Le présent travail porte sur la photodégradation de polluants aqueux utilisant des catalyseurs à base de ZnO. La première étape a consisté à fonctionnaliser ZnO avec des nanoparticules d'argent. Deux méthodes ont été utilisées : la photodéposition et l'imprégnation des particules d'argent sur ZnO. L’activité des catalyseurs obtenus vis-à-vis de la dégradation du bisphenol-A, du triclosan et de la rhodamine-B a été ensuite étudiée. L'effet du pH, des concentrations du photocatalyseur et du polluant et de la longueur d'onde sur la dégradation du bisphenol-A a été analysée et la constante cinétique déterminée. L'optimisation a montré qu'une teneur faible en argent et un pH alcalin, tant pour la fonctionnalisation de ZnO que pour la photodégradation, maximisent la constante cinétique de dégradation du bisphenol-A. Un modèle a également prédit que le système obtenu par photodéposition présente une activité photocatalytique supérieure à celle de celui obtenu par imprégnation. D'autre part, pour surmonter des problèmes d'agrégation, les particules d’Ag/ZnO ont été immobilisées grâce à leur incorporation dans une matrice d'acide polyacrylique réticulé. La surface des particules de catalyseur a, au préalable, été modifiée grâce à un agent de couplage silané qui a permis (i) la dispersion et l'ancrage par estérification des nanoparticules sur la matrice polyacrylique (ii) de promouvoir la cristallisation du polymère. Les composites obtenus ont été testés avec succès sous rayonnement UV avec une efficacité comparable à celle des particules non-immobilisées. L'immobilisation permet par ailleurs d'empêcher la photocorrosion du catalyseur et d'utiliser ces composites en mode continu / The present work concerns photodegradation of water contaminants using ZnO-based catalysts. The first step consisted in designing a new catalytic system by functionalizing ZnO with silver nanoparticles. Two methods were used: photodeposition and impregnation of silver nanoparticles (AgNPs) on ZnO. The photocatalytic activity of the resulting catalyst towards the degradation of bisphenol-A, triclosan and rhodamine-B was studied. The effect of pH, photocatalyst and contaminant concentrations and wavelength, on bisphenol-A degradation was studied and the kinetic rate constant was determined. The optimization showed that a low silver content and an alkaline pH, during both functionalization of ZnO and photodegradation, maximized the kinetic rate constant of bisphenol-A degradation. A model also predicted that Ag/ZnO obtained by photodeposition showed higher photocatalytic activity that of Ag/ZnO obtained by impregnation.On the other hand, to overcome aggregation problems, Ag/ZnO were immobilized owing to their incorporation in a cross-linked poly(acrylic acid) matrix . The surface of Ag/ZnO was previously modified, using a silane coupling agentwhich allowed (i) dispersing and anchoring NPs on the polyacrylic matrix by formation ester bonds (ii) promoting crystallization of the polymer. The composites were successfully tested under UV light with an efficiency comparable to that of non-immobilized NPs. The immobilization provides additional advantages e.g. hindrance of catalyst photocorrosion and possible use of the composite in continuous mode

Le photovoltaïque est une énergie renouvelable pouvant aider à lutter contre le réchauffement climatique et l’épuisement des ressources fossiles utilisées pour la production d’énergie. La filière émergente à base de matériaux pérovskites (photovoltaïque de 3ème génération) est très prometteuse car elle utilise des matériaux abondants et faciles à mettre en œuvre (technologie bas-coût) et a montré de plus des rendements record compétitifs en peu de temps. Il reste cependant des verrous technologiques à lever afin de pouvoir développer cette technologie à grande échelle. L’un deux consiste à améliorer la couche de TiO₂ qui transporte les électrons et dont les défauts limitent les performances et la durée de vie des cellules photovoltaïques pérovskites. Ce travail propose l’utilisation de matériaux à base de nanostructures de carbone et de TiO₂ pour améliorer le transport et la collecte des électrons au sein de ces cellules photovoltaïques et ainsi améliorer leur rendement. Pour cela, la pyrolyse laser, technique singulière de production continue de nanoparticules, a été adaptée pour l’élaboration de nanocomposites TiO₂/graphène aux propriétés contrôlées. Ces matériaux ont été caractérisés puis intégrés aux cellules photovoltaïques pérovskites qui ont démontré une meilleure efficacité en présence de graphène. Par ailleurs, ce travail présente une architecture innovante à base de nanotubes de carbone alignés