A fuel cell is an electrochemical energy conversion device, the continuous-flow analogue of the popular electrochemical storage device known as the battery. While the potential of fuel cells as power sources was recognized well over a century ago, they have since found limited application; a myriad of chemical, engineering and materials issues can be cited for this disappointing showing. Recent growing concern over the fate of the environment, however, has helped to renew interest in fuel cell research. This paper describes the methanol fuel cell and catalytic problems associated with the anode. On this task, the adsorption of carbon monoxide on platinum has been investigated.

The reliability of microelectronic systems is often limited by electromigration failure in Al-based thin-film conducting lines which interconnect devices to form an integrated circuit. Under an applied electric field Al atoms migrate with the electron flow, causing a counterflow of vacancies that accumulate into voids, eventually leading to an open circuit failure. The work reported here is concerned with clarifying the microstructural mechanism of electromigration failure, and with developing a metallurgical method to improve the electromigration resistance of Al-based interconnects. Pure Al, Al-2Cu, and Al-2Cu-1Si lines with quasi-bamboo microstructures are explored as a function of heat treatment conditions and current density. The {open_quotes}weakest{close_quotes} microstructural unit that causes failure is identified by electron microscopy; with rare exceptions, failure occurs at the upstream end of the longest polygranular segment in a given line. This microstructural characteristic of electromigration failure is even observed in lines whose maximum segment lengths are less than a few microns. The time to failure appears to increase exponentially with decreasing longest polygranular segment length. A simple constitutive equation is reported to describe the failure kinetics as a function of the polygranular segment length that leads to failure. Given correct values of the kinetic constants included in the equation, …

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A strong need exists today for more efficient energy-conversion systems. Our reliance on limited fuel resources, such as petroleum for the majority of our energy needs makes it imperative that we utilize these resources as efficiently as possible. Higher-efficiency energy conversion also means less pollution, since less fuel is consumed and less exhaust created for the same energy output. Additionally, for many industrialized nations, such as the United States which must rely on petroleum imports, it is also imperative from a national-security standpoint to reduce the consumption of these precious resources. A substantial reduction of U.S. oil imports would result in a significant reduction of our trade deficit, as well as costly military spending to protect overseas petroleum resources. Therefore, energy-conversion devices which may utilize alternative fuels are also in strong demand. This paper describes research on fuel cells for transportation.

We performed fluorescence spectroscopy of single and pairs of dye molecules on a surface at room temperature. Near field scanning optical microscope (NSOM) and far field scanning optical microscope with multi-color excitation/detection capability were built. The instrument is capable of optical imaging with 100nm resolution and has the sensitivity necessary for single molecule detection. A variety of dynamic events which cannot be observed from an ensemble of molecules is revealed when the molecules are probed one at a time. They include (1) spectral jumps correlated with dark states, (2) individually resolved quantum jumps to and from the meta-stable triplet state, (3) rotational jumps due to desorption/readsorption events of single molecules on the surface. For these studies, a computer controlled optical system which automatically and rapidly locates and performs spectroscopic measurements on single molecules was developed. We also studied the interaction between closely spaced pairs of molecules. In particular, fluorescence resonance energy transfer between a single resonant pair of donor and acceptor molecules was measured. Photodestruction dynamics of the donor or acceptor were used to determine the presence and efficiency of energy transfer Dual molecule spectroscopy was extended to a non-resonant pair of molecules to obtain high resolution differential distance information. …

X-ray spectroscopy has long been used to elucidate electronic and structural information of molecules. One of the weaknesses of x-ray absorption is its sensitivity to all of the atoms of a particular element in a sample. Through out this thesis, a new technique for enhancing the site- and spin-selectivity of the x-ray absorption has been developed. By high resolution fluorescence detection, the chemical sensitivity of K emission spectra can be used to identify oxidation and spin states; it can also be used to facilitate site-selective X-ray Absorption Near Edge Structure (XANES) and site-selective Extended X-ray Absorption Fine Structure (EXAFS). The spin polarization in K fluorescence could be used to generate spin selective XANES or spin-polarized EXAFS, which provides a new measure of the spin density, or the nature of magnetic neighboring atoms. Finally, dramatic line-sharpening effects by the combination of absorption and emission processes allow observation of structure that is normally unobservable. All these unique characters can enormously simplify a complex x-ray spectrum. Applications of this novel technique have generated information from various transition-metal model compounds to metalloproteins. The absorption and emission spectra by high resolution fluorescence detection are interdependent. The ligand field multiplet model has been used for the …

