limite inférieure sur l'efficacité du veto muon a été extraite à partir des données bolomètres. Une nouvelle méthode basée sur l'utilisation d'une source d'AmBe a été développée afin d'extraire l'efficacité de chaque module de la simulation. À partir de ces résultats, il a été montré que le bruit de fond attendu est négligeable pour la recherche de WIMPs avec les données du Run308 et ne limitera pas la sensibilité future d'EDELWEISS-III<br>The aim of the EDELWEISS-III experiment is to detect the elastic scattering of WIMPs from the galactic dark matter halo on germanium bolometers. The most problematic background arises from neutrons, which can mimic a WIMP interaction in a detector. Neutrons are notably induced by high energy cosmic ray muons reaching the underground laboratory despite the 4800 m w.e. of rock overburdened. Remaining muons are tagged using an active muon-veto system of 46 plastic scintillator modules surrounding the experiment, which allows to reject most of the associated background. The goal of this thesis was to give a precise estimation of the irreducible muon-induced neutron background, needed to identify a potential WIMP signal. The expected background depends on the geometry of the experiment as well as on the used materials, both strongly modified since EDELWEISS-II. Geant4-based simulations of muons through the modified geometry were performed to derive the rate of events induced by muons in the bolometer array. This rate has been shown to be in good agreement with the measured one extracted from the Run308 data. In parallel, a lower limit on the muon-veto efficiency was derived using bolometer data only. A new method based on an AmBe source was developed to extract precisely the detection efficiency of individual modules from the simulation. From these results, it was shown that the expected background is negligible for the WIMP search analyses performed with the Run308 data and won't limit the future sensitivity of the EDELWEISS-III experiment

Les lasers femtosecondes sont un outil efficace pour induire des modifications structurelles localisées en volume dans les matériaux diélectriques. Initialement transparents, les diélectriques ne commencent à absorber efficacement l’énergie laser que lorsque l’intensité excède le seuil de claquage optique du matériau. Cette propriété, couplée à une durée d’impulsion femtoseconde plus courte que les temps caractéristiques de relaxation de la matière, permet d’obtenir un dépôt d’énergie précis et localisé dans le volume irradié. Pour modéliser la formation de telles structures, un modèle thermo-élasto-plastique en géométrie 2D planaire, incluant la transition solide-liquide via un modèle de ramollissement, a été implémenté dans un code hydrodynamique lagrangien. Des études de la formation d’une cavité et de l’interaction de multiple cavités ont tout d’abord été réalisées en supposant un dépôt instantané d’énergie laser dans le volume d’une cible de silice fondue. La relaxation de la matière chauffée, portée à l’état de plasma dense, induit alors la propagation d’ondes de choc dans le solide froid environnant. Des déformations permanentes peuvent apparaître dans le matériau si la contrainte, induite par ces ondes, excède la limite élastique. Ces premières études ont notamment permis de comprendre et de décrire les différentes étapes de la formation de micro-structures, fortement corrélées au comportement élasto-plastique du solide environnante. De plus, en utilisant une loi de Weibull, tenant compte de la densité de défauts dans la matière, des probabilités de fractures dans le matériau ont été calculées. Dans un second temps, la structuration de la silice fondue par un faisceau de Bessel a été considérée. Un solveur de Maxwell 3D, couplé à une description fluide de la dynamique électronique, a été utilisé pour modéliser le dépôt d’énergie laser. Les résultats ont permis de comprendre comment s’établit le dépôt d’énergie et rendent compte des effets des différents processus d’ionisation sur les évolutions des profils de densité et d’énergie électronique. Des simulations thermo-élasto-plastiques ont ensuite étaient réalisées en utilisant le dépôt d’énergie calculé. Différents types de déformations induites dans la silice ont pu être mis en évidence en fonction de l’énergie et de la durée de l’impulsion incidente, en accord avec les observations expérimentales<br>Femtosecond laser pulses are an efficient tool to induce localized structural modifications in the bulk of dielectrics materials. The dielectrics, initially transparent, start to efficiently absorb the energy when the laser intensity exceeds the optical breakdown threshold of the material. This property, coupled to a femtosecond pulse duration smaller than the caracteristic relaxation times of matter, allows to induce a localized and accurate energy deposition in the irradiated volume. In order to model the formation of such structures, a 2D thermo-elasto-plastic model, including solid-liquid transitions through a softening model, has been implemented in a lagrangian hydrodynamic code. Studies on the formation of a single cavity and several interacting cavities have been firstly performed, assuming an instantaneous energy deposition in the bulk of fused silica. The relaxation of the heated matter, transformed to a warm dense plasma, induces shock waves in the surrounding cold solid. Permanent deformations may appear if the stress, induced by the waves, exceeds the yield strength of the material. This first study allowed to understand and describe the various steps of the micro-structures formation, which are strongly correlated to the elasto-plastic behavior of the surrounding solid. Furthermore, by using a Weibull’s law, accounting for defects density in the material, cracks probabilities have been predicted. Secondly, the structuration of fused silica by a Bessel beam has been considered. For that purpose, a 3D Maxwell solver coupled to a fluid description of the electron dynamics has been used to model the laser energy deposition. Results allow to understand how the energy deposition establishes and show the effects of the different ionization processes on the electron density and energy profiles. Then, thermo-elasto-plastic simulations have been carried out including the calculated energy deposition. Various kinds of induced deformations in fused silica have been obtained depending on the incident pulse energy and duration, which is in agreement with experimental observations

