Experimentation validated a simple moisture conditioning scheme to prepare Gr/Ep composite parts for precision applications by measuring dimensional changes over 90 days. It was shown that an elevated temperature moisture conditioning scheme produced a dimensionally stable part from which precision structures could be built/machined without significant moisture induced dimensional changes after fabrication. Conversely, that unconditioned Gr/Ep composite panels exhibited unacceptably large dimensional changes (i.e., greater than 125 ppM). It was also shown that time required to produce stable parts was shorter, by more than an order of magnitude, employing the conditioning scheme than using no conditioning scheme (46 days versus 1000+ days). Two final use environments were chosen for the experiments: 50% RH/21C and 0% RH/21C. Fiberite 3034K was chosen for its widespread use in aerospace applications. Two typical lay-ups were chosen, one with low sensitivity to hygrothermal distortions and the other high sensitivity: [0, {plus_minus} 45, 90]s, [0, {plus_minus} 15, 0]s. By employing an elevated temperature, constant humidity conditioning scheme, test panels achieved an equilibrium moisture content in less time, by more than an order of magnitude, than panels exposed to the same humidity environment and ambient temperature. Dimensional changes, over 90 days, were up to 4 times lower …

One of the key engineered barriers in the design of the proposed Yucca Mountain repository is the waste canister that encapsulates the spent fuel elements. Current candidate metals for the canisters to be emplaced at Yucca Mountain include cast iron, carbon steel, Incoloy 825 and titanium code-12. This project was designed to evaluate passive electrochemical noise techniques for measuring pitting and corrosion characteristics of candidate materials under prototypical repository conditions. Experimental techniques were also developed and optimized for measurements in a radiation environment. These techniques provide a new method for understanding material response to environmental effects (i.e., gamma radiation, temperature, solution chemistry) through the measurement of electrochemical noise generated during the corrosion of the metal surface. In addition, because of the passive nature of the measurement the technique could offer a means of in-situ monitoring of barrier performance.

Results of this thesis show that STM measurements can provide information about the surfaces and their adsorbates. Stability of Pt(110) under high pressures of H2, O2, and CO was studied (Chap. 4). In situ UHV and high vacuum experiments were carried out for sulfur on Pt(111) (Chap.5). STM studies of CO/S/Pt(111) in high CO pressures showed that the Pt substrate undergoes a stacking-fault-domain reconstruction involving periodic transitions from fcc to hcp stacking of top-layer atoms (Chap.6). In Chap.7, the stability of propylene on Pt(111) and the decomposition products were studied in situ with the HPSTM. Finally, in Chap.8, results are presented which show how the Pt tip of the HPSTM was used to locally rehydrogenate and oxidize carbonaceous clusters deposited on the Pt(111) surface; the Pt tip acted as a catalyst after activation by short voltage pulses.

We have measured and assigned rate constants for energy transfer between chromophores in the light-harvesting protein C-phycocyanin (PC), in the monomeric and trimeric aggregation states, isolated from Synechococcus sp. PCC 7002. In order to compare the measured rate constants with those predicted by Fdrster`s theory of inductive resonance in the weak coupling limit, we have experimentally resolved several properties of the three chromophore types ({beta}{sub 155} {alpha}{sub 84}, {beta}{sub 84}) found in PC monomers, including absorption and fluorescence spectra, extinction coefficients, fluorescence quantum yields, and fluorescence lifetimes. The cpcB/C155S mutant, whose PC is missing the {beta}{sub 155} chromophore, was, useful in effecting the resolution of the chromophore properties and in assigning the experimentally observed rate constants for energy transfer to specific pathways.

