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At least 37 records · Page 2

Discrete component bonding and thick film materials study

The results are summarized of an investigation of discrete component bonding reliability and a fundamental study of new thick film resistor materials. The component bonding study examined several types of solder bonded components with some processing variable studies to determine their influence upon bonding reliability. The bonding reliability was assessed using the thermal cycle: 15 minutes at room temperature, 15 minutes at +125 C 15 minutes at room temperature, and 15 minutes at -55 C. The thick film resistor materials examined were of the transition metal oxide-phosphate glass family with several elemental metal additions of the same transition metal. These studies were conducted by preparing a paste of the subject composition, printing, drying, and firing using both air and reducing atmospheres. The resulting resistors were examined for adherence, resistance, thermal coefficient of resistance, and voltage coefficient of resistance.

Kinser, D. L.↗

The Development of Erosion and Impact Resistant Turbine Airfoil Thermal Barrier Coatings

Thermal barrier coatings are used in gas turbine engines to protect engine hot-section components in the harsh combustion environments and extend component lifetimes. For thermal barrier coatings designed for turbine airfoil applications, further improved erosion and impact resistance are crucial for engine performance and durability. Advanced erosion resistant thermal barrier coatings are being developed, with a current emphasis on the toughness improvements using a combined rare earth- and transition metal-oxide doping approach. The performance of the doped thermal barrier coatings has been evaluated in burner rig and laser heat-flux rig simulated engine erosion and thermal gradient environments. The results have shown that the coating composition optimizations can effectively improve the erosion and impact resistance of the coating systems, while maintaining low thermal conductivity and cyclic durability. The erosion and impact damage mechanisms of the thermal barrier coatings will also be discussed.

Zhu, Dongming↗

Advanced Low Conductivity Thermal Barrier Coatings: Performance and Future Directions (Invited paper)

Thermal barrier coatings will be more aggressively designed to protect gas turbine engine hot-section components in order to meet future engine higher fuel efficiency and lower emission goals. In this presentation, thermal barrier coating development considerations and performance will be emphasized. Advanced thermal barrier coatings have been developed using a multi-component defect clustering approach, and shown to have improved thermal stability and lower conductivity. The coating systems have been demonstrated for high temperature combustor applications. For thermal barrier coatings designed for turbine airfoil applications, further improved erosion and impact resistance are crucial for engine performance and durability. Erosion resistant thermal barrier coatings are being developed, with a current emphasis on the toughness improvements using a combined rare earth- and transition metal-oxide doping approach. The performance of the toughened thermal barrier coatings has been evaluated in burner rig and laser heat-flux rig simulated engine erosion and thermal gradient environments. The results have shown that the coating composition optimizations can effectively improve the erosion and impact resistance of the coating systems, while maintaining low thermal conductivity and cyclic durability. The erosion, impact and high heat-flux damage mechanisms of the thermal barrier coatings will also be described.

Zhu, Dongming↗

Advanced Low Conductivity Thermal Barrier Coatings: Performance and Future Directions

Thermal barrier coatings will be more aggressively designed to protect gas turbine engine hot-section components in order to meet future engine higher fuel efficiency and lower emission goals. In this presentation, thermal barrier coating development considerations and performance will be emphasized. Advanced thermal barrier coatings have been developed using a multi-component defect clustering approach, and shown to have improved thermal stability and lower conductivity. The coating systems have been demonstrated for high temperature combustor applications. For thermal barrier coatings designed for turbine airfoil applications, further improved erosion and impact resistance are crucial for engine performance and durability. Erosion resistant thermal barrier coatings are being developed, with a current emphasis on the toughness improvements using a combined rare earth- and transition metal-oxide doping approach. The performance of the toughened thermal barrier coatings has been evaluated in burner rig and laser heat-flux rig simulated engine erosion and thermal gradient environments. The results have shown that the coating composition optimizations can effectively improve the erosion and impact resistance of the coating systems, while maintaining low thermal conductivity and cyclic durability. The erosion, impact and high heat-flux damage mechanisms of the thermal barrier coatings will also be described.

