A novel on-line capillary rheometer (OLR) was used to examine the shear and extensional characteristics of polyolefin melts during twin screw extrusion (TSE). Comparisons with off-line rheometry were made using a twin-bore capillary rheometer and a modular in-line slit die rheometer (ILR) provided in-line rheometry comparisons. Both capillary rheometers were controlled via PCs running dedicated software, and the extrusion line and ELR were fully instrumented allowing real-time process monitoring to be carried out by IBM compatible PCs via data acquisition hardware and software. The prototype OLR was developed by the re-design of several key features including an instrumented transfer section and capillary die block which facilitated the use of various die geometries. Shear and extensional on-line rheometry of three polyethylenes (linear and branched), and four molecular weight grades of polypropylene were examined, and a direct comparison with off-line capillary rheometry showed a good correlation. The effect of a high loading of filler on two of the polyethylenes was investigated. In-line shear stress and entry pressure measurements showed a reasonable correlation with on-line rheometry. A study of entry flows in the OLR using capillary dies approaching orifice showed non-linearities occurred at very low capillary length to diameter(L:D) ratios, and this was repeatable using off-line rheometry. Predicted zero length entry pressures (Po) were used to estimate apparent extensional viscosity using a number of standard models. Melt instability and capillary wall slip were also investigated using on-line rheometry. Melt pressure and temperature in the twin screw extruder and OLR were monitored at various process conditions to examine the ability of the OLR to condition melt during testing, and the effect of OLR testing on extrusion conditions. Pressure variation in the extruder, OLR and off-line rheometer were compared in order to quantify process noise. The effect of OLR testing on melt rheology and polymer molecular weight were examined using off-line rheometry and gel permeation chromatography(GPC).

Capillarity is often exploited in self-cleaning, drag reducing and fluid absorption/storage (sanitary products) purposes just to name a few. Formulating the underlying physics of capillarity helps future design and development of optimized structures. This work reports on developing computational models to quantify the capillary pressure and capillary forces on the fibrous surfaces. To this end, the current study utilizes a novel mass-spring-damper approach to incorporate the mechanical properties of the fibers in generating virtual fibrous structures that can best represent fibrous membranes. Such virtual fibrous structures are then subjected to a pressure estimation model, developed for the first time in this work, to estimate the liquid entry pressure (LEP) for a hydrophobic fibrous membrane. As for accurate prediction (and not just estimation) of the capillary pressure, this work also presents an energy minimization method, implemented in the Surface Evolver code, for tracking the air–water interface intrusion in a hydrophobic fibrous membrane comprised of orthogonally oriented fibers. This novel interface tracking algorithm is used to investigate the effects of the membrane’s microstructure and wetting properties on its resistance to water intrusion (i.e., LEP). The simulation method developed in this work is computationally affordable and it is accurate in its predictions of the air–water interface shape and position inside the membrane as a function of pressure. Application of the simulation method in studying effects of fiber diameter or contact angle heterogeneity on water intrusion pressure is reported for demonstration purposes. Capillary forces between fibrous surfaces are also studied experimentally and numerically via the liquid bridge between two parallel plates coated with electrospun fibers. In the experiment, a droplet was placed on one of the polystyrene- or polyurethane-coated plates and then compressed, stretched, or sheared using the other plate and the force was measured using a sensitive scale. In the simulation, the liquid bridge was mathematically defined for the Surface Evolver finite element code to predict its 3-D shape and resistance to normal and shearing forces, respectively, in presence of the contact angle hysteresis effect. Despite the inherent non-uniformity of the fibrous surfaces used in the experiments and the simplifying assumptions considered for the simulations, reasonable agreement was observed between the experiments and simulations. Results reveal that both normal and shear force on the plates increase by increasing the liquid volume, or decreasing the spacing between the plates.

A novel on-line capillary rheometer (OLR) was used to examine the shear and extensional characteristics of polyolefin melts during twin screw extrusion (TSE). Comparisons with off-line rheometry were made using a twin-bore capillary rheometer and a modular in-line slit die rheometer (ILR) provided in-line rheometry comparisons. Both capillary rheometers were controlled via PCs running dedicated software, and the extrusion line and ELR were fully instrumented allowing real-time process monitoring to be carried out by IBM compatible PCs via data acquisition hardware and software. The prototype OLR was developed by the re-design of several key features including an instrumented transfer section and capillary die block which facilitated the use of various die geometries. Shear and extensional on-line rheometry of three polyethylenes (linear and branched), and four molecular weight grades of polypropylene were examined, and a direct comparison with off-line capillary rheometry showed a good correlation. The effect of a high loading of filler on two of the polyethylenes was investigated. In-line shear stress and entry pressure measurements showed a reasonable correlation with on-line rheometry. A study of entry flows in the OLR using capillary dies approaching orifice showed non-linearities occurred at very low capillary length to diameter(L:D) ratios, and this was repeatable using off-line rheometry. Predicted zero length entry pressures (Po) were used to estimate apparent extensional viscosity using a number of standard models. Melt instability and capillary wall slip were also investigated using on-line rheometry. Melt pressure and temperature in the twin screw extruder and OLR were monitored at various process conditions to examine the ability of the OLR to condition melt during testing, and the effect of OLR testing on extrusion conditions. Pressure variation in the extruder, OLR and off-line rheometer were compared in order to quantify process noise. The effect of OLR testing on melt rheology and polymer molecular weight were examined using off-line rheometry and gel permeation chromatography(GPC). / Rosand Precision Ltd. and Raychem Ltd.