La production des boues résiduaires au niveau de l’Union Européenne ne cesse d’augmenter et devient un défi sociétal majeur. Pour réduire les volumes et faciliter la réutilisation de la matière organique, le séchage thermique est l’une des opérations les plus couramment mises en œuvre dans les stations d’épuration de grande capacité. Cependant le procédé reste énergivore : maîtriser la facture énergétique implique de contrôler les paramètres opératoires, parmi lesquels le temps de séjour, et donc la vitesse d’écoulement dans le sécheur. Contrôler le temps de séjour implique donc de connaître l’évolution des propriétés rhéologiques des boues au cours du séchage. Or, la littérature scientifique s’est avérée très peu documentée sur la caractérisation rhéologique des boues fortement concentrées, principalement en raison de difficultés techniques rencontrées pour effectuer les mesures telles que les fractures et l’évaporation lorsque les boues sont chauffées. Pour tenir compte de ces phénomènes perturbateurs, nous avons développé deux procédures expérimentales compatibles avec tous les rhéomètres rotatifs conventionnels. La première procédure dont le principe est basé sur la détermination de la surface réellement cisaillée, permet de corriger l’impact des fractures sur une gamme de déformations allant de 0 à 200 %. La deuxième procédure a pour objectif de limiter efficacement l’évaporation de l’eau jusqu’à 80 °C pendant au moins 2 h d’expérience. De plus, au-dessus de la limite de plasticité SiP =43 %, la boue étudiée devient un matériau granulaire-divisé. L’utilisation d’un rhéomètre à poudres, basée sur le principe de Jenike et classiquement utilisé dans les milieux granulaires, a ainsi été validée pour les plus fortes concentrations, notamment par la comparaison avec un rhéomètre classique. Ensuite, l’impact de la concentration sur la nature du comportement rhéologique a été évalué. Nous montrons qu’il existe 4 différents régimes dans la gamme de siccité allant de 2 à 48 %. Pour des siccités inférieures à 6 %, la boue est définie comme une suspension très diluée et son comportement rhéologique est dominé par les forces visqueuses (interactions physico-chimique et/ou hydrodynamique). Lorsque la siccité est dans la gamme 14-43 %, la boue ressemble à un matériau pâteux/plastique dont le comportement est régi par des forces frictionnelles qui se manifestent par l’apparition de la dilatance. Dans la gamme intermédiaire de siccité, 6-14 %, le comportement rhéologique de la boue est gouverné par une compétition entre les forces visqueuses et les forces de frictionnelles. Au delà de 43 %, la boue déshydratée de consistance granulaire se comporte comme une poudre cohésive. Nous démontrons que la relation entre les paramètres de type solide (comme la contrainte seuil) et la siccité peut être modélisée par un modèle composé d’une loi de puissance et d’une loi d’Eilers. La première composante domine dans le régime visqueux, la deuxième dans le régime frictionnel et aucune des deux composantes n’est dominante dans le régime intermédiaire. L'ensemble de ces résultats nous permet de construire un diagramme rhéophysique qui relie le comportement rhéologique de la boue à sa consistance<br>In EU, sludge production is increasing every year and is becoming a real challenge for the waste water treatment plants (WWTP). To reduce volumes and facilitate the reuse of organic matter, thermal drying is one of the most commonly used operations in large WWTP. Optimisation of the paddle dryer energy consumption can be obtained by an accurate control of the operating parameters, among which the residence time which is directly connected to the flow velocity in the dryer. Controlling the residence time implies the knowledge of the rheological parameters of sludge for total solid contents (TS) higher than 20 wt.% and their temperature dependency during drying. However, rheological measurements are difficult to perform at high TS as uncontrolled effects such as fractures and evaporation appear. Consequently, the obtained rheological measurements are not fully representative of a controlled state of the sludge.In this work, we show how to correct fractures impact with a well-controlled procedure allowing the exact determination of the surface really sheared in the range of strain 0-200 %, and so, of intrinsic rheological parameters. Moreover, we show how to control the evaporation of water at high temperatures, up to 80 °C, during at least 2 h of rheological measurements. These procedures are suitable for sludge having a pasty/plastic consistency and are compatible with any commercial rotational rheometer. Furthermore, above the plasticity limit TSP=43 wt.%, the studied sludge looks like a divided material that we characterize using a powder rheometer. The use of a powder rheometer, based on the Jenike principle and conventionally used in granular media, has been validated for the highest concentrations, in particular by means of a comparison with a conventional rheometer. Then, based on these procedures, the impact of concentration on the nature of sludge rheological behaviour has been investigated. We show the existence of 4 different regimes in the 2 48 wt.% TS range. Under 6 wt.% TS, the sludge is defined as a diluted suspension and the rheological behaviour is governed by viscous forces (physico-chemical and/or hydrodynamic interactions). When the TS content is higher than 14 but lower than 43 wt.%, the sludge looks like a pasty/plastic material and the behaviour is governed by frictional forces which manifested by the appearance of dilatancy. In the intermediate range of TS, that is 6-14 wt.%, the rheological behaviour is governed by a competition between viscous and frictional forces. Above 43 wt.%, the divided granular-like sludge behaves like a cohesive powder. We demonstrate that the relation between solid-like parameters (such as the yield stress) and the TS content can be modelled using a model combining a power and an Eilers laws. The power law dominates in the viscous regime, the Eilers law in the frictional regime and neither is dominant in the transitional regime. All of these results allowed us to propose a rheophysical scheme that links the rheological behaviour of the sludge to its consistency

