I. Thermochemistry and reaction kinetics of disolvated protons by ion cyclotron resonance spectroscopy. II. Thermochemical studies of small fluorocarbons by photoionization mass spectrometry

The disolvated proton, H(OH₂)₂⁺ is employed as a chemical reagent in low pressure (˂ 10^-5 torr) investigations by ion cyclotron resonance spectroscopy. Since termolecular reactions are absent at low pressure, disolvated protons are not generally observed. However H(OH₂)₂⁺ is produced in a sequence of bimolecular reactions in mixtures containing H₂O and one of a small number of organohalide precursors. Then a series of hydrated Lewis bases is produced by H₃O⁺ transfer from H(OH₂)₂⁺. In Chapter II, the relative stability of hydrated bases containing heteroatoms of both first and second row elements is determined from the preferred direction of H₃O⁺ transfer between BH(OH₂)⁺ complexes. S and P containing bases are shown to bind H₃O⁺ more weakly than O and N bases with comparable proton affinities. A simple model of hydrogen bonding is proposed to account for these observations.

H⁺ transfer from H(OH₂)₂⁺ to several Lewis bases also occurs at low pressure. In Chapter III the relative importance of H₃O⁺ transfer and H⁺ transfer from H(OH₂)₂⁺ to a series of bases is observed to be a function of base strength. Beginning with CH₃COOH, the weakest base for which H⁺ transfer is observed, the importance of H⁺ transfer increases with increasing proton affinity of the acceptor base. The nature of neutral products formed from H(OH₂)₂⁺ by loss of H⁺ is also considered.

Chapters IV and V deal with thermochemistry of small fluorocarbons determined by photoionization mass spectrometry. The enthalpy of formation of CF₂ is considered in Chapter IV. Photoionization of perfluoropropylene, perfluorocyclopropane, and trifluoromethyl benzene yield onsets for ions formed by loss of a CF₂ neutral fragment. Earlier determinations of ΔH^°_f298 (CF₂) are reinterpreted using updated thermochemical values and compared with results of this study. The heat of formation of neutral perfluorocyclopropane is also derived. Finally, the energetics of interconversion of perfluoropropylene and perfluorocyclopropane are considered for both the neutrals and their molecular ions.

In Chapter V the heats of formation of CF₃⁺ and CF₃I⁺are derived from photoionization of CF₃I. These are considered with respect to ion-molecule reactions observed in CF₃I monitored by the techniques of ion cyclotron resonance spectroscopy. Results obtained in previous experiments are also compared.

Experimental, Numerical and Analytical Studies of the MHD-driven plasma jet, instabilities and waves

This thesis describes a series of experimental, numerical, and analytical studies involving the Caltech magnetohydrodynamically (MHD)-driven plasma jet experiment. The plasma jet is created via a capacitor discharge that powers a magnetized coaxial planar electrodes system. The jet is collimated and accelerated by the MHD forces.

We present three-dimensional ideal MHD finite-volume simulations of the plasma jet experiment using an astrophysical magnetic tower as the baseline model. A compact magnetic energy/helicity injection is exploited in the simulation analogous to both the experiment and to astrophysical situations. Detailed analysis provides a comprehensive description of the interplay of magnetic force, pressure, and flow effects. We delineate both the jet structure and the transition process that converts the injected magnetic energy to other forms.

When the experimental jet is sufficiently long, it undergoes a global kink instability and then a secondary local Rayleigh-Taylor instability caused by lateral acceleration of the kink instability. We present an MHD theory of the Rayleigh-Taylor instability on the cylindrical surface of a plasma flux rope in the presence of a lateral external gravity. The Rayleigh-Taylor instability is found to couple to the classic current-driven instability, resulting in a new type of hybrid instability. The coupled instability, produced by combination of helical magnetic field, curvature of the cylindrical geometry, and lateral gravity, is fundamentally different from the classic magnetic Rayleigh-Taylor instability occurring at a two-dimensional planar interface.

In the experiment, this instability cascade from macro-scale to micro-scale eventually leads to the failure of MHD. When the Rayleigh-Taylor instability becomes nonlinear, it compresses and pinches the plasma jet to a scale smaller than the ion skin depth and triggers a fast magnetic reconnection. We built a specially designed high-speed 3D magnetic probe and successfully detected the high frequency magnetic fluctuations of broadband whistler waves associated with the fast reconnection. The magnetic fluctuations exhibit power-law spectra. The magnetic components of single-frequency whistler waves are found to be circularly polarized regardless of the angle between the wave propagation direction and the background magnetic field.

