Optimisation of Smart Grid performance using centralised and distributed control techniques

A massive change is currently taking place in the manner in which power networks are operated. Traditionally, power networks consisted of large power stations which were controlled from centralised locations. The trend in modern power networks is for generated power to be produced by a diverse array of energy sources which are spread over a large geographical area. As a result, controlling these systems from a centralised controller is impractical. Thus, future power networks will be controlled by a large number of intelligent distributed controllers which must work together to coordinate their actions. The term Smart Grid is the umbrella term used to denote this combination of power systems, artificial intelligence, and communications engineering. This thesis focuses on the application of optimal control techniques to Smart Grids with a focus in particular on iterative distributed MPC. A novel convergence and stability proof for iterative distributed MPC based on the Alternating Direction Method of Multipliers is derived. Distributed and centralised MPC, and an optimised PID controllers' performance are then compared when applied to a highly interconnected, nonlinear, MIMO testbed based on a part of the Nordic power grid. Finally, a novel tuning algorithm is proposed for iterative distributed MPC which simultaneously optimises both the closed loop performance and the communication overhead associated with the desired control.

Application of mesoporous silica for the oral delivery of poorly water-soluble drugs

The objective of this thesis was to improve the dissolution rate of the poorly waters-soluble drug, fenofibrate by processing it with a high surface area carrier, mesoporous silica. The subsequent properties of the drug – silica composite were studied in terms of drug distribution within the silica matrix, solid state and release properties. Prior to commencing any experimental work, the properties of unprocessed mesoporous silica and fenofibrate were characterised (chapter 3), this allowed for comparison with the processed samples studied in later chapters. Fenofibrate was a highly stable, crystalline drug that did not adsorb moisture, even under long term accelerated storage conditions. It maintained its crystallinity even after SC-CO2 processing. Its dissolution rate was limited and dependent on the characteristics of the particular in vitro media studied. Mesoporous silica had a large surface area and mesopore volume and readily picked up moisture when stored under long term accelerated storage conditions (75% RH, 40 oC). It maintained its mesopore character after SC-CO2 processing. A variety of methods were employed to process fenofibrate with mesoporous silica including physical mixing, melt method, solvent impregnation and novel methods such as liquid and supercritical carbon dioxide (SC-CO2) (chapter 4). It was found that it was important to break down the fenofibrate particulate structure to a molecular state to enable drug molecules enter into the silica mesopores. While all processing methods led to some increase in fenofibrate release properties; the impregnation, liquid and SC-CO2 methods produced the most rapid release rates. SC-CO2 processing was further studied with a view to optimising the processing parameters to achieve the highest drug-loading efficiency possible (chapter 5). In this thesis, it was that SC-CO2 processing pressure had a bearing on drug-loading efficiency. Neither pressure, duration or depressurisation rate affected drug solid state or release properties. The amount of drug that could be loaded onto to the mesoporous silica successfully was also investigated at different ratios of drug mass to silica surface area under constant SC-CO2 conditions; as the drug – silica ratio increased, the drug-loading efficiency decreased, while there was no effect on drug solid state or release properties. The influence of the number of drug-loading steps was investigated (chapter 6) with a view to increasing the drug-loading efficiency. This multiple step approach did not yield an increase in drug-loading efficiency compared to the single step approach. It was also an objective in this chapter to understand how much drug could be loaded into silica mesopores; a method based on the known volume of the mesopores and true density of drug was investigated. However, this approach led to serious repercussions in terms of the subsequent solid state nature of the drug and its release performance; there was significant drug crystallinity and reduced release extent. The impact of in vitro release media on fenofibrate release was also studied (chapter 6). Here it was seen that media containing HCl led to reduced drug release over time compared to equivalent media not containing HCl. The key findings of this thesis are discussed in chapter 7 and included: 1. Drug – silica processing method strongly influenced drug distribution within the silica matrix, drug solid state and release. 2. The silica surface area and mesopore volume also influenced how much drug could be loaded. It was shown that SC-CO2 processing variables such as processing pressure (13.79 – 41.37 MPa), duration time (4 – 24 h) and depressurisation rate (rapid or controlled) did not influence the drug distribution within the SBA- 15 matrix, drug solid state form or release. Possible avenues of research to be considered going forward include the development and application of high resolution imaging techniques to visualise drug molecules within the silica mesopores. Also, the issues surrounding SBA-15 usage in a pharmaceutical manufacturing environment should be addressed.