L'hydrogène gazeux va être produit par la corrosion anaérobique des containers dans le stockage géologique de déchets radioactifs. Ce gaz peut avoir un impact sur la stabilité de la couche géologique, du fait d'une part de son caractère réducteur et d'autre part de sa production en continu pendant environ 100 000 ans. Une augmentation de pression locale peut affecter les propriétés hydro-gazo dynamiques des transferts en hydrogène. Le caractère réducteur de H2 peut modifier les propriétés d'oxydo-réduction de l'argilite du Callovo-Oxfordien (COx) et les propriétés hydrauliques de la barrière, et donc (1) sa minéralogie, (2) la spéciation des radionucléides sortant du container et (3) leur transfert. De plus, si le transport de l'hydrogène gazeux est difficile au sein de la couche géologique, l'augmentation de pression pourrait en induire la fissuration et ainsi créer des chemins préférentiels favorables à cette migration. Un dispositif expérimental a été mis en place afin d'évaluer tant la pression d'entrée de H2(g) que les paramètres de transport par perméation et diffusion à travers le COx. La pression d'entrée de l'hydrogène gazeux au sein de l'argilite du Callovo-Oxfordien saturé est comprise entre 49 et 63 bar. Sachant que la pression maximale attendue est d'environ 80 bar, on pourra donc avoir un déplacement du gaz dans la roche saturée en eau. Pour une saturation supérieure à 0,90 et avec T = 23°C, la perméabilité mesurée est proche de 10-23 m2 et le coefficient de diffusion de 10-12 m2.s-1. Ceci laisse donc envisager un déplacement lent de l'hydrogène dans la roche, par exemple il lui faudra environ 31 710 ans pour traverser un mètre de roche sous l'effet de la diffusion. Il a également été mis en évidence que les paramètres de transport dépendent essentiellement de la saturation de l'échantillon et dépendent peu de la température. Concernant la réactivité, dans des conditions proches de celles dans le stockage, H2 va réduire jusqu'à 9 wt% du Fe(III) structural sous 90°C et PH2 = 5 bar. Cette réaction n'est pas totale et le mécanisme majoritaire va être la sorption de gaz. Les niveaux d'hydrogène ainsi prélevés par le solide atteignent 0,05 wt% à 90°C et PH2 = 0,45 bar. Ce phénomène dépend fortement de la saturation de l'échantillon en eau du fait de la compétition entre H2 et H2O pour se sorber sur les sites de sorption à la surface de l'échantillon. Au total jusqu'à 18 m3 de H2 vont se sorber par m3 de COx sous PH2 = 0,45 bar et T = 90°C en conditions sèches. Ce processus va permettre, en complément du transport de gaz, de diminuer localement la pression en hydrogène. / Hydrogen gas will be produced by anaerobic corrosion of radioactive waste containers in the geological repository. This gas could affect the geological layer (Callovo-Oxfordian) stability, first due to its reductive capacity and then also due to its continuous production for about 100,000 years. The local pressure increase could affect the properties of hydro-gaseous dynamic of hydrogen transfers. The reductive capacity of H2 could change the redox properties of the Callovo-Oxfordian and the barrier hydraulic properties, and therefore (1) its mineralogy, (2) the speciation of outgoing radionuclides and (3) their transfer. Moreover, if the hydrogen gas transport is difficult within the geological layer, the pressure increase could cause cracking and create preferential pathways for radionuclides migration. An experimental device was developed to measure the entry pressure of H2(g) and transport parameters as permeability and diffusion coefficient through the COx. The entry pressure is estimated to be between 49 and 63 bar. Knowing that the maximum expected pressure is about 80 bar, there may therefore be a displacement of hydrogen gas into the water saturated clayrock. Moreover, for a saturation greater than 0.90 and at T = 23°C, permeability is measured to be close to 10-23 m2 and the diffusion coefficient to be as low as 10-12 m2.s-1. Therefore hydrogen gas will move slowly in the geological layer, for example it will take about 31,710 years to go through one meter of clayrock by diffusion. These transport parameters are found to depend mainly on the sample water saturation and not much on temperature. Regarding hydrogen reactivity, under conditions close to those in the storage, H2 will reduce up to 9 wt% of structural Fe (III) at 90°C and PH2 = 5 bar. This reaction is not complete and hydrogen gas will mainly sorb on the material, with a sorption up to 0.05 wt% at 90°C and PH2 = 0.45 bar. This process depends strongly on the water saturation of the sample, because of a competition between H2 and H2O to sorb on the surface. As a whole, more than 18 m3 of H2 per m3 of COx will sorb in dried conditions. This process will allow, during gas transport, to reduce locally the hydrogen pressure.