verticalement, en vue d’une application pour la collecte des électrons photo-générés des cellules photovoltaïques pérovskites. Les matériaux carbonés présentent donc de fortes potentialités pour l’optoélectronique, et plus particulièrement pour le photovoltaïque de 3ème génération. / Photovoltaic is a promising renewable energy to tackle global warming and the depletion of fossil resources. The emerging field of perovskite solar cells (3rd generation photovoltaic) is very attractive because it uses abundant and easy-processing materials (low-cost technology) and provides competitive efficiencies.Still, efforts remain to be performed to develop this technology, especially concerning the improvement of efficient and reliable charge transporting electrodes. Titanium dioxide layer, commonly used for electron extraction, presents defects that limit the performance and lifetime of the perovskite solar cells.This work proposes the use of materials based on TiO₂ and carbon nanostructures to improve the electron transport and collection within the solar cells, in order to enhance the power conversion efficiency. The singular technique of laser pyrolysis, which is a continuous process of nanoparticles synthesis, was adapted to produce TiO₂/graphene nanocomposites with well-controlled properties. These materials have been characterized and integrated into perovskite solar cells that demonstrate an improved efficiency in presence of graphene.Besides, this work presents an innovating architecture based on vertically aligned carbon nanotubes for the electron collection of a perovskite solar cell. We show then the strong potential of carbon materials for optoelectronic, especially 3rd generation photovoltaic.

Ce mémoire de thèse est consacré au développement d'anodes et de photonanodes efficaces pour l'oxydation électrocatalytique et photocatalytique de l'eau à base de nanocomposites dans lesquels des nanoparticules d'oxyde de nickel ou de cobalt ont été insérées dans un film de poly(pyrrole-alkylammonium) chargé positivement. Les anodes nanocomposites renferment des petites nanoparticules d'oxydes de nickel ou de cobalt avec une excellente nanostructuration induite par le film polypyrrole, et des performances catalytiques très élevées par rapport à des anodes sur lesquelles des oxydes de nickel et de cobalt ont été directement déposés sans polypyrrole. Ces électrodes nanocomposites surpassent les anodes à base de nickel de la littérature (non dopées par du fer) et celles utilisant des oxydes de métaux précieux, tels que RuO2 et IrO2.Cette stratégie a été étendue avec succès à la conception de photoanodes hybrides en introduisant un chromophore de pérylène diimine dans ces nanocomposites d’oxydes de nickel ou de cobalt. Ces photoanodes présentent une densité de photocourant très élevé avec l'oxyde de nickel et l'oxyde de cobalt sous irradiation dans le visible avec une stabilité relativement bonne dans le temps. Ces valeurs de photocourant dépassent largement celles obtenues par des photoanodes hybrides similaires de la littérature combinant un colorant organique et un oxyde métallique comme catalyseur, démontrant les grandes potentialités de notre approche pour élaborer des cellules (photo)électrochimiques dédiées à la dissociation de l’eau en H2 et O2. / This thesis is focused on the development of efficient anodes and photonanodes for electrocatalytic and photocatalytic water oxidation based on nanocomposite materials in which nickel or cobalt oxide nanoparticles have been inserted in a positively charged poly(pyrrole-alkylammonium) film.The nanocomposite anodes exhibit small nanoparticles of nickel or cobalt oxides and high nanostructuration induced by the polypyrrole matrix leading to very high catalytic performance in comparison with bare anodes on which nickel and cobalt oxides have been deposited without polypyrrole. These nanocomposite electrodes outperform the nickel-based anodes of the literature (undoped by iron) and those using precious metal oxides, such as RuO2 and IrO2.This strategy has been successfully extended to the design of hybrid photoanodes by introducing a perylene diimine chromophore in these nickel or cobalt oxide nanocomposite materials. These photoanodes display very high photocurrent density with nickel oxide and cobalt oxide under visible light illumination along with a relatively good stability over time. These photocurrent density values largely exceed those reached by similar hydrid photoanodes of literature combining an organic dye and a metal oxide as catalyst, demonstrating the great potentialities of our approach to implement (photo)electrochemical cells devoted to water splitting into H2 and O2.

