When designing a direct methanol fuel cell and evaluating the appropriateness of new materials, it is helpful to consider the impact of material properties on the performance of a complete system. To some degree, poor fuel utilization and performance losses from methanol crossover and low reactant concentrations can be mitigated by proper system design. In order to facilitate system design, an analytical model is developed to evaluate the methanol and oxygen concentration profiles across the membrane electrode assembly of the direct methanol fuel cell. In the first part of this work, the model is used to determine fuel utilization as a function of the feed concentration, backing layer properties, and membrane properties. A minimum stoichiometric ratio is determined based on maintaining zero-order methanol kinetics, which allows the fuel efficiency to be optimized by controlling these physical properties. The size of system components such as the methanol storage tank and the fuel pump can be estimated based on the minimum methanol flow rate that those components must produce to deliver a specified current; in this way, the system-level benefits of reduced membrane crossover can be evaluated. In the second section, the model is extended by using the Bulter-Volmer equation to describe the anodic and cathodic overpotentials along a single cross-section of the fuel cell. An iterative technique is then used to determine the methanol and oxygen concentration profiles in the flow channels. The model is applied to examine the benefits of new low-crossover membranes and to suggest new design parameters for those membranes. Also, the tradeoff between the power output of the fuel cell stack and the size of system components is examined across a range of methanol and oxygen flow rates. / text

No description available.

The direct methanol fuel cell (DMFC) is considered to be a promising power source for portable electronic applications and transportation. At present there are several challenges that need to be addressed before the widespread commercialization of the DMFC technology can be implemented. The methanol electro oxidation reaction is sluggish, mainly due to the strong adsorption of the reaction intermediate carbon monoxide on platinum. Further, methanol crosses over to the cathode, which decreases the fuel utilization and causes cathode catalyst poisoning. Another issue is the accumulation of the reaction product CO₂ (g) in the anode, which increases the Ohmic resistance and blocks reactant mass transfer pathways. A novel anode configuration is proposed to address the aforementioned challenges. An extended reaction zone (thickness = ∼100-300 µm) is designed to facilitate the oxidation of methanol on sites that are not close to the membrane-electrode interface. Thus, the fuel concentration near the membrane may decrease significantly, which may mitigate adverse effects caused by methanol cross-over. The structure of the fibrous electrode, with its high void space, is believed to aid the disengagement of CO₂ gas. In this thesis the first objective was to deposit dispersed nanoparticle PtRu(Mo) catalysts onto graphite felt substrates by surfactant mediated electrodeposition. Experiments, in which the surfactant concentration, current density, time and temperature were varied, were conducted with the objective of increasing the active surface area and thus improving the reactivity of the electrodes with respect to methanol electro-oxidation. The three-dimensional electrodes were characterized with respect to their deposit morphology, surface area, composition and catalytic activity. The second objective of this work was to utilize the catalyzed electrodes as anodes for direct methanol fuel cell operation. The fuel cell performance was studied as a function of methanol concentration, flow rate and temperature by using a single cell with a geometric area of 5 cm². Increased power densities were obtained with an in-house prepared 3D PtRu anode compared to a conventional PtRu catalyst coated membrane. Coating graphite felt substrates with catalytically active nanoparticles and the utilization of these materials, is a new approach to improve the performance of direct fuel cells.

No description available.

In methanol processing plants, steam-methane reformers consist of hundreds of vertical tubes operating at temperatures up to 1000°C. These reformer tubes fail by creep through the formation of creep voids during service. Preliminary research showed that the occurrence of these voids was not random and may be related to certain microstructural features of the material. In the present research, the technique of serial sectioning was used to generate threedimensional reconstructions of voids in several steam-methane reformer tube samples with creep damage. The serial sectioning method and subsequent 3D reconstruction revealed creep void information such as size, density, location, and shape in three-dimensions, information that cannot be obtained from two-dimensional micrographs alone. Samples were obtained at various locations along the length of an ex-service reformer tube to investigate the effects of service conditions on the characteristics of creep voids. In addition, samples were taken from various positions along the wall thickness where there were differences in temperature, stress, and microstructure. Additionally, the identity and crystallographic orientations of the phases adjacent to creep voids were studied by electron backscatter diffraction (EBSD) to determine the crystallographic trends in creep void locations. Three dimensional observations revealed that creep voids were indeed not uniformly distributed through the volume in terms of their size, shape, and location. All voids appeared next to carbides and these voids came into contact with M₂₃C₆ precipitates somewhere along their perimeter. Most of the voids were found on austenite (ɣ) grain facets (the interface between two ɣ grains) but the larger voids were generally found at grain edges and corners. The grain boundaries where voids were located were generally oriented at 45 degrees with respect to the hoop stress direction. Here, the effective stress due to a combination of loading and temperature were highest. xviii Abstract EBSD results showed that 80% of the M₂₃C₆ precipitates surrounding these voids have an irrational crystallographic orientation relationship (OR) with the austenite matrix. In contrast, grain boundary precipitates in an aged sample always show a rational OR with respect to one adjacent grain. This implied that the preferred sites for creep voids are low registry boundaries between M₂₃C₆ precipitates and austenite. The data obtained from 3D observations were applied to a classic void growth model. Various permutations of the parameters obtained from this work were applied to the model to simulate conditions that may be beneficial to extending the service lives of reformer tubes. It was shown that the void growth model required accurate and representative materials constants for good estimation of life. Furthermore, the model revealed that more work was required in terms of observations of void nucleation in 3D, in order to fully utilize the model. Finally, it was shown that void density measurements are the most critical item for accurate prediction of growth of voids.

