Master of Science / Department of Mechanical and Nuclear Engineering / William L. Dunn / A prototype system for detecting explosives at standoff distances, using a signature based radiation scanning approach, is being developed at Kansas State University. The prototype will incorporate both a machine x-ray source and a machine neutron source to generate signatures from unknown samples of material. These signatures can be compared to templates measured or calculated from known explosive samples using a figure-of-merit. The machine neutron source uses the fusion of deuterium and tritium to create 14.1 MeV neutrons. Due to its radioactivity, the tritium must be sealed within the system. A new method of controlling the gas pressure with the DT generator was developed using a Zr-V-Fe getter supplied by a commercial firm. The shielding and collimation of the 14.1 MeV neutron source is accomplished using layers of steel, high-density polyethylene and borated high-density polyethylene. This thesis describes the development of the gas control method for the sealed neutron source, design studies for the shielding and collimation of the neutron source and modifications made to the building in which the prototype is being housed.

Hawking radiation, despite its presence in theoretical physics for over thirty years, remains elusive and undetected. It also suffers, in its original context of gravitational black holes, from conceptual difficulties. Of particular note is the trans-Planckian problem, which is concerned with the apparent origin of the radiation in absurdly high frequencies. In order to gain better theoretical understanding and, it is hoped, experimental verification of Hawking radiation, much study is being devoted to systems which model the spacetime geometry of black holes, and which, by analogy, are also thought to emit Hawking radiation. These analogue systems typically exhibit dispersion, which regularizes the wave behaviour at the horizon but does not lend itself well to analytic treatment, thus rendering Hawking’s prediction less secure. A general analytic method for dealing with Hawking radiation in dispersive systems has proved difficult to find. This thesis presents new numerical and analytic results for Hawking emission spectra in dispersive systems. It examines two black-hole analogue systems: it begins by introducing the well-known acoustic model, presenting some original results in that context; then, through analogy with the acoustic model, goes on to develop the lesser-known fibre-optical model. The following original results are presented in the context of both of these models: • an analytic expression for the low-frequency temperature is found for a hyperbolic tangent background profile, valid in the entire parameter space; it is well-known that the spectrum is approximately thermal at low frequencies, but a universally valid expression for the corresponding temperature is an original development; • an analytic expression for the spectrum, valid over almost the entire frequency range, when the velocity profile parameters lie in the regime where the low-frequency temperature is given by the Hawking prediction; previous work has focused on the low-frequency thermal spectrum and the characterization of the deviations from thermality, rather than a single analytic expression; and • a new unexplored regime where no group-velocity horizon exists is examined; the Hawking spectra are found to be non-zero here, but also highly non-thermal, and are found, in the limit of small deviations, to vary with the square of the maximum deviation; the analytic expression for the case with a horizon is found to carry over to this new regime, with appropriate modifications. Furthermore, the thesis examines the results of a classical frequency-shifting experiment in the context of fibre-optical horizons. The theory of this process is presented for both a constant-velocity and a constantly-decelerating pulse, the latter case taking account of the Raman effect. The resulting spectra are at least qualititively explained, but there is a discrepancy between theory and experiment that has not yet been accounted for.

<p>During operation of heavy ion accelerators a significant pressure rise has been observed when the intensity of the high energy beam was increased. The cause for this pressure rise is ion induced desorption, which is the result when beam ions collide with residual gas molecules in the accelerator, whereby they undergo charge exchange. Since the change in charge state will affect the bending radius of the particles after they have passed a bending magnet, they will not follow the required trajectory but instead collide with the vacuum chamber wall and gas are released. For the Future GSI project FAIR (Facility for Antiproton and Ion Research) there is a need to upgrade the SIS18 synchrotron in order to meet the requirements of the increased intensity. The aim of this work was to measure the desorption yields, η, (released molecules per incident ion) from materials commonly used in accelerators: 316LN stainless steel, Cu, Etched Cu, gold coated Cu, Ta and TiZrV coated stainless steel with argon and uranium beams at the energies 5-100 MeV/u. The measurements were performed at GSI and at The Svedberg Laboratory where a new dedicated teststand was built. It was found that the desorption yield scales with the electronic energy loss to the second power, decreasing for increasing impact energy above the Bragg Maximum. A feasibility study on the possibility to use laser refractometry to improve the accuracy of a specific throughput system was performed. The result was an improvement by up to 3 orders of magnitude, depending on pressure range.</p>