Mestrado em Engenharia do Ambiente - Instituto Superior de Agronomia<br>The use of plastic mulch in agriculture had its beginning in the middle of last century and since then its use has been intensified and the costs of send this residue to appropriate final destination lead it often to be left or burned in open field, causing huge environmental concerns. The biodegradable mulch films, which can be incorporated in the soil at the end of the crop appear as a possible solution for this problem. The goal of this work was to test the biodegradability of 5 plastic mulches, made from biodegradable polymers, comparing to conventional Polyethylene (PE). The biodegradability was tested in laboratory by means of a respirometric test that followed the standard EN ISO 17 556, and in field conditions, by observation and calculation of the percentage of area lost, along the time, in net frames containing the various biodegradable plastics. The field trials to assess fruit productivity and quality were performed during two years. One of the biodegradable mulches stands out for its good performance and seems as a very promising mulch that may be a viable replacement for conventional polyethylene.

Le procédé d'hydroformage est largement utilisé dans les industries automobile et aéronautique. L'optimisation déterministe a été utilisée pour le contrôle et l'optimisation du procédé durant la dernière décennie. Cependant,dans des conditions réelles, différents paramètres comme les propriétés matériaux,les dimensions géométriques, et les chargements présentent des aléas qui peuvent affecter la stabilité et la fiabilité du procédé. Il est nécessaire d'introduire ces incertitudes dans les paramètres et de considérer leur variabilité. L'objectif principal de cette contribution est l'évaluation de la fiabilité et l'optimisation du procédé d'hydroformage en présence d'incertitudes.La première partie de cette thèse consiste à proposer une approche générale pour évaluer la probabilité de défaillance spatiale du procédé d'hydroformage, principalement dans les régions critiques. Avec cette approche, il est possible d'éviter les instabilités plastiques durant une opération d'hydroformage. Cette méthode est basée sur des simulations de Monte Carlo couplée avec des métamodèles. La courbe limite de formage est utilisée comme critère de défaillance pour les instabilités plastiques potentielles.La seconde partie de cette thèse est l'optimisation avec prise en compte d'incertitudes dans le procédé d'hydroformage. En utilisant des exemples illustratifs, on montre que l'approche probabiliste est une méthode efficace pour l'optimisation du procédé pour diminuer la probabilité de défaillance et laisser le procédé insensible ou peu sensible aux sources d'incertitudes. La difficulté est liée à la considération des contraintes fiabilistes qui nécessitent d'énormes efforts de calcul et impliquent des problèmes numériques classiques comme la convergence, la précision et la stabilité. Pour contourner ce problème, la méthode de surface de réponse couplée à des simulations Monte Carlo est utilisée pour évaluer les contraintes probabilistes.L'approche probabiliste peut assurer la stabilité et la fiabilité du procédé et minimise considérablement le pourcentage des pièces défectueuses. Dans cette partie, deux méthodes sont utilisées : l'optimisation fiabiliste et l'optimisation robuste.La dernière partie consiste à optimiser le procédé avec une stratégie Multi-Objectif(MO) avec prise en compte d'incertitudes. Le procédé d'hydroformage est un problème MO qui consiste à optimiser plus d'une performance simultanément.L'objectif principal est d'étudier l'évolution du front de Pareto lorsque des incertitudes affectent les fonctions objectifs ou les paramètres. Dans cette partie, on propose une nouvelle méthodologie qui présente les solutions dans un nouvel espace et les classifie suivant leurs probabilités de défaillances. Cette classification permet d'identifier la meilleure solution et fournit une idée sur la fiabilité de chaque solution.

Історія пластики твердої мозкової оболонки (ТМО) нараховує більш ніж 130 років – від операції Beach А., який використав золоту фольгу для попередження менінгоцеребральної адгезії. На сьогодні налічується безліч синтетичних та натуральних засобів медичного призначення, які використовуються в нейрохірургії для заміщення ТМО, проте пошук ідеального матеріала продовжується. Ідеальний матеріал для пластики ТМО не повинен викликати імунологічної чи запальної реакції, має бути резорбуючим з наступним формуванням власної сполучної тканини, підтримувати форму та бути міцним. Крім цього у даних матеріалів має бути відсутня цито- та нейротоксичність. Нажаль, матеріали, які задовольняють більшості з даних вимог, є високовартісними та не можуть широко використовуватись у вітчизняній медицині. Тому розробка вітчизняного матеріалу для пластики ТМО є актуальною медико-соціальною проблемою.

