The Quality of Service (QoS) is a profound concept which is gaining increasing attention in the Internet industry. Best-effort applications are now no longer acceptable in certain situations needing high bandwidth provisioning, low loss and streaming of multimedia applications. New emerging multimedia applications are requiring new levels of quality of services beyond those supported by best-effort networks. Quality of service routing is an essential part in any QoS architecture in communication networks. QoS routing aims to select a path among the many possible choices that has sufficient resources to accommodate the QoS requirements. QoS routing can significantly improve the network performance due to its awareness of the network QoS state. Most QoS routing algorithms require maintenance of the global network's state information to make routing decisions. Global state information needs to be periodically exchanged among routers since the efficiency of a routing algorithm depends on link-state information accuracy. However, most QoS routing algorithms suffer from scalability due to the high communication overhead and the high computation effort associated with maintaining accurate link state information and distributing global state information to each node in the network. The ultimate goal of this thesis is to contribute towards enhancing the scalability of QoS routing algorithms. Towards this goal, the thesis is focused on Localised QoS routing algorithms proposed to overcome the problems of using global network state information. Using such an approach, the source node makes routing decisions based on the local state information for each node in the path. Localised QoS routing algorithms avoid the problems associated in the global network state, like high communication and processing overheads. In Localised QoS routing algorithms each source node maintains a predetermined set of candidate paths for each destination and avoids the problems associated with the maintenance of a global network state by using locally collected flow statistics and flow blocking probabilities.

Localised QoS routing is a relatively new, alternative and viable approach to solve the problems of traditional QoS routing algorithms which use global state information resulting in the imposition of a large communication overhead and route flapping. They make use of a localised view of the network QoS state in source nodes to select paths and route flows to destination nodes. Proportional Sticky Routing (PSR) and Credit Based Routing (CBR) have been proposed as localised QoS routing schemes and these can offer comparable performances. However, since network state information for a specific path is only updated when the path is used, PSR and CBR operate with decision criteria that are often stale for paths that are used infrequently. The aim of this thesis is to focus on localised QoS routing and contribute to enhancing the scalability of QoS routing algorithms. In this thesis we have developed three new localised QoS routing schemes which are called Score Based QoS Routing (SBR), Bandwidth Based QoS Routing (BBR) and Delay Based Routing (DBR). In some of these schemes, the path setup procedure is distributed and uses the current network state to make decisions thus avoiding problems of staleness. The methods also avoid any complicated calculations. Both SBR and BBR use bandwidth as the QoS metric and mean delay is used as the QoS metric in DBR. Extensive simulations are applied to compare the performance of our proposed algorithms with CBR and the global Dijkstra's algorithm for different update intervals of link state, different network topologies and using different flow arrival distributions under a wide range of traffic loads. It is demonstrated by simulation that the three proposed algorithms offer a superior performance under comparable conditions to the other localised and global algorithms.

A numerical implementation of the direct Boundary-Domain Integral Equation (BDIE)/ Boundary-Domain Integro-Differential Equations (BDIDEs) and Localized Boundary-Domain Integral Equation (LBDIE)/Localized Boundary-Domain Integro-Differential Equations (LBDIDEs) related to the Neumann and Dirichlet boundary value problem for a scalar elliptic PDE with variable coefficient is discussed in this thesis. The BDIE and LBDIE related to Neumann problem are reduced to a uniquely solvable one by adding an appropriate perturbation operator. The mesh-based discretisation of the BDIE/BDIDEs and LBDIE/LBDIDEs with quadrilateral domain elements leads to systems of linear algebraic equations (discretised BDIE/BDIDEs/LBDIE/BDIDEs). Then the systems obtained from BDIE/BDIDE (discretised BDIE/BDIDE) are solved by the LU decomposition method and Neumann iterations. Convergence of the iterative method is analyzed in relation with the eigen-values of the corresponding discrete BDIE/BDIDE operators obtained numerically. The systems obtained from LBDIE/LBDIDE (discretised LBDIE/LBDIDE) are solved by the LU decomposition method as the Neumann iteration method diverges.

