Publications

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.