A twenty barrel hydrogen pellet injector has been designed, built and tested both in the laboratory and on the Alcator C-Mod Tokamak at MIT. The injector functions by firing pellets of frozen hydrogen or deuterium deep into the plasma discharge for the purpose of fueling the plasma, modifying the density profile and increasing the global energy confinement time. The design goals of the injector are: (1) Operational flexibility, (2) High reliability, (3) Remote operation with minimal maintenance. These requirements have lead to a single stage, pipe gun design with twenty barrels. Pellets are formed by in- situ condensation of the fuel gas, thus avoiding moving parts at cryogenic temperatures. The injector is the first to dispense with the need for cryogenic fluids and instead uses a closed cycle refrigerator to cool the thermal system components. The twenty barrels of the injector produce pellets of four different size groups and allow for a high degree of flexibility in fueling experiments. Operation of the injector is under PLC control allowing for remote operation, interlocked safety features and automated pellet manufacturing. The injector has been extrusively tested and shown to produce pellets reliably with velocities up to 1400 m/sec. During the period from …

Thousands of wildland firefighters are exposed to high levels of toxic materials every year. Carbon monoxide, formaldehyde and acrolein gases, along with high particulate concentrations, are the major toxics encountered. Currently, the only respiratory protection wildland firefighters use is a bandanna over the mouth and nose. In this study, a modem activated carbon cartridge with an electrostatic prefilter was compared to a typical bandanna for its ability to filter wildland smoke toxics such as formaldehyde and particulates. The results of the tests were disappointing; neither filter performed very well. The activated carbon cartridge and prefilter efficiently collected formaldehyde gas for up to 60 minutes; however, it only collected 85 percent of the challenge particulate. ]Me bandanna, as expected, was only partially effective at collecting smoke particulate and filtered no toxic gases.

Mechanisms and associated energetics for adatom diffusion on the (100) and (110) surfaces of Ni, Cu, Rh, Pd, and Ag are investigated. Self-diffusion was studied on (100) and (I 10) surfaces of Ni, Cu, Pd and Ag using corrected effective medium method (CEM) and approximation to CEM used for molecular dynamics and Monte Carlo studies (MD/MC-CEM). Self-diffusion on Pd(100), Ag(100), Ni(110), Cu(110), Pd(110), and Ag(110) is accomplished by classical diffusion: the adatom hops from its equilibrium adsorption site over an intervening bridge site to an adjacent equilibrium site. Self-diffusion on Ni(100) and Cu(100) proceeds by atomic-exchange diffusion: the adatom on the surface displaces an atom in the first surface layer. Aside from explicit inclusion of the kinetic-exchange-correlation energy, it is critical to include enough movable atoms in the calculation to insure correct energetics. Distortions induced by these diffusion mechanisms, especially atomic exchange, are long ranged in surface plane, owing to small distortions of many atoms being energetically favored over large distortions of few atoms. Energetics and rates of heterogeneous adatom diffusion on the (100) surfaces of Ni, Cu, Rh, Pd, and Ag show that the final state energies differ due to variation of metallic bonding with coordination for different types …

This thesis contains the results of organometallic studies of thiophene and selenophene coordination in transition metal complexes. Chromium tricarbonyl complexes of thiophene, selenophene, and their alkyl-substituted derivatives were prepared and variable-temperature {sup 13}C NMR spectra of these complexes were recorded in dimethyl ether. Bandshape analyses of these spectra yielded activation parameters for restricted rotation of the thiophene and selenophene ligands in these complexes. Extended Hueckel molecular orbital calculations (EHMO) of the free thiophene and selenophene ligands and selected chromium tricarbonyl thiophene complexes were performed to better explain the activation barriers of these complexes. The structure of Cr(CO){sub 3}({eta}{sup 5}-2,5-dimethylthiophene) was established by a single crystal X-ray diffraction study.

The nature of fast electron generation and transport in the Madison Symmetric Torus (MST) reversed field pinch (RFP) is investigated using two electron energy analyzer (EEA) probes and a thermocouple calorimeter. The parallel velocity distribution of the fast electron population is well fit by a drifted Maxwellian distribution with temperature of about 100 eV and drift velocity of about 2 {times} 10{sup 6} m/s. Cross-calibration of the EEA with the calorimeter provides a measurement of the fast electron perpendicular temperature of 30 eV, much lower than the parallel temperature, and is evidence that the kinetic dynamo mechanism (KDT) is not operative in MST. The fast electron current is found to match to the parallel current at the edge, and the fast electron density is about 4 {times} 10{sup 11} cm{sup {minus}3} independent of the ratio of the applied toroidal electric field to the critical electric field for runaways. First time measurements of magnetic fluctuation induced particle transport are reported. By correlating electron current fluctuations with radial magnetic fluctuations the transported flux of electrons is found to be negligible outside r/a{approximately}0.9, but rises the level of the expected total particle losses inside r/a{approximately}0.85. A comparison of the measured diffusion coefficient is …