De nombreux capteurs d'ammoniac existent, mais la prise en compte de l'effet de l'humidité sur la mesure capteur est rarement assurée, y compris chez les fabricants. L'objectif de cette thèse est de proposer un transducteur conductimétrique capable de mesurer le taux d'ammoniac de façon sélective, avec une précision suffisante, pour une application au contrôle de la qualité de l'air dans un environnement à taux d'humidité variable. Le moyen employé pour atteindre cet objectif est l'utilisation de résistors à base de phtalocyanines de cobalt, sous forme de films minces, comme matériaux semi-conducteurs. L'étude porte sur la mise en forme de ces films minces réalisés par évaporation sous vide, évaporation de solvant et électrodéposition. Des bancs de mesures automatisés ont été mis en place pour effectuer les mesures électriques sous argon et pour étudierles réponses à l'ammoniac sec ou humide en appliquant des cycles exposition / repos. A partir de ces cycles de 1 min et 4 min, des réponses relatives sont calculées pour obtenir des valeurs proportionnelles aux concentrations d'ammoniac. Les effets de l'humidité seule et de l'ozone ont également été étudiés. Des tests sur la sensibilité croisée ammoniac / humidité ont été réalisés sur quatre résistors différents, dans des gammes de concentration allant de 25 à 90 ppm et dans des gammes d'humidité allant de 0 à 80% d'HR, à température ambiante. Deux d'entre eux, un résistor de phtalocyanine de cobalt (PcCo) et un résistor hybride de phtalocyanine de cobalt sulfonée /polypyrrole (s-PcCo/PPy), ont donné des résultats particulièrement intéressants.PcCo permet de discriminer des concentrations de 25, 45 et 90 ppm d'ammoniac dans une gammede 20 à 60% d'HR, avec une réponse relative de 40% à 45 ppm. De plus, mêmes si les RRs à 80%d'HR divergent légèrement, la discrimination est toujours possible entre les différentesconcentrations de NH3.s-PcCo / PPy est moins sensible à l'ammoniac, mais son étude a permis de démontrer que l'ajout dephtalocyanine dans une matrice polypyrrole augmente la sensibilité de ce matériau. Il donne uneréponse relative de 3,3% à 45 ppm. Cependant, la gamme d'humidité couverte est plus large, allant de 20 à 80% d'HR.Cette étude a donc permis de comparer des matériaux et d'estimer leur potentiel pour des applications au contrôle de la qualité de l'air avec différents taux d'humidité

Laser-Induced Breakdown Spectroscopy (LIBS) is an analytical technique that has the potential to detect all the elements present in the periodic table. The limit of detection can go below a few ppm and this regardless of the physical phase of the analyzed sample (solid, liquid or gas). Its simplicity of use, its rapidity to get results and its versatility provide this technique with attractive features. The technique is currently developed for applications in a large number of domains such as online control, spatial explorations and the environment. However the weakness of the LIBS technique, compared to other more conventional ones, is still its difficulty in providing reliable quantitative results, especially for inhomogeneous and complex matrix such as organic or biological materials. The work presented in this thesis includes a study of the properties of plasma induced from different organic materials. First, a study of the plasma induced on the surface of a Nylon sample at short time delays (~ns) was carried out using the time-resolved shadowgraph technique for different experimental parameters (laser energy, pulse duration, wavelength). Then, a complete diagnostics of the plasma was performed using the plasma emission spectroscopy. A detailed analysis of the emission spectra at different detection delays allowed us to determine the evolution of the temperatures of the different species in the plasma (atoms, ions and molecules). The homogeneity and the local thermodynamic equilibrium within the plasma was then experimentally checked and validated. We demonstrated that the optimisation of the signalto- noise ratio and a quantitative procedure, such as the calibration-free LIBS, can be put in place within a properly chosen detection window. In our experiments, such optimised detection configuration was further employed to record LIBS spectra from different families of polymer in order to identify and classify them. For this purpose, the chemometrics procedure of artificial neural networks (ANN) was used to process the recorded LIBS spectroscopic data. The promising results obtained in this thesis makes LIBS stand out as a potentially useful tool for real time identification of plastic materials. Finally, this work can also be considered as a base for the further studies of more complex materials such as biological tissues with LIBS.

Etude du vieillissement de polymeres renforces ou non de fibres de verre ou de mousses syntactiques immerges dans l'eau sous des pressions de 0 a 300 bars. Adsorption d'eau, proprietes mecaniques, eclatement des microspheres dans les mesures syntactiques

Questo studio nasce come ricerca pilota per un progetto della regione Emilia-Romagna sulla riduzione dell'uso della plastica in frutticoltura; nello specifico, si è occupato di verificare la validità economica e ambientale dei teli di pacciamatura biodegradabili e delle possibili opzioni di gestione a fine vita delle reti antigrandine e antinsetto. I risultati ottenuti indicano che i teli di pacciamatura in Mater-Bi sono una valida alternativa ai teli in polietilene a bassa densità, sia a livello ambientale che a livello economico, sia per le coltivazioni brevi che per le coltivazioni di durata maggiore, come la fragola unifera. Sono necessari, tuttavia, ulteriori studi a lungo termine per verificare l’effettiva compatibilità ambientale. Attualmente le reti antigrandine e antinsetto dismesse vengono ritirate da aziende private e inviate a riciclo in quanto realizzate in HDPE. Questa tipologia di gestione presenta però alcune potenziali inefficienze dovute ad una mancata coordinazione delle realtà coinvolte. Si conclude che l’implementazione di un sistema di gestione integrato possa sfruttare appieno le potenzialità di questo ingente flusso di materiale. Poiché non risulterebbero studi approfonditi né sui teli di pacciamatura né sulle reti antigrandine, l’analisi condotta è stata accompagnata da un’estensiva e sistematica trattazione necessaria alla completa comprensione dei temi indagati. La collaborazione dei fornitori, delle aziende agricole e dei riciclatori coinvolti nella filiera di questi prodotti polimerici è stata fondamentale per il compimento di questa ricerca e sarà cruciale anche nella futura razionalizzazione dell’utilizzo della plastica in agricoltura.