De par leur faible coût, leurs propriétés mécaniques ajustables et leur potentielle transparence, les matériaux polymères sont des candidats de choix pour le packaging biomédical. Cependant, il est souvent nécessaire d'améliorer leurs propriétés barrière à O2 et H2O afin de garantir une conservation optimale du produit conditionné. Dans ce contexte, l'approche choisie a été d'associer une phase inorganique à la matrice polymère. Ainsi, après un choix des systèmes polymères les plus adaptés aux conditionnements pharmaceutiques souples d'une part et rigides d'autre part, nous avons étudié deux voies d'optimisation des propriétés barrière : le dépôt de couches minces organosiliciées à la surface du polymère et la voie nanocomposites. Le but est d'établir pour ces deux types de systèmes hétérogènes les relations Structure/Morphologie/Propriétés. Le dépôt de couches minces organosiliciées a été effectué par le procédé de dépôt chimique en phase vapeur assisté par plasma. Nous avons étudié deux types de monocouches, la première de type céramique SiOx et l'autre de type SiCH. La combinaison de ces couches sous forme d'empilements sur le substrat polymère permet, outre l'augmentation conséquente des propriétés barrière, une meilleure conservation des propriétés fonctionnelles sous des sollicitations de type thermique ou mécanique. Les nanocomposites ont été préparés par voie fondu à partir d'un poly(propylène) et de charges oxyde de zinc ou doubles hydroxydes lamellaires. Nous avons étudié les effets d'un agent compatibilisant et de modifications de surface des charges. Les propriétés barrière sont reliées à l'état de dispersion des charges et aux interactions charges/matrice / Due to their good handling properties, potential transparency and low cost, polymers are key components for the biomedical industry. However, high barrier properties towards gases or vapors are required for packaging applications in order to retain the quality of the product. To achieve the improvements in barrier properties of polymers, two different ways based on the combination of an inorganic phase with the polymer material were studied. The aim was to establish Structure/Morphology/Properties relationships. Thin inorganic coatings deposited on polymer substrates are of particular interest for improving barrier properties. In the current work, thin transparent silicon based layers were deposited on flexible polymer films by plasma-enhanced chemical vapor deposition. Monolayers (SiOx type and SiCH type) and piles with an alternation of these different monolayers were studied. The interest of multilayer barrier coatings was highlighted for higher barrier properties and resistance to solicitations such as thermal treatment or mechanical deformation. The second approach consisted in preparing poly(propylene) based nanocomposites with inorganic nanoparticles such as zinc oxide and layered double hydroxides. The transport properties of these materials depend on the quality of the filler dispersion in the polymer, but also on the interface between the fillers and the polymer matrix. Thus, the influence of a compatibilizer and of the nanoparticle surface modification was investigated on the properties of the nanocomposites

Depuis quelques années, les polyoléfines et en particulier le Polyéthylène présentent un intérêt économique qui se traduit par un marché en croissance constante. Cependant, il est souvent nécessaire d’améliorer leurs propriétés d’usage notamment pour des problématiques liées à l’industrie automobile. Dans ce contexte, une amélioration des propriétés thermomécaniques et barrière aux vapeurs et liquides du Polyéthylène sur une gamme de température étendue constitue un nouveau challenge scientifique et environnemental. Dans cette étude, nous avons tout d’abord étudié l’impact de charges inorganiques et d’un recuit à 125°C sous air sur les propriétés thermomécaniques d’un HDPE. Le deuxième axe de recherche s’est concentré sur l’amélioration des propriétés barrière aux essences de ce polymère en favorisant les charges lamellaires pour leur haut facteur de forme induisant un effet de tortuosité élevé. L’impact de ce type de charges sur les phénomènes de sorption et d’extraction a été étudié dans le but de définir une formulation à base HDPE optimale pour limiter la perte physique d’oligomères et d’antioxydants. Le but de ces travaux étant de mieux comprendre les différents mécanismes mis en jeu, nous avons cherché à établir les relations Structure / Morphologie / Propriétés pour les deux axes d’étude développés / In the recent years, the use of polyolefin and especially Polyethylene are of economic interest resulting in a growing attention concerning the improvement of its properties of use, especially for automotive application. In this context, the reinforcement of its thermomechanical properties and the improvement of its barrier properties to different fuels over an extended temperature range constitute a major scientific and environmental challenge. In this study, we first decided to analyze the impact of silica particles and of an annealing at 125°C under air atmosphere on thermomechanical properties of a HDPE. The second area of research was focused on the improvement of its barrier properties to fuels by the addition of lamellar charges known for their high aspect ratio inducing a tortuosity effect. The impact of these particles on sorption and extraction phenomena was also studied to determine an optimal HDPE-based formulation in order to limit the physical loss of oligomers and antioxidants. The guideline of this project was the determination of Structure / Morphology / Properties relationships to have a better understanding of the involved mechanisms

No description available.