The research reported in this doctoral thesis involves constructing physiochemical models that reproduce the transport behaviour of aqueous chemical species present in environments relevant to the oil and gas industry to gain an improved insight into the local electrochemistry near the electroactive surface (uniform corrosion) or inside the pit (pitting corrosion). The first part of the project involved constructing physiochemical models with one dimensional geometry with aqueous chemical species and chemical and electrochemical processes observed in oxygen (O2) containing brine environments to determine the changes in the local electrolyte composition and the potential within an initiated pit for a variety of external physical and chemical conditions. It was determined that the bottom of the pit suffers greatly from the effects of iR drop (Ohmic drop) if the pit geometry is taken to be macroscopic. The model was extended to include additional aqueous chemical species in conjunction with the chemical and electrochemical processes observed in carbon dioxide (CO2) rich environment to investigate the effects of CO2 on the local electrolyte chemistry at the bottom of the pit. It was found that the proton reduction electrochemical process on its own was incapable of supplying the high currents experimentally measured in CO2 environments via the buffering effect. The second part of the project was to investigate the influence of different experimental conditions on the polarisation behaviour of near static carbon steels in CO2 saturated brine electrolyte via multiple electrochemical measurement techniques. The key observation from this study was the presence of two distinct mass transport limited regions on the cathodic polarisation curve at natural pH (3.775). From the physiochemical model fitted to the experimental cathodic curve, the first mass transport limited region, occurring at lower cathodic potentials, was identified to be the direct reduction of carbonic acid while the second wave, occurring at slightly higher cathodic potentials, was shown to be the direct reduction of aqueous carbon dioxide. Based on the polarisation scans under forced convection, the rate of the direct reduction of carbon dioxide was determined to be under neither potential nor mass transport control. The third part of the project involved extending the existing one dimensional models to include the precipitation of salt films (iron chloride – FeCl2(s) and iron carbonate – FeCO3(s)) in O2 and CO2 saturated brine electrolyte respectively along with the capability to track their respective thickness. Furthermore, the ability of the underlying metal to undergo a change in its state from active to passive is implemented in the model via a set of rules based on the Pourbaix diagram. It was determined that the precipitation of salt films is greatly influenced by the mass transport with no or minimal thickness observed under even natural convection conditions. Furthermore the successful precipitation of salt film was determined to be a precursor step to the metal attaining passivation.

In den letzten Jahren ist eine Vielzahl neuer organischer Polymere und niedermolekularer Verbindungen synthetisiert worden, die sich als aktive Komponente für Elektrolumineszenz-Bauelemente und andere elektronische Anwendungen eignen. Trotz der großen technologischen Bedeutung und des erheblichen Fortschrittes, der bei der Herstellung solcher Materialien erzielt worden ist, sind grundlegende physikalische Eigenschaften dieser Materialklassen noch nicht ausreichend erforscht. Insbesondere das Auftreten lokalisierter Zustände innerhalb der Bandlücke hat besondere Bedeutung für ihre elektronischen Eigenschaften. Sowohl die Präsenz dieser flachen traps (Fallen, Löcher) als auch der Einfluß der Herstellungsbedingungen auf die tiefen und flachen lokalisierten Zustände wurden bisher nicht systematisch untersucht.<br /> Thermische Techniken sind wichtige Methoden, um lokalisierte Niveaus in organischen und anorganischen Materialien zu erforschen. Themisch-Stimulierte Lumineszenz (TSL), Thermisch-Stimulierte Ströme (TSC) und Thermisch-Stimulierte Depolarisierte Ströme (TSDC) ermöglichen die Untersuchung flacher und tiefer traps; in Verbindung mit DiElektrischer Spektroskopie (DES) können außerdem Polarisations- und Depolarisationseffekte studiert werden.<br /> Mit Hilfe numerischer Simulationen haben wir die kinetischen Gleichungen erster und zweiter Ordnung untersucht, die sich durch schwaches bzw. starkes Wieder-Fangen beschreiben lassen. In diesen Gleichungen haben wir Gaussian-, exponentielle und quasi-kontinuierliche Verteilungen von lokalisierten Zustände berücksichtigt. Durch Veränderung der beiden wichtigsten Parameter (Tiefe der traps E und Häufigkeit) konnte die Form der thermischen Maxima untersucht werden. Auch die die Gaussian-Verteilung bestimmenden Faktoren wurden verändert. <br /> Diese theoretischen Ergebnisse wurden auf die experimentellen Glow-Kurven angewandt. Dünne Filme aus polymeren und niedermolekularen Verbindungen (Polyphenylquinoxaline, Trisphenylquinoxaline und Oxadiazole), die wegen ihrer technologischen Bedeutung ausgewählt wurden, zeigen komplexes thermisches Verhalten.