Publications

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.

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.

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.

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.

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.

Adsorption/desorption were studied using combined surface analytical techniques. An approximate initial sticking coefficient for Cs on sapphire was measured using reflection mass spectrometry and found to be 0.9. Thermal Desorption Mass Spectrometry (TDMS) and Auger Electron Spectroscopy (AES) were used to verify that a significant decrease in sticking coefficient occurs as the Cs coverage reaches a critical submonolayer value. TDMS analysis demonstrates that Cs is stabilized on a clean sapphire surface at temperatures (1200 K) in excess of the temperatures experienced by sapphire in a TOPAZ-2 thermionic fuel element (TFE). Surface contaminants on sapphire can enhance Cs adsorption relative to the clean surface. C contamination eliminates the high temperature state of Cs desorption found on clean sapphire but shifts the bulk of the C desorption from 400 to 620 K. Surface C is a difficult contaminant to remove from sapphire, requiring annealing above 1400 K. Whether Cs is stabilized on sapphire in a TFE environment will most likely depend on relation between surface contamination and surface structure.