Thermally induced evolution of morphology on ceramic surfaces in a thermionic converter

The morphology of alumina and scandia ceramics exposed to controlled vacuum and diffusion modes in a thermionic converter has been studied. Evidence for vaporization at a temperature of 1,770 K is manifest in the resulting surface morphologies of both ceramics, consistent with reported sample mass loss. Alumina shows intergranular relief with the formation of terrace--step structure on the grain surfaces. Terrace formation is not directly observed on scandia, however the development of vertical structure and maintenance of voids indicates that vaporization is initiated by structure at the grain edges. Extensive Sc{sub 2}O{sub 3} re-deposition occurs on the scandia surface, possibly mediated by the presence of molybdenum and tungsten. Evidence exists for refractory metal secondary phase formation in this deposit in the form of Sc{sub 6}MO{sub 12} (M = W or Mo). Alumina also shows evidence for materials` interactions in the form of tantalum assisted vaporization which significantly alters the terrace structure

Generation of Chloride Active Defects at the Aluminum Oxide Surface for the Study of Localized Corrosion Initiation

The generation of surface defects on electron cyclotron resonance (ECR) plasma derived aluminum oxide films has been studied. We find that Cl active O vacancies can be generated using electron and ion irradiation yielding surface concentrations of 3 xl 013 to 1X1014 sites"cm-2. These values correspond to surface defect concentrations of 3 to 10% when compared to ordered, crystalline u-alumina. The vacancies appear to be responsible for increased surface O concentrations when immersed in water. Anodic polarization of irradiated films yields a decrease in the stable pitting potential which correlates with electron dose

Evaluation of the metal/adhesive interfaces in the MC2370 fire set

Several analysis methods have been applied to evaluate the structure and composition of the electrode/adhesive interfaces i previously fielded M2370 Fire Sets. A method of interfacial fracture at cryogenic temperatures as been employed to expose regions of these interfaces at multiple levels in a SFE stack. Electron microscopy shows that bond failure induced by the fracture is predominantly adhesive with an equal probability of failure of the Au and Cu interfaces. Some evidence for cohesive, indicative of a possible microstructure related to electrical breakdown. Pinhole-free larger regions of adhesive also exist which may explain the observed high resistance in impedance measurements

Cesium/oxide interactions for ultrathin films on {alpha}-Al{sub 2}O{sub 3}(0001) and {alpha}-Al{sub 2}O{sub 3}(1{bar 1}02)

The interaction of cesium at the (0001) and (1{bar 1}02) surfaces of sapphire has been investigated using a variety of surface analytical techniques. Reflection mass spectrometric measurements yield initial Cs adsorption probabilities of 0.9 and 0.85 for the unreconstructed (0001) and (1{bar 1}02) surfaces, respectively. The adsorption probability decreases dramatically for these surfaces at critical Cs coverages of 2.O {times} 10{sup 14} and 3.4 {times} 10{sup 14} atoms/cm{sup 2}, respectively. Thermally induced reconstruction of the (0001) surface to form an oxygen deficient surface results in a decrease in the initial probability and capacity for Cs adsorption. Low energy electron diffraction (LEED) demonstrates that an intermediate, mixed domain surface yields an initial adsorption probability of 0.5 while a ({radical}31 {times} {radical}31) R {plus_minus} 9{degree} reconstructed surface yields a value of 0.27. Thermal desorption mass spectrometry (TDMS) shows that surface reconstruction eliminates the high binding energy states of Cs (2.7 eV/atom), consistent with the observed changes in adsorption probability. In contrast, reconstruction of the (1{bar 1}02) surface produces only minor changes in Cs adsorption. X-ray photoelectron spectroscopy (XPS) indicates that no formal reductive/oxidative chemistry takes place at the interface. We interpret the facile adsorption and strong binding of Cs on sapphire to result from Cs interacting with coordinatively unsaturated oxygen

Electron induced surface chemistry at the Cs/sapphire interface

Electron induced etching of sapphire in the presence of Cs has been studied using a variety of surface analytical techniques. We find that this process occurs on both the (0001) and (1102) orientations of sapphire. Monolayer amounts of Al and sub-oxides of Al are thermally desorbed from the surface at temperatures as low as 1000 K when the surface is irradiated with electrons in the presence of Cs. Etching is highly dependent on Cs coverage with the (0001) and (1102) surfaces requiring 2.0 {times} 10{sup 14} and 3.4 {times} 10{sup 14} atoms/cm{sup 2} to support etching, respectively. Adsorption profiles demonstrate that these coverages correspond to initial saturation of the surface with Cs. Electron damage of the surface in the absence of Cs also produces desorption of Al and sub-oxides of Al indicating a possible mechanism for etching. The impact of etching on the surface is to increase the adsorption capacity on the (0001) surface while decreasing both initial adsorption probability and capacity on the (1102) surface

Low work function thermionic emission materials

Thermionic energy conversion in a microminiature format shows potential as a viable, high efficiency, on-chip power source. Microminiature thermionic converters (MTC) with inter-electrode spacings on the order of microns are currently being prototyped and evaluated at Sandia. The remaining enabling technology is the development of low work function materials and processes than can be integrated into these converters. In this report, the authors demonstrate a method of incorporating thin film emitters into converters using rf sputtering. They find that the resultant films possess a minimum work function of 1.2 eV. Practical energy conversion is hindered by surface work function non-uniformity. They postulate the source of this heterogeneity to be a result of limited bulk and surface transport of barium. Several methods are proposed for maximizing transport, including increased film porosity and the use of metal terminating layers. They demonstrate a novel method for incorporating film porosity based on metal interlayer coalescence

Electrochemical and spectroscopic evaluation of lithium intercalation in tailored polymethacrylonitrile carbons

Disordered polymethacrylonitrile (PMAN) carbon monoliths have been studied as potential tailored electrodes for lithium ion batteries. A combination of electrochemical and surface spectroscopic probes have been used to investigate irreversible loss mechanisms. Voltammetric measurements show that Li intercalates readily into the carbon at potentials 1V positive of the reversible Li potential. The coulometric efficiency rises rapidly from 50% for the first potential cycle to greater than 85% for the third cycle, indicating that solvent decomposition is a self-limiting process. Surface film composition and thickness, as measured by x-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS), does not vary substantially when compared to more ordered carbon surfaces. Li{sup +} profiles are particularly useful in discriminating between the bound states of Li at the surface of solution permeable PMAN carbons

Characterization of Sputter Deposited Thin Film Scandate Cathodes for Miniaturized Thermionic Converter Applications

We have successfully developed a method for fabricating scandate-based thermionic emitters in thin film form. The primary goal of our effort is to develop thin film emitters that exhibit low work fimction, high intrinsic electron emissivity, minimum thermal activation properties and that can be readily incorporated into a microgap converter. Our approach has been to incorporate BaSrO into a SqOq matrix using rf sputtering to produce thin films. Diode testing has shown the resulting films to be electron emissive at temperatures as low as 900 K with current densities of 0.1 mA.cm-2 at 1100 K and saturation voltages. We calculate an approximate maximum work function of 1.8 eV and an apparent emission constant (Richardson's constant, A*) of 36 mA.cm-2.K-2. Film compositional and structural analysis shows that a significant surface and subsurface alkaline earth hydroxide phase can form and probably explains the limited utilization and stability of Ba and its surface complexes. The flexibility inherent in sputter deposition suggests alternate strategies for eliminating undesirable phases and optimizing thin film emitter properties