The microstructure - interface - property relationships in nanometer-period x-ray multilayer mirrors (W/C, WC/C, Cr/C, CrC/C, Cu/C, Ru/C, and Ru/B{sub 4}C) were studied using cross-sectional high resolution TEM and x-ray scattering. Microstructural and morphological evolution of as-prepared multilayers, and their behavior under thermal activation were discussed in terms of the materials thermodynamic and kinetic properties. Effects of the microstructural and the morphological evolution in reactive- component (W-C, Cr-C, and Ru-B{sub 4}C) and conjugate-component (Ru-C and Cu-C) multilayers on the normal incidence reflectance and long term stability of the mirrors are presented.

Quantum mechanical methods are developed to describe the dynamics of bimolecular chemical reactions. We focus on developing approaches for directly calculating the desired quantity of interest. Methods for the calculation of single matrix elements of the scattering matrix (S-matrix) and initial state-selected reaction probabilities are presented. This is accomplished by the use of absorbing boundary conditions (ABC) to obtain a localized (L{sup 2}) representation of the outgoing wave scattering Green`s function. This approach enables the efficient calculation of only a single column of the S-matrix with a proportionate savings in effort over the calculation of the entire S-matrix. Applying this method to the calculation of the initial (or final) state-selected reaction probability, a more averaged quantity, requires even less effort than the state-to-state S-matrix elements. It is shown how the same representation of the Green`s function can be effectively applied to the calculation of negative ion photodetachment intensities. Photodetachment spectroscopy of the anion ABC{sup -} can be a very useful method for obtaining detailed information about the neutral ABC potential energy surface, particularly if the ABC{sup -} geometry is similar to the transition state of the neutral ABC. Total and arrangement-selected photodetachment spectra are calculated for the H{sub 3}O{sup -} …

The photodissociation spectroscopy and dynamics of free radicals is studied by the technique of fast beam photofragment translational spectroscopy. Photodetachment of internally cold, mass-selected negative ions produces a clean source of radicals, which are subsequently dissociated and detected. The photofragment yield as a function of photon energy is obtained, mapping out the dissociative and predissociative electronic states of the radical. In addition, the photodissociation dynamics, product branching ratios, and bond energies are probed at fixed photon energies by measuring the translational energy, P(E{sub T}), and angular distribution of the recoiling fragments using a time- and position-sensitive detector. Ab initio calculations are combined with dynamical and statistical models to interpret the observed data. The photodissociation of three prototypical hydrocarbon combustion intermediates forms the core of this work.

The rotational energy release in the dissociation of ketene (CH{sub 2}CO) along its singlet potential energy surface is observed and compared with several statistical and dynamical theories. Rotational distributions for the product, CO(X{sup 1}{Sigma}+)(v=1), are measured from the threshold for production of CH{sub 2}(a {sup 1}A{sub 1}) (0,0,0) + CO(X{sup 1}{Sigma}+)(v=1) to 1720 cm{sup -1} above. Near threshold (E{le} 200 cm{sup -1} over threshold), phase space theory (PST) matches the observed distributions. At 357 and 490 cm{sup -1}, PST constrained by the measured state distributions of the methylene fragment, provides a good fit to these CO(v=1) rotational distributions. For E > 490 cm{sup -1}, the constrained PST matches the average rotational energy observed but predicts distributions which are broader than observed. This contrasts to the rotational distributions of the {sup 1}CH{sub 2} fragment which become shifted to lower rotational states than PST as energy increases from 200 cm{sup -1} above threshold. Dynamical models, the impulsive model and Franck-Condon mapping, do not account for the product rotational state distributions. The CO(v=1) rotational distributions for E > 200 cm{sup -1} contain no measurable product from triplet channel fragmentation. Therefore, they can be compared with the previously determined CO(v=0) rotational distributions in order …

