The purpose of this study was to observe penetration profiles of lysozyme on a variety of contact lens materials by confocal microscopy, to analyze influential factors that are involved in these penetration curves and to suggest possible mechanisms related to the in-eye clinical performance of these materials. An FITC-lysozyme conjugate was synthesized in-house by amine reaction. Contact lenses were incubated in a lysozyme solution with a final concentration of 1.9 mg/mL for various periods before undergoing microscopic analysis. Optimal parameters for confocal scanning were successfully obtained to acquire desired fluorescence signals on various contact lenses. Measurement units were converted into absolute amounts of lysozyme using lysozyme data from ^(125)I gamma counting studies. A rhodamine labeled dextran solution was applied to distingush the surface of the contact lenses under examination. The data from these studies were then used to calculate the theoretical numbers of layers of adsorbed lysozyme on the lens surface. The results show that there were distinct differences in lysozyme penetration in the twelve hydrogel materials examined. A pure pHEMA lens, with a water content of 38%, deposited lysozyme primarily on the lens surface after 24 hours, with full penetration occurring after 4-weeks of incubation. Three types of non-ionic contact lens materials with water contents > 50% exibited rapid penetration within the lens bulk after 24-hours incubation, with increased deposition within the matrix after 4 weeks. Two ionic, high water content polymers (Acuvue 2 and Focus Monthly) exhibited markedly different penetration profiles, particularly after 24 hours, with very rapid and total penetration in Acuvue 2, as compared with partial penetration in Focus Monthly. Modern silicone hydrogel contact lenses can be nominally divided into first generation, plasma-modified materials and second generation materials which incorporate an internal wetting agent such as polyvinyl pyrrolidone (PVP). These materials exhibited different lysozyme deposition profiles. Lysozyme fully penetrated PureVision after 24 hours, whereas no lysozyme penetration occurred on lenses manufactured from Focus Night & Day or O_2Optix, even after 4 weeks. Lenses manufactured from Acuvue Advance and Acuvue OASYS, two second generation silicone hydrogel lenses, also displayed their own characteristic deposition profile. Acuvue Advance always exhibited a partial penetration of lysozyme within the matrix, even after 4 weeks of doping. Interestingly, Acuvue OASYS showed a similar profile to Focus Night & Day and O_2Optix, with predominantly surface deposition occurring. To confirm possible surface adsorption of lysozyme on surface-coated Focus Night & Day and O_2Optix, a rigid polymethylmethacrylate (PMMA) contact lens was used as a model of surface adsorption. A mounting medium containing rhodamine labeled dextran was scanned to distinguish the lens surface, as it was assumed that no surface penetration of the very high molecular weight dextran would occur. Using this model, it was confirmed that surface adsorption of lysozyme occurred on these plasmacoated lens materials, which is similar to that seen with PMMA. In a further experiment, it was seen that lysozyme sorption on Acuvue OASYS exhibits a penetration profile which is different to that seen in Focus Night & Day and O_2Optix, with lysozyme just penetrating the lens surface. The results from the studies described above demonstrated that in 24 hours lysozyme sorption did not achieve a complete monolayer. However, after 4 weeks multi-layer adsorption occurred, with the more hydrophilic materials depositing the most lysozyme. The quantitative measurement of lysozyme penetration on and into contact lens materials by confocal microscopy combined with ^(125)I labelling offers a valuable tool to discover the potential mechanisms of interactions between protein and polymer materials. This study reveals some important information that may be beneficial to contact lens development and will prove to be valuable in other more broad areas of biomedical research in which polymers and biological fluids come into contact. / Thesis / Master of Applied Science (MASc)

Silicones are industrially important polymers characterized by a wide spectrum of chemical and physical properties with a number of important applications including automotive components, construction materials, isolating parts in electronic devices, flexible electronics, and medical products. Development of additive manufacturing methods for silicones enable production of complex and custom designed shapes and structures at both the micro- and macro-scale, economically feasible. In general, such materials can be fabricated using stereolithographic, extrusion-based, or inkjet printing techniques, in which silicones are polymerized using either photo- or heat-initiators. Silicones can also be crosslinked based on chemical reactions. Although this approach is supposedly the simplest, it has not been widely applied in additive manufacturing, as suitable technology for mixing and curing reactive inks without clogging nozzles has not be developed yet. To address this issue, a new 3D printer, that enables the fabrication of highly reactive and low viscous materials, has been developed and tested experimentally. The