Zhu, Dongming↗

Isolation and Monitoring of Cleanroom-Associated Microbial Contaminates From Geological Collections

Microbial contamination is of particular interest to geological curation as many microorganisms can change mineral composition and produce compounds used as biosignatures used for the detection of life. Microbial cells can change the mineral composition of rocks through organic acid production and direct enzymatic oxidation/reduction of transition metals. Enzymatic oxidation of iron and manganese can occur at a rate several orders of magnitude faster than under abiotic conditions and produce highly reactive nanoparticle- sized oxides that can react and sorb other metals and organic compounds. Many fungi can also produce organic acids that dissolve and chelate mineral matrices chemically reducing and dissolving rock surfaces. Finally, several common soil-associated bacteria and fungi produce secondary metabolites that contain unusual amino acid analogs and non-ribosomal peptides containing both L- and D- chirality used in characterizing carbonaceous chondrites and the detection of extraterrestrial life.

Davis, Richard E.↗

Ceruloplasmin copper induces oxidant damage by a redox process utilizing cell-derived superoxide as reductant

Oxidative damage by transition metals bound to proteins may be an important pathogenic mechanism. Ceruloplasmin (Cp) is a Cu-containing plasma protein thought to be involved in oxidative modification of lipoproteins. We have previously shown that Cp increased cell-mediated low-density lipoprotein (LDL) oxidation by a process requiring cell-derived superoxide, but the underlying chemical mechanism(s) is (are) unknown. We now show that superoxide reduction of Cp Cu is a critical reaction in cellular LDL oxidation. By bathocuproine disulfonate (BCS) binding and by superoxide utilization, we showed that exogenous superoxide reduces a single Cp Cu atom, the same Cu required for LDL oxidation. The Cu atom remained bound to Cp during the redox cycle. Three avenues of evidence showed that vascular cells reduce Cp Cu by a superoxide-dependent process. The 2-fold higher rate of Cp Cu reduction by smooth muscle cells (SMC) compared to endothelial cells (EC) was consistent with their relative rates of superoxide release. Furthermore, Cp Cu reduction by cells was blocked by Cu,Zn superoxide dismutase (SOD1). Finally, the level of superoxide produced by EC and SMC was sufficient to cause the amount of Cu reduction observed. An important role of Cp Cu reduction in LDL oxidation was suggested by results showing that SOD1 inhibited Cp Cu reduction and LDL oxidation by SMC with equal potency, while tumor necrosis factor-alpha stimulated both processes. In summary, these results show that superoxide is a critical cellular reductant of divalent transition metals involved in oxidation, and that protein-bound Cu is a substrate for this reaction. The role of these mechanisms in oxidative processes in vivo has yet to be defined.

NASA Discipline Regulatory Physiology↗

Catalyst for Oxidation of Volatile Organic Compounds

Disclosed is a process for oxidizing volatile organic compounds to carbon dioxide and water with the minimal addition of energy. A mixture of the volatile organic compound and an oxidizing agent (e.g. ambient air containing the volatile organic compound) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Wood, George M.↗

Catalytic process for formaldehyde oxidation

Disclosed is a process for oxidizing formaldehyde to carbon dioxide and water without the addition of energy. A mixture of formaldehyde and an oxidizing agent (e.g., ambient air containing formaldehyde) is exposed to a catalyst which includes a noble metal dispersed on a metal oxide which possesses more than one oxidation state. Especially good results are obtained when the noble metal is platinum, and the metal oxide which possesses more than one oxidation state is tin oxide. A promoter (i.e., a small amount of an oxide of a transition series metal) may be used in association with the tin oxide to provide very beneficial results.

Kielin, Erik J.↗

The importance of atomic and molecular correlation on the bonding in transition metal compounds

The determination of accurate spectroscopic parameters for molecular systems containing transition metal atoms is shown to require extensive data sets and a high level correlation treatment, and techniques and their limitations are considered. Extensive results reported on the transition metal atoms, hydrides, oxides, and dimers makes possible the design of a calculation to correctly describe the mixing of different atomic asymptotes, and to give a correct balance between molecular bonding and exchange interactions. Examples considered include the dipole moment of the 2Delta state of NiH, which can help determine the mixture of 3d(8)4s(2) and 3d(9)4s(1) in the NiH wavefunction, and the bonding in CrO, where an equivalent description of the relative energies associated with the Cr 3d-3d atomic exchange and the Cr-O bond is important.

Bauschlicher, Charles W., Jr.↗

Role of phonons in the metal-insulator phase transition.