Polymers are widely used as insulating materials in high voltage power apparatus because of their excellent electrical insulating properties and good thermomechanical behavior. However, under high electrical stress, polymeric materials can get deteriorated which can eventually lead to the failure of the insulation and thereby the power apparatus. Electrical treeing is one such phenomena whereby dendritic paths progressively grow from a region of high electrical stress and branch into conducting channels in a solid dielectric. The propagation of electrical trees is of particular interest for the power industry as it is one of the major causes of failure of high voltage insulation especially in high voltage cables, cast resin transformers as well as rotating machines. To improve the life time of the electrical insulation systems there is a need to improve the electrical treeing resistance of the insulating material for high voltage application. With the development of nanotechnology, polymer nanocomposites containing nano sized particles have drawn much attention as these materials are found to exhibit unique combinations of physical, mechanical and thermal properties that are advantageous as compared to the traditional polymers or their composites. Literature reveals that significant progress has been made with respect to the mechanical, optical, electronic and photonic properties of these functional materials. Some efforts have also been directed towards the study of dielectric/electrical insulation properties of these new types of materials. Considering the above facts, the present research work focuses on utilizing these new opportunities which have been opened up by the advent of nanocomposites to develop tree resistant insulating materials for high voltage power applications. Electrical treeing is a common failure mechanism in most of the polymeric insulation systems and hence electrical treeing studies have been carried out on two types of polymers (viz. polyethylene used in high voltage cable and epoxy used in rotating machines and resin cast transformers) along with three different types of nano-fillers, viz. Al2O3, SiO2 and MgO and with different filler loadings (0.1, 1, 3, 5 wt%). Furthermore, considering the fact that electrical treeing is a discharge phenomenon, the partial discharge characteristics during electrical tree growth in polymer nanocomposites was studied. As morphological changes in the polymer influence the electrical tree growth, the influence of nano-particle induced morphological changes on the electrical treeing has also been studied. Above all, an attempt has also been made to characterize and analyze the interaction dynamics at the interface regions in the polymer nanocomposite and the influence of these interface regions on the tree growth phenomena in polymer nanocomposites. A laboratory based nanocomposite processing method has been successfully designed and adopted to prepare the samples for treeing studies. Treeing experimental results show that there is a significant improvement in tree initiation time as well as tree inception voltage with nano-filler loading in polymer nanocomposites. It is observed that even with the addition of a small amount (0.1 and 1 % by weight) of nano-particles to epoxy results in the improvement of electrical treeing resistance as compared to the unfilled epoxy. In fact, different tree growth patterns were observed for the unfilled epoxy and epoxy nanocomposites. Surprisingly, even though there is not much improvement in tree inception time, a saturation tendency in tree growth with time was observed at higher filler loadings. To understand the influence of nano-particles on electrical treeing, the interaction dynamics in the epoxy nanocomposites were studied and it was shown that the nature of the bonding at the interface play an important role on the electrical tree growth in epoxy nanocomposites. The results of electrical treeing experiments in polyethylene nanocomposites obtained in this study also reveal some interesting findings. An improved performance of polyethylene against electrical treeing with the inclusion of nano-fillers is observed. It is observed that there is a significant improvement in the tree inception voltage even with low nano-filler loadings in polyethylene. Other interesting results such as change in tree growth pattern from branch to bush as well as slower tree growth with increase in filler loading were also observed. Another peculiar observation is that tree inception voltage increased with increase in filler loading upto a certain filler loadings (3 % by weight) and then decreased in its value at high filler loading. The morphology of polyethylene nanocomposites was studied and a good correlation between morphological changes and treeing results was observed. Effect of cross-linking on electrical treeing has also been studied and a better performance of cross-linking of nano-filled polyethylene samples as compared to the polyethylene samples without cross-linking was observed. The partial discharge (PD) activity during electrical tree growth was monitored and different PD characteristics for unfilled and nano-filled polyethylene samples were observed. Interestingly, a decrease in PD magnitude as well as the number of PD pulses with electrical tree growth in polyethylene nanocomposites was observed. It is known that PD activity depends on the tree channel conductivity, charge trapping and gas pressure inside the tree channel. The ingress of nano-particles into the tree channel influences the above known phenomena and affects the PD activity during electrical tree growth. The observed decrease in PD magnitude with increase in filler loading leads to the slow propagation of electrical trees in polyethylene nanocomposites. In summary, it can be concluded that polymer nanocomposites performed better against electrical treeing as compared to the unfilled and the conventional micron sized filled polymer composites. Even with low filler loading an improved electrical treeing resistance was observed in polymer nanocomposites. An optimum filler loading and a suitable filler to inhibit electrical treeing in the polymers studied are proposed. This work also establishes the fact that the characteristics of the interface region and the induced morphological changes have a strong influence on the electrical treeing behaviors of nanocomposites. These encouraging results showed that epoxy and polyethylene nanocomposites can be used as tree resistant insulating materials for high voltage applications. These results also contribute to widen the scope of applications of polymer nanocomposites in electrical power sector as well as development of multifunctional insulation systems.

