Publications

Abstract not provided.

A series of arylalcohols [H-OAr where OAr = OC{sub 6}H{sub 5} (OPh), OC{sub 6}H{sub 4}(2-Me) (oMP), OC{sub 6}H{sub 3}(2,6-Me){sub 2} (DMP), OC{sub 6}H{sub 4}(2-Pr{prime}) (oPP), OC{sub 6}H{sub 3}(2,6-Pr{prime}){sub 2} (DIP), OC{sub 6}H{sub 4}(2-Bu{prime}) (oBP), OC{sub 6}H{sub 3}(2,6-Bu{prime}){sub 2} (DBP) where Me = CH{sub 3}, Pr{prime} = CHMe{sub 2}, and Bu{prime} = CMe{sub 3}] were reacted with LiN(SiMe{sub 3}){sub 2} in pyridine (py) to generate the appropriate ``Li(OAr)(py){sub x}'' complex. The resultant products were characterized by single crystal X-ray diffraction as: [Li(OPh)(py){sub 2}]{sub 2} (1), [Li(oMP)(py){sub 2}]{sub 2} (2), [Li(DMP)(py){sub 2}]{sub 2} (3), [Li(oPP)(py){sub 2}]{sub 2} (4), [Li(DIP)(py){sub 2}]{sub 2} (5), [Li(oBP)(py){sub 2}]{sub 2} (6), and [Li(DBP)(py)]{sub 2} (7). Compounds 1--6 adopt a dinuclear, edge-shared tetrahedral complex. For 7, due to the steric crowding of the DBP ligand, only one py is coordinated yielding a dinuclear fused trigonal planar arrangement. Two additional structure types were also characterized for the DIP ligand as [Li(DIP)(H-DIP)(py)]{sub 2} (5b) and [Li{sub 2}(DIP){sub 2}(py){sub 3}] (5c). {sup 6,7}Li and {sup 13}C NMR solid state MAS spectroscopy indicated that the bulk powder was consistent with the crystalline material. Solution state NMR spectroscopy revealed a symmetric molecule existed in solution for 1--7.

Erbium hydride thin films are grown onto polished, a-axis {alpha} Al{sub 2}O{sub 3} (sapphire) substrates by reactive ion beam sputtering and analyzed to determine composition, phase and microstructure. Erbium is sputtered while maintaining a H{sub 2} partial pressure of 1.4 x 10{sup {minus}4} Torr. Growth is conducted at several substrate temperatures between 30 and 500 C. Rutherford backscattering spectrometry (RBS) and elastic recoil detection analyses after deposition show that the H/Er areal density ratio is approximately 3:1 for growth temperatures of 30, 150 and 275 C, while for growth above {approximately}430 C, the ratio of hydrogen to metal is closer to 2:1. However, x-ray diffraction shows that all films have a cubic metal sublattice structure corresponding to that of ErH{sub 2}. RBS and Auger electron that sputtered erbium hydride thin films are relatively free of impurities.

A substantial decrease in hydrostatic ferroelectric (FE) to antiferroelectric (AFE) transformation pressure was measured for Pb(Zr{sub 0.949}Ti{sub 0.051}){sub 0.989}Nb{sub 0.0182}O{sub 3} ceramics with decreasing grain size. The 150 MPa decrease in hydrostatic FE to AFE transformation pressure over the grain size range of 8.5 {micro}m to 0.7{micro}m was shown to be consistent with enhanced internal stress with decreasing grain size. Further, the Curie Point decreased and the dielectric constant measured at 25 C increased with decreasing grain size. All three properties: dielectric constant magnitude, Curie point shift and FE to AFE phase transformation pressure were shown to be semi-quantitatively consistent with internal stress differences on the order of 100 MPa. Calculations of Curie point shifts from the Clausius-Clapeyron equation, using internal stress levels derived from the hydrostatic depoling characteristics, were consistent with measured values.

The authors have investigated LiNi{sub 0.8}Co{sub 0.2}O{sub 2} (Sumitomo) and LiNi{sub 5/8}Co{sub 1/4}Mn{sub 1/16}Al{sub 1/16}O{sub 2} (Sandia chemical preparation method) cathode powders via in-situ X-ray Diffraction and Cyclic Voltammetry using a coffee-bag type electrochemical cell. Both cathode materials did not show a monoclinic distortion during de-intercalation but sustained the hexagonal structure up to 4.3 V. The doping of Co into the LiNiO{sub 2} structure appears to stabilize this lattice as the hexagonal structure over the full range of charging (up to 4.3 V). The LiNi{sub 5/8}Co{sub 1/4}Mn{sub 1/16}Al{sub 1/16}O{sub 2} cathode material exhibited a 160 mAh/g capacity (to 4.1 V) on its 1{sup st} cycle, while displaying a much smaller volume change (as compared to LiNi{sub 0.8}Co{sub 0.2}O{sub 2}) during de-intercalation. This reduced overall volume change (2.5 vol%) may have important implications for cycle life of this material.