The foundation of vacuum nanoelectronics was laid as early as in 1961 when Kenneth Shoulders proposed the development of vertical field-emission micro-triodes. After years of conspicuous stagnancy in the field much interest has reemerged for the vacuum nanoelectronics in recent years. Electron field emission under high electric field from conventional and exotic nanoemitters, which have now been made possible with the use of modern day technology, has been the driving force behind this renewal of interest in vacuum nanoelectronics. In the research reported in this thesis self-assembled silicon nanostructures were studied as a potential source of field emission for vacuum nanoelectronic device applications. Whiskerlike protruding silicon nanostructures were grown on untreated n- and p-type silicon surfaces using electron-beam annealing under high vacuum. The electrical transport characteristics of the silicon nanostructures were investigated using conductive atomic force microscopy (C-AFM). Higher electrical conductivities for the nanostructured surface compared to that for the surrounding planar silicon substrate region were observed. Non-ideal diode behaviour with high ideality factors were reported for the individual nanostructure-AFM tip Schottky nanocontacts. This demonstration, indicative of the presence of a significant field emission component in the analysed current transport phenomena was also detailed. Field emission from these nanostructures was demonstrated qualitatively in a lift-mode interleave C-AFM study. A technique to fabricate integrated field emission diodes using silicon nanostructures in a CMOS process technology was developed. The process incorporated the nanostructure growth phase at the closing steps in the process flow. Turn-on voltages as low as ~ 0.6 V were reported for these devices, which make them good candidates for incorporation into standard CMOS circuit applications. Reproducible I V characteristics exhibited by these fabricated devices were further studied and field emission parameters were extracted. A new consistent and reliable method to extract field emission parameters such as effective barrier height, field conversion factor, and total emitting area at the onset of the field emission regime was developed and is reported herein. The developed parameter extraction method used a unified electron emission approach in the transition region of the device operation. The existence of an electron-supply limited current saturation region at very high electric field was also confirmed. Both the C-AFM and the device characterization studies were modelled and simulated using the finite element method in COMSOL Multiphysics. The experimental results – the field developed at various operating environments – are explained in relation to these finite element analyses. Field enhancements at the atomically sharp nanostructure apexes as suggested in the experimental studies were confirmed. The nanostructure tip radius effect and sensitivity to small nanostructure height variation were investigated and mathematical relations for the nanostructure regime of our interest were established. A technique to optimize the cathode-opening area was also demonstrated. Suggestions related to further research on field emission from silicon nanostructures, optimization of the field emission device fabrication process, and fabrication of field emission triodes are elaborated in the final chapter of this thesis. The experimental, modelling, and simulation works of this thesis indicate that silicon field emission devices could be integrated into the existing CMOS process technology. This integration would offer goods from both the worlds of vacuum and solid-sate nanoelectronics – fast ballistic electron transport, temperature insensitivity, radiation hardness, high packing density, mature technological backing, and economies of scale among other features.

Cette thèse vise à évaluer le potentiel d'un nouveau couple cathode / électrolyte pour une application en IT-SOFC (700°C), par le biais de l'élaboration et du test de cellules à anode support de configuration planaire. Les matériaux concernés sont l'électrolyte BaIn0.3Ti0.7O2.85 (BIT07), de structure perovskite, et les nickelates de terres rares Ln2-xNiO4+ (LnN, Ln = La, Nd, Pr) en tant que cathodes ; ces matériaux ont montré des propriétés prometteuses dans des travaux préliminaires effectués à l'IMN et l'ICMCB. La première partie de cette thèse porte sur la mise en place d'un protocole d'élaboration de cellules complètes utilisant des techniques bas coûts et industrialisables (cellules de taille 3 x 3 cm2) : l'anode Ni / BIT07 a été élaborée par coulage en bande, l'électrolyte BIT07 par vacuum slip casting et les cathodes par sérigraphie. Les mesures électrochimiques réalisées sur une première génération de cellules ont mis en évidence la nécessité d'ajouter une couche barrière de GDC entre les cathodes LnN et l'électrolyte BIT07. Les meilleures performances ont été obtenues pour une cellule BIT07 / Ni | BIT07 | GDC | PrN, avec une densité de puissance à 700°C et 0.7 V de 176 mW cm-2 pour une faible résistance de polarisation de 0. 29 Ω cm2. La principale limitation des performances a été identifiée comme étant la résistance interne du banc de test, donnant lieu à des valeurs de résistances séries anormalement élevées. Cette cellule a été opérée avec succès durant plus de 500 heures sous courant, avec néanmoins une vitesse de dégradation extrapolée élevée de l'ordre de 27% / kh.

