Cette thèse montre comment l'astérosismologie, basée sur l'observation et la modélisation, peut rendre compte de la structure interne d'une étoile naine blanche DAV, notamment comment il est possible de déduire la masse de son enveloppe d'hydrogène résiduel. Nous avons étudié 2 ZZ Ceti: HL Tau 76 (bord rouge de la bande d'instabilité) et G 185-32 (bord bleu). La modélisation indique que ces 2 étoiles possèdent une enveloppe d'hydrogène de masse sensiblement identique: M(H)= 2.0(+/-0.3)x 10e-4 Mstar. Cela suggèrerait une possible constance de la masse de cette enveloppe pour l'ensemble des étoiles DA et par là même d'éventuelles implications pour la cosmochronologie et les mécanismes de l'évolution stellaire. Par ailleurs, cette thèse illustre comment la modélisation permet de révéler certaines caractéristiques physiques comme une rotation de l'étoile non-uniforme, un couplage non-linéaire au sein d'un triplet de modes résonants, une intéraction entre les pulsations et la convection.

<p>A power assisted wheelchair combines human power, which is delivered by the arms through the pushrims, with electrical motors, which are powered by a battery. Today’s electric power assisted wheelchairs use force sensors to measure the torque exerted on the pushrims by the user. The force sensors in the pushrims are rather expensive and this approach also makes the wheels a little bit clumsy. The objective with this project is to find a new, better and cheaper solution that does not use expensive force sensors in the pushrims. The new power assisted wheelchair will instead only rely on its velocity, which is measured with rotational encoders, as feedback signal and thereby the project name “Torque Sensor Free Power Assisted Wheelchair”. </p><p> </p><p>The project consisted of two main parts; an extensive construction part, where an ordinary joystick controlled motorized wheelchair has been rebuild to the new power assisted wheelchair without torque sensors and a development part, where different torque sensor free controllers has been designed, simulated, programmed and tested.</p><p>The project resulted in a torque sensor free power assisted wheelchair, where the final implemented design is a proportional derivative controller, which gives a very good assisting system that is robust and insensitive to measurement noise. The proportional derivative control design gives two adjustable parameters, which can be tuned to fit a certain user; one parameter is used to adjust the amplification of the user’s force and the other one is used to change the lasting time of the propulsion influence.</p><p>Since the new assisting control system only relies on the velocity, the torque sensor free power assisted wheelchair will besides giving the user assisting power also give an assistant, which pushes the wheelchair, additional power. This is a big advantage compared to the pushrim activated one, where this benefit for the assistant is not possible.</p>

Hydropower maintains its position as the most important source of renewable electric energy in the world. The efficiency of large hydropower plants is unsurpassed, and after more than hundred years of development, the technology is mature and highly reliable. While new hydro resources are currently being developed in Asia and South America, most European countries go through a phase of intense refurbishment and upgrading of existing plants. Challenges faced by the hydropower industry include a knowledge transfer to new generations and the adaptation of unit designs to meet new operational requirements. As with all branches of engineering, the use of computerized design tools has revolutionized the art of hydropower plant design and the analysis of its performance. In the present work, modern tools like coupled field-circuit models and semi-analytic permeance models are used to address different aspects of electromagnetic analysis of generators in large hydropower plants. The results include the presentation of a mathematical model that uses concepts from rotating field theory to determine the air-gap flux density waveform in a hydroelectric generator. The model was succesfully used to evaluate armature voltage harmonics and damper bar currents at no-load and load conditions. A second study is concerned with the importance of losses due to rotational fields in core loss calculations. It is found that dynamic and rotational effects typically increase the total core loss estimates with about 28% in large hydroelectric generators. In a third study, linear models for the calculation of salient pole shoe form factors at an arbitrary level of magnetic loading are presented. The effect of the damper winding configuration on the damping capability of salient-pole generators is then evaluated in a separate study. The predicted impact of the coupling between damper cages on adjacent poles on the damping torque production is verified in a set of experiments.

