Studies of the effects of molecular encounters on N.M.R. spin-lattice relaxation times

This thesis is concerned with investigations of the effects of molecular encounters on nuclear magnetic resonance spin-lattice relaxation times, with particular reference to mesitylene in mixtures with cyclohexane and TMS. The purpose of the work was to establish the best theoretical description of T1 and assess whether a recently identified mechanism (buffeting), that influences n.m.r. chemical shifts, governs Tl also. A set of experimental conditions are presented that allow reliable measurements of Tl and the N. O. E. for 1H and 13C using both C. W. and F.T. n.m.r. spectroscopy. Literature data for benzene, cyclohexane and chlorobenzene diluted by CC14 and CS2 are used to show that the Hill theory affords the best estimation of their correlation times but appears to be mass dependent. Evaluation of the T1 of the mesitylene protons indicates that a combined Hill-Bloembergen-Purcell-Pound model gives an accurate estimation of T1; subsequently this was shown to be due to cancellation of errors in the calculated intra and intemolecular components. Three experimental methods for the separation of the intra and intermolecular relaxation times are described. The relaxation times of the 13C proton satellite of neat bezene, 1,4 dioxane and mesitylene were measured. Theoretical analyses of the data allow the calculation of Tl intra. Studies of intermolecular NOE's were found to afford a general method of separating observed T1's into their intra and intermolecular components. The aryl 1H and corresponding 13C T1 values and the NOE for the ring carbon of mesitylene in CC14 and C6H12-TMS have been used in combination to determine T1intra and T1inter. The Hill and B.P.P. models are shown to predict similarly inaccurate values for T1linter. A buffeting contribution to T1inter is proposed which when applied to the BPP model and to the Gutowsky-Woessner expression for T1inter gives an inaccuracy of 12% and 6% respectively with respect to theexperimentally based T1inter.

The development of calibration and adaptive filtering procedures for neuromagnetic studies of human visual function

This thesis first considers the calibration and signal processing requirements of a neuromagnetometer for the measurement of human visual function. Gradiometer calibration using straight wire grids is examined and optimal grid configurations determined, given realistic constructional tolerances. Simulations show that for gradiometer balance of 1:104 and wire spacing error of 0.25mm the achievable calibration accuracy of gain is 0.3%, of position is 0.3mm and of orientation is 0.6°. Practical results with a 19-channel 2nd-order gradiometer based system exceed this performance. The real-time application of adaptive reference noise cancellation filtering to running-average evoked response data is examined. In the steady state, the filter can be assumed to be driven by a non-stationary step input arising at epoch boundaries. Based on empirical measures of this driving step an optimal progression for the filter time constant is proposed which improves upon fixed time constant filter performance. The incorporation of the time-derivatives of the reference channels was found to improve the performance of the adaptive filtering algorithm by 15-20% for unaveraged data, falling to 5% with averaging. The thesis concludes with a neuromagnetic investigation of evoked cortical responses to chromatic and luminance grating stimuli. The global magnetic field power of evoked responses to the onset of sinusoidal gratings was shown to have distinct chromatic and luminance sensitive components. Analysis of the results, using a single equivalent current dipole model, shows that these components arise from activity within two distinct cortical locations. Co-registration of the resulting current source localisations with MRI shows a chromatically responsive area lying along the midline within the calcarine fissure, possibly extending onto the lingual and cuneal gyri. It is postulated that this area is the human homologue of the primate cortical area V4.

Active vibration control at machinery feet

The unmitigated transmission of undesirable vibration can result in problems by way of causing human discomfort, machinery and equipment failure, and affecting the quality of a manufacturing process. When identifiable transmission paths are discernible, vibrations from the source can be isolated from the rest of the system and this prevents or minimises the problems. The approach proposed here for vibration isolation is active force cancellation at points close to the vibration source. It uses force feedback for multiple-input and multiple-output control at the mounting locations. This is particularly attractive for rigid mounting of machine on relative flexible base where machine alignment and motions are to be restricted. The force transfer function matrix is used as a disturbance rejection performance specification for the design of MIMO controllers. For machine soft-mounted via flexible isolators, a model for this matrix has been derived. Under certain conditions, a simple multiplicative uncertainty model is obtained that shows the amount of perturbation a flexible base has on the machine-isolator-rigid base transmissibility matrix. Such a model is very suitable for use with robust control design paradigm. A different model is derived for the machine on hard-mounts without the flexible isolators. With this model, the level of force transmitted from a machine to a final mounting structure using the measurements for the machine running on another mounting structure can be determined. The two mounting structures have dissimilar dynamic characteristics. Experiments have verified the usefulness of the expression. The model compares well with other methods in the literature. The disadvantage lies with the large amount of data that has to be collected. Active force cancellation is demonstrated on an experimental rig using an AC industrial motor hard-mounted onto a relative flexible structure. The force transfer function matrix, determined from measurements, is used to design H and Static Output Feedback controllers. Both types of controllers are stable and robust to modelling errors within the identified frequency range. They reduce the RMS of transmitted force by between 30?80% at all mounting locations for machine running at 1340 rpm. At the rated speed of 1440 rpm only the static gain controller is able to provide 30?55% reduction at all locations. The H controllers on the other hand could only give a small reduction at one mount location. This is due in part to the deficient of the model used in the design. Higher frequency dynamics has been ignored in the model. This can be resolved by the use of a higher order model that can result in a high order controller. A low order static gain controller, with some tuning, performs better. But it lacks the analytical framework for analysis and design.