Synthesis and characterization of oxide materials

Nanostructured materials are central to the evolution of future electronics and biomedical applications amongst other applications. This thesis is focused on developing novel methods to prepare a number of nanostructured metal oxide particles and films by a number of different routes. Part of the aim was to see how techniques used in nanoparticle science could be applied to thin film methods to develop functional surfaces. Wet-chemical methods were employed to synthesize and modify the metal oxide nanostructures (CeO2 and SiO2) and their structural properties were characterized through advanced X-ray diffraction, electron microscopy, photoelectron spectroscopy and other techniques. Whilst particulates have uses in many applications, their attachment to surfaces is of importance and this is frequently challenging. We examined the use of block copolymer methods to form very well defined metal oxide particulate-like structures on the surface of a number of substrates. Chapter 2 describes a robust method to synthesize various sized silica nanoparticles. As-synthesized silica nanoparticles were further functionalized with IR-820 and FITC dyes. The ability to create size controlled nanoparticles with associated (optical) functionality may have significant importance in bio-medical imaging. Thesis further describes how non-organic modified fluorescent particles might be prepared using inorganic oxides. A study of the concentrations and distributions of europium dopants within the CeO2 nanoparticles was undertaken and investigated by different microscopic and spectroscopic techniques. The luminescent properties were enhanced by doping and detailed explanations are reported. Additionally, the morphological and structural evolution and optical properties were correlated as a function of concentrations of europium doping as well as with further annealing. Further work using positron annihilation spectroscopy allowed the study of vacancy type defects formed due to europium doping in CeO2 crystallites and this was supported by complimentary UV-Vis spectra and XRD work. During the last few years the interest in mesoporous silica materials has increased due to their typical characteristics such as potential ultra-low dielectric constant materials, large surface area and pore volume, well-ordered and uniform pores with adjustable pores between 2 and 50 nm. A simple, generic and cost-effective route was used to demonstrate the synthesis of 2D mesoporous silica thin films over wafer scale dimensions in chapter 5. Lithographic resist and in situ hard mask block copolymer followed by ICP dry etching were used to fabricate mesoporous silica nanostructures. The width of mesoporous silica channels can be varied by using a variety of commercially available lithographic resists whereas depth of the mesoporous silica channels can be varied by altering the etch time. The crystal structure, morphology, pore arrangement, pore diameters, thickness of films and channels were determined by XRD, SEM, ellipsometry and the results reported. This project also extended work towards the study of the antimicrobial study of nanopatterned silver nanodot arrays formed using the block copolymer approach defined above. Silver nanodot arrays were successfully tested for antimicrobial activity over S. aureus and P. aeruginosa biofilms and results shows silver nanodots has good antimicrobial activity for both S. aureus and P. aeruginosa biofilms. Thus, these silver nanodot arrays shows a potential to be used as a substitute for the resolution of infection complications in many areas.

Highly sensitive surface enhanced Raman scattering (SERS) detection platforms formed by large area self-assembled Au nanorod arrays

This thesis explores a new method to fabricate SERS detection platforms formed by large area self-assembled Au nanorod arrays. For the fabrication of these new SERS platforms a new droplet deposition method for the self-assembly of Au nanorods was developed. The method, based in the controlled evaporation of organic suspensions of Au nanorods, was used for the fabrication of horizontal and vertical arrays of Au nanorods over large areas (100μm2). The fabricated nanorods arrays showed a high degree of order measured by SEM and optical microscopy over mm2 areas, but unfortunately they detached from the support when immersed in any analyte solutions. In order to improve adhesion of arrays to the support and clean off residual organic matter, we introduced an additional stamping process. The stamping process allows the immobilization of the arrays on different flexible and rigid substrates, whose feasibility as SERS platforms were tested satisfactory with the model molecule 4ABT. Following the feasibility study, the substrates were used for the detection of the food contaminant Crystal Violet and the drug analogue Benzocaine as examples of recognition of health menaces in real field applications.

