Nowadays, polymer chemists undertake considerable efforts to achieve the preparation of new macromolecules and a perfect control over the macromolecular engineering, i.e. the mass parameters but also over the chain and end-group compositions, topology, etc… is definitively expected. In addition, more complex architectures, such as brush (co)polymers, jellyfish-like topologies…, are required to improve or drastically modify the physicochemical properties of the materials. As a direct consequence of the development of such complex molecular objects, sophisticated techniques are required for the in-depth characterization of the macromolecules, since the exact compositions and structures should be fully and unambiguously identified. Given the fact that the usual characterization tools such as Nuclear Magnetic Resonance (NMR) and Gel Permeation Chromatography (GPC) are extensively used, their abilities have been intensively developed to account for the increasing complexity and diversity of the targeted molecules. Nevertheless, all the usual techniques are averaging methodologies since they only provide pieces of information about the polymer mixture instead of affording data on the individual macromolecules. Since few decades, mass spectrometry (MS) has become as used as NMR and GPC for polymer characterization. In the context of large molecules analysis, MS undoubtedly underwent an impressive craze with the development of two modern ionization procedures, namely Electrospray Ionization (ESI) and Matrix-assisted Laser Desorption/Ionization (MALDI). Those ionization procedures permit the vaporization of macromolecules allowing the intact polymers to be analyzed without a too extensive level of degradation. ESI and MALDI are often considered as soft ionization methods since they offer the possibility to observe ions corresponding to the intact molecules. After their production in the ion source, ions corresponding to the polymer molecules can be mass analyzed by the mass spectrometer and important parameters such as the molecular weight distribution (Mn and Mw), polydispersity index (PDI), the nature of the monomer units and the end-groups can be derived from the measure of the mass-to-charge ratios of the produced ions. In the first part of the present thesis, we studied the MS behavior of different classes of polymers when submitted to ESI and MALDI ionizations. The investigations were devoted to the validation of MS as a truly reliable methodology for fragile polymers such as aliphatic polyesters for instance. In this context, a preliminary MS investigation on semi-telechelic polyethers revealed the importance of the source parameters for the characterization of polymers presenting fragile moieties. We also demonstrated the huge importance of the matrix molecule selection for the MALDI analyses of polymers. In particular, we introduced a new matrix for the MALDI measurements of electroconjugated polymers such as polythiophenes. After the study of the influence of the source parameters on the MS data, a complete study by single stage MS and double stage MS (MS/MS) on newly synthesized polylactides (PLA) was performed. The PLA samples were prepared following original procedures using carbene as catalyst. Finally, to achieve the MS study of PLA ions, we used ion mobility-mass spectrometry (IM-MS) experiments to obtained information on the tridimensional structure of the gas phase PLA ions. In particular, we put a special emphasis on the influence of the charge and size of the polymer chains on their gas-phase conformations. The conclusions derived from the MS/MS and IM-MS results were fully supported by theoretical calculations. In the second part of the thesis, the acquired MS experience was applied to the fine characterization of macromolecules presenting complex architectures obtained by two different polymerization procedures: (i) cobalt-mediated radical polymerization of inter alia acrylonitrile and vinyl acetate and (ii) ring-opening polymerization (ROP) of lactones using non-organometallic catalysts. In particular, mass spectrometry was used to tune the experimental conditions for the ROP of â-lactones using different phosphazenes as catalysts. As an ultimate conclusion, this work points to the very efficient synergy between polymer synthesis, mass spectrometry and theoretical calculations. We believe that this thesis paves the way for innumerable possibilities in the future.

Plasmas seeded with solid particulates of nanometer to micron sizes (complex plasma systems) are a ubiquitous feature of intergalactic, interstellar and planetary environments but also of plasma processing applications or even fusion devices. Their novel aspects compared with ideal multi-component plasmas stem from (i) the large number of elementary charges residing on the grain surface, (ii) the variability of the charge over mass ratio of the dust component, (iii) the inherent openness and dissipative nature of such systems.   Their statistical description presents a major challenge; On one hand by treating dust grains as point particles new phase space variables must be introduced augmenting the classical Hamiltonian phase space, while the microphysics of interaction between the plasma and the grains will introduce additional coupling between the kinetic equations of each species, apart from the usual fine-grained electromagnetic field coupling. On the other hand complex plasma systems do not always exist in a gaseous state but can also condensate, i.e. form liquid, solid or crystalline states.   In this thesis we study gaseous partially ionized complex plasma systems from the perspective of the Klimontovich technique of second quantization in phase space. Initially, in regimes typical of dust dynamics. Starting from the Klimontovich equations for the exact phase space densities, theory deliverables such as the permittivity, the spectral densities of fluctuations and the collision integrals are implemented either for concrete predictions related to low frequency electrostatic waves or for diagnostic purposes related to the enhancement of the ion density and electrostatic potential fluctuation spectra due to the presence of dust grains. Particular emphasis is put to the comparison of the self-consistent kinetic model with multi-component kinetic models (treating dust as an additional massive charged species) as well as to the importance of the nature of the plasma particle source. Finally, a new kinetic model of complex plasmas (for both constant and fluctuating sources) is formulated. It is valid in regimes typical of ion dynamics, where plasma discreteness can no longer be neglected, and, in contrast to earlier models, does not require relatively large dust densities to be valid. / QC 20120316