Subspace modelling for structured noise suppression

The problem of structured noise suppression is addressed by i)modelling the subspaces hosting the components of the signal conveying the information and ii)applying a nonlin- ear non-extensive technique for effecting the right separation. Although the approach is applicable to all situations satisfying the hypothesis of the proposed framework, this work is motivated by a particular scenario, namely, the cancellation of low frequency noise in broadband seismic signals.

Pitch shifts on mistuned harmonics in the presence and absence of corresponding in-tune components

Mistuning a harmonic produces an exaggerated change in its pitch, a component-pitch shift. The origin of these pitch shifts was explored by manipulations intended to alter the grouping status of a mistuned target component in a periodic complex tone. In experiment 1, which used diotic presentation, reinstating the corresponding harmonic (in-tune counterpart) caused the pitch shifts on the mistuned target largely to disappear for components 3 and 4, although they remained for component 2. A computational model of component-pitch shifts, based on harmonic cancellation, was unable to explain the near-complete loss of pitch shifts when the counterpart was present; only small changes occurred. In experiment 2, the complex tone and mistuned component 4 were presented in the left ear and the in-tune counterpart was presented in the right. The in-tune counterpart again reduced component-pitch shifts, but they were restored when a captor complex into which the counterpart fitted as harmonic 3 was added in the right ear; presumably by providing an alternative grouping possibility for the counterpart. It is proposed that component-pitch shifts occur only if the mistuned component is selected to contribute to the complex-tone percept; these shifts are eliminated if it is displaced by a better candidate.

A Note on Div-Curl Lemma

2000 Mathematics Subject Classification: 42B30, 46E35, 35B65.

Practical and cost-effective high-fidelity optical carrier dissemination using coherent communication techniques

We report a unidirectional frequency dissemination scheme for high-fidelity optical carriers deployable over telecommunication networks. For the first time, a 10 Gb/s Binary Phase Shift Keying (BPSK) signal from an ultra-narrow linewidth laser was transmitted through a field-installed optical fibre with round-trip length of 124 km between Cork City and town of Clonakilty, without inline optical amplification. At the receiver, using coherent communication techniques and optical injection-locking the carrier was recovered with noise suppression. The beat signal between the original carrier at the transmitter and recovered carrier at the receiver shows a linewidth of 2.8 kHz. Long term stability measurements revealed fractional instabilities (True Allan deviation) of 3.3 × 10-14 for 1 s averaging time, prior to phase noise cancellation.

A Public-Private Partnership Magyarországon– egy félreértés volt? (Public-Private Partnerships in Hungary – was it a mistake?)

Az elemzés a PPP (Public-Private Partnership) magyarországi felfutásának és visszaesésének izgalmas éveit tárja fel, amelynek alapján megállapítható, hogy a magyar gyakorlatban körvonalazódó PPP nem az a PPP, amely a nemzetközi tapasztalatok alapján a közfeladatok megvalósításának közgazdaságilag megalapozott eszköze lehetne. A szerző úgy gondolja, hogy nem a PPP-módszer elvetése a megfelelő válasz a létező hibákra, hanem alkalmazásának módján kell javítani, a fokozatosan halmozódó tapasztalatok értő felhasználásával. ______ Public-Private Partnership (PPP) has quickly become a well-known phenomenon in Hungary. Despite its proliferation in various areas of activities, and the fact that most of these projects are still running, interest for starting new PPP projects has ceased, and even the cancellation of the project has become an issue. My research objective was to understand better how the concept of PPP has been interpreted by the wider public, through the assessment of the projects appearance in the main economic newspapers. The analysis shows that what has been implemented as PPP projects in Hungary are conceptually different from what PPP as an economically justified concept substantiates. PPP seems to be a phenomenon grossly misunderstood in Hungary.