Caracterisation de la tenue dielectrique des couches minces, sur des echantillons mim autocicatrisants. Methode statistique permettant le calcul des parametres de claquage. Resultats obtenus avec un film de silicone et un film polytetrafluorethylene

Cette patisserie industrielle, d'activite de l'eau fixee a 0,85 est un produit sensible aux alterations microbiologiques et physico-chimiques. Pour la conserver, sans ajouter d'additifs ni modifier sa formulation, plusieurs techniques ont ete testees: le conditionnement sous atmosphere modifiee, l'irradiation, les rayonnements hautes frequences, hyper frequences et infra-rouges. Cette etude a conduit a retenir et optimiser trois techniques aux caracteristiques suivantes: un conditionnement sous atmosphere modifiee, qui comporte une atmosphere interne et un film aux proprietes bien determinees. L'etude de l'atmosphere interne a permis, notamment, de tenter une evaluation de la consommation en oxygene de moisissures se developpant en presence d'un fort taux de gaz carbonique, un traitement en infra-rouge court a forte densite de puissance et un traitement micro-ondes qui permettent un traitement de pasteurisation tres court. Ces trois techniques ont ete comparees au niveau d'un essai industriel d'un point de vue qualite et cout du produit traite. Dans les conditions d'utilisation choisies, le traitement qui parait le plus performant et a moindre cout est le traitement par infra-rouge court a forte densite de puissance

Etude sur des decharges electriques prenant naissance dans des microcanaux de faibles dimensions analogues a ceux qui peuvent se creer dans un isolant solide soumis a un champ intense. Les criteres classiques de transition a l'arc, etablis pour des decharges a l'air libre sont quantitativement compatibles avec les valeurs limites qui sont obtenues pour les canaux lorsque le rapport entre le diametre du canal (phi) et l'espace interelectrode (d) est superieur a 0,2. Etude de la rupture du polyethylene par le mecanisme de l'arborescence hygrostimulee et tout d'abord la possibilite de transition d'une hygroarborescence a une electroarborescence. L'interface eau-polymere posant un probleme de duree de vie du solide, l'influence des liquides au contact du polyethylene a ete etudiee

碩士<br>高雄醫學院<br>藥學研究所<br>85<br>The aim of the study was to investigate the particulate matters in variouslocally produced and imported intravenous administration sets and disaposable plastic syringes. The particulate matters of the products was obtained by running a known volume of normal saline solution with known particle count through the sets; however, which was performed by filling the syringes with the normal salinesolution. The particle count of the resultant solution samples was determined using a Coulter Counter Multisizer II. It was found that the locally produced administration sets and plastic syringes contained less particle count than the imported ones. The flow rateof the normal saline solution through the sets has no effect on the particle count of the solution obtained. Repeated use of the plastic syringe wouldincrease the number of particle count. Microscopic examination showed that the particles obtained from the administration sets are mainly irregular in shape, having rough surface, and those from the syringes are mainly spherical.Large volume parenteral is commonly used in medical care, the container materials are either glass or plastic. Plastic materials include polyethylene, polyvinyl chloride and polyolefin based multilayer. Studies were made to evaluatethe properties of polyolefin based multilayer and polyvinyl chloride by undergoingtests such as thickness, flexibility, transparency, residue of ignition, resistance to pressure, particulate contamination of the solutions as well as adsorption of drugs such as Ketamine, atropine, diazepam and insulin in the administration solutions. The container made of polyvinyl chloride is thicker than that of polyolefinbased multilayer. Residue of ignition for polyvinyl chloride was much higher than thatof the polyolefin based multilayer. Polyvinyl chloride has a relatively poorer transparency. No significant loss of either Ketamine, atropine or insulin was observed during the adsorption study for both types of plastic containers. However, therewas a significant loss of diazepam due to apparent adsorption of the drug to the polyvinyl chloride container and the amount of loss was time dependent. The loss of diazepam due to adsorption was not observed when the plastic container was polyolefin based multilayer.

The marine ecosystems are inter-connected with the terrestrial ecosystem; thus, any alteration in one system has impacts on another. The impacts of the micro-plastics on marine ecosystem plants and organisms are presently, the subject of intense study. When the plastic debris can enter into the marine ecosystem the debris of the micro-plastics can harm the plants present in the marine but grounded on the novel investigation, micro-plastics has the negligible effects on the plants. Floras can be therefore, symbolize a sustainable pathway for the micro-plastics to arrive in the marine food webs. In spite of this, the strong interfaces of the plastic debris by floras can be used for their phyto-stabilization and then the ultimate elimination from marine ecosystem. The chief purposes of the review here is to deliberate about micro-plastics and sources or transfer of them into the marine ecosystem. We were also discussing the impacts of marine plants and organisms when the micro-plastics enter into the marine ecosystem and what are the outcomes. The small debris of the micro-plastics when enter the marine ecosystem, the marine organisms directly or indirectly consumed the micro-plastic particleswhich result in the contamination of the seafood. As micro-plastics are already present in a variety of sea-food matters, there is powerful encouragement for the transfer of micro-plastic particles to the humans. The ingestion can cause skin irritation, digestive problems, cardiovascular disease, respiratory problems, reproductive effects, and cancer in the humans.