The analysis of light-cone wavefunctions seems the most promising theoretical approach to a detailed understanding of the structure of relativistic bound states, particularly hadrons. However, there are numerous complications in this approach. Most importantly, the light-cone approach sacrifices manifest rotational invariance in exchange for the elimination of negative-energy states. The requirement of rotational invariance of the full theory places important constraints on proposed light-cone wavefunctions, whether they are modelled or extracted from some numerical procedure. A formulation of the consequences of the hidden rotational symmetry has been sought for some time; it is presented in Chapter 2. In lattice gauge theory or heavy-quark effective theory, much of the focus is on the extraction of numerical values of operators which are related to the hadronic wavefunction. These operators are to some extent interdependent, with relations induced by fundamental constraints on the underlying wavefunction. The consequences of the requirement of unitarity are explored in Chapter 3, and are found to have startling phenomenological relevance. To test model light-cone wavefunctions, experimental predictions must be made. The reliability of perturbative QCD as a tool for making such predictions has been questioned. In Chapter 4, the author presents a computation of the rates for nucleon-antinucleon …

The process of high order harmonic generation in atomic gases has shown great promise as a method of generating extremely short wavelength radiation, extending far into the extreme ultraviolet (XUV). The process is conceptually simple. A very intense laser pulse (I {approximately}10{sup 13}-10{sup 14} W/cm{sup 2}) is focused into a dense ({approximately}10{sup l7} particles/cm{sup 3}) atomic medium, causing the atoms to become polarized. These atomic dipoles are then coherently driven by the laser field and begin to radiate at odd harmonics of the laser field. This dissertation is a study of both the physical mechanism of harmonic generation as well as its development as a source of coherent XUV radiation. Recently, a semiclassical theory has been proposed which provides a simple, intuitive description of harmonic generation. In this picture the process is treated in two steps. The atom ionizes via tunneling after which its classical motion in the laser field is studied. Electron trajectories which return to the vicinity of the nucleus may recombine and emit a harmonic photon, while those which do not return will ionize. An experiment was performed to test the validity of this model wherein the trajectory of the electron as it orbits the nucleus or …

Role of H spillover to the silica support was studied using chemisorption; a strongly bound component of spilled over H was found in the silica support which interfered with accurate measurements of active metal sites via volumetric strong H chemisorption. The volumetric chemisorption technique was modified so that measurement times were reduced from 12--36 h to 1 h. The active Ru surface was characterized means of changes in proton spin counts and NMR Knight shifts vs alkali loading. Na, K blocked the active surface of Ru metal, but Cs was pushed off by H chemisorption. The alkali promoters restricted H mobility on both metal surface and at the metal support interfaces; this is consistent with effects on Fischer-Tropsch synthesis. {sup 1}H NMR was used to study the effect of the active metal and promoter on support hydroxyl groups. The OH group density in the silica support decreased with metal and/or promoter loading, but not on a one-to-one basis; the exchange efficiency of the hydroxyls decreased with atomic size of the alkali metal. An additional downfield proton resonance was detected which was assigned to the alkali hydroxide species in the support.

The vortex method is a numerical scheme for solving the vorticity transport equation. Chorin introduced modern vortex methods. The vortex method is a Lagrangian, grid free method which has less intrinsic diffusion than many grid schemes. It is adaptive in the sense that elements are needed only where the vorticity is non-zero. Our description of vortex methods begins with the point vortex method of Rosenhead for two dimensional inviscid flow, and builds upon it to eventually cover the case of three dimensional slightly viscous flow with boundaries. This section gives an introduction to the fundamentals of the vortex method. This is done in order to give a basic impression of the previous work and its line of development, as well as develop some notation and concepts which will be used later. The purpose here is not to give a full review of vortex methods or the contributions made by all the researchers in the field. Please refer to the excellent review papers in Sethian and Gustafson, chapters 1 Sethian, 2 Hald, 3 Sethian, 8 Chorin provide a solid introduction to vortex methods, including convergence theory, application in two dimensions and connection to statistical mechanics and polymers. Much of the information …