An aquatic risk assessment of ethion and bromacil inputs to the C-25 Canal and Indian River Lagoon

Pesticide monitoring in St. Lucie County by various local, state and federal agencies has indicated consistent residues of several pesticides, including ethion and bromacil. Although pesticides have long been known to pose a threat to non-target species and much background monitoring has been done, no pesticide aquatic risk assessment has been done in this geographical area. Several recognized United States Environmental Protection Agency (USEPA) methods of quantifying risk are employed here to include hazard quotients (HQ) and probabilistic modeling with sensitivity analysis. These methods are employed to characterize potential impacts to aquatic biota of the C-25 Canal and the Indian River Lagoon (in St. Lucie County, Florida) based on current agricultural pesticide use and drainage patterns. The model used in the analysis incorporates available physical-chemical property data, local hydrology, ecosystem information, and pesticide use practices. HQ's, probabilistic distributions, and field sample analyses resulted in high levels of concern (LOCs), which usually indicates a need for regulatory action, including restrictions on use, or cancellation. ^

Mechanisms governing the eyewall replacement cycle in numerical simulations of tropical cyclones

Eyewall replacement cycle (ERC) is frequently observed during the evolution of intensifying Tropical Cyclones (TCs). Although intensely studied in recent years, the underlying mechanisms of ERC are still poorly understood, and the forecast of ERC remains a great challenge. To advance our understanding of ERC and provide insights in improvement of numerical forecast of ERC, a series of numerical simulations is performed to investigate ERCs in TC-like vortices on a f-plane. The simulated ERCs possess key features similar to those observed in real TCs including the formation of a secondary tangential wind maximum associated with the outer eyewall. The Sawyer-Eliassen equation and tangential momentum budget analyses are performed to diagnose the mechanisms underlying the secondary eyewall formation (SEF) and ERC. Our diagnoses reveal crucial roles of outer rainband heating in governing the formation and development of the secondary tangential wind maximum and demonstrate that the outer rainband convection must reach a critical strength relative to the eyewall before SEF and the subsequent ERC can occur. A positive feedback among low-level convection, acceleration of tangential winds in the boundary layer, and surface evaporation that leads to the development of ERC and a mechanism for the demise of inner eyewall that involves interaction between the transverse circulations induced by eyewall and outer rainband convection are proposed. The tangential momentum budget indicates that the net tendency of tangential wind is a small residual resultant from a large cancellation between tendencies induced by the resolved and sub-grid scale (SGS) processes. The large SGS contribution to the tangential wind budget explains different characteristics of ERC shown in previous numerical studies and poses a great challenge for a timely correct forecast of ERC. The sensitivity experiments show that ERCs are strongly subjected to model physics, vortex radial structure and background wind. The impact of model physics on ERC can be well understood with the interaction among eyewall/outer rainband heating, radilal inflow in the boundary layer, surface layer turbulent processes, and shallow convection in the moat. However, further investigations are needed to fully understand the exhibited sensitivities of ERC to vortex radial structure and background wind.

Universal Non-Debye Scaling in the Density of States of Amorphous Solids.

At the jamming transition, amorphous packings are known to display anomalous vibrational modes with a density of states (DOS) that remains constant at low frequency. The scaling of the DOS at higher packing fractions remains, however, unclear. One might expect to find a simple Debye scaling, but recent results from effective medium theory and the exact solution of mean-field models both predict an anomalous, non-Debye scaling. Being mean-field in nature, however, these solutions are only strictly valid in the limit of infinite spatial dimension, and it is unclear what value they have for finite-dimensional systems. Here, we study packings of soft spheres in dimensions 3 through 7 and find, away from jamming, a universal non-Debye scaling of the DOS that is consistent with the mean-field predictions. We also consider how the soft mode participation ratio evolves as dimension increases.

Mechanisms Governing the Eyewall Replacement Cycle in Numerical Simulations of Tropical Cyclones

Eyewall replacement cycle (ERC) is frequently observed during the evolution of intensifying Tropical Cyclones (TCs). Although intensely studied in recent years, the underlying mechanisms of ERC are still poorly understood, and the forecast of ERC remains a great challenge. To advance our understanding of ERC and provide insights in improvement of numerical forecast of ERC, a series of numerical simulations is performed to investigate ERCs in TC-like vortices on a f-plane. The simulated ERCs possess key features similar to those observed in real TCs including the formation of a secondary tangential wind maximum associated with the outer eyewall. The Sawyer-Eliassen equation and tangential momentum budget analyses are performed to diagnose the mechanisms underlying the secondary eyewall formation (SEF) and ERC. Our diagnoses reveal crucial roles of outer rainband heating in governing the formation and development of the secondary tangential wind maximum and demonstrate that the outer rainband convection must reach a critical strength relative to the eyewall before SEF and the subsequent ERC can occur. A positive feedback among low-level convection, acceleration of tangential winds in the boundary layer, and surface evaporation that leads to the development of ERC and a mechanism for the demise of inner eyewall that involves interaction between the transverse circulations induced by eyewall and outer rainband convection are proposed. The tangential momentum budget indicates that the net tendency of tangential wind is a small residual resultant from a large cancellation between tendencies induced by the resolved and sub-grid scale (SGS) processes. The large SGS contribution to the tangential wind budget explains different characteristics of ERC shown in previous numerical studies and poses a great challenge for a timely correct forecast of ERC. The sensitivity experiments show that ERCs are strongly subjected to model physics, vortex radial structure and background wind. The impact of model physics on ERC can be well understood with the interaction among eyewall/outer rainband heating, radilal inflow in the boundary layer, surface layer turbulent processes, and shallow convection in the moat. However, further investigations are needed to fully understand the exhibited sensitivities of ERC to vortex radial structure and background wind.