This work focuses on understanding deformation mechanisms and responsiveness associated with the wrinkling, folding, and snapping of thin polymer films. We demonstrated the use of elastic instabilities in confined regimes, such as the crumpling and snapping of surface attached sheets. We gained fundatmental insight into a thin film's ability to localize strain. By taking advantage of geometric strain localization we were able to develop new strategies for responsive surfaces that will have a broad impact on adhesive, optical, and patterning applications. Using the rapid closure of the Venus flytrap's leaflets as dictated by the onset of a snap instability as motivation, we created surfaces with patterned structures to transition through a snap instability at a prescribed stress state. This mechanism causes surface topography to change over large lateral length scales and very short timescales. Changes in the stress state can be related to triggers such as chemical swelling, light-induced architecture transitions, mechanical pressure, or voltage. The primary advantages of the snap transition are that the magnitude of change, the rate of change, and the sensitivity to change can be dictated by a balance of materials properties and geometry. The patterned structures that exhibit these dynamics are elastomeric shells that geometrically localize strain and can snap between concave and convex curvatures. We have demonstrated the control of the microlens shell geometry and that the transition time follows scaling relationships presented for the Venus flytrap. Furthermore, the microlens arrays have been demonstrated as surfaces that can alter wettability. Using a similar novel processing technique, microarrays of freestanding elastomeric plates were placed in equibiaxial compression to fabricate crumpled morphologies with strain localized regions that are difficult to attain through traditional patterning techniques. The microstructures that form can be initially described using classical plate buckling theory for circular plates under an applied compressive strain. Upon the application of increasing compressive strain, axisymmetric microstructures undergo a secondary bifurcation into highly curved, nonaxisymmetric structures. The inherent interplay between geometry and strain in these systems provides a mechanism for generating responsiveness in the structures. By swelling the elastomeric plates with a compatible solvent, we demonstrated the microstructures ability to reversibly switch between axisymmetric and nonaxisymmetric geometries. To further explore the localization of strain in materials, we have fabricated sharply folded films of glassy, homogenous polymers directly on rigid substrates. The films were uniaxially compressed and buckle after delaminating from the substrate. As the applied strain is increased, we observed strain localization at the center of the delaminated features. We found that normally brittle, polystyrene films can accommodate excessive compressive strains without fracture by undergoing these strain localizing fold events. This technique provided a unique way to examine the curvature and stability of folded features, but was not adequate for understanding the onset of folding. By taking thin films, either glassy or elastomeric, and simply lifting them from the surface of water, we observed and quantified the wrinkle-to-fold transition in an axisymmetric geometry. The films initially wrinkle as they are lifted with a wavelength that is determined by the film thickness and material properties. The wrinkle-to-fold transition is analogous to the transition observed in uniaxially compressed films, but the axisymmetric geometry caused the fold to act as a disclination that increased the radial stress in the film, thereby decreasing the wavelength of the remaining wrinkles. Further straining the films caused the remaining wrinkles to collapse into a discrete number of folds that is independent of film thickness and material properties.