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In this thesis we have developed a simplified spherical harmonic method (SP{sub N} method) and associated efficient solution techniques for 2-D multigroup electron-photon transport calculations. The SP{sub N} method has never before been applied to charged-particle transport. We have performed a first time Fourier analysis of the source iteration scheme and the P{sub 1} diffusion synthetic acceleration (DSA) scheme applied to the 2-D SP{sub N} equations. Our theoretical analyses indicate that the source iteration and P{sub 1} DSA schemes are as effective for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. Previous analyses have indicated that the P{sub 1} DSA scheme is unstable (with sufficiently forward-peaked scattering and sufficiently small absorption) for the 2-D S{sub N} equations, yet is very effective for the 1-D S{sub N} equations. In addition, we have applied an angular multigrid acceleration scheme, and computationally demonstrated that it performs as well for the 2-D SP{sub N} equations as for the 1-D S{sub N} equations. It has previously been shown for 1-D S{sub N} calculations that this scheme is much more effective than the DSA scheme when scattering is highly forward-peaked. We have investigated the applicability of the SP{sub N} approximation to two …

Studies of surface structure and dynamics of atoms and molecules on metal surfaces are presented. My research has focused on understanding the nature of adsorbate-adsorbate and adsorbate-substrate interactions through surface studies of coverage dependency and coadsorption using both scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). The effect of adsorbate coverage on the surface structures of sulfur on Pt(111) and Rh(111) was examined. On Pt(111), sulfur forms p(2x2) at 0.25 ML of sulfur, which transforms into a more compressed ({radical}3x{radical}3)R30{degrees} at 0.33 ML. On both structures, it was found that sulfur adsorbs only in fcc sites. When the coverage of sulfur exceeds 0.33 ML, it formed more complex c({radical}3x7)rect structure with 3 sulfur atoms per unit cell. In this structure, two different adsorption sites for sulfur atoms were observed - two on fcc sites and one on hcp site within the unit cell.

The numerical stability and accuracy of the vortex method are studied. The effect of the ordinary differential equations (ODE) solver and of the time step on the numerical stability is analyzed. Various ODE solvers are compared and a best performer is chosen. A new constraint on the time step based on numerical stability is proposed and verified in numerical simulations. It is shown through numerical examples that empirical rules for selecting the spatial discretization obtained in simple test problems may not be extended to more general problems. The thin tube vortex filament method is applied to the problem of Widnall`s instability on vortex rings. Numerical results different from previous calculations are presented and the source of the discrepancies is explained. The long time behavior of the unstable mode on thin vortex rings is simulated and analyzed. The short wave instability on vortex filaments is investigated both theoretically and numerically. It is shown that the short wave instability always occurs on co-rotating vortex filaments of fixed core structure. Furthermore when they are close to each other, vortex filaments produce short wave unstable modes which lead to wild stretching and folding. However, when the inter-filament distance is large in comparison with the …

High energy particle accelerators are now the primary means of discovering the basic building blocks of matter and understanding the forces between them. In order to minimize the cost of building these machines, superconducting magnets are used in essentially all present day high energy proton and heavy ion colliders. The cost of superconducting magnets is typically in the range of 20--30% of the total cost of building such machines. The circulating particle beam goes through these magnets a large number of times (over hundreds of millions). The luminosity performance and life time of the beam in these machines depends significantly on the field quality in these magnets. Therefore, even a small error in the magnetic field shape may create a large cumulative effect in the beam trajectory to throw the particles of the magnet aperture. The superconducting accelerator magnets must, therefore, be designed and constructed so that these errors are small. In this thesis the research and development work will be described 3which has resulted in significant improvements in the field quality of the superconducting magnets for the Relativistic Heavy Ion Collider (RHIC). The design and the field quality improvements in the prototype of the main collider dipole magnet for …

