Building effectiveness communication ratios (BECs): an integrated ‘life-cycle’ methodology for mitigating energy-use in buildings

Current building regulations are generally prescriptive in nature. It is widely accepted in Europe that this form of building regulation is stifling technological innovation and leading to inadequate energy efficiency in the building stock. This has increased the motivation to move design practices towards a more ‘performance-based’ model in order to mitigate inflated levels of energy-use consumed by the building stock. A performance based model assesses the interaction of all building elements and the resulting impact on holistic building energy-use. However, this is a nebulous task due to building energy-use being affected by a myriad of heterogeneous agents. Accordingly, it is imperative that appropriate methods, tools and technologies are employed for energy prediction, measurement and evaluation throughout the project’s life cycle. This research also considers that it is imperative that the data is universally accessible by all stakeholders. The use of a centrally based product model for exchange of building information is explored. This research describes the development and implementation of a new building energy-use performance assessment methodology. Termed the Building Effectiveness Communications ratios (BECs) methodology, this performance-based framework is capable of translating complex definitions of sustainability for energy efficiency and depicting universally understandable views at all stage of the Building Life Cycle (BLC) to the project’s stakeholders. The enabling yardsticks of building energy-use performance, termed Ir and Pr, provide continuous design and operations feedback in order to aid the building’s decision makers. Utilised effectively, the methodology is capable of delivering quality assurance throughout the BLC by providing project teams with quantitative measurement of energy efficiency. Armed with these superior enabling tools for project stakeholder communication, it is envisaged that project teams will be better placed to augment a knowledge base and generate more efficient additions to the building stock.

Grid integration of wave energy & generic modelling of ocean devices for power system studies

The work presented in this thesis covers four major topics of research related to the grid integration of wave energy. More specifically, the grid impact of a wave farm on the power quality of its local network is investigated. Two estimation methods were developed regarding the flicker level Pst generated by a wave farm in relation to its rated power as well as in relation to the impedance angle ψk of the node in the grid to which it is connected. The electrical design of a typical wave farm design is also studied in terms of minimum rating for three types of costly pieces of equipment, namely the VAr compensator, the submarine cables and the overhead line. The power losses dissipated within the farm's electrical network are also evaluated. The feasibility of transforming a test site into a commercial site of greater rated power is investigated from the perspective of power quality and of cables and overhead line thermal loading. Finally, the generic modelling of ocean devices, referring here to both wave and tidal current devices, is investigated.

Characteristics of the wave energy resource at the Atlantic marine energy test site

The wave energy industry is progressing towards an advanced stage of development, with consideration being given to the selection of suitable sites for the first commercial installations. An informed, and accurate, characterisation of the wave energy resource is an essential aspect of this process. Ireland is exposed to an energetic wave climate, however many features of this resource are not well understood. This thesis assesses and characterises the wave energy resource that has been measured and modelled at the Atlantic Marine Energy Test Site, a facility for conducting sea trials of floating wave energy converters that is being developed near Belmullet, on the west coast of Ireland. This characterisation process is undertaken through the analysis of metocean datasets that have previously been unavailable for exposed Irish sites. A number of commonly made assumptions in the calculation of wave power are contested, and the uncertainties resulting from their application are demonstrated. The relationship between commonly used wave period parameters is studied, and its importance in the calculation of wave power quantified, while it is also shown that a disconnect exists between the sea states which occur most frequently at the site and those that contribute most to the incident wave energy. Additionally, observations of the extreme wave conditions that have occurred at the site and estimates of future storms that devices will need to withstand are presented. The implications of these results for the design and operation of wave energy converters are discussed. The foremost contribution of this thesis is the development of an enhanced understanding of the fundamental nature of the wave energy resource at the Atlantic Marine Energy Test Site. The results presented here also have a wider relevance, and can be considered typical of other, similarly exposed, locations on Ireland’s west coast.

Ab initio calculations of group 4 metallocene reaction mechanisms: atomic layer deposition and bond activation catalysis