Outdoor electrical insulator is one of the important components of a power system which directly influences the system reliability. Traditionally ceramic insulators have been used for close to a century in both transmission and distribution lines. In the last few decades, polymer based outdoor insulators are being increasingly used in the above application. Polymeric insulators offer attractive advantages such as light weight, resistance to vandalism and they also outperform conventional ceramic insulators under contaminated wet conditions at least in the initial stages of their usage. However, there are certain disadvantages with polymeric insulators which have made the utilities hesitant to replace readily the ceramic insulators with polymeric insulators. One of the major concerns with the polymeric insulators is the aging w.r.t time due to the presence of multiple environmental stresses (fog, humidity, temperature, rain as well as contamination due to industrial, sea and agricultural pollution) along with electrical stress. The manifestations of the aging of insulators include tracking or/and erosion of the weathersheds. Polymers in pure form (unfilled) can not perform satisfactorily all the required functions (electrical, mechanical, thermal etc.) of an insulator used in such high voltage transmission lines. Polymers have inherently poor thermal stability. Thermal stability directly influences the tracking and erosion resistance of the weathershed. Without adequate tracking and erosion resistance, polymeric insulators can not perform satisfactorily under contaminated wet conditions. Hence the common practice to improve the tracking and erosion resistance (and other properties such as mechanical, thermal) is by filling the base polymer with large loadings (> 30 wt %) of micron sized fillers. This makes the processing of the polymer composite difficult as the viscosity of the material rises substantially at such large loadings. Due to the large filler loadings beyond a certain limit, the flexibility of the end product also suffers. Though tracking and erosion resistance of the polymer has been improved substantially at these large filler loadings, the recent failures in the field suggest the need for an alternate material with higher tracking and erosion resistance than what is achieved at these large loadings of micron sized fillers. Of late nanocomposites are emerging as promising alternatives which can offer the above mentioned functionalities at low filler loadings itself without sacrificing the flexibility in the end product as well as ease of processing. There are even indications suggesting that the tracking and erosion resistance performance is better than what is obtained using micronsized fillers. As the development of nanocomposite dielectrics/insulation is still at its infancy, it is required to investigate their specific properties needed for outdoor applications and to understand the various mechanisms responsible for the interesting behaviour of the nanocomposites. Also, it is known that dc pollution performance of ceramic insulators is much inferior to the performance under ac stress. With the introduction of higher ac/dc transmission voltages in many countries including India, it is required to design insulators with better performing materials so as to get a reliable performance under polluted wet conditions. Due to the hydrophobic nature of the polymers, it is believed that polymers especially silicone rubber insulators can perform better as compared to the ceramic insulators under polluted conditions under ac and dc. As the dc tracking and erosion (T&E) resistance of polymer is poor compared to the ac tracking and erosion resistance, it is required to investigate the T&E resistance characteristics of the nanocomposites under dc stress. In addition, due to the enhanced electric fields at the line end of the insulators in extra and ultra high voltage transmission lines, there is always a possibility of corona generation on the hardware at the metal-sheath junction and at the water droplet tips on the weathersheds of the polymeric insulators especially under foul weather conditions. It is reported that the long-term exposure to such corona has the potential to degrade the polymeric material. The effects include reduction of the hydrophobicity, surface oxidation of the weathersheds and development of microcracks on the surface of the polymeric material. These cracks (corona cutting) can worsen the wet pollution performance of the insulator. If the cracks grow deeper, then FRP rod would get exposed to the atmospheric conditions leading to brittle fracture of the FRP rod and finally resulting in the line drop. Hence, the corona aging resistance of nanocomposites has also been studied especially at low filler concentrations to see its performance under the above mentioned adverse conditions. Therefore, the research work presented here deals with three aspects