Embedded resistor circuits have been generated with the use of a Micropen system Ag conductor paste (DuPont 6142D), a new experimental resistor ink from DuPont (E84005-140), and Low Temperature Co-fired Ceramic (LTCC) green tape (DuPont A951). Sample circuits were processed under varying peak temperature ranges (835 C-875 C) and peak soak times (10 min-720 min). Resistors were characterized by SEM, TEM, EDS, and high-temperature XRD. Results indicate that devitrification of resistor glass phase to Celcian, Hexacelcian, and a Zinc-silicate phase occurred in the firing ranges used (835-875 C) but kinetics of divitrification vary substantially over this temperature range. The resistor material appears structurally and chemically compatible with the LTCC. RuO{sub 2} grains do not significantly react with the devitrifying matrix material during processing. RuO{sub 2} grains coarsen significantly with extended time and temperature and the electrical properties appear to be strongly affected by the change in RuO{sub 2} grain size.

Magnesium vanadates are potentially important catalytic materials for the conversion of alkanes to alkenes via oxidative dehydrogenation. However, little is known about the active sites at which the catalytic reactions take place. It may be possible to obtain a significant increase in the catalytic efficiency if the effects of certain material properties on the surface reactions could be quantified and optimized through the use of appropriate preparation techniques. Given that surface reactivity is often dependent upon surface structure and that the atomic level structure of the active sites in these catalysts is virtually unknown, we desire thin film samples consisting of a single magnesium vanadate phase and a well defined crystallographic orientation in order to reduce complexity and simplify the study of active sites. We report on the use of reactive RF sputter deposition to fabricate very highly oriented, stoichiometric Mg{sub 3}(VO{sub 4}){sub 2} thin films for use in these surface analysis studies. Deposition of samples onto amorphous substrates resulted in very poor crystallinity. However, deposition of Mg{sub 3}(VO{sub 4}){sub 2} onto well-oriented, lattice-matched thin film ''seed'' layers such as Ti(0001), Au(111), or Pt(111) resulted in very strong preferential (042) crystallographic orientation (pseudo-hexagonal oxygen planes parallel to the substrate). This strong preferential growth of the Mg{sub 3}VO{sub 4}{sub 2} suggests epitaxial (single-crystal) growth of this mixed metal oxide on the underlying metal seed layer. The effects of the seed layer material, deposition temperature, and post-deposition reactive treatments on thin film properties such as stoichiometry, crystallographic orientation, and chemical interactions will be discussed.

Chemically prepared Pb(Zr{sub 0.951}Ti{sub 0.949}){sub 0.982}Nb{sub 0.018}O{sub 3} ceramics were fabricated that were greater than 95% dense for sintering temperatures as low as 925 C. Achieving high density at low firing temperatures permitted isolation of the effects of grain size, from those due to porosity, on both dielectric and pressure induced transformation properties. Specifically, two samples of similar high density, but with grain sizes of 0.7 {micro}m and 8.5 {micro}m, respectively, were characterized. The hydrostatic ferroelectric (FE) to antiferroelectric (AFE) transformation pressure was substantially less (150 MPa) for the lower grain size material than for the larger grain size material. In addition, the dielectric constant increased and the Curie temperature decreased for the sample with lower grain size. All three properties: dielectric constant magnitude, Curie point shift, and FE to AFE phase transformation pressure were shown to be semi-quantitatively consistent with internal stress levels on the order of 100 MPa.

The electrical properties were investigated for ruthenium oxide based devitrifiable resistors embedded within low temperature co-fired ceramics. Special attention was given to the processing conditions and their affects on resistance and temperature coefficient of resistance (TCR). Results indicate that the conductance for these buried resistors is limited by tunneling of charge carriers through the thin glass layer between ruthenium oxide particles. A modified version of the tunneling barrier model is proposed to more accurately account for the microstructure ripening observed during thermal processing. The model parameters determined from curve fitting show that charging energy (i.e., the energy required for a charge carrier to tunnel through the glass barrier) is strongly dependent on particle size and particle-particle separation between ruthenium oxide grains. Initial coarsening of ruthenium oxide grains was found to reduce the charging energy and lower the resistance. However, when extended ripening occurs, the increase in particle-particle separation increases the charging energy, reduces the tunneling probability and gives rise to a higher resistance. The trade-off between these two effects results an optimum microstructure with a minimum resistance and TCR. Furthermore, the TCR of these resistors has been shown to be governed by the magnitude of the charging energy. Model parameters determined by our analysis appear to provide quantitative physical interpretations to the microstructural change in the resistor, which in turn, are controlled by the processing conditions.