proposed fabrication method involves the ejection of two reactive droplets simultaneously from individual dispensers, merging and mixing them in free space outside the nozzle followed by deposition of the merged drop in a patterned format on a substrate. It was shown that the printing process is robust and stable more than 4 hours and it can be used on demand. By incorporating an XYZ positioner, it was possible to deposit droplets in an overlapping fashion to print any programmable shape featuring homogeneous structure, with a small number of pores. Moreover, due to the almost instantaneous reaction between two components (< 10s), the fabrication of very high aspect ratio (AR > 50) objects is possible. Lastly, the presented method can be easily adapted to print in free space without the use of support materials. / Thesis / Master of Applied Science (MASc)

The Tissue Engineering Lab at California Polytechnic State University San Luis Obispo focuses on creating tissue-engineered Blood Vessel Mimics (BVMs) designed for the preclinical testing of neurovascular devices. These BVMs are composed of silicone models, representing anatomically accurate neurovasculatures, that are sodded with vascular cell types and then cultivated in bioreactors (which maintain physiologic conditions). These silicone models are currently sourced externally from industry partners, so the primary goal of this thesis was to develop the means and methods for the Tissue Engineering Lab to manufacture silicone models in-house. The first aim of this thesis was to develop and explore injection molding as a possible technique for manufacturing silicone models; this included prototyping various designs of molds, developing a viable workflow for injection molding, then assessing the resulting silicone models through measurement characterization, cytotoxicity screening, and BVM set-ups. The first aim found that injection molding was a viable manufacturing technique for making silicone models. The second aim of this thesis explored an alternative manufacturing method, dip-casting, to produce silicone models. The development of dip-casting was similar to injection molding, where several prototyping stages resulted in a viable workflow for making silicone models; the resulting silicone models were then assessed via measurement characterization and a BVM set-up. The second aim found that, in addition to injection molding, dip-casting was a viable technique for making silicone models, although the overall morphology of the resulting models was less desirable than those made by injection molding. The third and final aim of this thesis compared both manufacturing techniques (i.e., injection molding and dip-casting); this aim established that injection molding was preferable for making simple (less intricate) silicone models, whereas dip-casting was preferable for producing complex (more intricate) silicone models. Although the dip-casting technique requires more development to capture complex shapes and produce models with desirable morphologies, the injection molding protocol was formalized into a prescribed workflow for the Tissue Engineering Lab to reference. Overall, this thesis developed and explored two different manufacturing techniques for making silicone models and found that both were capable of making silicone models that could be used to create tissue-engineered BVMs, with injection molded models being ready to implement as the dip-casting process continues to be refined.

Yes / Soft silicone's flexibility, adhesive capacity and non-toxic, non-odourous and hypoallergenic nature have made it an established material for adhesive and protective therapeutic devices. In wound care, silicone is a component of contact layer dressings for superficial wounds and silicone gel sheeting for reducing the risk of scarring, as well as of barriers for incontinence-associated dermatitis. Regarding stoma accessories, silicone is established in barrier films to prevent contact dermatitis, adhesive removers to prevent skin stripping and filler gels to prevent appliance leaks. Until recently, silicone has not been used in stoma appliances flanges, as its hydrophobic nature has not allowed for moisture management to permit trans-epidermal water loss and prevent maceration. Traditional hydrocolloid appliances manage moisture by absorbing water, but this can lead to saturation and moisture-associated skin damage (MASD), as well as increased adhesion and resultant skin tears on removal, known as medical adhesive-related skin injury (MARSI). However, novel silicone compounds have been developed with a distinct evaporation-based mechanism of moisture management. This uses colloidal separation to allow the passage of water vapour at a rate equivalent to normal trans-epidermal water loss. It has been shown to minimise MASD, increase wear time and permit atraumatic removal without the use of adhesive solvents. Trio Healthcare has introduced this technology with a range of silicone-based flange extenders and is working with the University of Bradford Centre for Skin Sciences on prototype silicone-based stoma appliance flanges designed to significantly reduce the incidence of peristomal skin complications, such as MARSI and MASD. It is hoped that this will also increase appliance wear time, reduce costs and improve patient quality of life.

