Sulfonylammonium Ions: Applications In Mechanistic And Synthetic Organosulfur Chemistry

This thesis describes the results obtained from two projects in organosulfur chemistry; both of which involve the use of sulfonylammonium ions. The two projects undertaken involved sulfenes and 3-alkoxysulfonyl trialkylpropanaminium salts ( {lcub}3{rcub}betylates ).;The first project describes efforts undertaken to delineate more precisely the reaction mechanisms of sulfenes, a highly reactive species. The reaction mechanism of sulfene was studied by allowing multiexchange to occur with deuterated traps. Methanol-d was used as the trapping agent in benzene-acetonitrile and deuterium oxide as the trap in a buffered deuterium oxide-dimethoxyethane system. The investigations made use of methanesulfonyl chloride and a series of trialkyl(methylsulfonyl)ammonium fluorosulfate salts as starting materials. The multiexchange results were used to deduce aspects of the mechanism. The results obtained showed that nucleophilic catalysis was not a significant path for formation of sulfene from sulfonyl chlorides when triethylamine was used to promote sulfene formation cut that less hindered amines may react with methane sulfonyl chloride via nucleophilic catalysis to some extent.;The second project involves the synthesis and reactions of {lcub}3{rcub}Betylates(3-(Alkoxysulfonyl)propanaminium salts). {lcub}3{rcub}Betylates are an example of a new type of substrate for aliphatic nucleophilic substitution which enhance the applicability of nucleophilic substitution reactions to problems in organic synthesis by providing a good nucleofuge and phase transfer reagent in one substrate. Unlike their lower homologs, the 2-(alkoxysulfonyl)-ethanimium salts ({lcub}2{rcub}betylates), the {lcub}3{rcub}betylates were found to be quite stable to elimination and thus allow clean nucleophilic substitution with a wider variety of nucleophiles. Although {lcub}3{rcub}betylates are somewhat less reactive than {lcub}2{rcub}betylates they appear to be able to undergo any reaction characteristics of a {lcub}2{rcub}betylates. The {lcub}3{rcub}betylates were synthesized by the reaction of a cyclic sulfonylammonium ion (2,2-dimethylisothiazolidinium 1,1-dioxide fluorosulfate) with alcohols and triethylamine

Experimental testing of four correction algorithms for the forward scattering spectrometer probe

Three number density correction algorithms and one size distribution correction algorithm for the Forward Scattering Spectrometer Probe (FSSP) were compared with data taken by the Phase Doppler Particle Analyzer (PDPA) and an optical number density measuring instrument (NDMI). Of the three number density correction algorithms, the one that compared best to the PDPA and NDMI data was the algorithm developed by Baumgardner, Strapp, and Dye (1985). The algorithm that corrects sizing errors in the FSSP that was developed by Lock and Hovenac (1989) was shown to be within 25 percent of the Phase Doppler measurements at number densities as high as 3000/cc

Variable-camber systems integration and operational performance of the AFTI/F-111 mission adaptive wing

The advanced fighter technology integration, the AFTI/F-111 aircraft, is a preproduction F-111A testbed research airplane that was fitted with a smooth variable-camber mission adaptive wing. The camber was positioned and controlled by flexing the upper skins through rotary actuators and linkages driven by power drive units. The wing camber and control system are described. The measured servoactuator frequency responses are presented along with analytical predictions derived from the integrated characteristics of the control elements. A mission adaptive wing system chronology is used to illustrate and assess the reliability and dependability of the servoactuator system during 1524 hours of ground tests and 145 hours of flight testing

Detection Sensitivity Optimization of Optical Signals Generated by Fiber Optic Bragg Gratings Under Dynamic Excitation

The dynamic response of a fiber optic Bragg grating to mechanical vibrations is examined both theoretically and experimentally. The theoretical expressions describing the consequences of changes in the grating\u27s reflection spectrum are derived for partially coherent beams in an interferometer. The analysis is given in terms of the dominant wavelength, optical bandwidth, and optical path difference of the interfering signals. Changes in the reflection spectrum caused by a periodic stretching and compression of the grating are experimentally measured using an unbalanced Michelson interferometer, a Michelson interferometer with a nonzero optical path difference. The interferometer\u27s sensitivity to changes in the dominant wavelength of the interfering beams is measured as a function of interferometer unbalance and is compared to theoretical predictions. The theoretical analysis enables the user to determine the optimum performance for an unbalanced interferometer. (C) 2003 Society of Photo-Optical Instrumentation Engineers

Cost analysis for the development and operation of a mobile wireless research facility

MBA Professional ReportThe Nemesis program's primary objective is to provide a mobile wireless research facility for Federal agencies and other authorized agencies. The report provides estimates of the Nemesis program's original cost, replication cost, scheduled costing for operational requirements, and budgeting guidelines. The report provides future funding request justification for both labor and equipment lifecycle costs. The report also provides the program funding agencies a more precise cost benefit analysis, to project future operating costs, and to provide standardized budget guidelines. The estimate of the original cost includes equipment acquisitions, software and reference material acquisition, inventory validation, billed labor, estimated non-billed labor, estimated nonbilled infrastructure support, billed training and certification, estimated project management, and estimated administrative support. The estimate of the original cost does not include legal support and Governmental administrative requirements. The replicating cost is determined from the original cost with discovery costs removed. The discovery cost includes initial research/evaluation of alternate methods of system implementation, reduced expertise in labor due to documented replicating procedures, and an improved training process for operators. The costing schedule is based on the projected program-operating tempo. The budgeting guidelines provide the budget format, target parameters for inventory, and capital reinvestment to offset depreciation expenses.Approved for public release; distribution is unlimited.Lieutenant, United States Navyhttp://archive.org/details/costnalysisforde10945994