<div> Design rules and application spaces for closed-shell conjugated polymers have been well established in the field of organic electronics, and this has allowed for significant breakthroughs to occur in myriad device platforms [e.g., organic field-effect transistors (OFETs) and organic light-emitting devices (OLEDs)]. Conversely, organic electronic materials that are based on the emerging design motif that includes open-shell stable radicals have not been evaluated in such detail, despite the promise these materials show for charge transfer, light-emission, and spin manipulation platforms. Moreover, recent results have demonstrated that the materials performance of hybrid systems will allow for future applications to harness both of these platform design archetypes to generate composites that combine the performance of current state-of-the-art conjugated polymer systems with the novel functions provided by open-shell species. Thus, establishing the underlying physical phenomena associated with the interactions between both classes of materials is imperative for the effective utilization of these soft materials.</div><div><br></div><div> In the first part of this work, Förster resonance energy transfer (FRET) is demonstrated to be the dominant mechanism by which energy transfer occurs from a common conjugated polymer to various radical species using a combination of experimental and computational approaches. Specifically, this is determined by monitoring the fluorescence quenching of poly(3hexylthiophene) (P3HT) in the presence of three radical species: (1) the galvinoxyl; (2) the 2phenyl-4,4,5,5-tetramethylimidazoline-3-oxide-1-oxyl (PTIO); and (3) the 4-hydroxy-2,2,6,6tetramethylpiperidine-1-oxyl (TEMPO) radicals. Both in solution and in the solid-state, the galvinoxyl and PTIO radicals show quenching on par with that of a common fullerene electronaccepting derivative. Conversely, the TEMPO radical shows minimal quenching at similar concentrations. Using both ultrafast transient absorption spectroscopy and computational studies, FRET is shown to occur at a significantly faster rate than other competing processes. These findings suggest that long-range energy transfer can be accomplished in applications when radicals that can act as FRET acceptors are utilized, forming a new design paradigm for future applications involving both closed- and open-shell soft materials.</div><div><br></div><div> Following this, addition of the galvinoxyl radical to P3HT is shown to alter the thin film transistor response from semiconducting to conducting. This is accompanied by a modest enhancement in electrical conductivity. This interaction is not seen with either the TEMPO or PTIO radicals. While an increase in charge carrier concentration is observed, the interaction is not otherwise consistent with a simple charge-transfer doping mechanism, due to the mismatched reduction and oxidation potentials of the two species. Additionally, no freeze-out of charge carriers is observed at reduced temperatures. It is also not due to parallel conduction through the radical fraction of the bulk composite, as the radical species is non-conductive. Hole mobility is enhanced at lower concentrations of the radical, but it decreases at higher concentrations due to the reduced fraction of conductive material in the polymer bulk. Despite the increase in mobility at lower concentrations, the activation energy for charge transport is increased by the presence of the radical. This suggests that the radical is not improving the charge transport through filling of deep trap states or by reducing the activation energy for the charge transport reaction; however, the galvinoxyl radical is likely filling shallow trap states within the P3HT for the composite thin film.</div><div><br></div><div> Finally, a novel analysis technique for polymer relaxation is investigated through dielectric spectroscopy of model polyalcohols. An understanding of relaxation phenomena and the physics of amorphous solids in general remains one of the grand open challenges in the field of condensed matter physics. This problem is particularly relevant to organic electronics as many organic electronic materials are found in the amorphous state, and their physical relaxation can lead to undesirable effects such as hysteresis and instability. Current procedures describe relaxation phenomena in terms of empirical functions, but the physical insights provided by this representation are limited. The new approach instead represents the dielectric response as a spectrum of Debye processes. Rather than varying the spectral strength at fixed time points as traditional spectral analysis implicitly does, this approach instead varies the characteristic time of each spectral element while the strength remains fixed. This allows the temperature dependence on relaxation time of each spectral element to be determined, and the <i>α</i>- and <i>β</i>-relaxation are interpreted in light of this analysis. </div><div> </div>