<br /> Insbesondere hoch geordnete Filme eines amphiphil substituierten 2-(p-nitrophenyl)-5-(p-undecylamidophenyl)-1,3,4-oxadiazols (NADPO) zeichnen sich durch komplexe TSL-Diagramme aus. Im Bereich von Em = 4 meV wurde eine Region flacher traps gefunden. Zwei weitere TSL-Maxima treten bei Tm = 221.5 K bzw. Tm = 254.2 K auf. Sie besitzen Aktivierungsenergien von Em= 0.63 eV bzw. Em = 0.66 eV, ihre Frequenzfaktoren betragen s = 2.4x1012 s-1 bzw. s = 1.85x1011 s-1, sie zeigen Breiten der Verteilung von s = 0.045 eV bzw. s = 0.088 eV. <br /> Des weiteren zeigt diese Arbeit, daß die Form der Glow-Kurven stark von der Anregungstemperatur und vom thermischen Kreislauf beeinflußt wird. / New polymers and low molecular compounds, suitable for organic light emitting devices and organic electronic applications, have been synthesised in this years in order to obtain electron transport characteristics compatible with requirements for applications in real plastic devices. However, despite of the technological importance and of the relevant progress in devices manufacture, fundamental physical properties of such class of materials are still not enough studied. In particular extensive presence of distributions of localised states inside the band gap has a deep impact on their electronic properties. Such presence of shallow traps as well as the influence of the sample preparation conditions on deep and shallow localised states have not been, until now, systematically explored.<br /> The thermal techniques are powerful tools in order to study localised levels in inorganic and organic materials. Thermally stimulated luminescence (TSL), thermally stimulated currents (TSC) and thermally stimulated depolarisation currents (TSDC) allow to deeply look to shallow and deep trap levels as well as they permit to study, in synergy with dielectric spectroscopy (DES), polarisation and depolarisation effects. <br /> We studied, by means of numerical simulations, the first and the second order kinetic equations characterised by negligible and strong re-trapping respectively. We included in the equations Gaussian, exponential and quasi-continuous distributions of localised states. The shapes of the theoretical peaks have been investigated by means of systematic variation of the two main parameters of the equations, i. e. the energy trap depth E and the frequency factor a and of the parameters regulating the distributions, in particular for a Gaussian distribution the distribution width s and the integration limits. <br /> The theoretical findings have been applied to experimental glow curves. Thin films of polymers and low molecular compounds. Polyphenylquinoxalines, trisphenylquinoxalines and oxadiazoles, studied because of their technological relevance, show complex thermograms, having several levels of localised states and depolarisation peaks. <br /> In particular well ordered films of an amphiphilic substituted 2-(p-nitrophenyl)-5-(p-undecylamidophenyl)-1,3,4-oxadiazole (NADPO) are characterised by rich TSL thermograms. A wide region of shallow traps, localised at Em = 4 meV, has been successfully fit by means of a first order kinetic equation having a Gaussian distribution of localised states. <br /> Two further peaks, having a different origin, have been characterised. The peaks at Tm = 221.5 K and Tm = 254.2 have activation energy of Em= 0.63 eV and Em = 0.66 eV, frequency factor s = 2.4x1012 s-1 and s = 1.85x1011 s-1, distribution width s = 0.045 eV and s = 0.088 eV respectively. <br /> Increasing the number of thermal cycle, a peak, probably connected with structural defects, appears at Tm = 197.7 K. The numerical analysis of this peak was performed by means of a first order equation containing a Gaussian distribution of traps. The activation energy of the trap level is centred at Em = 0.55 eV. The distribution is perfectly symmetric with a quite small width s = 0.028 eV. The frequency factor is s = 1.15 x 1012 s-1, resulting of the same order of magnitude of its neighbour peak at Tm = 221.5 K, having both, probably, the same origin.<br /> Furthermore the work demonstrates that the shape of the glow curves is strongly influenced by the excitation temperature and by the thermal cycles. For that reason Gaussian distributions of localised states can be confused with exponential distributions if the previous thermal history of the samples is not adequately considered.