Measurements of radon in groundwater before, during and after the 1995 Kobe earth-quake in Japan indicated that there might be a correlation between levels of 222Rn ingroundwater and seismological activity. The artEmis project investigates this possibleconnection with the goal of building a network of detectors in seismically active parts ofEurope. The detectors will be placed in groundwater and measure many factors, one ofthem being the radon level by measuring gamma radiation. The original vision for thedetectors also included alpha detection. The obtained data is analyzed with artificialintelligence. This thesis investigates a possible method for alpha detection under water. Specif-ically by seeing if it is possible for radon dissolved in water to diffuse from the water,through silicone tubes and into the air inside of the silicone tubes. There is a possibilityfor alpha detection of the radon decay if the radon gas could get into the air. This wasinvestigated by submerging an air-filled silicone construction in water with high levelsof radon. The level of radon in the water was increased by placing pieces of lightweightconcrete in the water. The construction was removed after a period of time and itsgamma-ray spectrum was measured. A statistically significant increase in radon levelscompared to the background radiation would indicate that diffusion happened. Measurements of the silicone construction with a germanium detector resulted ingamma spectra that were analyzed with a Python program to determine the activity of222Rn over time. Short measurements, around 1 hour long, showed a significant increaseof radon compared to the background. For longer measurements however, around one ortwo days, this effect was no longer apparent. The conclusion is that radon diffused intothe silicone construction, either into the silicone material itself or into the air inside theconstruction, but it comes out again quickly. If the radon diffused into the air inside ofthe silicone, the use of alpha detection to measure radon levels in groundwater is muchless far-fetched than before. Therefore, the artEmis project might be one step closer tousing alpha detection in their detector network.

Pour répondre aux problématiques d’usure précoce des pièces mécaniques causée par des pressions et températures élevées d’utilisation, des nanolubrifiants constitués de nanocarbones fluorés, connus pour leurs faibles coefficients de frottement et haute stabilité thermique ont été synthétisés. Pour améliorer ces propriétés, des précurseurs nanocarbonés de dimensionnalités différentes, et des procédés de synthèse gaz-solide variés ont été employés. Ainsi, une structure fermée comme les nanofibres de carbone NFCs (1D, tubulaire), ouverte comme le mélange nanodisques / nanocônes de carbone NDCs (majoritairement 2D, discotique) et intermédiaire avec les noirs de carbone graphitisés NCGs (0D, sphérique) ont été fluorés, d’une part avec le fluor moléculaire gazeux et d’autre part avec le fluor atomique produit par décomposition thermique d’un agent solide. Les mécanismes de fluoration / défluoration ont été proposés à l’aide de différentes techniques de caractérisation complémentaires (RMN du solide, MEB, MET, AFM, DRX) pour l’ensemble des matrices étudiées. Des matériaux présentant un gain de stabilité thermique de plusieurs dizaines de degrés comparativement aux matériaux fluorés de la littérature ont été élaborés, et une nouvelle méthode de synthèse dite « fluoration flash » a été mise au point pour étendre encore cette tenue en température. Les bonnes propriétés tribologiques de ces matériaux ont également été démontrées, notamment à 160°C et ceci quel que soit le mode de fluoration. Par la suite, des vernis à base de résines siliconées et chargés en nanofibres de carbone fluorées ont été formulés. Le revêtement composite présente une stabilité thermique supérieure à 400°C comme démontré par l’étude de son mécanisme de dégradation en température, notamment par couplage ATG-FTIR. D’un point de vue tribologique, les coefficients de frottement mesurés à température ambiante et 160°C sont inférieurs à 0,1 et les tribofilms obtenus ont été caractérisés par analyse MEB et EDX. / To address some issues to premature wear caused by high pressures and temperatures used on aircraft parts, nanolubricants made of fluorinated nanocarbons were synthesized. They are known for their low friction coefficients and high thermal stability in air. To improve these properties, carbonaceous nanomaterial precursors with different dimensionalities, and various gaz-solid synthesis methods were investigated. Thus, a closed structure such as carbon nanofibres (1D, tubular), opened such as carbon nanodiscs/nanocones (2D in majority, discotic) and intermediate with graphitized carbon blacks(0D, spherical) were fluorinated, firstly with molecular fluorine gas, and secondly with atomic fluorine released by the thermal decomposition of a solid fluorinating agent. Mechanisms of fluorination/defluorination were proposed thanks to complementary characterization techniques (solid NMR, SEM, TEM, AFM, XRD) for all the studied compounds. Materials with a gain of thermal stability of several tens of degrees compared to fluorinated materials of the litterature were prepared, and a new synthesis way called “flash fluorination” has been developed to further expand the thermal stability in air. Good tribological properties of these materials have been also demonstrated, including high temperature (160°C) regardless of the fluorination method. Then, polysiloxane resins loaded with fluorinated carbon nanofibres were formulated. The composite coatings exhibit thermal stability above 400°C as demonstrated by the study of the degradation mechanism as a function of the temperature, in particular by coupling TGA-FTIR. From a tribological point of view, friction coefficients measured at room temperature and 160°C are below 0.1 and the tribofilms obtained were characterized by SEM and EDX analysis.