of the aging (1) Study the ac and dc tracking and erosion resistance performance of silicone rubber nanocomposites with low concentrations of fillers and their suitability for outdoor applications (2) Study the corona aging performance of silicone rubber nanocomposites with low concentrations of fillers and (3) To develop a model to explain the unusual behaviour of nanocomposites observed in the above studies. The thesis also reports results of the accelerated multistress weathering studies conducted on normal polymeric outdoor insulators under prolonged dry conditions. The major challenge in case of the polymer nanocomposite processing is getting uniform distribution of the fillers. A protocol has been standardised for the processing which comprises high shear mechanical mixing followed by sonication to get good dispersion of the fillers. Room Temperature Vulcanised (RTV) silicone rubber was successfully processed with different micron and nanosized fillers and with different weight (wt.) percentages in the present work. For carrying out the T & E resistance, corona aging and multistress aging studies, facilities (such as Inclined Plane T & E Resistance Test Apparatus in line with IEC/ASTM standards and aging chambers) have been designed and developed in house as a part of the thesis work. The ac tracking and erosion resistance performance of the unfilled, microcomposite (filled with alumina trihydrate filler of 5, 10, 15, 20 and 30 % by wt) and nanocomposite (filled with alumina, silica and magnesium hydroxide fillers of 2.5 and 4 % by wt) have been compared in inclined plane (IP) tracking and erosion resistance test facility specifically developed for the work. It was very interesting to observe that nanocomposites at 4 % performed on par with the microcomposites at 30 % filler loadings. Leakage current was also measured during the IP test and it was found that the form factor (ratio of r.m.s to average leakage current) was in good agreement with the variation in the erosion resistance of the silicone rubber composites and hence it can be used as a diagnostic tool for assessing the aging state of the polymeric materials. It was also observed that the performance under positive dc stress was much inferior to the performance under ac stress. The dissipation of power under dc stress was estimated by measuring the leakage current through the sample and is found to be about four times (towards the end of the test) higher as compared to the power dissipation under ac stress. Intense electrolytic corrosion has been observed (under positive dc) on the grounded electrode and on the sample and chemical studies of the same have been carried out. The poor performance under dc is due to the absence of the voltage zero crossing, more accumulation of the contaminant (scaling) and electrolytic corrosion. It was also observed that to get the same tracking and erosion resistance under dc as in the case of ac during IP test, dc stress levels have to be reduced to about 60 % of the ac stress. This information would be helpful to the design engineer of the outdoor insulators for the HVDC transmission lines. To understand the different mechanisms responsible in improving the tracking and erosion resistance of the micro and nanocomposites, thermal, SEM and FTIR studies have been carried out. Thermal stability of the samples was measured using thermogravimetric analysis (TGA) and differential thermo gravimetric (DTG) studies. It was observed that thermal stability of nanocomposites even at low filler loadings (4 wt %) was comparable with the microcomposites at higher filler loadings (30 wt %). SEM studies indicate that the barrier resistance (against discharges) offered by the fillers in the nanocomposites even at low filler loadings (4 %) could be comparable with the microcomposites at higher filler loadings (30 %). The interaction between the fillers and the host matrix has been studied using various techniques. SEM studies done on the eroded regions of the composites revealed that a honey comb type formation had taken place on the nanocomposites during the IP test which was believed to be due to the interaction of the filler and the polymer. This honey comb structure formation at the eroded site in the nanocomposites greatly helps to protect the sample from further damage due to the discharges. The interaction at the interface between the polymer and fillers could also lead to further improvement in the thermal stability of the nanocomposite. A model was proposed which considers barrier resistance and a single-layer interaction around the fillers to explain the improvements offered by the nanocomposites. Corona aging studies have been carried out on unfilled silicone rubber, micro and nanocomposites for 25 h and 50 h of aging using a needle-plane electrode arrangement. Different parameters such as hydrophobicity, surface roughness, microcracks width on the aged surface, FTIR and SEM