Thin film dielectrics based on titanium, zirconium or hafnium oxides are being introduced to increase the permittivity of insulating layers in transistors for micro/nanoelectronics and memory devices. Atomic layer deposition (ALD) is the process of choice for fabricating these films, as it allows for high control of composition and thickness in thin, conformal films which can be deposited on substrates with high aspect-ratio features. The success of this method depends crucially on the chemical properties of the precursor molecules. A successful ALD precursor should be volatile, stable in the gas-phase, but reactive on the substrate and growing surface, leading to inert by-products. In recent years, many different ALD precursors for metal oxides have been developed, but many of them suffer from low thermal stability. Much promise is shown by group 4 metal precursors that contain cyclopentadienyl (Cp = C5H5-xRx) ligands. One of the main advantages of Cp precursors is their thermal stability. In this work ab initio calculations were carried out at the level of density functional theory (DFT) on a range of heteroleptic metallocenes [M(Cp)4-n(L)n], M = Hf/Zr/Ti, L = Me and OMe, in order to find mechanistic reasons for their observed behaviour during ALD. Based on optimized monomer structures, reactivity is analyzed with respect to ligand elimination. The order in which different ligands are eliminated during ALD follows their energetics which was in agreement with experimental measurements. Titanocene-derived precursors, TiCp*(OMe)3, do not yield TiO2 films in atomic layer deposition (ALD) with water, while Ti(OMe)4 does. DFT was used to model the ALD reaction sequence and find the reason for the difference in growth behaviour. Both precursors adsorb initially via hydrogen-bonding. The simulations reveal that the Cp* ligand of TiCp*(OMe)3 lowers the Lewis acidity of the Ti centre and prevents its coordination to surface O (densification) during both of the ALD pulses. Blocking this step hindered further ALD reactions and for that reason no ALD growth is observed from TiCp*(OMe)3 and water. The thermal stability in the gas phase of Ti, Zr and Hf precursors that contain cyclopentadienyl ligands was also considered. The reaction that was found using DFT is an intramolecular α-H transfer that produces an alkylidene complex. The analysis shows that thermal stabilities of complexes of the type MCp2(CH3)2 increase down group 4 (M = Ti, Zr and Hf) due to an increase in the HOMO-LUMO band gap of the reactants, which itself increases with the electrophilicity of the metal. The reverse reaction of α-hydrogen abstraction in ZrCp2Me2 is 1,2-addition reaction of a C-H bond to a Zr=C bond. The same mechanism is investigated to determine if it operates for 1,2 addition of the tBu C-H across Hf=N in a corresponding Hf dimer complex. The aim of this work is to understand orbital interactions, how bonds break and how new bonds form, and in what state hydrogen is transferred during the reaction. Calculations reveal two synchronous and concerted electron transfers within a four-membered cyclic transition state in the plane between the cyclopentadienyl rings, one π(M=X)-to-σ(M-C) involving metal d orbitals and the other σ(C-H)-to-σ(X-H) mediating the transfer of neutral H, where X = C or N. The reaction of the hafnium dimer complex with CO that was studied for the purpose of understanding C-H bond activation has another interesting application, namely the cleavage of an N-N bond and resulting N-C bond formation. Analysis of the orbital plots reveals repulsion between the occupied orbitals on CO and the N-N unit where CO approaches along the N-N axis. The repulsions along the N-N axis are minimized by instead forming an asymmetrical intermediate in which CO first coordinates to one Hf and then to N. This breaks the symmetry of the N-N unit and the resultant mixing of MOs allows σ(NN) to be polarized, localizing electrons on the more distant N. This allowed σ(CO) and π(CO) donation to N and back-donation of π*(Hf2N2) to CO. Improved understanding of the chemistry of metal complexes can be gained from atomic-scale modelling and this provides valuable information for the design of new ALD precursors. The information gained from the model decomposition pathway can be additionally used to understand the chemistry of molecules in the ALD process as well as in catalytic systems.

Redox remodelling in diaphragm muscle adaptation to chronic sustained hypoxia

Chronic sustained hypoxia (CH) induces functional weakness, atrophy, and mitochondrial remodelling in the diaphragm muscle. Animal models of CH present with changes similar to patients with respiratory-related disease, thus, elucidating the molecular mechanisms driving these adaptations is clinically important. We hypothesize that ROS are pivotal in diaphragm muscle adaptation to CH. C57BL6/J mice were exposed to CH (FiO2=0.1) for one, three, and six weeks. Sternohyoid (upper airway dilator), extensor digitorum longus (EDL), and soleus were studied as reference muscles as well as the diaphragm. The diaphragm was profiled using a redox proteomics approach followed by mass spectrometry. Following this, redox-modified metabolic enzyme activities and atrophy signalling were assessed using spectrophotometric assays and ELISA. Diaphragm isotonic performance was assessed after six weeks of CH ± chronic antioxidant supplementation. Protein carbonyl and free thiol content in the diaphragm were increased and decreased respectively after six weeks of CH – indicative of protein oxidation. These changes were temporally modulated and muscle specific. Extensive remodelling of metabolic proteins occurred and the stress reached the cross-bridge. Metabolic enzyme activities in the diaphragm were, for the most part, decreased by CH and differential muscle responses were observed. Redox sensitive chymotrypsin-like proteasome activity of the diaphragm was increased and atrophy signalling was observed through decreased phospho-FOXO3a and phospho-mTOR. Phospho-p38 MAPK content was increased and this was attenuated by antioxidant treatment. Hypoxia decreased power generating capacity of the diaphragm and this was restored by N-acetyl-cysteine (NAC) but not by tempol. Redox remodelling is pivotal for diaphragm adaptation to chronic sustained hypoxia. Muscle changes are dependent on duration of the hypoxia stimulus, activity profile of the muscle, and molecular composition of the muscle. The working respiratory muscles and slow oxidative fibres are particularly susceptible. NAC (antioxidant) may be useful as an adjunct therapy in respiratory-related diseases characterised by hypoxic stress.

Chemistry and synthesis of 3(2H)-furanones and 4,5-dihydro analogues: mechanistic investigations and stereochemical control

The subject matter of this thesis relates to the chemistry of the five-membered oxygen heterocycles – 3(2H)-furanones and their 4, 5-dihydro analogues. Chapter one of the thesis is a review of the relevant chemistry of the compounds: their synthesis and key transformations. In chapter two, new research on 3(2H)-furanones is outlined in two parts. The first describes an investigation into the cyclisation of α'-trialkylsilyloxyenone adducts with arenesulfenyl and selenenyl chlorides into the corresponding sulfur and selenium substituted 3(2H)-furanones without the involvement of a Lewis acid catalyst. The study, largely involving in situ NMR techniques, identified key features associated with the formation and reaction of the chlorosulfide and chloroselenide intermediates, including operation of the Thorpe-Ingold effect. The knowledge gained in this study was applied (the second part) to the synthesis of vinyl substituted furanone systems from α'-trialkylsilyloxydienones where choice of the reaction conditions and electrophilic reagent was a key feature. An important difference in the behaviour of arenesulfenyl and selenenyl halides towards conjugated dienes emerged from this work. This phase of the research concluded with a new synthesis of geiparvarin, a natural product possessing anti-tumour properties.