The principal Water target of the Millennium Development Goals (MDG) is to Ensure environmental sustainability by halving the proportion of people without access to safe water by 2015. Although great strides have been made in meeting this challenge in terms of provision of services since the year 2000, the safety of many these water supplies remains unknown. One of the biggest challenges therefore facing water development professionals is how to ensure sufficient levels of both quantity and guality of safe water. One of the principal mechanisms for monitoring the progress towards attaining the MDG goals for access to safe water is the UNICEF/WHO Joint Monitoring Programme (JMP). However, the JMP acknowledges that one of its current weaknesses is in assessing safety related to different technology types. In acknowledgement of these weaknesses and of the weakness of reliance on "end product testing" as a means of assuring microbiological safety, the thesis proposes improved methods of assessment and management of microbiological water safety based on a "risk" paradigm. Coinciding with proposed new risk based methods of assessing water safety outlined in the 3d edition of the World Health Organization Guidelines for Drinking Water Quality (2004), the thesis researches the risk to three well technology types in Mozambique. Principal pathways to microbiological contamination of shallow groundwater were assessed which included both the conventional aquifer pathways and preferential or localised pathways. The research adopted an experimental design that uses a mix of qualitative and quantitative data collection techniques. Data were collected over 12 months in 25 well sites in Lichinga, Mozambique. Findings from the research demonstrated that risk assessment and management are effective tools in understanding the level of safety associated with the well technologies under study. The research indicated firstly that risk assessment aids the identification of specific risk variables (of which animal faeces is a predominant risk), secondly that the use of alternative indicator organisms (e.g. enterococci) may improve risk understanding, thirdly that there is a strong statistical correlation between use of surrogates (e. g. turbidity) and microbes and fourthly that Water Safety Plans are an appropriate method of risk management. Furthermore, the research supports the JMP definitions of improved water sources, which suggest that upgraded wells are not an improved source due to their high vulnerability to contamination through localised pathways. The recommendations from the thesis include; non-inclusion of upgraded wells in the JMP in Mozambique, greater use of enterococci and turbidity as surrogate indicators of faecal pollution, the need for the development of rapid risk assessment and management techniques for rural areas in developing countries and the inclusion of localised pathways as a principal route of assessment. Potential areas of further research include field-based studies of assessment of faecal sources of Enterococci bacteria, and rapid methods for the development of model Water Safety Plans.