studies were carried out to study the corona aging resistance of the new and aged samples. The studies indicate that silicone rubber samples containing nanofillers at 3 wt % are able to impart significantly enough corona resistance compared to the unfilled and microcomposite samples. It is known that the discharge resistance offered by the fillers and the interaction/bonding between the fillers and polymers directly influences the corona aging resistance. Hence, the model proposed (discussed above) is valid for understanding the corona aging performance of the nanocomposites which is better than the unfilled and ATH filled silicone rubber. In addition to the tracking and erosion resistance and corona aging studies, multistress aging of commercially available polymeric insulators containing micron sized fillers has been carried out. The aging behaviour of the polymeric insulators under tropical and subtropical conditions (in the absence of discharges under wet conditions) has not been explored. Further, the long-term influence of the UV radiation on silicone rubber in the presence of temperature and electric stress is also not explored. Hence, to understand the aging phenomena (weathering characteristics) under multistress (electric, thermal and UV), distribution class composite polymeric insulators were aged for 30,000 h in a multistress aging chamber developed specifically for the studies. Insulators were continuously subjected to the accelerated electric and thermal stresses as well as UV radiation. Different studies like leakage current, SEM, hydrophobicity, surface roughness and low molecular weight (LMW) molecules content in the samples before and after the aging have been investigated. It is interesting to observe that even in the absence of electrical discharges on the surface of the material, significant monotonous reduction in LMW molecules has been observed w.r.t weathering time. Appreciable increase in the surface roughness (at least 200 % as that of the new material) as well as increased oxygen levels on the surface has also been observed. The results indicate that surface hydrophobicity is dynamic in nature and may not reflect the slow and permanent changes taking place in the bulk of the material. The results obtained for the nanocomposites enable us to design a better material with improved tracking, erosion and corona resistance without sacrificing the flexibility in the end product as well as ease of processing. The silicone rubber nanocomposites also open up the possibility for economically designing a smart material possibly with a higher reliability for outdoor insulator application.

Increasing emphasis has been placed on the use of renewable resources, on decreased reliance on petroleum in order to better utilize global energy needs. Biological structures available in nature have been a constant inspiration to the design and fabrication of the new line of functional biomaterials whose unique phenomena can be exploited in novel applications. In tissue engineering for example, a natural biomimetic material with close resemblance to the profile features existed in a native extracellular matrix could provide a temporary functional platform to regulate and control cellular interactions at a molecular level and to subsequently direct a tissue regeneration. However, the lack of rigidity of natural materials typically limits their mass production. One promising approach to address this shortcoming is to introduce a biomimetic composite material reinforced by high purity nanofibers found in nature. As an attractive reinforcing filler phase, cellulose nanowhiskers (CNWs) offer exceptional properties such as high aspect ratio, large interface area, and significant mechanical performance. As such, CNWs could integrate a viable nanofibrous porous candidate, resulting in superior structural diversity and functional versatility. Inspired by the fascinating properties of cellulose and its derivatives, we have designed two bio-inspired nanocomposite materials reinforced with CNWs in this work. The successful grafting of CNWs within the host matrix and their tendency to interconnect with one another through strong hydrogen bonding gave rise to the formation of a three-dimensional rigid percolating network, fact which imparted considerable mechanical strength and thermal stability to the entire structure with only a small amount of filler content, i.e. 3 wt.%. Also, the biocompatibility of the nanocomposite was probed by in-vitro incubation of human-bone-marrow-derived mesenchymal stem cells (MSCs), which resulted in the invasion and proliferation of MSCs around the nanocomposite at day 8 of culture. The green functional biomaterial with its unique features in this work could open new perspectives in the self-assembly of nanobiomaterial for tissue-engineered scaffolding, while it could make the design of the next generation of fully green functional biomaterial a reality.