Cette thèse s’inscrit dans le cadre de l’amélioration du comportement électrique des isolateurs de lignes haute tension ; l’objectif est d’assurer une meilleure fiabilité et qualité d’alimentation en énergie électrique. Ce travail a été motivé par la nécessité de répondre à trois questions liées au comportement des isolateurs verre en zone polluée. La première porte sur la recherche d’une méthode permettant de calculer la tension de contournement des chaînes polluées selon le type d’isolateur et ses caractéristiques. La deuxième question concerne la différence de comportement entre les isolateurs en verre et les isolateurs en porcelaine de type « outerrib » ; ce type d’isolateurs présente une forme spécifique adaptée aux environnements à forte pollution. Les tensions de contournement ainsi que les trajectoires de l’arc sur les isolateurs en verre sont très différentes de celles observées avec les isolateurs en porcelaine. Et la troisième question est relative à la défaillance des isolateurs recouverts de silicone lors des essais en chocs (des impulsions de tension) à front raide. En effet, les isolateurs recouverts d’une couche de 0.3 mm (ou plus) de silicone hydrophobe explosent lorsqu’ils sont soumis à des impulsions de tension à front raide d’amplitude très élevée pendant un temps très court. Différents mécanismes pouvant être à l’origine de l’explosion/éclatement des isolateurs recouverts d’une couche de silicone sont discutés. Il ressort des différents tests et analyses que le mécanisme le plus probable semble être la fragmentation par plasma. En effet, suite à l’application d’une tension à front raide, d’amplitude très élevée, des canaux (fissures) microscopiques prennent naissance là où le champ électrique est le plus intense. L’application répétitive des chocs de tension conduit au développement de décharges dans ces canaux (rupture diélectrique de l’air) c’est-à-dire des arcs (canaux de plasma) qui se développent/propagent dans le volume de l’isolateur. La puissance déchargée (c’est-à-dire l’énergie stockée dans les condensateurs du générateur en des temps très courts) dans ces canaux à chaque choc étant très élevée, elle conduit à l’explosion de l’isolateur après quelques chocs (parfois 5 ou 6 suffisent): c’est la fragmentation par plasma. / This thesis deals with the improvement of the electrical behavior of insulators of high voltage lines; the objective is to ensure better reliability and quality of power supply. This work was motivated by the need to answer three questions related to the behavior of glass insulators in polluted areas. The first one concerns the search for method for calculating the flashover voltage of polluted chains according to the type of insulator and its characteristics. The second question concerns the difference in behavior between glass insulators and "outerrib" porcelain insulators; this type of insulator has a specific shape adapted to environments with high pollution. The flashover voltages as well as the trajectories of the arc on glass insulators are very different from those observed with porcelain insulators. And the third issue is the failure of silicon-coated insulators during shock tests (pulses) with a steep front. Indeed, insulators coated with a layer of 0.3 mm (or more) of hydrophobic silicone explode when subjected to very high amplitude steep-edge voltage pulses for a very short time. Different mechanisms that may be responsible for the explosion / puncturing of insulators covered with a layer of silicone are discussed. It appears from the various tests and analyzes that the most probable mechanism seems to be plasma fragmentation (cracking). Indeed, following the application of a steep front voltage, of very high amplitude, microscopic channels (fissures) originate where the electric field is most intense. The repetitive application of impulse voltages (shocks) leads to the development of discharges in these channels (breakdown of the air), i.e.; arcs (plasma channels) which develop / propagate in the volume of the insulator. The discharged power (i.e.; the energy stored in the capacitors of the generator in a very short times) in these channels (cracks) at each shock being very high, leads to the explosion of the insulator after some shocks (5 to 6 sometimes): it is the fragmentation by plasma or plasma cracking.