Procedures required for minimizing structural defects generated during ion beam synthesis of SiGe alloy layers were studied. Synthesis of 200 mm SiGe alloy layers by implantation of 120-keV Ge ions into <100> oriented Si wafers yielded various Ge peak concentrations after the following doses, 2{times}10{sup 16}cm{sup {minus}2}, 3{times}10{sup 16}cm{sup {minus}2} (mid), and 5{times}10{sup 16}cm{sup {minus}2} (high). Following implantation, solid phase epitaxial (SPE) annealing in ambient N2 at 800C for 1 hr. resulted in only slight redistribution of the Ge. Two kinds of extended defects were observed in alloy layers over 3{times}l0{sup 16}cm{sup {minus}2}cm dose at room temperature (RT): end-of-range (EOR) dislocation loops and strain-induced stacking faults. Density of EOR dislocation loops was much lower in alloys produced by 77K implantation than by RT implantation. Decreasing the dose to obtain 5 at% peak Ge concentration prevents strain relaxation, while those SPE layers with more than 7 at% Ge peak show high densities of misfit- induced stacking faults. Sequential implantation of C following high dose Ge implantation (12 at% Ge peak concentration in layer) brought about a remarkable decrease in density of misfit-induced stacking faults. For peak implanted C > 0.55 at%, stacking fault generation in the epitaxial layer was suppressed, owing …

The left-right asymmetry for b quarks, A{sub b}, is precisely predicted by the Weinberg-Salam-Glashow model of particle interactions, now the standard model for high-energy particle physics. As a test of this model, A{sub b} is directly measured at the SLC Large Detector (SLD) by taking advantage of the unique polarized electron beam at the Stanford Linear Collider (SLC) and measuring the left-right forward-backward asymmetry of b quarks. To measure the asymmetry, b quarks are identified using muons of high total and transverse momenta. The result for the 1993 data sample of 37,843 hadronic Z`s is A{sub b} = 0.91 {+-} 0.19 {+-} 0.06, where the first error is statistical and the second systematic. This result is in agreement with the standard model prediction of A{sub b} = 0.935.

Design and performance of high-T{sub c} dc superconducting quantum interference devices (SQUEDs), junctions that comprise them, and magnetometers made from them are described, with attention to sources of 1/f noise. Biepitaxial junctions are found to have large levels of critical current fluctuations which make them unsuitable for low-noise SQUIDS; this suggests a poorly connected interface at the grain boundary junction. SQUIDs from bicrystal junctions have levels of critical current noise controllable using bias current reversal techniques which leave the noise white down to frequencies of a few Hz. A SQUID with an energy resolution of 1.5{times}10{sup {minus}30} J Hz{sup {minus}1} at 1 Hz is reported. Magnetometers in which a (9 mm){sup 2} pickup loop is directly coupled to a SQUID body have achieved field resolutions of 93 fT Hz{sup {minus}1/2} down to frequencies below I Hz, improving to 39 fT Hz{sup {minus}1/2} at 1 Hz with the addition of a 50mm-diameter single-turn flux transformer. Poor coupling to pickup loop makes it difficult to satisfy competing goals of high field resolution and small detector size necessary for multichannel biomagnetic imaging. Improved coupling is demonstrated by the use of multiturn-input-coil flux transformers, and a resolution of 35 fT Hz{sup {minus}1/2} in the …

Multigrid methods are studied for solving elliptic partial differential equations. Focus is on parallel multigrid methods and their use for reservoir simulation. Multicolor Fourier analysis is used to analyze the behavior of standard multigrid methods for problems in one and two dimensions. Relation between multicolor and standard Fourier analysis is established. Multiple coarse grid methods for solving model problems in 1 and 2 dimensions are considered; at each coarse grid level we use more than one coarse grid to improve convergence. For a given Dirichlet problem, a related extended problem is first constructed; a purification procedure can be used to obtain Moore-Penrose solutions of the singular systems encountered. For solving anisotropic equations, semicoarsening and line smoothing techniques are used with multiple coarse grid methods to improve convergence. Two-level convergence factors are estimated using multicolor. In the case where each operator has the same stencil on each grid point on one level, exact multilevel convergence factors can be obtained. For solving partial differential equations with discontinuous coefficients, interpolation and restriction operators should include information about the equation coefficients. Matrix-dependent interpolation and restriction operators based on the Schur complement can be used in nonsymmetric cases. A semicoarsening multigrid solver with these operators …