Model of Effect of Hot Gas Ingress on Temperatures of Turbine Disks

Ingress is the leakage of hot mainstream gas through the rim-seal clearance into the wheel-space between the rotating turbine disk (the rotor) and the adjacent stationary casing (the stator). The high-pressure rotor is purged by a radial outflow of air from the high-pressure compressor, and this cooling air is also used to reduce the ingress. The engine designer needs to predict the stator and rotor temperatures as a function of cooling-flow rate. The sealing effectiveness determines how much air is needed to reduce or prevent ingress; although there are numerous theoretical and experimental papers on the effectiveness of different seal geometries, there are few papers on the effect of ingress on the temperature of the rotating disk. This is an unsolved problem of great practical importance: under high stress, a small increase in metal temperature can significantly reduce operating life. In this paper, conservation equations and control volumes are used to develop theoretical equations for the exchange of mass, concentration and enthalpy in an adiabatic rotor-stator system when ingress occurs. It is assumed that there are boundary layers on the rotor and stator, separated by an inviscid rotating core, and the fluid entrained from the core into the boundary layer on the rotor is recirculated into that on the stator. The superposed cooling flow protects the rotor surface from the adverse effects of hot-gas ingress, which increases the temperature of the fluid entrained into the rotor boundary layer. A theoretical model has been developed to predict the relationship between the sealing effectiveness on the stator and the adiabatic effectiveness on the rotor, including the effects of both ingress and frictional heating. The model involves the use of a nondimensional buffer parameter, Ψ, which is related to the relative amount of fluid entrained into the rotor boundary layer. The analysis shows that the cooling flow acts as a buffer, which attenuates the effect of hot gas ingress on the rotor, but frictional heating reduces the buffer effect. The theoretical effectiveness curves are in good agreement with experimental data obtained from a rotor-stator heat-transfer rig, and the results confirm that the buffer effect increases as the sealing effectiveness of the rim seals decreases. The analysis quantifies the increase in the adiabatic rotor temperature due to direct frictional heating, which is separate from the increase due to the combined effects of the ingress and the indirect frictional heating of the entrained fluid. These combined effects are reduced as Ψ increases, and Ψ = 1 at a critical flow rate above which there is no entrained fluid and consequently no indirect heating of the rotor. The model also challenges the conventional physical interpretation of ingress as, in general, not all the hot gas that enters the rim-seal clearance can penetrate into the wheel-space. The ingress manifests itself through a mixing of enthalpy, which can be exchanged even if no ingested fluid enters the wheel-space.</p

Ignorance management: an alternative perspective on knowledge management in multinational organisations

This paper identifies an alternative perspective on Knowledge Management (KM) in multinational organisations by definition of the concept of Ignorance Management. Furthermore, this paper discusses the difficulties employees face in understanding and comprehending what they need to know to do their jobs, and what implications this can have within global technology intensive environments. The focus is given in particular on multinational organisations where innovation and new knowledge is essential to both short-term opportunistic value capture and longer term business sustainability. Hence, this paper discusses why managing ignorance is essential for maintaining a strategic knowledge sharing culture within multinational organisations. Furthermore, it develops a novel theory on the nature of knowledge and ignorance while making the distinction between knowns and unknowns as well as between consciousness and ignorance. The theoretical findings have been applied to technology intensive and innovative environments. A case study is explored within the paper, based on findings from one of the largest military contractors in the world, which employs over 100,000 people across the globe. The paper adopts an interpretivist philosophy, using the primary strategy of qualitative research. In addition, due to the complexity of the topic, a mixed methods approach has been used for the data collection process. Moreover, participatory action research is undertaken to study individuals’ actions in a particular context and improve organisational strategies and KM practices. The study shows that managing ignorance and adaptiveness in multinational organisations is becoming increasingly important. Thus, the critical question is not just managing what is known but also trying to find ways to manage the unknown. This viewpoint of acknowledging ignorance, if successfully incorporated within a company’s KM strategy, will not only facilitate and enhance knowledge storage and transmission processes but will also undoubtedly play a vital role when referring to a company’s efficiency, productivity and overall performance

Rayleigh-Brillouin Scattering to Determine One-Dimensional Temperature and Number Density Profiles of a Gas Flow Field

Rayleigh-Brillouin spectra for heated nitrogen gas were measured by imaging the output of a Fabry-Perot interferometer onto a CCD array The spectra were compared with the theoretical 6-moment model of Rayleigh-Brillouin scattering convolved with the Fabry-Perot instrument function. Estimates of the temperature and a dimensionless parameter proportional to the number density of the gas as functions of position in the laser beam were calculated by least-squares deviation fits between theory and experiment