Publications

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A series of pressurized sulfuric acid decomposition tests are being performed to (1) obtain data on the fraction of sulfuric acid catalytically converted to sulfur dioxide, oxygen, and water as a function of temperature and pressure, (2) demonstrate real-time measurements of acid conversion for use as process control in the Sulfur-Iodine (SI) thermochemical cycle, and (3) obtain multiple measurements of conversion as a function of temperature within a single experiment. Acid conversion data are presented at pressures of 6 and 11 bars in the temperature range of 750 - 875 °C. The design for an acid decomposer section with heat and mass recovery of undecomposed acid using a direct contact heat exchanger are presented.

In an effort to produce hydrogen without the unwanted greenhouse gas byproducts, high-temperature thermochemical cycles driven by heat from solar energy or next-generation nuclear power plants are being explored. The process being developed is the thermochemical production of Hydrogen. The Sulfur-Iodide (SI) cycle was deemed to be one of the most promising cycles to explore. The first step of the SI cycle involves the decomposition of H{sub 2}SO{sub 4} into O{sub 2}, SO{sub 2}, and H{sub 2}O at temperatures around 850 C. In-situ removal of O{sub 2} from this reaction pushes the equilibrium towards dissociation, thus increasing the overall efficiency of the decomposition reaction. A membrane is required for this oxygen separation step that is capable of withstanding the high temperatures and corrosive conditions inherent in this process. Mixed ionic-electronic perovskites and perovskite-related structures are potential materials for oxygen separation membranes owing to their robustness, ability to form dense ceramics, capacity to stabilize oxygen nonstoichiometry, and mixed ionic/electronic conductivity. Two oxide families with promising results were studied: the double-substituted perovskite A{sub x}Sr{sub 1-x}Co{sub 1-y}B{sub y}O{sub 3-{delta}} (A=La, Y; B=Cr-Ni), in particular the family La{sub x}Sr{sub 1-x}Co{sub 1-y}Mn{sub y}O{sub 3-{delta}} (LSCM), and doped La{sub 2}Ni{sub 1-x}M{sub x}O{sub 4} (M = Cu, Zn). Materials and membranes were synthesized by solid state methods and characterized by X-ray and neutron diffraction, SEM, thermal analyses, calorimetry and conductivity. Furthermore, we were able to leverage our program with a DOE/NE sponsored H{sub 2}SO{sub 4} decomposition reactor study (at Sandia), in which our membranes were tested in the actual H{sub 2}SO{sub 4} decomposition step.

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A series of three pressurized sulfuric acid decomposition tests were performed to (1) obtain data on the fraction of sulfuric acid catalytically converted to sulfur dioxide, oxygen, and water as a function of temperature and pressure, (2) demonstrate real-time measurements of acid conversion for use as process control, (3) obtain multiple measurements of conversion as a function of temperature within a single experiment, and (4) assess rapid quenching to minimize corrosion of metallic components by undecomposed acid. All four of these objectives were successfully accomplished. This report documents the completion of the NHI milestone on high pressure H{sub 2}SO{sub 4} decomposition tests for the Sulfur-Iodine (SI) thermochemical cycle project. All heated sections of the apparatus, (i.e. the boiler, decomposer, and condenser) were fabricated from Hastelloy C276. A ceramic acid injection tube and a ceramic-sheathed thermocouple were used to minimize corrosion of hot liquid acid on the boiler surfaces. Negligible fracturing of the platinum on zirconia catalyst was observed in the high temperature decomposer. Temperature measurements at the exit of the decomposer and at the entry of the condenser indicated that the hot acid vapors were rapidly quenched from about 400 C to less than 20 C within a 14 cm length of the flow path. Real-time gas flow rate measurements of the decomposition products provided a direct measurement of acid conversion. Pressure in the apparatus was preset by a pressure-relief valve that worked well at controlling the system pressure. However, these valves sometimes underwent abrupt transitions that resulted in rapidly varying gas flow rates with concomitant variations in the acid conversion fraction.