Thermal resistance per unit thickness for Vacuum Insulation Panel (VIP) is 5 to 10 times higher than conventional insulation materials. This makes VIP an attractive option for retrofitting exterior building envelopes. Insulation can be added in an exterior wall either on the interior side, exterior side or in the available stud cavity. VIP has high vapor diffusion resistance factor and could lead to moisture management risk in the wall layers because of the steep temperature gradient in the wall generated due to very high thermal resistance of VIP. VIP is a relatively new insulation material for building envelope construction, thus the hygrothermal or moisture management performance of VIP-insulated exterior building envelopes need to be critically analyzed before its application. This study aims to evaluate the moisture management risk associated with wood-frame stucco-cladded exterior walls retrofitted with VIP using a 2-D hygrothermal simulation tool WUFI-2D. Eight North American locations were considered, based on Moisture Index (MI) which varied between 0.13 and 1.17, and two different indoor hygrothermal loading conditions as prescribed by the ASHRAE 160P and EN 13788, respectively. The outputs from hygrothermal simulations (water content, relative humidity and temperature) were critically analysed and expressed further using freeze-thaw cycles and RHT indices. The results show that the appropriately designed VIP retrofitted walls can have superior moisture management performance as compared to conventional stucco-cladded wall. / Graduate

Information about protein structures is important in many areas of life sciences, including structure-based drug design. Gas phase methods, like electrospray ionization and mass spectrometry are powerful tools for the analysis of molecular interactions and conformational changes which complement existing solution phase methods. Novel techniques such as single particle imaging with X-ray free electron lasers are emerging as well. A requirement for using gas phase methods is that we understand what happens to proteins when injected into vacuum, and what is the relationship between the vacuum structure and the solution structure. Molecular dynamics simulations in combination with experiments show that protein structures in the gas phase can be similar to solution structures, and that hydrogen bonding networks and secondary structure elements can be retained. Structural changes near the surface of the protein happen quickly (ns-µs) during transition from solution into vacuum. The native solution structure results in a reasonably well defined gas phase structure, which has high structural similarity to the solution structure. Native charge locations are in some cases also preserved, and structural changes, due to point mutations in solution, can also be observed in vacuo. Proteins do not refold in vacuo: when a denatured protein is injected into vacuum, the resulting gas phase structure is different from the native structure. Native structures can be protected in the gas phase by adjusting electrospray conditions to avoid complete evaporation of water. A water layer with a thickness of less than two water molecules seems enough to preserve native conditions. The results presented in this thesis give confidence in the continued use of gas phase methods for analysis of charge locations, conformational changes and non-covalent interactions, and provide a means to relate gas phase structures and solution structures.

Organic photovoltaics have attracted considerable research and commercial interest due to their lightness, mechanical flexibility and low production costs. There are two main approaches for the fabrication of organic solar cells – solution and vacuum processing. The former relies on morphology control in polymer-fullerene blends resulting from natural phase separation in these systems. The latter takes advantage of solvent-free processing allowing highly complex multi-junction architectures similar to inorganic solar cells. This work aims to combine the benefits of both by depositing conjugated polymers using vacuum thermal evaporation. By employing this unconventional approach it aims to enhance the efficiency of organic photovoltaics through increased complexity of the thin-film architecture while improving the nanoscale morphology control of the individual active layers. The thesis explores the vacuum thermal deposition of polythiophenes, mainly poly(3-hexylthiophene) (P3HT) and side-group free poly(thiophene) (PTh). A variety of chemical techniques, such as NMR, FT-IR, GPC, DSC and TGA, are used to examine the effect of heating on chemical structure of the polymers. Optimal processing parameters are identified and related to the resulting thin-film morphology and charge transport properties. Efficient photovoltaic devices based on polythiophene donors and fullerene acceptors are fabricated. Materials science techniques AFM, XRD, SEM, TEM and MicroXAM are used to characterize topography and morphology of the thin films, and UV-Vis, EQE, I-V and C-V measurements relate these to the optical and electronic properties. The results of the study show that polymer side groups have a strong influence on molecular packing and charge extraction in vacuum-deposited polymer thin films. Unlike P3HT, evaporated PTh forms highly crystalline films. This leads to enhanced charge transport properties with hole mobility two orders of magnitude higher than that in P3HT. The effect of molecular order is demonstrated on polymer/fullerene planar heterojunction solar cells. PTh-based devices have significantly better current and recombination characteristics, resulting in improved overall power conversion efficiency (PCE) by 70% as compared to P3HT. This confirms that the chemical structure of the molecule is a crucial parameter in deposition of large organic semiconductors. It is also the first-ever example of vacuum-deposited polymer photovoltaic cell. Next, vacuum co-deposited PTh:C60 bulk heterojunctions with different donor-acceptor compositions are fabricated, and the effect of post-production thermal annealing on their photovoltaic performance and morphology is studied. Co-deposition of blended mixtures leads to 60% higher photocurrents than in thickness-optimized PTh/C60 planar heterojunction counterparts. Furthermore, by annealing the devices post-situ the PCE is improved by as much as 80%, achieving performance comparable to previously reported polythiophene and oligothiophene equivalents processed in solution and vacuum, respectively. The enhanced photo-response is a result of favourable morphological development of PTh upon annealing. In contrast to standard vacuum-processed molecular blends, annealing-induced phase separation in PTh:C60 does not lead to the formation of coarse morphology but rather to an incremental improvement of the already established interpenetrated nanoscale network. The morphological response of the evaporated PTh within the blend is further verified to positively differ from that of its small-molecule counterpart sexithiophene. This illustrates the morphological advantage of polymer-fullerene combination over all other vacuum-processable material systems. In conclusion, this processing approach outlines the conceptual path towards the most beneficial combination of solution/polymer- and vacuum-based photovoltaics. It opens up a fabrication method with considerable potential to enhance the efficiency of large-scale organic solar cells production.