We have studied fundamental aspects of time-resolved two-photon excited fluorescence depolarisation. The thesis presents experimental as well as theoretical progress. We show that a multi-photon induced instrumental response function obtained from a suspension of gold nanoparticles is appropriate for the analysis of two-photon excited fluorescence decays obtained using time-correlated single photon counting detection. Theoretical expressions have been derived for the fluorescence anisotropy decay obtained upon two-photon excitation of various molecular systems in liquid solutions: a) an anisotropic rigid rotor that undergoes rotational diffusion in the presence of ultrafast unresolved restricted reorientations, e.g. librations. b) a molecular group covalently attached to a stationary macromolecule, and undergoing local reorientation in a uniaxial ordering potential. A new approach to the analysis of two-photon excited fluorescence depolarisation experiments was developed, which combines data obtained by using linearly and circularly polarised excitation light, in a global manner. In the analysis, knowledge about unresolved reorientations was obtained from one-photon excitation studies of the corresponding systems. By means of this procedure it has been possible to obtain quantitative information about the molecular two-photon absorption tensor for perylene and two of its derivatives. Thereby the symmetry of the final excited and intermediate vibronic states could be assigned. The analysis reveals that the two-photon transition studied with the 800 nm laser exhibits mixed character. An important finding from the experiments was that the two-photon absorption tensor appears to be solvent dependent. Furthermore, the thesis presents the first theoretical treatment of two-photon excited donor-donor energy migration in the presence of molecular reorientation and which applies the extended Förster theory. Explicit expressions for molecules that belong to the point groups D2h, D2 and C2v are given. Preliminary experiments are finally also reported on a two-photon excited donor-donor energy migration system consisting of a bisanthryl-bisteroid.

Work reported in this thesis mainly comprises of the assignments and analysis of the rotational spectra and structures of three weakly bound complexes: C2H4•••H2S, C6H5CCH•••H2O and C6H5CCH•••H2S. All the data have been collected using a home built Pulsed Nozzle Fourier Transform Microwave Spectrometer. Apart from this, the thesis also deals with a criterion of classifying a weakly bound complex to a ‘hydrogen-bonded’ one. First chapter of the thesis gives a brief intermolecular interactions and molecular clusters of π system. It also briefly touches on the structural determination by rotational spectroscopy and the basic information one can gain from the rotational spectrum. Second chapter of the thesis gives a brief introduction to the experimental and theoretical methodology. It also gives a description of the software used in the FTMW spectrometer which was rebuilt using Labview 7.1. Third chapter of the thesis deals with the rotational spectra and structure of eight isotopologoues of C2H4•••H2S complex. The lines are split into four components for the parent isotopologue due to the presence of large amplitude motion. The smaller splitting is 0.14 MHz and the higher splitting is 1.67 MHz in (B+C)/2 for the parent isotopologue. Spectral splitting pattern of the isotopologues confirmed that smaller splitting is due to the rotation of ethylene about its C-C bond axis along with the contraction of S-H bond whereas the larger motion arises due to the interchange of equivalent hydrogens of H2S in the complex. A detailed spectral analysis and ab initio calculation for this system have been described in chapter III. The fourth chapter of the thesis describes the rotational spectroscopic studies of five isotopologues of C6H5CCH•••H2O complex. Rotational spectra unequivocally confirm the structure of the complex to be a one where H2O is donating one of its hydrogen to the acetylenic π cloud forming a O-H••• π bond whereas the ring ortho C-H bond forms C-H•••O bond with the water oxygen. For theparent isotopomer the lines are split into two components due to the rotation of H2O about its C2 symmetric axis. The fifth chapter of thesis describes the rotational spectroscopic and ab initio studies of five isotopologues of C6H5CCH•••H2S complex. Rotational spectra indicate the structure to be the one where H2S is sitting on the top of the phenyl ring and shifted towards the acetylenic group. The sixth chapter of the thesis describes a criterion for calling a complex to be hydrogen bonded based on the dynamic structure rather than the static structure of the complex. The question asked is if the anisotropy of the interaction is strong enough to hold the ‘hydrogen bond’ when one takes dynamics into account. The proposed criterion is that the zero point energy of the motion which takes the hydrogen away from the acceptor should be much less than the barrier height of the respective motion supporting at least one bound level below the barrier. Ab initio calculations have been done on four model systems Ar2•••H2O, Ar2•••H2S, C2H4••• H2O and C2H4••• H2S to emphasize this criterion.