Cette thèse s'inscrit dans la thématique technologique des décharges électrostatiques sur les panneaux solaires des satellites de télécommunication en orbite géostationnaire. Son objectif est de déterminer les évolutions des propriétés électriques d'un adhésif silicone commercial en environnement spatial et de les corréler aux évolutions de sa structure chimique. Les principaux constituants du matériau ont été identifiés et des échantillons dépourvus de particules de renfort - assimilés à la matrice polymère isolée - ont été élaborés. Afin d'évaluer l'influence des particules, ils ont été systématiquement comparés aux échantillons nominaux dans l'ensemble de ces travaux. La structure physico-chimique du matériau à l'état initial a été caractérisée en étudiant ses relaxations enthalpiques, mécaniques et en pratiquant des analyses chimiques. Son comportement électrique (relaxations dipolaires et conductivité) a été sondé grâce à une approche expérimentale inédite croisant la technique de relaxation de potentiel électrostatique de surface, la spectroscopie diélectrique dynamique et l'analyse des courants thermo-stimulés. Le vieillissement du matériau en environnement spatial a été simulé expérimentalement par l'exposition des échantillons à des flux élevés d'électrons de haute énergie. Les analyses chimiques, notamment en RMN du solide, ont montré la prédominance d'un processus de réticulation du matériau sous irradiation, et des mécanismes de dégradation à l'échelle microscopique ont été proposés. Le comportement électrique du matériau est fortement impacté par l'évolution de sa structure chimique : sa résistivité augmente considérablement avec la dose ionisante. Il est suggéré que la résistivité de ce matériau soit directement liée à son degré de réticulation, influant sur la mobilité des porteurs dans le cadre du hopping et de la percolation électrique. Cette augmentation est beaucoup plus marquée en présence de particules, ce qui a été attribué à la formation de nœuds de réticulation matrice-particules qui constituent des pièges plus profonds pour les porteurs de charges. Ces travaux apportent une meilleure compréhension des phénomènes de vieillissement des élastomères silicones en environnement spatial. Ils permettront d'anticiper des évolutions structurales qui pourraient mettre en péril leur fonction d'adhésion, ainsi que des évolutions de résistivité électrique intrinsèque, facteur décisif dans le déclenchement de décharges électrostatiques. / This PhD thesis falls within the technical field of electrostatic discharges occurring on the solar arrays of communications satellites in the geostationary orbit. Its main objective consists in assessing the evolutions of a space-used commercial silicone adhesive's electrical properties, and to correlate them with the evolutions of its chemical structure. The main components of this material have been identified, and neat samples (deprived of fillers) were elaborated so as to study the isolated polymer matrix. In order to assess the influence of filler incorporation, neat samples were systematically compared with the commercial ones in this study. The material's physicochemical structure in the initial state was characterized by studying its enthalpy relaxations, mechanical response, and by performing chemical analysis. Its electrical behavior (dipole relaxations and conductivity) was investigated thanks to an original experimental approach combining surface potential decay measurements, broadband dielectric spectroscopy, and thermally stimulated depolarization currents. Aging in the space environment was experimentally simulated by exposing the samples to high fluxes of high energy electrons. Chemical analysis (solid state NMR in particular) revealed the predominant crosslinking tendency of this material under ionizing radiations, and allowed to suggest degradation mechanisms at the microscopic scale. These structural evolutions also strongly impact its electrical behavior: a great increase in electrical resistivity has been observed with increasing ionizing dose. It is believed that electrical resistivity directly depends on the degree of crosslinking, which affects charge carrier mobility, in the theoretical frame of hopping and percolation models. The increase in resistivity is considerably more pronounced in the filled material, which could be associated with crosslinking occurring at the matrix-particles interface. Such crosslinks are thought to represent deeper traps for charge carriers. This work brought better understanding of aging phenomena in silicone elastomers exposed to the ionizing space environment. This knowledge will help predicting structural evolutions that may compromise vital properties such as adhesion, and the evolutions of intrinsic conductivity, a critical factor involved in the triggering of electrostatic discharges.