PhDENV<br>Department of Ecology and Resource Management<br>Some industries such as textiles, ceramics, paper and printing are known to use significant amounts of dye to colour their products and during the colouring process, certain quantities of dyes are absorbed by the products, and some of them end up in wastewater. Depending on their application, some synthetic dyes are designed to be chemically or biologically resistant and their presence in the environment can cause severe environmental problems because of their colour impartation to water bodies. Therefore, proper treatment is required to remove these pollutants from wastewater before discharge into the environment. In this thesis, the potential of dye removal from wastewater by calcined magnesite, halloysite nanoclay and calcined magnesite - halloysite nanoclay composite was evaluated. To this end, the study was subdivided to four segments. The first segment of the study focused on evaluating the efficiency of using calcined magnesite to remove Methylene Blue (MB), Direct Red 81 (DR81), Methyl Orange (MO) and Crystal Violet (CV) dyes from aqueous systems using a batch study. To achieve that, several operational factors like residence time, adsorbent dosage, dye concentration and temperature were appraised. The adsorbent was subjected to different kinds of physicochemical characterization to determine the various characteristics that would assist in the dye uptake process. Characterization results showed that the adsorbent material was highly crystalline with magnesite, periclase, dolomite, and quartz as some of the crystalline phases. The batch study proved that calcined magnesite is effective in the treatment of dye contaminated water and moreover it performed well in terms of colour removal, though exceptional results were recorded for CV removal with complete decolourisation occurring in first few minutes of contact. In terms of experimental adsorption capacity, the performance of calcined magnesite was in the order CV (14.99 mg/g) > DR81 (12.56 mg/g) > MO (0.64 mg/g) > MB (0.39 mg/g). Mechanisms of adsorption where explained by fitting the experimental data into adsorption isotherms, kinetics, and thermodynamic parameters. Neither, the Langmuir, nor the Freundlich nor the Dubinin Radushkevich, nor the Temkin model could perfectly describe the adsorption of the four dyes onto calcined magnesite, however adsorption kinetics obeyed the pseudo second order model, implying that, the dye removal process was primarily a chemical process. In accordance with the results of this study, it can be concluded that calcined magnesite can be used effectively for the removal of dyes in aqueous solution and thus can be applied to treat wastewater containing dyes. The second segment of the study focused on the removal of MB, DR81, MO and CV dyes by halloysite nanoclay. Physicochemical characterisation revealed that the nanoclay has a surface area of 42 m²/g and its ABSTRACT iv morphology is predominated by tubular structures, which exhibit some hollow rod like structures. Various important parameters namely contact time, initial concentration of dyes, dosage, solution temperature and solution pH were optimized to achieve maximum adsorption capacity and it was observed that the effect of initial pH and temperature of the aqueous solution was neglibible on removal of the four dyes. The experimental adsorption capacities towards 40 mg/L of MB, DR81, MO and CV dyes were 17.51, 14.11, 0.38, and 4.75 mg/g respectively. The results indicate that natural halloysite nanoclay is an efficient material for the removal of the selected dyes. Due to its low cost and non-toxicity, halloysite nanoclay can be considered a good replacement option of other high cost materials used to treat coloured wastewater especially in developing countries like South Africa. Having observed the performance of calcined magnesite and halloysite nanoclay individually in the removal of selected dyes, a third study was designed with the aim of preparing a nanocomposite adsorbent from the aforementioned adsorbent materials and then evaluating the synergistic influence of the mechanochemical modification by a ball miller on the removal of MB, DR81, MO and CV dyes. Physicochemical characterization was carried out to get an insight of pre- and -post adsorption characteristics of the nanocomposite material and results showed major changes which could be an indication of dye uptake by the nanocomposite material. According to the results, the nanocomposite material outcompeted its component individual constituent materials i.e (calcined magnesite and halloysite nanoclay material) in the removal of DR81, which in turn was the highest removal efficiency observed for the whole batch adsorption study recording a maximum adsorption capacity and percentage removal of 19.89 mg/g and 99.40% respectively. Experimental results fitted the Langmuir and pseudo-second order models perfectly hence demonstrating that adsorption took place on a homogenous adsorbent layer via chemisorption. In overall, the results suggested that the nanocomposite is a suitable adsorbent for decolourising industrial wastewater. Based on the overall performance of the adsorbents in removing the four dyes, it was observed that the nanocomposite material had a high affinity for DR81 dye hence it was chosen as the model dye for further application in column studies. The effect of flow rate, bed height and initial dye concentration on the removal of DR81 was investigated. Maximum bed capacity and equilibrium dye uptake were determined and break through curves were plotted. Percentage dye removal increased with decrease in flow rate and increase in bed height. The maximum capacity of column was found to be about 51.73 mg DR81 per gram of the nanocomposite adsorbent for a flow rate of 3 mL/min, initial concentration of 10 mg/L and 4 cm bed height. Data from column studies was fitted to the Thomas model and Adams-Bohart models. The comparison of the R2 values obtained from both models showed a better fit for the nanocomposite material than the individual halloysite nanoclay and calcined magnesite materials. The study revealed the applicability of calcined magnesite- halloysite nanoclay composite in fixed bed column for the removal of DR81 dye from aqueous solution. v The reuse of an adsorbent is essential in order to make the adsorption process economic and environmentally friendly. To recover the adsorbate and renew the adsorbent for further use, a chemical method of regeneration was applied by using 0.1 M NaOH as the desorbent. Regeneration with 0.1 M NaOH proved very efficient for some dyes and less efficient for others depending on the adsorbent material used at the time. The general observation was that the adsorption capacity of the adsorbent materials decreased with successive adsorption – desorption cycles. Furthermore, regeneration with NaOH, favoured the acidic dyes (DR81 and MO) more than the basic dyes (MB and CV) possibly due to electrostatic interactions between oppositely charged molecules allowing for reversible reactions to take place. The three tested adsorbents namely calcined magnesite, halloysite nanoclay and their nanocomposite thereof were applied for the treatment of real wastewater effluent from a printing and ink industry. The adsorbents performed very well in terms of colour removal as recommended by the South African standards of wastewater discharge, However, in terms of pH, calcined magnesite and the nanocomposite produced a highly alkaline solution hence wastewater neutralisation by an acid is recommended before discharge. These findings show that the two natural clay-based materials (calcined magnesite and halloysite nanoclay) and their nanocomposite thereof have a great potential for application in dye wastewater remediation since the materials used in the process are inexpensive, abundant and require minimal modifications.<br>NRF

<div>Despite the abundant current applications for ionic hydrogels, much about the stimuli-responsive behavior of these materials remains poorly understood. Due to the soft nature of these materials, the number of traditional characterization methods which can be applied to these systems is limited. Many studies have been conducted to characterize bulk property responses of these materials, and experimental studies have been produced examining the distribution of free ions around single polyelectrolyte chains. However, little experimental work has been published in which molecular-scale interactions are elucidated in confined polyelectrolyte networks. Furthermore, the way in which responsive properties, other than bulk swelling capacity, scale with ionic fraction in mixed polyelectrolyte-non-polyelectrolyte hydrogel systems has not been thoroughly investigated.</div><div>The distribution and strength of polymer-counter-ion bonds has a remarkable effect on hydrogel properties such as absorption capacity, mechanical strength, and size and chemical selectivity. In order to tailor these properties for targeted applications in ionic environments, it is imperative that we thoroughly understand the character of these polymer-ion interactions and their arrangement within the bulk hydrogel. In order to do so, however, non-traditional methods of analysis must be employed.</div><div>This dissertation focuses on a model part-ionic hydrogel system, poly(sodium acrylate-co-acrylamide), in order to assess not only the polymer-counter-ion interactions but also the impact of gel ionic fraction on these interactions and the responses which they induce in gel performance properties. A model alkali (NaCl), alkaline earth (CaCl2), and transition (CuSO4) metal salt are employed to investigate changes in polymer properties from the macroscale to the nanoscale. The aim of this dissertation is to lay the foundation for the development of fundamental structure-property relationships by which we may fully understand the ionically-induced performance properties of polyelectrolyte networks.</div>