The field quality in superconducting magnets has been improved to a level that it does not appear to be a limiting factor on the performance of RHIC. The many methods developed, improved and adopted during the course of this work have contributed significantly to that performance. One can not only design and construct magnets with better field quality than in one made before but can also improve on that quality after construction. The relative field error ({Delta}B/B) can now be made as low as a few parts in 10{sup {minus}5} at 2/3 of the coil radius. This is about an order of magnitude better than what is generally expected for superconducting magnets. This extra high field quality is crucial to the luminosity performance of RHIC. The research work described here covers a number of areas which all must be addressed to build the production magnets with a high field quality. The work has been limited to the magnetic design of the cross section which in most cases essentially determines the field quality performance of the whole magnet since these magnets are generally long. Though the conclusions to be presented in this chapter have been discussed at the end of each …

If fusion energy is to achieve its full potential for safety and environmental (S&E) advantages, the S&E characteristics of fusion power plant designs must be quantified and understood, and the resulting insights must be embodied in the ongoing process of development of fusion energy. As part of this task, the present work compares S&E characteristics of five inertial and two magnetic fusion power plant designs. For each design, a set of radiological hazard indices has been calculated with a system of computer codes and data libraries assembled for this purpose. These indices quantify the radiological hazards associated with the operation of fusion power plants with respect to three classes of hazard: accidents, occupational exposure, and waste disposal. The three classes of hazard have been qualitatively integrated to rank the best and worst fusion power plant designs with respect to S&E characteristics. From these rankings, the specific designs, and other S&E trends, design features that result in S&E advantages have been identified. Additionally, key areas for future fusion research have been identified. Specific experiments needed include the investigation of elemental release rates (expanded to include many more materials) and the verification of sequential charged-particle reactions. Improvements to the calculational methodology are …

Many typical chemical engineering operations are multi-fluid systems. They are carried out in distillation columns (vapor/liquid), liquid-liquid contactors (liquid/liquid) and other similar devices. An important parameter is interfacial area concentration, which determines the rate of interfluid heat, mass and momentum transfer and ultimately, the overall performance of the equipment. In many cases, the models for determining interfacial area concentration are empirical and can only describe the cases for which there is experimental data. In an effort to understand multiphase reactors and the mixing process better, a multi-fluid model has been developed as part of a research effort to calculate interfacial area transport in several different types of in-line static mixers. For this work, the ensemble-averaged property conservation equations have been derived for each fluid and for the mixture. These equations were then combined to derive a transport equation for the interfacial area concentration. The final, one-dimensional model was compared to interfacial area concentration data from two sizes of Kenics in-line mixer, two sizes of concurrent jet and a Tee mixer. In all cases, the calculated and experimental data compared well with the highest scatter being with the Tee mixer comparison.

In this thesis we have studied the non-equilibrium phonons in GaAs/AlAs quantum wells via Raman scattering. We have demonstrated experimentally that by taking into account the time-reversal symmetry relation between the Stokes and anti-Stokes Raman cross sections, one can successfully measure the non-equilibrium phonon occupancy in quantum wells. Using this technique, we have studied the subject of resonant intersubband scattering of optical phonons. We find that interface roughness plays an important role in resonant Raman scattering in quantum wells. The lateral size of the smooth regions in such interface is estimated to be of the order of 100 {Angstrom}. Through a study of photoluminescence of GaAs/AlAs quantum wells under high intensity laser excitation, we have found that band nonparabolicity has very little effect on the electron subband energies even for subbands as high as a few hundred meV above the lowest one. This finding may require additional theoretical study to understand its origin. We have also studied phonon confinement and propagation in quantum wells. We show that Raman scattering of non-equilibrium phonons in quantum wells can be a sensitive measure of the spatial extent of the longitudinal optical (LO) phonons. We deduce the coherence length of LO phonons in GaAs/Al{sub …

A study was undertaken to examine permeable zones identified in boreholes open to the underlying basalt and to describe the vertical cross flows present in the boreholes. To understand the permeable zones in the boreholes detailed descriptions and measurements of three outcrops in the Snake River Plain, three cores at the Idaho Chemical Processing Plant (ICPP) at the INEL, and over fifty borehole TV logs from the INEL were carried out. Based on the observations made on the three outcrops an idealized basalt lava flow model was generated that used a set of nomenclature that would be standard for the basalt lava flows studied. An upper vesicular zone, a sometimes absent columnar zone, central zone, and lower vesicular zone make up the basalt lava flow model. The overall distinction between the different zones are based on the vesicle shape size, vesicularity, and fractures present. The results of the studies also indicated that the basalt lava flows at the INEL are distal to medial facies pahoehoe lava flows with close fitting contacts. The most permeable zones identified in these basalts are fractured vesiculated portions of the top of the lava flow, the columnar areas, and basalt-flow contacts in order of importance. …