Effects produced in GaAs by MeV ion bombardment

Presented in the first part of this thesis is work performed on the ionizing energy beam induced adhesion enhancement of thin (~ 500 Angstrom) Au films on GaAs substrates. The ionizing beam, employed in the present thesis, is the MeV ions (i.e., ¹⁶O, ¹⁹F, and ³⁵Cl), with energies between 1 and 20 MeV. Using the "Scratch" test for adhesion measurement, and ESCA for chemical analysis of the film-substrate interface, the native oxide layer at the interface is shown to play an important role in the adhesion enhancement by the ionizing radiation. A model is discussed which explains the experimental data on the the dependence of adhesion enhancement on the energy which was deposited into electronic processes at the interface. The ESCA data indicate that the chemical bonds (or compounds), which are responsible for the increase in the thin film adherence, are hydroxides rather than oxides.

In the second part of the thesis we present a research performed on the radiation damage in GaAs crystals produced by MeV ions. Lattice parameter dilatation in the surface layers of the GaAs crystals becomes saturated after a high dose bombardment at room temperature. The strain produced by nuclear collisions is shown to relax partially due to electronic excitation (with a functional dependence on the nuclear and electronic stopping power of bombarding ions). Data on the GaAs and GaP crystals suggest that low temperature recovery stage defects produce major crystal distortion. The x-ray rocking curve technique with a dynamical diffraction theory analysis provides the depth distribution of the strain and damage in the MeV ion bombarded crystals.

High energy heavy ion induced enhanced adhesion

The work described in this thesis represents an attempt to summarize to date the information collected on the process of high energy heavy ion induced enhanced adhesion. Briefly, the process involves the irradiation of materials covered by thin (≾3μm) films with high energy (E > 200 keV I nucleon) heavy ion beams (such as Fluorine or Chlorine). Enhanced adhesion has been observed on all material combinations tested, including metal on metal, metal on semiconductor, metal on dielectric and dielectric on dielectric systems. In some cases, the enhancement can be quite large, so that a film that could be wiped off a substrate quite easily before irradiation can withstand determined scrubbing afterwards.

Very little is understood yet about this adhesion mechanism, so what is presented are primarily observations about systems studied, and descriptions of the actual preparation and irradiation of samples used. Some discussion is presented about mechanisms that have been considered but rejected.

I. Nuclear magnetic resonance analysis of ferrocenylcarbonium ion. II. Ferrocene catalyzed photochemistry

I. Nuclear magnetic resonance spectra of appropriately substituted ferrocenylcarbonium ions reveal the α-protons of the substituted ring to be more shielded than β-protons. The observation is discussed in terms of various models proposed for the ferrocenylcarbonium ion and is found to support a model in which the iron is bonded to all six carbona of the substituted ring.

II. Ferrocene catalyzes the photoisomerization of the piperylenes and the photodimerization of isoprene. Our results suggest a mechanism in which a complex of ferrocene and diene is excited to its second singlet state which dissociates to a triplet-state ferrocene molecule and a triplet-state diene molecule. The triplet-state diene, then, proceeds to isomerize or attack ground-state diene to form dimers.

Oxygen flux through salmonid spawning gravels

Laboratory and field studies have shown that the survival of salmonid fish eggs and alevins is dependent upon the supply rate or flux of dissolved oxygen through gravel beds used for spawning. Although there have been a number of studies concerned with North American species there are few data for Atlantic salmon (Salmo salar) and the brown trout (S. trutta). For this study intragravel seepage velocities and dissolved oxygen concentrations have been measured throughout the incubation period in spawning gravels utilized by brown trout (Salmo trutta). Variation in the hatching success of batches of trout and salmon (Salmo salar) can, in part, be attributed to a critical threshold of oxygen flux through the gravels.