Outdoor insulators are one of the most important parts of a power system. The reliability of a power system depends also on the reliability of the insulators. The main functions of an insulator used for outdoor applications are to give the necessary insulation, provide the necessary mechanical support to the transmission line conductor and also to resist the various environmental stresses like pollution, ultra violet rays etc. Traditionally porcelain and glass insulators have been used for outdoor insulator applications. They are good insulators under normal conditions and the cap and pin arrangement allows them to take up the mechanical load of the line. But owing to their large weight and brittle nature they are susceptible to vandalism and also they have increased cost of installation and commissioning. But the main problem of porcelain and glass insulators is its performance under polluted environmental condition. Under wet and polluted conditions, the porcelain insulators allow the formation of a conducting layer on the surface which results in setting up of leakage current, dry band arcing and power loss. This problem is further augmented under dc voltages where the stress is unidirectional and the contaminant deposition is higher as compared to ac. Polymeric insulators are a good alternative for porcelain and ceramic insulators for use especially under dc voltages because of their good pollution performance. The property of surface hydrophobicity resists the setting up of leakage currents and hence polymeric insulators help in reducing power loss. They are also light in weight and vandalism resistant and hence easier to install. But being polymeric, they form conductive tracks and erode when exposed to high temperatures which occur at the surface during dry band arcs and when exposed to corona discharges. The surface hydrophobicity is also temporarily lost when exposed to different electrical stresses. Silicone rubber is the most popular among the various choices of polymers for outdoor insulator applications. They have good surface hydrophobicity and tracking performance. But polymers in their pure form cannot be used as insulators because of their poor mechanical strength. Adding inorganic fillers into the polymer matrix not only improves its mechanical properties but also its erosion resistance. Micron sized Alumina Trihydrate (ATH) is used traditionally to improve the tracking and erosion resistance of polymeric insulators. A very high loading (up to 60%) is used. Adding such a high filler loading to the base polymer hampers its flexibility and the material processing. With the advent of nanotechnology, nano fillers have come into vogue. Studies conducted on nano filled polymers showed exciting results. A small amount of nano fillers in the polymer matrix showed significant improvement in the mechanical strength without hampering its flexibility. The electrical properties like tracking and erosion also improved with filler loading. Hence the use of nano filled silicone rubber is a good alternative for use as a high voltage insulator especially under dc voltages. Reports suggest that adding nano fillers into the silicone rubber matrix improves the tracking and erosion resistance and the corona degradation as compared to the unfilled samples under ac voltages. The literature on the dc performance of silicone rubber nano composites is scarce. So the present study aims to evaluate the performance of silicone rubber nano composites for tracking and erosion resistance and corona degradation under dc voltages. The tracking and erosion resistance under dc voltages was measured using the Inclined Plane Tracking and Erosion Resistance set up as per ASTM D2303 which was modified for dc voltage studies. The performance of nano Alumina and nano Silica fillers were evaluated under negative dc and the performance was compared with micron sized Alumina Trihydrate filled samples. The effect of filler loading was also studied. It was seen that the performance of the silicone rubber improved with filler loading. A small loading percentage of nano fillers were enough to give performance similar to silicone rubber filled with micron sized ATH filler. The silicone rubber performed better under negative dc as compared to ac and positive dc. The positive dc tests showed a migration of ions from the electrodes onto the sample surface. The increased surface conductivity resulted in very heavy erosion in the case of positive dc tested samples. The corona aging studies were also conducted on silicone rubber nano composites. Nano silica was used as filler in this case. Different filler loadings were employed to understand the effect of filler loading. The corona was generated using a needle plane electrode and samples were exposed to both positive and negative dc corona. The samples were exposed to corona for different time intervals – 25 and 50 hours to study the effect of exposure time. The hydrophobicity, crack width and surface roughness were measured after the tests. Adding nano fillers into the polymer matrix improved the corona performance. With filler loading, the performance improved. The samples exposed to positive dc corona performed better than those under negative dc corona. The loss of hydrophobicity, surface cracks and the surface roughness was less in the case of positive dc corona tested samples. With exposure time, the performance of silicone rubber became poorer for positive dc corona tested samples. For the negative dc corona tested samples, the performance seemed to improve with exposure time. The tracking and erosion resistance and the corona aging studies conducted showed that the performance of silicone rubber is improved by adding nano fillers into the polymer matrix. A small amount of nano filler loading was enough to perform similar to a heavily loaded micron filled sample. Hence nano fillers can be used as a good functional material to improve the performance of silicone rubber insulators especially under wet and polluted conditions.