Cancer is a disease of the genome, requiring mutation or epimutation of specific genes to develop. The subsequent progression of cancer and response to therapies is also dictated to some degree by new mutation and clonal selection on that novel variation. However, it is thought that the majority of somatic mutations that occur in cancer are inconsequential passengers, and only a subset of functionally important driver mutations are of importance for cancer biology. This project set out to adapt and apply well-established methods from the field of molecular evolution to measure the selective forces driving the development of cancers. The ultimate objective being an improved understanding of which mutations help or hinder the progression of a cancer. Somatic cancer mutations were identified through the analysis of paired tumour and non-tumour whole-exome sequence data from the same individual. Primary data from 1005 patients was processed and complemented with additional publicly available pre-processed somatic variant calls from 4728 patients. Tumours were classified by tissue of origin and also their spectrum of substitution mutations. An advanced evolutionary analysis framework was established, allowing somatic single nucleotide variant data to be analysed as traditional organismal DNA sequence. Estimates of amino acid changing (non-synonymous) and synonymous mutation rates were derived and maximum likelihood tests of selection applied to identify genes and regions of genes subject to selective pressure during oncogenesis. While the meta-analysis of all patients provided unprecedented power for such a study, more refined analyses based on the stratification of patients gave insights into the pathways of importance for specific tissues of origin. Additionally, stratification of patients by the relative frequencies of different mutation types in a tumour also provided insights into how mutation profile influences the sites, genes and pathways that are perturbed in the development of cancer. Of particular interest here, was to test the hypothesis that both (1.) mutation spectrum and (2.) tissue of origin, set the evolutionary trajectory of a cancer. Building on this I sought to estimate their relative contributions. During this work an unexpected, localised mutation pattern was discovered and subsequent analysis demonstrated some loci to be highly susceptible to small segmental deletions in a subset of cancers. In the absence of a justifiable model of neutral segmental deletion it was not possible to infer whether these major mutations could be considered passengers or drivers of cancer progression. In contrast, an advantage of the evolutionary approach applied to nucleotide substitutions in protein coding sequences is that there is a justified model of neutral evolution (synonymous changes). Using this approach, I have not only been able to detect genes harbouring putative cancer driver mutations, but have also found evidence for genes subject to purifying selection in cancers where potentially disruptive mutations appear to be deleterious to cancer progression. Such genes, if they are non-essential in the adult organism, could provide a novel type of target for anti-cancer therapeutics.

La croissance localisée de SiC dopé p par un mécanisme Vapeur-Liquide-Solide (VLS) a été effectuée sur substrats SiC-4H (0001) 8°off et diamant (100). Pour ce faire, des motifs constitués d'un empilement silicium-aluminium sont fondus puis alimentés en propane. Dans le cas de l'homoépitaxie de SiC-4H, il a été démontré que la quantité limitée de phase liquide initiale entraine une évolution constante des paramètres de croissance en raison de l'appauvrissement graduel en silicium. Il est toutefois possible de trouver des conditions de croissance satisfaisantes (alliage contenant 40 at% Si, 1100 °C) résultant en un dépôt conforme sur l'ensemble des motifs avec une morphologie step-bunchée. A partir de tels dépôts, des contacts ohmiques de très faible résistivité (jusqu'à 1,3.10-6 Ω.cm2) ont été mesurés et des diodes PiN ont été fabriquées et caractérisées. Dans le cas de la croissance de SiC sur diamant, la forte réactivité entre l'alliage Si-Al liquide et le substrat diamant conduit à la formation d'un dépôt dense et polycristallin de SiC-3C par un mécanisme de dissolution-précipitation. Nous avons montré que la formation préalable d'une couche tampon nanométrique de SiC par siliciuration du substrat de diamant (réaction solide-solide entre une couche de Si et le diamant) permet d'obtenir une croissance épitaxiale de SiC-3C en ilots, avec les relations [110] SiC // [110] diamant et (100) SiC // (100) diamant. Il n'a cependant pas été possible de former une couche complète et épitaxiale de SiC sur diamant par VLS localisée. Nous avons toutefois montré que cela est réalisable par dépôt chimique en phase vapeur (CVD) en utilisant la même étape de siliciuration / The localized growth of p-doped SiC by Vapor-Liquid-Solid (VLS) mechanism was made on (0001) 8°off 4H-SiC and (100) diamond substrates. A silicon-aluminium stacking, localized on top of the substrate, is used after melting as the liquid phase for the growth, carbon being brought by the propane of the gas phase. Regarding the homoepitaxial growth of 4H-SiC, the limited amount of liquid phase leads to a significant consumption of silicon during the growth which is responsible for a continuous variation of the growth parameters. Satisfying growth conditions can therefore be found (40 at% Si alloy, 1100 °C) leading to the formation of a step-bunched layer on the initial Si-Al patterns. Very