The dynamics of S({sup 3}P{sub 2,1,0}, {sup 1}D{sub 2}) production from the 193 nm photodissociation of CH{sub 3}SCH{sub 3}, H{sub 2}S and CH{sub 3}SH have been studied using 2 + 1 resonance-enhanced multiphoton ionization (REMPI) techniques. The 193 nm photodissociation cross sections for the formation of S from CH{sub 3}S and HS initially prepared in the photodissociation of CH{sub 3}SCH{sub 3} and H{sub 2}S are estimated to be 1 {times} 10{sup {minus}18} and 1.1 {times} 10{sup {minus}18} cm{sup 2}, respectively. The dominant product from CH{sub 3}S is S({sup 1}D), while that from SH is S({sup 3}P). Possible potential energy surfaces involved in the 193 nm photodissociation of CH{sub 3}S({tilde X}) and SH(X) have been also examined. Threshold photoelectron (PE) spectra for SH and CH{sub 3}S formed in the ultraviolet photodissociation of H{sub 2}S and CH{sub 3}SH, respectively, have been measured using the nonresonant two-photon pulsed field ionization (N2P-PFI) technique. The rotationally resolved N2P-PFI-PE spectrum obtained for SH indicates that photoionization dynamics favors the rotational angular momentum change {Delta}N < 0 with the {Delta}N value up to {minus}3, an observation similar to that found in the PFI-PE spectra of OH (OD) and NO. The ionization energies for SH(X{sup 2}{product}{sub 3,2}) and …

Extreme ultraviolet lithographic masks are made by patterning multilayer reflective coatings with high normal incidence reflectivity. Masks can be patterned by depositing a patterned absorber layer above the coating or by etching the pattern directly into the coating itself. Electromagnetic simulations showed that absorber-overlayer masks have superior imaging characteristics over etched masks (less sensitive to incident angles and pattern profiles). In an EUVL absorber overlayer mask, defects can occur in the mask substrate, reflective coating, and absorber pattern. Electromagnetic simulations showed that substrate defects cause the most severe image degradation. A printability study of substrate defects for absorber overlayer masks showed that printability of 25 nm high substrate defects are comparable to defects in optical lithography. Simulations also indicated that the manner in which the defects are covered by multilayer reflective coatings can affect printability. Coverage profiles that result in large lateral spreading of defect geometries amplify the printability of the defects by increasing their effective sizes. Coverage profiles of Mo/Si coatings deposited above defects were studied by atomic force microscopy and TEM. Results showed that lateral spread of defect geometry is proportional to height. Undercut at defect also increases the lateral spread. Reductions in defect heights were observed for …

The relation of structure to lack of superconductivity in Pr-Ba-Cu-O was systematically investigated. First, the phase equilibria of this system was studied to find the processing parameters which maximize the cation-site ordering between Pr and Ba ions. Second, a comparative study between superconducting Nd-Ba-Cu-0 and non- superconducting Pr-Ba-Cu-0 was performed by forming solid-solution Nd- Pr-Ba-Cu-0. The relation between structure and superconductivity in Nd{sub 1{minus}x}Pr{sub x}Ba{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} is investigated. {Tc} decreases monotonically with increasing {times} and superconductivity disappears at around x=0.3-0.4. {Tc} is enhanced by 10K when the sample is processed at an oxygen partial pressure (PO{sub 2}) of 0.01 atm, followed by oxygenation at 450C. Depression of {Tc} as a function of {times} and PO {sub 2} is explained in terms of a charge-transfer model. It is suggested that destruction of superconductivity in the RE{sub 1{minus}x}Pr{sub x}Ba{sub 2}CU{sub 3}O{sub 7{minus}{delta}} (RE=rare-earth) system can be viewed as disruption of four-fold planar coordinated Cu ions in the chain-site due to permanent occupation of extra Pr ions on Ba sites.