A power assisted wheelchair combines human power, which is delivered by the arms through the pushrims, with electrical motors, which are powered by a battery. Today’s electric power assisted wheelchairs use force sensors to measure the torque exerted on the pushrims by the user. The force sensors in the pushrims are rather expensive and this approach also makes the wheels a little bit clumsy. The objective with this project is to find a new, better and cheaper solution that does not use expensive force sensors in the pushrims. The new power assisted wheelchair will instead only rely on its velocity, which is measured with rotational encoders, as feedback signal and thereby the project name “Torque Sensor Free Power Assisted Wheelchair”. The project consisted of two main parts; an extensive construction part, where an ordinary joystick controlled motorized wheelchair has been rebuild to the new power assisted wheelchair without torque sensors and a development part, where different torque sensor free controllers has been designed, simulated, programmed and tested. The project resulted in a torque sensor free power assisted wheelchair, where the final implemented design is a proportional derivative controller, which gives a very good assisting system that is robust and insensitive to measurement noise. The proportional derivative control design gives two adjustable parameters, which can be tuned to fit a certain user; one parameter is used to adjust the amplification of the user’s force and the other one is used to change the lasting time of the propulsion influence. Since the new assisting control system only relies on the velocity, the torque sensor free power assisted wheelchair will besides giving the user assisting power also give an assistant, which pushes the wheelchair, additional power. This is a big advantage compared to the pushrim activated one, where this benefit for the assistant is not possible.

Diffusion plays an important role in a number of processes like heterogeneous catalysis, corrosion, separation and purification of chemicals of industrial importance, steel hardening, fuel cells, and solid electrolytes for batteries. It also plays a vital role in several biological processes like transport across biomembranes, nerve impulse, flow of blood and permeation of ingested drug. The elementary process of diffusion in solids is quite different from those in liquids. Similarly, the mode of diffusion in porous solid where different regimes such Knudsen regime exists bears little similarity to those in a dense close-packed crystalline solid. Chapter 1 provides a brief introduction to basics of diffusion in different phases of condensed matter. Among the various phases discussed are liquids, close-packed crystalline solids (e.g., body-centered cubic solids), amorphous solids (e.g. glasses) and microporous crystalline solids (e.g., zeolites). Diffusion in these widely differing phases often bears no resemblance to each other; the rate of diffusion in these phases varies over many orders of magnitude and the elementary step and mechanism in the diffusion process are very different. Brief introduction to theories for diffusion in these phases is provided. Various experimental techniques to measure diffusivities are discussed. Different microscopic models to explain the Quasi Elastic Neutron Scattering (QENS) spectra of these phases yield an insight into the elementary step of the diffusion process. Notwithstanding the fact that completely different models are invoked to explain diffusion in different phases, there are certain underlying generic behaviour across these widely differing phases as the recent work on size dependence of diffusion in these phases demonstrate. Diffusion of a molecule or species (in the context of diffusion within condensed phases) without loss of generality may be said to occur in a medium. A universal behaviour observed is that self diffusivity exhibits a maximum as a function of the size of the diffusant when the diffusant is confined to a medium, as a result of what is known as the Levitation Effect. Such a maximum in self diffusivity has been seen in widely differing medium: microporous solids, dense liquids, ions in polar solvents, etc. The aim of the thesis is to investigate and further explore such universal behaviour and demonstrate for the first time the existence of common trends across different condensed phases in spite of difference in the detail at the microscopic level. In Chapter 2, we report a molecular dynamics study of diffusion of diatomic species AB within zeolite Y. The bond length of A-B as well as the interaction of A and B with the host zeolite atoms are varied. The results demonstrate that for the symmetric case (when A=B or AA), there exists a preferred bond length (determined by the bottleneck or window diameter) when the diffusivity is maximum. This is in agreement with previous results on monatomic species which also exhibit a similar diffusivity maximum. More importantly, no such maximum is seen when the interaction asymmetric is introduced in AB. Slight asymmetry in the