This study uses the PIC (Particle-in-cell) method to simulate unsteady three-dimensional dynamics of particles in argon plasma under low pressure, high density, and weak ionization between two planar electrodes subject to a sudden biased voltage. Plasma has been widely used in materials processing, film manufacturing, nuclear fusion, lamps, etc. Properties of plasmas are also becoming important area for research. This work includes elastic collisions between electrons and neutrals, ions and neutrals, and inelastic collisions resulting in ionization from impacting neutrals by electrons, and charge exchange between ions and neutrals, and Coulomb collisions between electrons and ions. The model ignores secondary electron emission, recombination between ions and electrons, and assumes uniform distribution of the neutrals having velocity of Maxwellian distribution. The computed results show the effects of elastic and inelastic collisions on the characteristics of plasma and sheath (space charge region) in front of the workpiece surface. Unsteady mass, momentum and energy transport from the bulk plasma through sheath to the workpiece is confirmatively and exploratorily studied after successful comparison between PIC prediction and experimental data has been made.

Infrastructure and transportation facilities have increased rapidly over the years. The progress has been accompanied by an increasing number of vehicle collisions with structures. This type of collision might lead to the damage, and often, collapse of the structure. In reinforced concrete (RC) structures, columns are usually the most vulnerable members exposed to collisions. However, the existing design guidelines and provisions for protection of these members against collision of vehicles are not adequate. In particular, the desired behavior and the associated performance levels of a structure during a vehicle collision are not defined. Therefore, there is need to assess the vulnerability of structures against such collisions. This research aims to develop a framework for the performance-based analysis and design of RC columns subject to vehicle impact. It helps mitigate maximum damage and achieve an economical design. The current research takes into account performance-based analysis and design as opposed to only collapse prevention design. The performance level is tied to the impact levels to estimate the reliability of the RC column for the desired performance objectives. The performance-based probabilistic models for estimating shear resistance of RC column and shear demand on RC column are developed. The reliability of the RC column subject for selected performance levels is evaluated. The performance levels are tied to impact demand and load and resistance factors are proposed to achieve desired performance objectives of the RC column subject to vehicle collision.

No description available.

Older adults are at an increased risk for motor-vehicle collisions (MVCs) once distance driven is considered, a finding that is partly attributed to a decline in attention related processes associated with age. MVCs typically occur in highly specific areas, suggesting a role of the complexity of the driving environment contributing to the occurrence of MVCs. The goal of this thesis was to explore the attentional demands of simulated driving events of varying complexity among young, mature and older drivers. In the present studies, attentional demand associated with driving was assessed through the peripheral detection task (PDT), a method in which a stimulus unrelated to the driving task is presented and drivers manually respond immediately upon its detection; latency to respond is recorded. The complexity of the driving environment was operationalized in terms of vehicle handling and of information processing elements. In the first study, inexperienced drivers completed a series simulated driving scenarios that varied according to their information processing and vehicle handling demands. The results showed a reduction in PDT performance at intersections where information processing is increased as well as when handling maneuvers behind a lead vehicle were required. Building on these findings, the second study employed the identical protocol as the first but examined differences in attentional demand between mid-aged and older drivers. The results indicated that when information processing demands were increased through the addition of traffic, and buildings, all participants exhibited greater workload regardless of age. The third study presented young, mid-aged, and older drivers with a simulated driving assessment course and administered several cognitive tasks. The results of the third study supported the hypothesis in that complex driving situations elicited greater attentional demand among drivers of all ages. Older adults showed greater attentional demand in comparison to young and mid-aged adults even after controlling for baseline response time. Older drivers also scored poorer on a global measure of driving safety. The results of this thesis highlight the roles of intrinsic and extrinsic factors involved in safe driving and are discussed in terms of appropriate interventions to improve road safety.