The life history and ecology of black scabbardfish (Aphanopus carbo Lowe 1839) in the north-east Atlantic

The black scabbardfish is a deep water species that supports commercial fisheries across a large area of the NE Atlantic shelf. The life history of black scabbardfish is poorly understood and a major unresolved issue is population structure. In this study it was used a combination of methodologies to get further knowledge in the life history and population structure of A. carbo over its wide distribution range in the Northeast Atlantic. The new knowledge acquired during this study, will increase our ability to better manage this species in the NE Atlantic. It has been postulated that fish caught to the west of the British Isles are pre-adults that migrate further south (to Madeira) for spawning, implying a single panmictic population. In this study, specimens of Aphanopus carbo were sampled between September 2008 and May 2010 from two different areas: NW Scotland (French trawlers and deep water surveys) and Madeira Islands (longliners commercial landings). Geographical differences in reproductive state of scabbardfish were evident, supportive of a north-south migration theory. In the northern area, all specimens found were immature, while in Madeira all maturity stages were observed. In Madeira, spawning occurred during the fourth quarter, with peak maturity in October (males) and in November (females). The age of this species has proven difficult and has led to different and contradictory age and growth estimates. For this study, we used two reading interpretations to determine age and estimate the growth parameters. To the west of the British Isles, specimens reached a lower maximum age and had a higher growth rate than those caught off Madeira. These differences are consistent with the theory of a single population of black scabbardfish in the NE Atlantic, highly segregate, with smaller, immature and younger fish caught to the west of the British Isles and bigger and mature caught in Madeira Islands. The feeding ecology showed strong evidence that the diet of black scabbardfish is associated with the spawning migration of blue whiting, which may support a northerly feeding migration theory for black scabbardfish. The stable isotope analyses in the muscle of black scabbardfish identified that black scabbardfish feeds on species with epipelagic and benthopelagic affinities. Comparison with stable isotope analysis in Madeira samples indicated that black scabbardfish feed at a similar trophic level and has the same trophic niche width in both areas, assuming similar baseline isotope compositions. Otolith stable isotopes (oxygen - δ18O and nitrogen - δ15N) analyses were used as a tool to clarify migratory behaviour. Otolith isotope ratios can provide insight into whether adults caught around Madeira fed in an isotopically depleted northerly ecosystem (NW Scotland) during their pre-adult period and then migrate towards south to spawn. Overall, the results support a south-north migration of pre adult fish from spawning areas around Madeira and a north-south migration from the west of Scotland to the spawning areas. Given its life cycle there is an urgent need that the management process recognizes the existence of a continuous widely distributed stock of black scabbardfish between the west of the British Isles and Madeira. The results highlight large scale dispersal in this species which needs to be treated as a highly migratory species and be managed as a single population.

Development of large-scale colloidal crystallisation methods for the production of photonic crystals

Colloidal photonic crystals have potential light manipulation applications including; fabrication of efficient lasers and LEDs, improved optical sensors and interconnects, and improving photovoltaic efficiencies. One road-block of colloidal selfassembly is their inherent defects; however, they can be manufactured cost effectively into large area films compared to micro-fabrication methods. This thesis investigates production of ‘large-area’ colloidal photonic crystals by sonication, under oil co-crystallization and controlled evaporation, with a view to reducing cracking and other defects. A simple monotonic Stöber particle synthesis method was developed producing silica particles in the range of 80 to 600nm in a single step. An analytical method assesses the quality of surface particle ordering in a semiquantitative manner was developed. Using fast Fourier transform (FFT) spot intensities, a grey scale symmetry area method, has been used to quantify the FFT profiles. Adding ultrasonic vibrations during film formation demonstrated large areas could be assembled rapidly, however film ordering suffered as a result. Under oil cocrystallisation results in the particles being bound together during film formation. While having potential to form large areas, it requires further refinement to be established as a production technique. Achieving high quality photonic crystals bonded with low concentrations (<5%) of polymeric adhesives while maintaining refractive index contrast, proved difficult and degraded the film’s uniformity. A controlled evaporation method, using a mixed solvent suspension, represents the most promising method to produce high quality films over large areas, 75mm x 25mm. During this mixed solvent approach, the film is kept in the wet state longer, thus reducing cracks developing during the drying stage. These films are crack-free up to a critical thickness, and show very large domains, which are visible in low magnification SEM images as Moiré fringe patterns. Higher magnification reveals separation between alternate fringe patterns are domain boundaries between individual crystalline growth fronts.