Processo de separação por membranas para remoção de sulfato de níquel e zinco de efluente sintético de indústrias metal-mecânicas

O objetivo do presente trabalho foi investigar o desempenho de membranas comerciais e funcionalizadas na remoção de metais pesados de efluentes sintéticos, simulando os efluentes gerados pelas indústrias metal-mecânicas. As membranas funcionalizadas foram preparadas em laboratório a partir de diferentes poli (éter imidas) sulfonadas, SPEI, que apresentavam alta hidrofilicidade e capacidade de troca iônica. As permeabilidades hidráulicas das membranas de SPEI aumentaram com o grau de sulfonação. Porém, as rejeições foram ainda muito baixas comparadas as membranas comerciais. Por esta razão, algumas membranas comerciais (NF-90, SW30, HRP98PP e BW30LE) foram investigadas e avaliadas quanto ao comportamento da permeabilidade de água e o grau de rejeição a metais pesados. Os resultados mostraram que a membrana de osmose inversa de baixa energia (BW30LE) tinha o melhor fluxo de água (48,44 L/h.m2) e grau de rejeição a cádmio (98%). Logo, ela foi selecionada para o tratamento dos efluentes sintéticos de indústrias metal-mecânicas contendo níquel e zinco. As indústrias da região de Valencia, na Espanha, forneceram amostras de seus efluentes para análise quantitativa, possibilitando o prepararo de soluções sintéticas modelos. Os resultados foram obtidos variando algumas condições de permeação, tais como a força motriz, o pH e a concentração dos metais na solução de alimentação. Os resultados indicaram que o processo de osmose inversa com a membrana BW30LE é altamente adequado para o tratamento de efluentes contendo metais pesados

Topology optimization of silicon anode structures for lithium-ion battery applications

This thesis presents a topology optimization methodology for the systematic design of optimal multifunctional silicon anode structures in lithium-ion batteries. In order to develop next generation high performance lithium-ion batteries, key design challenges relating to the silicon anode structure must be addressed, namely the lithiation-induced mechanical degradation and the low intrinsic electrical conductivity of silicon. As such, this work considers two design objectives of minimum compliance under design dependent volume expansion, and maximum electrical conduction through the structure, both of which are subject to a constraint on material volume. Density-based topology optimization methods are employed in conjunction with regularization techniques, a continuation scheme, and mathematical programming methods. The objectives are first considered individually, during which the iteration history, mesh independence, and influence of prescribed volume fraction and minimum length scale are investigated. The methodology is subsequently extended to a bi-objective formulation to simultaneously address both the compliance and conduction design criteria. A weighting method is used to derive the Pareto fronts, which demonstrate a clear trade-off between the competing design objectives. Furthermore, a systematic parameter study is undertaken to determine the influence of the prescribed volume fraction and minimum length scale on the optimal combined topologies. The developments presented in this work provide a foundation for the informed design and development of silicon anode structures for high performance lithium-ion batteries.

Study of ion movements in isolated chicken retinas during spreading depression

Spreading depression (SD) is a phenomenon observed in several sections of vertebrate central nervous system. It can occur spontaneously or be evoked by a variety of stimuli, and consists of a wave of depression of the normal electrical activity of the nervous tissue which spreads slowly in all directions in the tissue. This wave of depression is accompanied by several concomitants including ion movements. All the concomitants of SD can be explained by an increase in the sodium permeability of the plasma membranes of cellular elements involved in this phenomenon.

In the chicken retina, SD is accompanied by a transparency change which can be detected with the naked eye. The isolated retina is a thin (0.1 mm) membrane in which the extracellular fluid quickly and completely equilibrates with the incubation solutions. This preparation was therefore used to study the ion movements during SD by measuring and comparing the ion contents and the extracellular space (ECS) of retinas incubated in various solutions of which some inhibited SD, whereas others allowed this phenomenon to occur.

The present study has shown that during SD there is a shift of extracellular sodium into the intracellular compartment of the retina, a release of intracellular K and a decrease in the magnitude of ECS. These results are in agreement with previous postulates about SD, although the in vitro experimental condition makes the ion movements appear larger and the loss of ECS smaller than observed in the intact cortical tissue. The movements of Na and K, in opposite directions, are reversible. The development and magnitudes of SD is very little affected by deprivation of the oxygen supply.

It was established that the inward sodium shift is not a consequence of an arrest of the Na-pump. It can be prevented, together with SD by the membrane stabilizers, magnesium and procaine. Spreading depression and the ion movements are incompletely inhibited by tetrodotoxin, which blocks the sodium influx into nerve fibers during the action potential. The replacement of Na in the bathing solution by Li does not prevent SD, which is accompanied by Li accumulation in the intracellular compartment. From these experiments and others it was concluded that the mechanism underlying SD and the ion shifts is an increase in the sodium permeability of cell membranes.