The interaction between carbide coating formation rates and dissolution kinetics in the tantalum-carbon system was investigated. The research was driven by the need to characterize carbide coating formation rates. The characterization of the carbide coating formation rates was required to engineer an optimum processing scheme for the fabrication of the ultracorrosion-resistant composite, carbon-saturated tantalum. A packed-bed carburization process was successfully engineered and employed. The packed-bed carburization process produced consistent, predictable, and repeatable carbide coatings. A digital imaging analysis measurement process for accurate and consistent measurement of carbide coating thicknesses was developed. A process for removing the chemically stable and extremely hard tantalum-carbide coatings was also developed in this work.

The work presented here evaluates the dynamics of a beam of heavy ions propagating through a chamber filled with gas. The motivation for this research stems from the possibility of using heavy ion beams as a driver in inertial confinement fusion reactors for the purpose of generating electricity. Such a study is important in determining the constraints on the beam which limit its focus to the small radius necessary for the ignition of thermonuclear microexplosions which are the source of fusion energy. Nuclear fusion is the process of combining light nuclei to form heavier ones. One possible fusion reaction combines two isotopes of hydrogen, deuterium and tritium, to form an alpha particle and a neutron, with an accompanying release of {approximately}17.6 MeV of energy. Generating electricity from fusion requires that we create such reactions in an efficient and controlled fashion, and harness the resulting energy. In the inertial confinement fusion (ICF) approach to energy production, a small spherical target, a few millimeters in radius, of deuterium and tritium fuel is compressed so that the density and temperature of the fuel are high enough, {approximately}200 g/cm{sup 3} and {approximately}20 keV, that a substantial number of fusion reactions occur; the pellet microexplosion …

Molybdenum disilicide has been predominantly used for furnace heating elements, but recently there has been interest in its use for high temperature structural applications. The reason for this increased interest stems from its desirable characteristics which are a high melting point, relatively low density, good oxidation resistance, relatively good thermal conductivity and electronically conductive. The melting point of MoSi{sub 2} is approximately 2030{degrees}C as compared to a melting point of 1340{degrees}C for the Ni-based superalloys. This could potentially give MoSi{sub 2} a big advantage over the Ni-based superalloys in turbine applications because the operating temperature can be increased resulting in an increase in turbine efficiency and reduced emissions. The relatively low density (6.25g/cm{sup 3}) compared to the Ni-based superalloys (8.9 g/cm{sup 3}) is an important advantage in turbine applications because of the need for low weight. Good oxidation resistance stems from the ability of MoSi{sub 2} to form a protective SiO{sub 2} surface layer when exposed to oxygen. Another advantageous feature of MoSi{sub 2} is its thermal conductivity which is superior to Ni-based superalloys at low temperatures and comparable to the Ni-based superalloys at high temperatures. This allows heat to be dissipated at a rate better than ceramics and comparable …

Femtosecond lasers are a powerful tool for a wealth of applications in physics, chemistry and biology. In most cases, however, their use is fundamentally restricted to a rather narrow spectral range. This thesis deals with the construction and characterization of a femtosecond light source for spectroscopic applications which overcomes that restriction. It is demonstrated how the output of a continuously pumped Ti:sapphire femtosecond oscillator is amplified to the {mu}J level,while the pulse duration remains below 100 fs. A combination of continuous pumping, acousto-optic switching and Ti:Al{sub 2}O{sub 3} as a gain medium allows amplification at high repetition rates. By focusing the high energy pulses into a sapphire crystal, a broad-band continuum can be generated, extended in wavelengths over several hundred nanometers. To accomplish amplification of three orders of magnitude while maintaining the pulse length, a regenerative multipass amplifier system was built. The thesis describes theoretical design, realization and characterization of the system. Theoretical calculations and preliminary measurements were carried out and allow a critical evaluation of the final performance.