High temperature XRD has been employed to monitor the devitrification of Dupont 951 low temperature co-fired ceramic (LTCC) and Dupont E84005 resistor ink. The LTCC underwent devitrification to an anorthite phase in the range of 835-875 C with activation energy of 180 kJ/mol as calculated from kinetic data. The resistor paste underwent devitrification in the 835-875 C range forming monoclinic and hexagonal celcian phases plus a phase believed to be a zinc-silicate. RuO{sub 2} appeared to be stable within this devitrified resistor matrix. X-ray radiography of a co-fired circuit indicated good structural/chemical compatibility between the resistor and LTCC.

Many studies have investigated the behavior of transition metal dopants in the YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}} 123 superconductors. Much of this research has focused on the effects of metal ions such as Co, Fe, Zn, Ni when they are substituted for the copper ions at Cu(1) and Cu(2) sites, commonly referred to as the chain and plane sites, respectively. Trivalent ions such as Co{sup +3} and Fe{sup +3}have been shown to behave similarly in their substitution effects, displaying site preference on the Cu(1) site [3-8]. This site preference has been established with the use of techniques such as neutron diffraction and Moessbauer spectroscopy [4,5]. Thermogravimetry, electron diffraction, and analysis of lattice parameters as a function of dopant also yield results consistent with those of the structural studies with respect to the chain site preference of both Co and Fe [3,4,6-8]. The very fast convergence of a and b lattice parameters to that of the tetragonal structure, occurring at x = 0.3 Co dopant (i.e. YBa{sub 2}Cu{sub 2.7}Co{sub 0.3}O{sub 7{minus}{delta}}) for high-oxygen-content samples, coupled with information derived from diffuse scattering and oxidation behavior of these samples, has been described in detail by several authors in terms of the Co and Fe ions creating ''microchains'' at Cu(1) sites within the 123 compound [4,7-8]. The Cu(1) site dopants decrease T{sub c} at a rate of 2 to 5 K/at. %, varying to some extent with site preference [4,9].

An electrochemical cell suitable for in-situ XRD analysis is presented. Qualitative information such as phase formation and phase stability can be easily monitored using the in-situ cell design. Quantitative information such as lattice parameters and kinetic behavior is also straightforward. Analysis of the LiMn&sub2;O&sub4; spinel using this cell design shows that the lattice undergoes two major structural shrinkages at approx. 4.0 V and approx. 4.07 V during charging. These shrinkages correlate well with the two electrochemical waves observed and indicate the likelihood of two separate redox processes which charging and discharging.

LixMn2O4 materials are of considerable interest in battery research and development. The crystal structure of this material can significantly affect the electrochemical performance. The ability to monitor the changes of the crystal structure during use, that is during electrochemical cycling, would prove useful to verify these types of structural changes. We report in-situ XRD measurements of LiMn2O4 cathodes with the use of an electrochemical cell designed for in-situ X-ray analysis. Cells prepared using this cell design allow investigation of the changes in the LiMn2O4 structure during charge and discharge. We describe the variation in lattice parameters along the voltage plateaus and consider the structural changes in terms of the electrochemical results on each cell. Kinetic effects of LiMn2O4 phase changes are also addressed. Applications of the in-situ cell to other compounds such as LiCoO2 cathodes and carbon anodes are presented as well.

The Sr-Bi-Ta-O system is of interest for thin-film non-volatile ferroelectric memories. A better understanding of the process by which the perovskite phase forms can provide insight for improved processing of this ferroelectric compound. The authors have prepared thin-films by a chemical method using Sr-acetate, Bi-acetate and Ta-ethoxide; cation ratios were {approximately} 1:2:2 for Sr, Bi, and Ta, respectively. Results of in-situ crystallization studies using High-Temperature Grazing-Incidence X-ray Diffraction (HTGIXRD) have demonstrated that a fluorite structure, forming in the {approximately}600--700 C range, acts as an intermediate phase prior to the crystallization of the perovskite. Additional samples with cation ratios of {approximately} 1:0.8:2 were also investigated. Results for samples prepared with the 0.8 Bi content indicated that a pyrochlor phase forms which contains a substantial deficiency in Bi compared to the composition of the perovskite phase. The structures of the pyrochlore and fluorite phases and their relation to the formation of the perovskite ferroelectric are discussed.

We have refined the structures for YBa{sub 2}Cu{sub 2.94}Ni{sub 0.06}O{sub y} (2% Ni) and YBa{sub 2}Cu{sub 2.80}Ni{sub 0.20}O{sub y} (6.67% Ni) at y {approximately} 6.95 and y {approximately} 6.5 contents. Oxygen was reduced by two independent methods: quenching from 690{degrees}C and oxygen gettering at 450{degrees}C. Cu-0 bond lengths were calculated based on Rietveld structure refinements for the various samples; they indicate the likely occupancy of Ni in the plane (Cu2) site of the 123 superconductor.