interaction gives rise to a weak maximum while large asymmetry in interaction obliterates the diffusivity maximum. These results suggest that the importance of interaction between the diffusant and the medium in Levitation Effect or size-dependent diffusivity maximum. Further, it also demonstrates for the first time the close association between an inversion centre (in a statistical sense and not in the crystallographic sense) and the Levitation Effect. In Chapter 3, a study of size dependence of solutes in a Lennard-Jones liquid is reported. Einstein and others derived the reciprocal dependence of the self-diffusivity D on the solute radius ru for large solutes based on kinetic theory. We examine here (a) the range of ru over which Stokes-Einstein (SE) dependence is valid and (b) the precise dependence for small solutes outside of the SE regime. We show through molecular dynamics simulations that there are two distinct regimes for smaller solutes: (i) the interaction or Levitation Effect (LE) regime for solutes of intermediate sizes and (ii) the D 1/ru2 for still smaller solutes. We show that as the solute-solvent size ratio decreases, the breakdown in the Stokes-Einstein relationship leading to the LE regime has its origin in dispersion interaction between the solute and the solvent. These results explain reports of enhanced solute diffusion in solvents existing in the literature seen for small solutes for which no explanation exists. Several properties have been computed to understand the nature of solute motion in different regimes. We investigate in Chapter 4, the dependence of self diffusivity on the size of the diffusant in a disordered medium with the objective of understanding the experimentally observed correlation between self diffusivity and activation energy seen in a wide variety of glasses. Typically, it is found in many ionic glasses that a higher conductivity is associated with lower activation energy and vice versa. Our understanding of transport in glasses as provided by existing theories does not offer an explanation of this correlation. We have carried out molecular dynamics simulation as a function of the size of the impurity atom or diffusant (both neutral and charged) in a model host amorphous matrix. We find that there is a maximum in self diffusivity as a function of the size of the impurity atom suggesting that there is an appropriate size for which the diffusivity is maximum. The activation energy is found to be the lowest for this size of the impurity. A similar maximum has previously been found in other condensed phases such as confined fluids and dense liquids and has its origin in the Levitation Effect. The implications of this result for understanding ionic conductivity in glasses are discussed. Our result suggests that there is a relation between microscopic structure of the amorphous solid, diffusivity or conductivity and activation energy. The nature of this relationship is discussed in terms of the Levitation parameter showing that diffusivity is maximum when the size of the neck or doorway radius is comparable with the size of the diffusant. Our computational results here are in excellent agreement with independent experimental results which show that structural features of the glass are important in determining the ionic conductivity. In Chapter 5, we report results of molecular dynamics investigations into neutral impurity diffusing within an amorphous solid as a function of the size of the diffusant and density of the host amorphous matrix. We find that self diffusivity exhibits an anomalous maximum as a function of the size of the impurity species. An analysis of properties of the impurity atom with maximum diffusivity shows that it is associated with lower mean square force, reduced backscattering of velocity autocorrelation function, near-exponential decay of the intermediate scattering function (as compared to stretched-exponential decay for other sizes of the impurity species) and lower activation energy. These results demonstrate the existence of well known size-dependent diffusivity maximum in disordered solids. Further, we show that the diffusivity maximum is observed at lower impurity diameters with increase in density. This is explained in terms of the levitation parameter and the void structure of the amorphous solid. We demonstrate that these results imply contrasting dependence of self diffusivity (D) on the density of the amorphous matrix, . D increases with  for small sizes of the impurity but shows an increase followed by a decrease for intermediate sizes of the impurity atom. For large sizes of the impurity atom, D decreases with increase in . These contrasting dependence arises naturally from the existence of Levitation Effect. In Chapter 6, we discuss size dependence of impurity diffusion in an ordered system. We report molecular dynamics simulation studies to understand the role of impurity size and impurity-host interaction on impurity diffusivity in a body centered cubic solid. The simulation studies have been performed for a set of impurity-host interaction parameter ih (i=impurity, h=host atom) for a range of impurity sizes in rigid and flexible bcc solids. A double maximum is seen corresponding to two different sizes of the impurity species. Anomalous maximum is seen for a larger size of the impurity species in the case of the rigid host as compared to flexible host. The second anomalous diffusivity disappears with decrease in ih in flexible bcc solid. For one of the ih where double diffusivity maxima are observed, various properties are analysed to understand the anomalous diffusion behaviour. The impurity with anomalous diffusion has lower activation energy as compared to other impurities. Among the two anomalous impurities, the impurity with higher diffusivity has lower activation energy. The anomalous regime impurities as associated with velocity autocorrelation function with little or no backscattering, minimum average mean square force due to host atoms, lower activation energy. The self intermediate scattering function shows faster decay and a single relaxation time for anomalous regime impurity and two relaxation times for other impurity sizes. The wavenumber dependence of diffusivity of impurities shows oscillatory behaviour except for the anomalous regime impurities which show monotonic dependence on wavenumber. Chapter 7 discusses the influence of temperature induced solid-liquid phase transition on the size-dependent diffusivity. We report results for two distinct cases: (a) when the phase change is associated with corresponding changes in density and (b) when the phase change occurs at constant density. The latter is carried out so as to obtain the influence of disorder on the size-dependent diffusion or Levitation Effect. Studies with variable density are useful to understand the effect of disorder as well as change in density on size-dependent diffusivity. Two diffusivity maxima in the solid face-centred cubic phase is seen when the impurity-medium interaction is sufficiently large. One of these diffusivity maximum disappears with decrease in h. The impurities near the diffusivity maximum show velocity autocorrelation function with little backscattering, minimum in the average mean square force, lower activation energy, faster decay of self intermediate scattering function with a single relaxation time and a monotonic decay in wavevector dependence of diffusivity. Chapter 8 reports molecular dynamics simulations of a model guest tetrahedral molecule AX4 with differing bond lengths lAX have been carried out in a sphere with different surface roughness. The rotational-diffusion coefficient Dr shows a maximum for a particular value of lAX. This corresponds to the distance at which the interaction of the guest with the atoms of the host is most favourable. Although, the intensity of the maximum decreases with increase in the roughness of the confining surface, it is seen that the maximum exists even for a reasonably high degree of roughness. The observed maximum arises from the minimum in the torque on the tetrahedral molecule from its interaction with the confining medium due to mutual cancellation of forces. Activation energy for rotation is seen to be also a minimum for the bond length for which Dr is a maximum. These results suggest that there is a maximum in the rotational-diffusion coefficient when the rotating molecule is confined to a sphere of comparable size similar to the maximum in translational diffusion coefficient seen in porous solids and known as the Levitation Effect. On increase in the roughness of the sphere surface, the value of lAX at which the maximum in Dr is seen decreases. This is similar to the shift seen in the size of the diffusant corresponding to maximum diffusivity in the case of translational diffusivity. In Chapter 9 possible extensions to the work reported in the previous chapters and the directions to take are discussed. Symmetry plays an important role in size dependent diffusivity maximum in microporous crystalline solids; it would be interesting to investigate if similar role of symmetry exists in case of liquids and other disordered solids. Previous work from this laboratory on ions in water has shown the importance of electrostatic interactions. In the light of this, it would be interesting to see the influence of long-range interactions in breakdown of Stokes-Einstein relationship in liquids. Effect of density of the medium on impurity diffusion can be studied over a wide range of densities in case of supercritical fluids such as ions in water (where electrostatic interactions are present) and these can provide greater insight into dependence of diffusion on density. The origin of two diffusivity maxima in case of body-centered and face-centred cubic solids needs a detailed investigation to understand its origin. Quantification of disorder and its effect on size dependence of diffusion would be of interest. A detailed comparison with experimental data of matrix isolated molecules to understand and verify the dependence of rotational diffusivity on the size of the molecule as well as the cavity radius would be instructive.

No description available.

