Development of a direct evaporation bismuth Hall thruster

Hall thrusters have been under active development around the world since the 1960’s. Thrusters using traditional propellants such as xenon have been flown on a variety of satellite orbit raising and maintenance missions with an excellent record. To expand the mission envelope, it is necessary to lower the specific impulse of the thrusters but xenon and krypton are poor performers at specific impulses below 1,200 seconds. To enhance low specific impulse performance, this dissertation examines the development of a Hall-effect thruster which uses bismuth as a propellant. Bismuth, the heaviest non-radioactive element, holds many advantages over noble gas propellants from an energetics as well as a practical economic standpoint. Low ionization energy, large electron-impact crosssection and high atomic mass make bismuth ideal for low-specific impulse applications. The primary disadvantage lies in the high temperatures which are required to generate the bismuth vapors. Previous efforts carried out in the Soviet Union relied upon the complete bismuth vaporization and gas phase delivery to the anode. While this proved successful, the power required to vaporize and maintain gas phase throughout the mass flow system quickly removed many of the efficiency gains expected from using bismuth. To solve these problems, a unique method of delivering liquid bismuth to the anode has been developed. Bismuth is contained within a hollow anode reservoir that is capped by a porous metallic disc. By utilizing the inherent waste heat generated in a Hall thruster, liquid bismuth is evaporated and the vapors pass through the porous disc into the discharge chamber. Due to the high temperatures and material compatibility requirements, the anode was fabricated out of pure molybdenum. The porous vaporizer was not available commercially so a method of creating a refractory porous plate with 40-50% open porosity was developed. Molybdenum also does not respond well to most forms of welding so a diffusion bonding process was also developed to join the molybdenum porous disc to the molybdenum anode. Operation of the direct evaporation bismuth Hall thruster revealed interesting phenomenon. By utilizing constant current mode on a discharge power supply, the discharge voltage settles out to a stable operating point which is a function of discharge current, anode face area and average pore size on the vaporizer. Oscillations with a 40 second period were also observed. Preliminary performance data suggests that the direct evaporation bismuth Hall thruster performs similar to xenon and krypton Hall thrusters. Plume interrogation with a Retarding Potential Analyzer confirmed that bismuth ions were being efficiently accelerated while Faraday probe data gave a view of the ion density in the exhausted plume.

Soft Lewis acid catalyzed cycloisomerization of oxo-alkynes and enynes

In the literature, some transition metal salts have been used as soft Lewis acids to activate alkynes toward nucleophilic attack. For example, Pt(II), Au(I) and Pd(II) catalysts can catalyze cycloisomerization reactions of alkynyl compounds to give a variety of cyclic products. In order to expand the scope of these reactions, in chapter 2 of this dissertation, several alkynyl epoxides were isomerized to cyclic allyl vinyl ethers using PtCl2 as the catalyst. Three of these allyl vinyl ethers were hydrolyzed to 2-hydroxymorpholine derivatives and two were converted to piperidine derivatives by thermal Claisen rearrangement. In order to find more benign and inexpensive catalysts for these types of reactions, in chapter 3 of this dissertation, BiCl3 was used to catalyze the isomerization of eight enynes to pyrrolidine derivatives. This reaction was normally catalyzed by expensive noble metal catalysts, such as Pd(II), Pt(II) and Au(I). All the cyclic products are valuable intermediates in the synthesis of bioactive molecules, these soft Lewis acid catalyzed cycloisomerization may find applications in the synthesis of bioactive molecules.

SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS FOR DYE-SENSITIZED SOLAR CELLS

Graphene, which is a two-dimensional carbon material, exhibits unique properties that promise its potential applications in photovoltaic devices. Dye-sensitized solar cell (DSSC) is a representative of the third generation photovoltaic devices. Therefore, it is important to synthesize graphene with special structures, which possess excellent properties for dye-sensitized solar cells. This dissertation research was focused on (1) the effect of oxygen content on the structure of graphite oxide, (2) the stability of graphene oxide solution, (3) the application of graphene precipitate from graphene oxide solution as counter electrode for DSSCs, (4) the development of a novel synthesis method for the three-dimensional graphene with honeycomb-like structure, and (5) the exploration of honeycomb structured graphene (HSG) as counter electrodes for DSSCs. Graphite oxide is a crucial precursor to synthesize graphene sheets via chemical exfoliation method. The relationship between the oxygen content and the structures of graphite oxides was still not explored. In this research, the oxygen content of graphite oxide is tuned by changing the oxidation time and the effect of oxygen content on the structure of graphite oxide was evaluated. It has been found that the saturated ratio of oxygen to carbon is 0.47. The types of functional groups in graphite oxides, which are epoxy, hydroxyl, and carboxylgroups, are independent of oxygen content. However, the interplanar space and BET surface area of graphite oxide linearly increases with increasing O/C ratio. Graphene oxide (GO) can easily dissolve in water to form a stable homogeneous solution, which can be used to fabricate graphene films and graphene based composites. This work is the first research to evaluate the stability of graphene oxide solution. It has been found that the introduction of strong electrolytes (HCl, LiOH, LiCl) into GO solution can cause GO precipitation. This indicates that the electrostatic repulsion plays a critical role in stabilizing aqueous GO solution. Furthermore, the HCl-induced GO precipitation is a feasible approach to deposit GO sheets on a substrate as a Pt-free counter electrode for a dye-sensitized solar cell (DSSC), which exhibited 1.65% of power conversion efficiency. To explore broad and practical applications, large-scale synthesis with controllable integration of individual graphene sheets is essential. A novel strategy for the synthesis of graphene sheets with three-dimensional (3D) Honeycomb-like structure has been invented in this project based on a simple and novel chemical reaction (Li2O and CO to graphene and Li2CO3). The simultaneous formation of Li2CO3 with graphene not only can isolate graphene sheets from each other to prevent graphite formation during the process, but also determine the locally curved shape of graphene sheets. After removing Li2CO3, 3D graphene sheets with a honeycomb-like structure were obtained. This would be the first approach to synthesize 3D graphene sheets with a controllable shape. Furthermore, it has been demonstrated that the 3D Honeycomb-Structured Graphene (HSG) possesses excellent electrical conductivity and high catalytic activity. As a result, DSSCs with HSG counter electrodes exhibit energy conversion efficiency as high as 7.8%, which is comparable to that of an expensive noble Pt electrode.