Effects of resonant tunneling between bound quantum states of a current-biased Josephson tunnel junction is studied both theoretically and experimentally. Several effects are predicted to arise from resonant tunneling, including a series of voltage peaks along the supercurrent branch of the current-voltage characteristic, and enhanced rate of escape from zero voltage state to voltage state at particular values of bias current. A model is developed to estimate magnitude and duration of voltage peaks, and to estimate enhancement of the escape rate, which appears as peaks in the rate as a function of bias current. An experimental investigation was carried out in an attempt to observe these predicted peaks in the escape rate distribution in a current-biased DC SQUID, which is shown to be dynamically equivalent to a Josephson junction with adjustable critical current. Electrical contact to each SQUID (fabricated from aluminium) was made through high resistance thin film leads located on the substrate. These resistors provided a high impedance at the plasma frequency which is for the isolation of the SQUID from its electromagnetic environment. Measurements were carried out on a dilution refrigerator at temperatures as low as 19 mK. No evidence was found for resonant tunneling; this is attributed …

In 1985 Simpson reported evidence for the emission of a 17 keV mass neutrino in a small fraction of tritium beta decays. An experimental controversy ensued in which a number of both positive and negative results were reported. The beta spectrum of {sup 14}C was collected in a unique {sup 14}C-doped planar germanium detector and a distortion was observed that initially confirmed Simpson`s result. Further tests linked this distortion to a splitting of the collected charge between the central detector and the surrounding guard ring in a fraction of the events. A second {sup 14}C measurement showed no evidence for emission of a 17 keV mass neutrino. In a related experiment, a high statistics electron-capture internal-bremsstrahlung photon spectrum of {sup 55}Fe was collected with a coaxial germanium detector. A local search for departures from a smooth shape near the endpoint was performed, using a second-derivative technique. An upper limit of 0.65% (95% C.L.) for the mixing Of a neutrino in the mass range 5--25 keV was established. The upper limit on the mixing of a 17 keV mass neutrino was 0.14% (95% C.L.).

Kinetic data for elimination of silylene supports formation of a ``tighter`` transition state, indicating a silacyclopropene intermediate. This extends the silacyclopropene mechanism to the cyclicdialkyne system and validates the consistency of the mechanism for silylakynes, in general. Investigation into the other possible silacyclopropene product established the instability of the product. The work with silylketenes proved that an inherent difference exists between reactivity of monosilyl-substituted ketenes and polysilyl-substituted ketenes. Although the mechanism for thermal decomposition of bis(silyl)ketenes can be modified to account for the unexpected silylene elimination products, reasons for the difference are limited to speculation. The photochemistry of silylketenes has not been previously studied, so a model system does not exist for comparison with our polysilylketene work. The photochemical experimentation suggests that the photochemistry and thermochemistry of polysilylketenes is not the same. A more extensive study of the mechanism of the systems covered in this research as well as with monosilyl-substituted systems is needed.

Two numerical methods for the solution of the two-dimensional Euler equations for incompressible flow on locally refined grids are presented. The first is a second order projection method adapted from the method of Bell, Colella, and Glaz. The second method is based on the vorticity-stream function form of the Euler equations and is designed to be free-stream preserving and conservative. Second order accuracy of both methods in time and space is established, and they are shown to agree on problems with a localized vorticity distribution. The filamentation of a perturbed patch of circular vorticity and the merger of two smooth vortex patches are studied. It is speculated that for nearly stable patches of vorticity, an arbitrarily small amount of viscosity is sufficient to effectively eliminate vortex filaments from the evolving patch and that the filamentation process affects the evolution of such patches very little. Solutions of the vortex merger problem show that filamentation is responsible for the creation of large gradients in the vorticity which, in the presence of an arbitrarily small viscosity, will lead to vortex merger. It is speculated that a small viscosity in this problem does not substantially affect the transition of the flow to a statistical …