No description available.

Chromatography is a widely used separation technique including many different modes, for example supercritical fluid chromatography (SFC) which uses a supercritical fluid as mobile phase. A supercritical fluid is achieved when a substance is subjected to a temperature and pressure above the critical point and the boundary between the liquid phase and gas phase is erased. The interest for SFC has increased in recent years, mainly for separation of chiral molecules in the pharmaceutical industry. What makes SFC interesting is that it is a quick, cost-efficient and green method. This is in part due to less organic solvent used in the mobile phase in SFC compared with liquid chromatography and that the carbon dioxide that represents the major part of the mobile phase is a by-product from other processes. In SFC modifiers, often small alcohols, are added to carbon dioxide based mobile phase in order to increase the solubility of polar compounds. In this study the adsorption of methanol to two different stationary phases; Kromasil-Diol and chiral Lux Cellulose-4 were studied. Adsorption is a phenomenon where surface interactions crate a higher density of molecules at the surface than in the bulk. The aim of this work has been to study the adsorption of modifier (methanol) to the stationary phase both to determine the extent of adsorption and the kinetics for system equilibration. These findings were then put into perspective of normal use of SFC for separation of molecules. There are a number of techniques for measuring adsorption; in this study the tracer pulse method is used. This is a pulse method where a concentration plateau is created and an isotope labelled molecule is injected. This was performed in the mobile phase composition from pure carbon dioxide to pure methanol. In addition to the tracer pulse experiments the isotope effect, the eluent flow, equilibration times for the column and retention times for a set of analytes were measured. For the Diol column no large isotope effect was observed, the method was also proved to be highly reproducible since several runs gave consistent results. Calculations based on the experimental data showed that a 6.3 Å thick layer was built up at a methanol fraction of 13% (v/v), corresponding to a monolayer. Changes of the methanol fraction below the saturation level has has greater effect on the retention factor for the analytes than at higher methanol fractions, when the monolayer was saturated. The conclusion of this is that SFC is more stable in the area where the layer has been built up. A preliminary study has been made for the chiral Lux Cellulose-4 column which was not as conclusive as for the Kromasil-Diol column. This type of column needs further studies to confirm the deviating observations and to investigate the cause for these.

This thesis described the development of new catalytic system for the conversion of natural gas (methane) to liquid products such as methanol and formaldehyde. This technology can allow the exploitation of small and medium size gas fields without the need to build an expensive gas to liquid plants or long pipelines. The technology is based on a concept of non-separating membrane reactor where an inorganic membrane paper serves as a catalyst support through which a reaction mixture is flowing under mild conditions and short residence times.

The direct methanol fuel cell (DMFC) is considered to be a promising power source for portable electronic applications and transportation. At present there are several challenges that need to be addressed before the widespread commercialization of the DMFC technology can be implemented. The methanol electro oxidation reaction is sluggish, mainly due to the strong adsorption of the reaction intermediate carbon monoxide on platinum. Further, methanol crosses over to the cathode, which decreases the fuel utilization and causes cathode catalyst poisoning. Another issue is the accumulation of the reaction product CO₂ (g) in the anode, which increases the Ohmic resistance and blocks reactant mass transfer pathways. A novel anode configuration is proposed to address the aforementioned challenges. An extended reaction zone (thickness = ∼100-300 µm) is designed to facilitate the oxidation of methanol on sites that are not close to the membrane-electrode interface. Thus, the fuel concentration near the membrane may decrease significantly, which may mitigate adverse effects caused by methanol cross-over. The structure of the fibrous electrode, with its high void space, is believed to aid the disengagement of CO₂ gas. In this thesis the first objective was to deposit dispersed nanoparticle PtRu(Mo) catalysts onto graphite felt substrates by surfactant mediated electrodeposition. Experiments, in which the surfactant concentration, current density, time and temperature were varied, were conducted with the objective of increasing the active surface area and thus improving the reactivity of the electrodes with respect to methanol electro-oxidation. The three-dimensional electrodes were characterized with respect to their deposit morphology, surface area, composition and catalytic activity. The second objective of this work was to utilize the catalyzed electrodes as anodes for direct methanol fuel cell operation. The fuel cell performance was studied as a function of methanol concentration, flow rate and temperature by using a single cell with a geometric area of 5 cm². Increased power densities were obtained with an in-house prepared 3D PtRu anode compared to a conventional PtRu catalyst coated membrane. Coating graphite felt substrates with catalytically active nanoparticles and the utilization of these materials, is a new approach to improve the performance of direct fuel cells.

Zugl.: Stuttgart, Univ., Diss., 2007