Saline aquifers and depleted hydrocarbon fields situated beneath the North Sea are currently being proposed as storage repositories for anthropogenic CO2 captured from point source emitters in the UK and mainland Europe. Two experimental sites are already operating successfully offshore Norway: Sleipner since 1996 and Snøhvit since 2007, collectively storing several million tonnes of CO2/year in the sub-surface. Despite the apparent success of these current projects, one of the major public and scientific concerns is the ability of storage sites to retain CO2 on the millennial timescales required for CO2 plume stabilisation and dissolution. Some areas of the North Sea are also known to contain palaeo-gas seepage pathways within overburden sediments that overlie deeper hydrocarbon reservoirs (e.g. Witch Ground Graben). These areas either need to be avoided for CO2 storage or rigorously assessed in terms of leakage risk. Since the Sleipner storage site lies within such a province, this thesis delivers a detailed evaluation of the Nordland Group overburden and a critical assessment of its long-term sealing capability for CO2. From interpretation and detailed mapping of a baseline 3D seismic dataset (acquired before CO2 injection operations commenced in 1996), we have identified numerous palaeo-migration pathways and high-amplitude seismic anomalies within the Nordland Group overburden sediments deposited above the Sleipner CO2 storage site. We attributed these features to thermogenic or biogenic gas migration, accumulation and bio-degradation over geological time. We also mapped a complex network of sand-filled, glacial channels and tunnel valleys distributed within a few hundred metres below seabed and highlighted their significance as potential fluid migration networks and/or secondary storage containment for leaking CO2. Of further significance, we confirmed that these overburden features also create spatial density variations that impact on the accuracy of seismic time-depth conversions, resulting in the probability of topographic distortions being propagated into seismic interpretations and models. To the best of our knowledge no such detailed mapping of the Nordland Group overburden at Sleipner has been undertaken previously. To determine whether the top layer of the CO2 plume at Sleipner might encounter these relict pathways as it ascends and migrates laterally beneath the caprock, we evaluated the critical column heights required for a CO2 accumulation to enter such a pathway under a range of storage conditions for a CH4/CO2/brine system; assuming that these pathways currently contain methane gas. Risking scenarios were based on a range of phase saturation, pressure, temperature, density, viscosity, interfacial tension and wettability conditions likely to be encountered at depths commensurate with the caprock at Sleipner. We concluded that given certain conditions at the caprock, CO2 could leak more easily into palaeo-migration pathways than CH4 (i.e. at lower entry pressures and therefore smaller column heights), assuming that brine densities and, most importantly, pore radii have not changed significantly over geological time (i.e. no cementation or dissolution has taken place). To further understand the dynamic significance of these palaeo-migration pathways, channels and tunnel valleys, including their ability to form inter-connected leakage/migration networks, we constructed a series of high-resolution 3D models of the Sleipner storage site and overburden, then used stochastic basin modelling and simulation techniques to investigate the processes involved during the introduction of CO2 into the storage site over a prolonged time period. Models were populated with geological, stratigraphic and structural information derived from our seismic interpretation. Flow simulations were calibrated to published data and matched to the present-day plume distribution. The absence of observational reservoir pressure and temperature data from Sleipner introduces significant uncertainty to model outcomes with respect to CO2 density and column height estimates and to surmount this difficulty we constrained the caprock temperature to CO2 density estimates obtained from the most recent gravity data observations at Sleipner. We concluded that the overburden heterogeneity is significant and palaeo-migration pathways, highpermeability channels and tunnel valleys at Sleipner may become potential migration pathways for CO2 as the plume continues to spread laterally over the coming decade, but the possible storage response is difficult to quantify given the absence of sufficient overburden rock property information and accurate pressure and temperature data for the storage site. The overall conclusion from this work is that insufficient information was collected within the Sleipner area prior to storage site development and too many significant studies which should have been performed as a pre-requisite (e.g. obtaining a caprock sample for laboratory testing of potential seal capacity), were actually performed some years after CO2 injection operations had already commenced. The pressure and temperature conditions at the caprock depth for the Sleipner storage site are also marginal in terms of maintaining CO2 above critical point conditions in dense phase and thus maximising storage efficiency. Most significantly, no rigorous overburden mapping and risking was performed for Sleipner (such as the work described in this thesis), thus the fact that no leakage has been detected at Sleipner is more due to good fortune than following best practices. Hopefully, our work has highlighted these key deficiencies so that future CO2 storage site feasibility and development studies will be performed more diligently.