Review, for the transition series oxides, of the Mattis and Lander model, which is one of electrons interacting with lattice vibrations (electron and phonon interaction). The model displays superconducting, insulating, and metallic phases. Its basic properties evolve from a finite crystallographic distortion associated with a dominant phonon mode and the splitting of the Brillouin zone into two subzones, a property of simple cubic and body centered cubic lattices. The order of the metal-insulator phase transition is examined. The basic model has a second-order phase transition and the effects of additional mechanisms on the model are calculated. The way in which these mechanisms affect the magnetically ordered transition series oxides as described by the Hubbard model is discussed.

Langer, W. D.↗

Redox-mediated activation of latent transforming growth factor-beta 1

Transforming growth factor beta 1 (TGF beta) is a multifunctional cytokine that orchestrates response to injury via ubiquitous cell surface receptors. The biological activity of TGF beta is restrained by its secretion as a latent complex (LTGF beta) such that activation determines the extent of TGF beta activity during physiological and pathological events. TGF beta action has been implicated in a variety of reactive oxygen-mediated tissue processes, particularly inflammation, and in pathologies such as reperfusion injury, rheumatoid arthritis, and atherosclerosis. It was recently shown to be rapidly activated after in vivo radiation exposure, which also generates reactive oxygen species (ROS). In the present studies, the potential for redox-mediated LTGF beta activation was investigated using a cell-free system in which ROS were generated in solution by ionizing radiation or metal ion-catalyzed ascorbate reaction. Irradiation (100 Gray) of recombinant human LTGF beta in solution induced 26% activation compared with that elicited by standard thermal activation. Metal-catalyzed ascorbate oxidation elicited extremely efficient recombinant LTGF beta activation that matched or exceeded thermal activation. The efficiency of ascorbate activation depended on ascorbate concentrations and the presence of transition metal ions. We postulate that oxidation of specific amino acids in the latency-conferring peptide leads to a conformation change in the latent complex that allows release of TGF beta. Oxidative activation offers a novel route for the involvement of TGF beta in tissue processes in which ROS are implicated and endows LTGF beta with the ability to act as a sensor of oxidative stress and, by releasing TGF beta, to function as a signal for orchestrating the response of multiple cell types. LTGF beta redox sensitivity is presumably directed toward recovery of homeostasis; however, oxidation may also be a mechanism of LTGF beta activation that can be deleterious during disease mechanisms involving chronic ROS production.

Non-NASA Center↗

Ceruloplasmin and cardiovascular disease

Transition metal ion-mediated oxidation is a commonly used model system for studies of the chemical, structural, and functional modifications of low-density lipoprotein (LDL). The physiological relevance of studies using free metal ions is unclear and has led to an exploration of free metal ion-independent mechanisms of oxidation. We and others have investigated the role of human ceruloplasmin (Cp) in oxidative processes because it the principal copper-containing protein in serum. There is an abundance of epidemiological data that suggests that serum Cp may be an important risk factor predicting myocardial infarction and cardiovascular disease. Biochemical studies have shown that Cp is a potent catalyst of LDL oxidation in vitro. The pro-oxidant activity of Cp requires an intact structure, and a single copper atom at the surface of the protein, near His(426), is required for LDL oxidation. Under conditions where inhibitory protein (such as albumin) is present, LDL oxidation by Cp is optimal in the presence of superoxide, which reduces the surface copper atom of Cp. Cultured vascular endothelial and smooth muscle cells also oxidize LDL in the presence of Cp. Superoxide release by these cells is a critical factor regulating the rate of oxidation. Cultured monocytic cells, when activated by zymosan, can oxidize LDL, but these cells are unique in their secretion of Cp. Inhibitor studies using Cp-specific antibodies and antisense oligonucleotides show that Cp is a major contributor to LDL oxidation by these cells. The role of Cp in lipoprotein oxidation and atherosclerotic lesion progression in vivo has not been directly assessed and is an important area for future studies.

NASA Discipline Cell Biology↗

Transition metals in superheat melts

A series of experiments with silicate melts doped with transition element oxides was carried out at atmospheric pressures of inert gas at temperatures exceeding liquidus. As predicted from the shape of fO2 buffer curves in T-fO2 diagrams the reducing conditions for a particular oxide-metal pair can be achieved through the T increase if the released oxygen is continuously removed. Experimental studies suggest that transition metals such as Cr or V behave as siderophile elements at temperatures exceeding liquidus temperatures if the system is not buffered by the presence of other oxide of more siderophile element. For example the presence of FeO prevents the reduction of Cr2O3. The sequence of decreasing siderophility of transition elements at superheat conditions (Mo, Ni, Fe, Cr) matches the decreasing degree of depletion of siderophile elements in mantle rocks as compared to chondrites.