The focus of this research is to explore the molecular-level interactions between reactive metal surfaces and aqueous environments by combined ultra-high vacuum/electrochemistry (UHV-EC) methodology. The objectives of this work are to understand (1) the effects of sulfate ions on the passivity of metal oxide/hydroxide surface layer, (2) the effects of sulfur-modification on the evolution of metal oxide/hydroxide surface layer, and (3) the effects of sulfur adsorbate on cation adsorption at metal surfaces.

Dans ce mémoire, on étudie la désintégration d’un faux vide, c’est-à-dire un vide qui est un minimum relatif d’un potentiel scalaire par effet tunnel. Des défauts topologiques en 1+1 dimension, appelés kinks, apparaissent lorsque le potentiel possède un minimum qui brise spontanément une symétrie discrète. En 3+1 dimensions, ces kinks deviennent des murs de domaine. Ils apparaissent par exemple dans les matériaux magnétiques en matière condensée. Un modèle à deux champs scalaires couplés sera étudié ainsi que les solutions aux équations du mouvement qui en découlent. Ce faisant, on analysera comment l’existence et l’énergie des solutions statiques dépend des paramètres du modèle. Un balayage numérique de l’espace des paramètres révèle que les solutions stables se trouvent entre les zones de dissociation, des régions dans l’espace des paramètres où les solutions stables n’existent plus. Le comportement des solutions instables dans les zones de dissociation peut être très différent selon la zone de dissociation dans laquelle une solution se trouve. Le potentiel consiste, dans un premier temps, en un polynôme d’ordre six, auquel on y rajoute, dans un deuxième temps, un polynôme quartique multiplié par un terme de couplage, et est choisi tel que les extrémités du kink soient à des faux vides distincts. Le taux de désintégration a été estimé par une approximation semi-classique pour montrer l’impact des défauts topologiques sur la stabilité du faux vide. Le projet consiste à déterminer les conditions qui permettent aux kinks de catalyser la désintégration du faux vide. Il appert qu’on a trouvé une expression pour déterminer la densité critique de kinks et qu’on comprend ce qui se passe avec la plupart des termes. / In this thesis, we study the tunneling decay of the false vacuum, that is, a vacuum that is a relative minimum of a scalar potential. Topological defects in 1+1 dimension, called kinks, appear when the potential possesses a minimum that spontaneously breaks a discrete symmetry. In 3+1 dimensions, these kinks become domain walls. For instance, they appear in magnetic materials in condensed matter. A model with two coupled scalar fields will be studied, as well as the solutions to the equations of motion that arise from it. We will then analyze how the energy of the static solutions depend on the parameters of the model. A numerical survey of parameter space reveals that the stable solutions are located between dissociation zones, areas in parameter space where stable solutions no longer exist. The behavior of the unstable solutions in the dissociation zones can be very different depending on which dissociation zone a solution is found near the dissociation zone. The potential first consists in a sixth-order polynomial, to which is added a quartic polynomial multiplied by a coupling term, and is chosen such that the extremities of the kink are at distinct false vacua. The decay rate has been estimated by a semiclassical approximation to show the impact of topological defects on the stability of the false vacuum. The project consists in determining the conditions that allow the kinks to catalyze false vacuum decay. It appears that we found an expression for the critical kink density and that we understand what happens with most terms.