This thesis presents a 3D reconstruction approach to the detection of static obstacles from a single rear view parking camera. Corner features are tracked to estimate the vehicle’s motion and to perform multiview triangulation in order to reconstruct the scene. We model the camera motion as planar motion and use the knowledge of the camera pose to efficiently solve motion parameters. Based on the observed motion, we selected snapshots from which the scene is reconstructed. These snapshots guarantee a sufficient baseline between the images and result in more robust scene modeling. Multiview triangulation of a feature is performed only if the feature obeys the epipolar constraint. Triangulated features are semantically labelled according to their 3D location. Obstacle features are spatially clustered to reduce false detections. Finally, the distance to the nearest obstacle cluster is reported to the driver.

There is no international regulation for the frontal collision of the buses, protecting their occupants and partners in traffic. There are some regulation such as ECE R-80 which deals with strength of seat structure of the coaches and their anchorages strength. There is increasing need to focus issues like occupant protection and full scale crash testing regulation for buses. This thesis attempts to collect possible subjects required for international regulation required for crashworthiness of transit buses. This research attempts to develop and validate a model of transit bus for all three impact conditions. The full finite element model is developed with help hypermesh software and its validation and analysis is done with help Ls-Dyna nonlinear finite element solver. The cost of actual testing and secrecy maintained by manufacturers make research process difficult and increase the importance of computer simulations. To boost the research of crash worthiness of transit need for computer model is felt. This thesis examines several frontal crash test procedures and evaluates how well each procedure meets the objective. This validated model is used to analyze various real world impact scenarios and its analysis with European and federal regulation. This validated model is used to extract crash pulses of various impact scenarios at the center of gravity of the bus. These extracted crash pulses are applied to the madymo model to estimate the injuries to occupants of the bus. This thesis discusses the design aspects of bus frontal impact behavior as one of the main subjects of bus crashworthiness and results of previous full scale tests comparing the Fem simulation results carried out on the transit bus. / Thesis (M.S.)--Wichita State University, College of Engineering, Dept. of Mechanical Engineering / "December 2006."

Older adults are at an increased risk for motor-vehicle collisions (MVCs) once distance driven is considered, a finding that is partly attributed to a decline in attention related processes associated with age. MVCs typically occur in highly specific areas, suggesting a role of the complexity of the driving environment contributing to the occurrence of MVCs. The goal of this thesis was to explore the attentional demands of simulated driving events of varying complexity among young, mature and older drivers. In the present studies, attentional demand associated with driving was assessed through the peripheral detection task (PDT), a method in which a stimulus unrelated to the driving task is presented and drivers manually respond immediately upon its detection; latency to respond is recorded. The complexity of the driving environment was operationalized in terms of vehicle handling and of information processing elements. In the first study, inexperienced drivers completed a series simulated driving scenarios that varied according to their information processing and vehicle handling demands. The results showed a reduction in PDT performance at intersections where information processing is increased as well as when handling maneuvers behind a lead vehicle were required. Building on these findings, the second study employed the identical protocol as the first but examined differences in attentional demand between mid-aged and older drivers. The results indicated that when information processing demands were increased through the addition of traffic, and buildings, all participants exhibited greater workload regardless of age. The third study presented young, mid-aged, and older drivers with a simulated driving assessment course and administered several cognitive tasks. The results of the third study supported the hypothesis in that complex driving situations elicited greater attentional demand among drivers of all ages. Older adults showed greater attentional demand in comparison to young and mid-aged adults even after controlling for baseline response time. Older drivers also scored poorer on a global measure of driving safety. The results of this thesis highlight the roles of intrinsic and extrinsic factors involved in safe driving and are discussed in terms of appropriate interventions to improve road safety.

This thesis presents a 3D reconstruction approach to the detection of static obstacles from a single rear view parking camera. Corner features are tracked to estimate the vehicle’s motion and to perform multiview triangulation in order to reconstruct the scene. We model the camera motion as planar motion and use the knowledge of the camera pose to efficiently solve motion parameters. Based on the observed motion, we selected snapshots from which the scene is reconstructed. These snapshots guarantee a sufficient baseline between the images and result in more robust scene modeling. Multiview triangulation of a feature is performed only if the feature obeys the epipolar constraint. Triangulated features are semantically labelled according to their 3D location. Obstacle features are spatially clustered to reduce false detections. Finally, the distance to the nearest obstacle cluster is reported to the driver.