Jakes, Petr↗

Oxygen electrodes for rechargeable alkaline fuel cells

Electrocatalysts and supports for the positive electrode of moderate temperature single-unit rechargeable alkaline fuel cells are being investigated and developed. Candidate support materials were drawn from transition metal carbides, borides, nitrides and oxides which have high conductivity (greater than 1 ohm/cm). Candidate catalyst materials were selected largely from metal oxides of the form ABO sub x (where A = Pb, Cd, Mn, Ti, Zr, La, Sr, Na, and B = Pt, Pd, Ir, Ru, Ni (Co) which were investigated and/or developed for one function only, O2 reduction or O2 evolution. The electrical conductivity requirement for catalysts may be lower, especially if integrated with a higher conductivity support. All candidate materials of acceptable conductivity are subjected to corrosion testing. Materials that survive chemical testing are examined for electrochemical corrosion activity. For more stringent corrosion testing, and for further evaluation of electrocatalysts (which generally show significant O2 evolution at at 1.4 V), samples are held at 1.6 V or 0.6 V for about 100 hours. The surviving materials are then physically and chemically analyzed for signs of degradation. To evaluate the bifunctional oxygen activity of candidate catalysts, Teflon-bonded electrodes are fabricated and tested in a floating electrode configuration. Many of the experimental materials being studied have required development of a customized electrode fabrication procedure. In advanced development, the goal is to reduce the polarization to about 300 to 350 mV. Approximately six support materials and five catalyst materials were identified to date for further development. The test results will be described.

Swette, L.↗

Catalysis of carbon monoxide methanation by deep sea manganate minerals

The catalytic activity of deep sea manganese nodule minerals for the methanation of carbon monoxide was measured with a microcatalytic technique between 200 and 460 degrees C. The manganate minerals were activated at 248 degrees C by immersion into a stream of hydrogen in which pulses of carbon monoxide were injected. Activation energies for the methanation reaction and hydrogen desorption from the manganate minerals were obtained and compared with those of pure nickel. Similar energy values indicate that the activity of the nodule materials for the reaction appears to be related to the amount of reducible transition metals present in the samples (ca. 11 wt.-%). Since the activity of the nodule minerals per gram is comparable to that of pure nickel, most of the transition metal ions located between manganese oxide layers appear to be exposed and available to catalyze the reaction.

Non-NASA Center↗

Ceruloplasmin enhances smooth muscle cell- and endothelial cell-mediated low density lipoprotein oxidation by a superoxide-dependent mechanism

Cultured vascular smooth muscle cells (SMC) and endothelial cells (EC) stimulate low density lipoprotein (LDL) oxidation by free radical-mediated, transition metal-dependent mechanisms. The physiological source(s) of metal ions is not known; however, purified ceruloplasmin, a plasma protein containing 7 coppers, oxidizes LDL in vitro. We now show that ceruloplasmin also increases LDL oxidation by vascular cells. In metal ion-free medium, human ceruloplasmin increased bovine aortic SMC- and EC-mediated LDL oxidation by up to 30- and 15-fold, respectively. The maximal response was at 100-300 microg ceruloplasmin/ml, a level at or below the unevoked physiological plasma concentration. Oxidant activity was dependent on protein structure as a specific proteolytic cleavage or removal of one of the seven ceruloplasmin copper atoms inhibited activity. Three lines of evidence indicated a critical role for cellular superoxide (O2.) in ceruloplasmin-stimulated oxidation. First, the rate of production of O2. by cells correlated with their rates of LDL oxidation. Second, superoxide dismutase effectively blocked ceruloplasmin-stimulated oxidation by both cell types. Finally, O2. production by SMC quantitatively accounted for the observed rate of LDL oxidation. To show this, the course of O2. production by SMC was simulated by repeated addition of xanthine and xanthine oxidase to culture medium under cell-free conditions. Neither ceruloplasmin nor O2. alone increased LDL oxidation, but together they completely reconstituted the oxidation rate of ceruloplasmin-stimulated SMC. These results are the first to show that ceruloplasmin stimulates EC- and SMC-mediated oxidation of LDL and that cell-derived O2. accounts quantitatively for metal-dependent, free radical-initiated oxidation of LDL by these cells.

Non-NASA Center↗