This work describes the design, computational prototyping, fabrication, and characterization of a microfabricated thermal conductivity detector ({mu}TCD) to analyze the effluent from a micro-gas chromatograph column ({mu}GC) and to complement the detection efficacy of a surface acoustic wave detector in the micro-ChemLab{trademark} system. To maximize the detection sensitivity, we designed a four-filament Wheatstone bridge circuit where the resistors are suspended by a thin silicon nitride membrane in pyramidal or trapezoidal shaped flow cells. The geometry optimization was carried out by simulation of the heat transfer in the devices, utilizing a boundary element algorithm. Within microfabrication constraints, we determined and fabricated nine sensitivity-optimized geometries of the {mu}TCD. The nine optimal geometries were tested with two different flow patterns. We demonstrated that the perpendicular flow, where the gas directly impinged upon the membrane, yielded a sensitivity that is three times greater than the parallel flow, where the gas passed over the membrane. The functionality of the {mu}TCD was validated with the theoretical prediction and showed a consistent linear response to effluent concentrations, with a detection sensitivity of 1 ppm, utilizing less than 1 W of power.

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Experimental data are compiled and reviewed for aerosol particle releases due to combustion in air of Plutonium (Pu). The aerosol release fraction (ARF), which is the mass of Pu aerosolized, divided by the mass of Pu oxidized, is dependent on whether the oxidizing Pu sample is static (i.e. stationary) or dynamic (i.e. falling in air). ARF data are compiled for sample masses ranging from 30 mg to 1770 g, oxidizing temperatures varying from 113 C to {approx}1000 C, and air flow rates varying from 0.05 m/s to 5.25 m/s. The measured ARFs range over five orders of magnitude. The maximum observed static ARF is 2.4 x 10{sup -3}, and this is the recommended ARF for safety studies of static Pu combustion.

Three levels of fission product diffusional release models are solved exactly. First, the Booth model for a homogeneous uncoated spherical fuel particle is presented and an improved implementation is suggested. Second, the release from a fuel particle with a single barrier layer is derived as a simple alternative to account for a coating layer. Third, the general case of release from a multicoated fuel particle is derived and applied to a TRISO-coated fuel. Previous approaches required approximate numerical solutions for the case of an arbitrary number of coatings with arbitrary diffusivities and arbitrary coating interface conditions.

This work describes the design, simulation, fabrication and characterization of a microfabricated thermal conductivity detector to be used as an extension of the {micro}ChemLab{trademark}. The device geometry was optimized by simulating the heat transfer in the device, utilizing a boundary element algorithm. In particular it is shown that within microfabrication constraints, a micro-TCD optimized for sensitivity can be readily calculated. Two flow patterns were proposed and were subsequently fabricated into nine-promising geometries. The microfabricated detector consists of a slender metal film, supported by a suspended thin dielectric film over a pyramidal or trapezoidal silicon channel. It was demonstrated that the perpendicular flow, where the gas directly impinges on the membrane, creates a device that is 3 times more sensitive than the parallel flow, where the gas passed over the membrane. This resulted in validation of the functionality of a microfabricated TCD as a trace-level detector, utilizing low power. the detector shows a consistent linear response to concentration and they are easily able to detect 100-ppm levels of CO in He. Comparison of noise levels for this analysis indicates that sub part per million (ppm) levels are achievable with the selection of the right set of conditions for the detector to operate under. This detector was originally proposed as part of a high-speed detection system for the petrochemical gas industry. This system was to be utilized as a process monitor to detect reactor ''upset'' conditions before a run away condition could occur (faster than current full-scale monitoring systems were able to achieve). Further outlining of requirements indicated that the detection levels likely achievable with a TCD detector would not be sufficient to meet the process condition needs. Therefore the designed and fabricated detector was integrated into a detection system to showcase some technologies that could further the development of components for the current gas phase {micro}ChemLab as well as future modifications for process monitoring work such as: pressurized connections, gas sampling procedures, and packed columns. Component integration of a microfabricated planar pre-concentrator, gas-chromatograph column and TCD in the separation/detection of hydrocarbons, such as benzene, toluene and xylene (BTX) was also demonstrated with this system.