Low resistivity ohmic contacts (as low as 1.3x10-6 Ω.cm2) and PiN diodes were successfully fabricated from these deposits. Regarding the SiC growth on diamond, the high reactivity between the Si-Al liquid alloy and the diamond substrate leads to the polycrystalline growth of 3C-SiC by a dissolution-precipitation mechanism. It is thus necessary to use a SiC buffer layer in order to achieve an epitaxial growth. This buffer layer, grown by a solid-solid reaction between silicon (deposited by CVD) and the diamond called silicidation, favors the epitaxial growth of 3C-SiC ([110] SiC // [110] diamond and (100) SiC // (100) diamond) during the later VLS growth. Considering the 3D growth mechanism that takes place the formation of a single-crystalline layer from these epitaxial islands seems difficult. Such single-crystalline layer can be achieved using chemical vapor deposition (CVD) after the silicidation step of the diamond substrates

The need to inject treated seawater to enhance reservoir pressure and secondary oil recovery is increasing in the oil field, so also is the reservoir souring potential caused by the activities of Sulphate Reducing Bacteria (SRB) generating H2S in the reservoir. The total cost of SRB mediated corrosion in the United States alone is estimated to be 1-2 billion US dollars per year. In the last few years, a number of potential souring mitigation and prevention tools have been studied. These include: sulphate-reduction using membranes, biocide injection and nitrate injection. Out of all the various methods used for the mitigation and prevention of reservoir souring, the use of nitrate injection in conjunction with waterflood projects is becoming more popular because of its economic benefits and least environmental impact. However, nitrate injection is still widely considered as an emergent technology because there are still many unknowns. One of the major unknowns, of great concern is the susceptibility of subsea hardware components to nitrite, which is a by-product of nitrate anti-souring treatment. Any detrimental effect can compromise the technical integrity of subsea installations. The objective of this research is to study the corrosion susceptibility of CRA (13Cr- Martensitic, 22Cr, and 25Cr super duplex stainless steel) to pitting and stress corrosion cracking in the presence of nitrite. Research hitherto, has investigated corrosion susceptibility of carbon steel to nitrite and found out that nitrite causes pitting in carbon steel. This research work built on previous studies and extensively investigated the effect of nitrite on CRA materials in terms of pitting and stress corrosion cracking. Using electrochemistry techniques in conjunction with C-ring test and slow strain rate test, with variables such as temperature, and nitrite concentration all under anaerobic conditions. Metallographic examination and further evaluation using scanning electron microscopy confirmed pitting and intergranular stress corrosion cracking of 13Cr-L80 and 25Cr due to presence of nitrite.Test data confirmed that sodium nitrite is an anodic inhibitor; it shifts the corrosion potentials to more noble potential and also shifts the anodic curve to lower current, given a net reduction in corrosion rate. A critical concentration of 400ppm is required for inhibition to be effective on 13Cr-L80 and 25Cr. However, below the critical concentration, nitrite significantly increases the corrosion rate. The experimental data generated from this research work provides very valuable information that will tremendously assist the materials selection process for subsea and subsurface hardware components and also serve as a guide in the corrosion management process in existing systems.

School of Computing, Informatics and Media / Localised QoS routing is a relatively new, alternative and viable approach to solve the problems of traditional QoS routing algorithms which use global state information resulting in the imposition of a large communication overhead and route flapping. They make use of a localised view of the network QoS state in source nodes to select paths and route flows to destination nodes. Proportional Sticky Routing (PSR) and Credit Based Routing (CBR) have been proposed as localised QoS routing schemes and these can offer comparable performances. However, since network state information for a specific path is only updated when the path is used, PSR and CBR operate with decision criteria that are often stale for paths that are used infrequently. The aim of this thesis is to focus on localised QoS routing and contribute to enhancing the scalability of QoS routing algorithms. In this thesis we have developed three new localised QoS routing schemes which are called Score Based QoS Routing (SBR), Bandwidth Based QoS Routing (BBR) and Delay Based Routing (DBR). In some of these schemes, the path setup procedure is distributed and uses the current network state to make decisions thus avoiding problems of staleness. The methods also avoid any complicated calculations. Both SBR and BBR use bandwidth as the QoS metric and mean delay is used as the QoS metric in DBR. Extensive simulations are applied to compare the performance of our proposed algorithms with CBR and the global Dijkstra¿s algorithm for different update intervals of link state, different network topologies and using different flow arrival distributions under a wide range of traffic loads. It is demonstrated by simulation that the three proposed algorithms offer a superior performance under comparable conditions to the other localised and global algorithms.