Two-phase flow in porous media is an important subsurface process that has significant impacts on the global economy and environments. To study two-phase system in porous media, capillary pressure (Pc ), relative permeability (Kr), bulk electrical conductivity (σb) and bulk relative permittivity (εb) are often employed as characterization parameters. Interestingly, all of these parameters are functions of water saturation (S). However, the non-uniqueness in the Pc -S, Kr-S,σb-S and εb-S relationships pose considerable challenges in employing them for effective monitoring and control of the two-phase flow processes. In this work, laboratory scale experiments and numerical simulations were conducted to investigate the factors and conditions contributing to the non-uniqueness in the above relationships for silicone oil-water and supercritical CO2-water flow in porous media, with a special emphasis on geological carbon sequestration. Specifically, the dynamic capillary pressure effect, which indicates the dependence of the Pc - S relationship on the rate of change of saturation (αS/αt) during two-phase flow in porous media was investigated. Using a silicone oil-water system, the dynamic capillary pressure effect was quantified in term of the parameter named the dynamic coefficient, τ , and it was found to be dependent on the domain scale and the viscosity ratio of the two fluids. It was found that τ increases with the domain scale and the viscosity ratio. It is inversely affected by αS αt , which is related to the degree of resistance to the fluid motion, namely, viscosity. In almost all cases, τ was found to decrease monotonically with an increase in water saturation, S. An order increase in magnitude of τ was observed as the domain scale increases from 4cm scale to 8cm in height. A similar order of increase in τ was observed in the 12cm high domain scale. There is an order increase in the value of τ for the silicone oilwater system as the viscosity ratio increases from 200 to 500. For the supercritical CO2 (scCO2) and water system in porous media, the experiments and numerical simulations showed that τ increases with rising system temperature and decreasing porous media permeability. Dimensionless analysis of the silicone oil-water experimental results showed that by constructing non-dimensional groups of quantities expressing a relationship among different variables on which τ depends, it is possible to summarise the experimental results and determine their functional relationship. A generalised scaling relationship for τ was derived from the dimensionless analysis which was then validated against independent literature data. The exercise showed that the τ-S relationship obtained from the literature and the ii scaling relationship match reasonably well. This work also demonstrated the applicability of an artificial neural network (ANN) as an alternative computational platform for the prediction of the domain scale dependence of τ . The dependence of the Kr-S relationship on αS/αt was also investigated. The results showed that the Kr-S curve under dynamic flow condition is different from that under the quasi-static condition. Kr for water (Krw) increases with increasing water saturation and decreases with the increase in viscosity ratio while Kr for silicone oil (Krnw) increases with decreasing water saturation as well as with the increase in viscosity ratio. Also, Krw decreases while Krnw increases with the increasing boundary pressure. However, the εb-S and σb-S relationships were found to be independent of αS/αt for the scCO2-water system in carbonate and silicate porous media. Nevertheless, the εb and σb values decrease as the water saturation decreases in the two porous media samples. While εb decreases with increase in temperature in silica sand, the trend in the limestone showed a slight increase with temperature, especially at high water saturation. Also, the εb-S relationship is shown to be affected by pressure in silica sand increasing with the pressure of the domain. On the contrary, the σb-S relationship increases as the temperature increases with more significance at higher water saturation in the silica sand sample. This work further demonstrated the application of a membrane in the monitoring of the CO2 in geological sites used for carbon sequestration. Commercial silicone rubber coupled with a pressure transducer showed potential in the detection of CO2 leakage from geological sites. The response of the device in terms of the mass of permeated gas, permeability and gas flux were investigated for both CO2 and N2. In addition, the monitoring of potable water contamination in a shallow aquifer by the migrating or leaking of CO2 is demonstrated with the combination of the pH analysis, geoelectrical measurement techniques and the membrane-sensor system. Overall, the work in this PhD research demonstrated robust applications of two-phase systems'characterization parameters under different scenarios in the porous media. Implications of the findings in this work to the monitoring and control of two-phase systems in porous media are expatiated.