A grazing trial investigating the effect of season of grazing and stocking rate initiated at the Nortier Experimental Farm in 1988 provided an opportunity to assess the response of the veld to both grazing and environmental influences in an arid environment. The trial allowed an assessment of the relative influence of internal (equilibrium) and external (non-equilibrium) forces on the dynamics of an arid rangeland. This study involved the analysis of a nine year data set stretching from 1988 to 1996 and served to provide evidence supporting the existence of an equilibrium/non-equilibrium continuum in rangeland dynamics. The most significant implication of this result is that rangeland systems should not be classified as either equilibrial or non-equilibrial, but rather according to a continuum extending between equilibrium and non-equilibrium poles. The exact position of any system on this continuum is a function of the relative influence of internal and external forces on its species dynamics. The dynamics of the veld at the Nortier Experimental Farm showed significant response to both grazing and environmental variables suggesting conformity to both equilibrial and non-equilibrial paradigms. Both ordination and analysis of variance highlighted the importance of rainfall particularly in the fluctuations of the predominant grass species, Ehrharta calycina, which increased in abundance with rainfall. Partial ordination enabled the assessment of species variation following the removal of variation associated with rainfalL Partial ordinations revealed the gradual, directional movement of samples through multivariate space in response to grazing treatments. Individual plant species were also shown to be responding to grazing, the extent of which was influenced by season of grazing and stocking rate. Both the partial ordinations and the ANOVA showed Melothria sp., Tetragonia fruiticosa and Hermannia scordifolia as increasing and Ruschia caroli as decreasing in absolute abundance in response to grazing. Season of grazing was shown to significantly influence the abundance of H. scordifolia over time. The 'shrublherb complex', which constitutes the 'key resource' at the Nortier Experimental Farm displayed an increase in absolute abundance over the duration of the trial. This increase in absolute abundance was accompanied by an increase in the relative abundance of the palatable component of this resource. The application of medium to heavy stocking rates during spring, summer and autumn and low stocking rates during winter resulted in elevated absolute abundances of palatable plants. Furthermore, low stocking rates, when averaged across all season of grazing treatments, resulted in a significantly higher absolute abundance of unpalatable plants. These findings provide the basis for the development of management principles for the Strandveld Vegetation Type. The application of medium to heavy stocking rates within a rotational grazing system, as recommended by the literature dealing with grazing systems in the Karoo, is supported by the results of the Nortier grazing trial. Medium to heavy stocking rates should be applied during spring, summer and autumn and low stocking rates during the winter months. Furthermore, it is recommended that rests of between 12 and 14 months should be afforded to portions of the veld periodically due to the variability in growth, flowering and fruiting times ofdifferent plants in the Karoo. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2005.

The three dimensional Monte Carlo radiation transport model McArtim is extended to account for the simulation of the propagation of polarized radiation and the inelastic rotational Raman scattering which is the cause of the so called Ring effect. From the achieved and now sufficient precision of the calculated Ring effect new opportunities in optical absorption spectroscopy arise. In the calculation the method of importance sampling (IS) is applied. Thereby one obtains from an ensemble of Monte Carlo photon trajectories an intensity accounting for the elastic aerosol particle-, Cabannes- and the inelastic rotational Raman scattering (RRS) and simultaneously an intensity, for which Rayleigh scattering is treated as an elastic scattering process. By combining both intensities one obtains the so called filling-in (FI, which quantifies the filling-in of Fraunhofer lines) as a measure for the strength of the Ring effect with the same relative precision as the intensities. The validation of the polarized radiometric quantities and the Ring effect is made by comparison with partially published results of other radiation transport models. Furthermore the concept of discretisation of the optical domain into grid cells is extended by making grid cells arbitrarily joining into so called clusters, i.e. grid cell aggregates. Therewith the program is able to calculate derivatives of radiometrically or spectroscopically accessible quantities, namely the intensities at certain locations in the atmospheric radiation field and the light path integrals of trace gas concentrations associated thereto, i.e. the product of the DOAS (differential optical absorption spectroscopy) method, with respect to optical properties of aerosols and gases in connected spatial regions. The first and second order derivatives are validated through so called self-consistency tests. These derivatives allow the inversion of three dimensional tracegas and aerosol concentration profiles and pave the way down to 3D optical scattered light tomography. If such tomographic inversion scheme is based solely on spectral intensitites the available second order derivatives allows the consideration of the curvature in the cost function and therefore allows implementation of efficient optimisation algorithms. The influence of the instrument function on the spectra is analysed in order to mathematically assess the potential of DOAS to a sufficient degree. It turns out that the detailed knowledge of the instrument function is required for an advanced spectral analysis. Concludingly the mathematical separability of narrow band signatures of absorption and the Ring effect from the relatively broad band influence of the elastic scattering processes on the spectra is demonstrated which corresponds exactly to the DOAS principle. In that procedure the differential signal is obtained by approximately 4 orders of magnitude faster then by the separate modelling with and without narrow band structures. Thereby the fusion of the separated steps DOAS spectral analysis and subsequent radiation transport modeling becomes computationally feasible.