Thesis (MSc)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The main aim of this study was to use poly (ethylene-co-vinyl alcohol) (EVOH) as vehicle to incorporate nanofillers into low density polyethylene (LDPE). For this purpose, chitin and cellulose nanowhiskers were prepared through a process of acid hydrolysis and then incorporated into different EVOH copolymers with varying ethylene contents by means of two different experimental methods, namely solution casting and electrospinning. The extremely small dimensions of nanowhiskers make it difficult to observe the degree of dispersion in the electrospun fibers using methods such as transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Fluorescence microscopy was therefore investigated as an alternative characterization technique to obtain better results with regard to tracking the filler dispersion. TEM analysis proved to be the most successful method for observing the dispersion of nanowhiskers for solution cast EVOH nanocomposites as well as electrospun EVOH nanocomposites. Clear differences between EVOH composites with low nanowhisker and high nanowhisker loading were observed in TEM images for these nanocomposites. Thermal analysis of solution cast as well as electrospun fibers were carried out using techniques such as differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). These results revealed changes in crystallization behaviour as well as changes in thermal stability of the EVOH nanocomposites compared to the pure polymer matrix. The incorporation of cellulose and chitin nanowhiskers indicated a general increase in percentage crystallization which probably resulted from the nanowhiskers acting as nucleating agents and therefore increasing the crystallization of most EVOH nanocomposites. The thermal stability is observed to increase as the cellulose nanowhisker loading is increased. This increase in thermal stability proved to be partly attributed to the presence of sulphuric acid which were not completely removed during dialysis of cellulose nanowhiskers. Neutralisation of cellulose nanowhiskers and the treatment with a strong base was therefore further investigated to improve degradation within the EVOH nanocomposites during thermal treatment. The last step in this study involved the incorporation of electrospun EVOH nanofibers containing cellulose nanowhiskers into LDPE in order to improve the mechanical properties. The tensile strength and Young’s modulus of these LDPE nanocomposites were seen to improve quite significantly while a decrease in elongation at break was observed. / AFRIKAANSE OPSOMMING: Die hoofdoel van hierdie studie was om poliëtileen (ko-viniel alkohol) (EVOH) as voertuig te gebruik om nanofillers in lae digtheid poliëtileen (LDPE) te inkorporeer. Kitien en sellulose nanokristalle is vir hierdie doel geproduseer deur middel van ʼn suurhidrolise proses en daarna in verskillende EVOH-kopolimere met verskillende etileeninhoude geïnkorporeer met behulp van twee verskillende eksperimentele metodes, naamlik ʼn drogings- en elektrospinproses. Die uiters klein dimensies van die nanokristalle maak dit uitdagend om die mate van verspreiding van die nanokristalle binne in die elekrogespinde vesels waar te neem m.b.v. metodes soos transmissieelektronmikroskopie (TEM) en skandeerelektronmikroskopie (SEM). Fluoressensie is dus as ʼn moontlike alternatiewe karakteriserings tegniek bestudeer om beter resultate rakende die verspreiding van die nanokristalle te kan waarneem. In hierdie studie is gevind dat TEM-analise die suksesvolste metode was om die verspreiding van nanokristalle te bestudeer en dit geld vir beide die gedroogte en gespinde EVOH-nanosamestellings. Duidelike verskille is waargeneem vir monsters wat hoër en laer nanokristalinhoude gehad het. Saambondeling van die nanokristalle kom duideliker voor by dié wat ʼn hoër inhoud van nanokristalle bevat. Termiese analises van gedroogte EVOH-nanosamestellings en ook die gespinde nanosaamgestelde vesels is uitgevoer d.m.v. tegnieke soos differensieëlskandeerkalorometrie (DSC) en termiese-gravimetriese analise (TGA). Die resultate wat verkry is vanaf die bogenoemde tegnieke het bewys dat daar verandering in die kristallisasie, sowel as die degradasie temperatuur, van die EVOH-nanosamestelling is. Die byvoeging van sellulose en kitien nanokristalle het ʼn algemene verhoging in die persentasie kristallisasie van die EVOH-nanosamestelling te wee gebring. Die byvoeging van nanokristalle tree waarskynlik gedeeltelik op as kernvormings agent vir die EVOH-molekules. TGA analises toon dat die termiese stabiliteit van die EVOH-nanosamestelling verhoog met die byvoeging van nanokristalle. Die teenwoordigheid van die sulfaatgroepe wat nie heeltemal verwyder is tydens die wasproses nie, is bewys om gedeeltelik verantwoordelik te wees vir die verhoging in termiese stabiliteit van die EVOH-nanosamestellings. Die neutralisasie en behandeling van die nanokristalle met ʼn sterk basis is dus verder ondersoek om die degradasie van die EVOH-nanosamestellings tydens verhitting te verbeter. Die laaste stap in hierdie studie het behels dat elektrogespinde EVOH vesels wat verskillende hoeveelhede sellulose nanokristalle bevat, geïnkorporeer is in LDPE ten einde die meganiese eienskappe te verbeter. Die treksterkte en die Young’s modulus het met ʼn beduidendende hoeveelheid verbeter terwyl die verlenging by breekpunt verlaag het. / National Research Foundation