On the feasibility of time-lapse superconducting gravimetry for reservoir monitoring

The feasibility of monitoring fluid flow subsurface processes that result in density changes, using the iGrav superconducting gravimeter, is investigated. Practical targets include steam-assisted gravity drainage (SAGD) bitumen depletion and water pumping from aquifers, for which there is currently a void in low-impact, inexpensive monitoring techniques. This study demonstrates that the iGrav has the potential to be applied to multi-scale and diverse reservoirs. Gravity and gravity gradient signals are forward modeled for a real SAGD reservoir at two time steps, and for surface-fed and groundwater-fed aquifer pumping models, to estimate signal strength and directional dependency of water flow. Time-lapse gravimetry on small-scale reservoirs exhibits two obstacles, namely, a µgal sensitivity requirement and high noise levels in the vicinity of the reservoir. In this study, both limitations are overcome by proposing (i) a portable superconducting gravimeter, and (ii) a pair of instruments under various baseline geometries. This results in improved spatial resolution for locating depletion zones, as well as the cancellation of noise common in both instruments. Results indicate that a pair of iGrav superconducting gravimeters meet the sensitivity requirements and the spatial focusing desired to monitor SAGD bitumen migration at the reservoir scales. For SAGD reservoirs, the well pair separation, reservoir depth, and survey sampling determine the resolvability of individual well pair depletion patterns during the steam chamber rising phase, and general reservoir depletion patterns during the steam chamber spreading phase. Results show that monitoring water table elevation changes due to pumping and tracking whether groundwater or surface water is being extracted are feasible.

Operating cost based cruise speed reduction for ground delay programs: Effect of scope length

Ground delay programs typically involve the delaying of aircraft that are departing from origin airports within some set distance of a capacity constrained destination airport. Long haul flights are not delayed in this way. A trade-off exists when fixing the distance parameter: increasing the ‘scope’ distributes delay among more aircraft and may reduce airborne holding delay but could also result in unnecessary delay in the (frequently observed) case of early program cancellation. In order to overcome part of this drawback, a fuel based cruise speed reduction strategy aimed at realizing airborne delay, was suggested by the authors in previous publications. By flying slower, at a specific speed, aircraft that are airborne can recover part of their initially assigned delay without incurring extra fuel consumption if the ground delay program is canceled before planned. In this paper, the effect of the scope of the program is assessed when applying this strategy. A case study is presented by analyzing all the ground delay programs that took place at San Francisco, Newark Liberty and Chicago O’Hare International airports during one year. Results show that by the introduction of this technique it is possible to define larger scopes, partially reducing the amount of unrecovered delay.

Cruise Speed Reduction for Ground Delay Programs: A Case Study for San Francisco International Airport Arrivals

Ground Delay Programs (GDP) are sometimes cancelled before their initial planned duration and for this reason aircraft are delayed when it is no longer needed. Recovering this delay usually leads to extra fuel consumption, since the aircraft will typically depart after having absorbed on ground their assigned delay and, therefore, they will need to cruise at more fuel consuming speeds. Past research has proposed speed reduction strategy aiming at splitting the GDP-assigned delay between ground and airborne delay, while using the same fuel as in nominal conditions. Being airborne earlier, an aircraft can speed up to nominal cruise speed and recover part of the GDP delay without incurring extra fuel consumption if the GDP is cancelled earlier than planned. In this paper, all GDP initiatives that occurred in San Francisco International Airport during 2006 are studied and characterised by a K-means algorithm into three different clusters. The centroids for these three clusters have been used to simulate three different GDPs at the airport by using a realistic set of inbound traffic and the Future Air Traffic Management Concepts Evaluation Tool (FACET). The amount of delay that can be recovered using this cruise speed reduction technique, as a function of the GDP cancellation time, has been computed and compared with the delay recovered with the current concept of operations. Simulations have been conducted in calm wind situation and without considering a radius of exemption. Results indicate that when aircraft depart early and fly at the slower speed they can recover additional delays, compared to current operations where all delays are absorbed prior to take-off, in the event the GDP cancels early. There is a variability of extra delay recovered, being more significant, in relative terms, for those GDPs with a relatively low amount of demand exceeding the airport capacity.