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At least 19 records

Properties of TiO2 thin films and a study of the TiO2-GaAs interface

Titanium dioxide (TiO2) films prepared by chemical vapor deposition were investigated in this study for the purpose of the application in the GaAs metal-insulator-semiconductor field-effect transistor. The degree of crystallization increases with the deposition temperature. The current-voltage study, utilizing an Al-TiO2-Al MIM structure, reveals that the d-c conduction through the TiO2 film is dominated by the bulk-limited Poole-Frenkel emission mechanism. The dependence of the resistivity of the TiO2 films on the deposition environment is also shown. The results of the capacitance-voltage study indicate that an inversion layer in an n-type substrate can be achieved in the MIS capacitor if the TiO2 films are deposited at a temperature higher than 275 C. A process of low temperature deposition followed by the pattern definition and a higher temperature annealing is suggested for device fabrications. A model, based on the assumption that the surface state densities are continuously distributed in energy within the forbidden band gap, is proposed to interpret the lack of an inversion layer in the Al-TiO2-GaAs MIS structure with the TiO2 films deposited at 200 C.

Chen, C. Y.

A TiO2 abundance map for the northern maria

A map of TiO2 abundance for most of the northern maria is presented. The telescopic data base used is the 0.38/0.56-micron ratio mosaic from Johnson et at. (1977). The titanium content has been estimated using the correlation established by Charette et al. (1974). The combination of observational, processing, and calibration errors indicates that the TiO2 map is accurate to + or - 2% (wt% TiO2) for high TiO2 content (more than 5%) and + or - 1% for low values of TiO2. Analysis of the lunar sample and telescopic data suggests strongly that the spectral parameter mapped is sensitive primarily to TiO2 abundance in the range 3-9% and does not correlate directly with iron content. It is suggested, however, that for the low TiO2 mare regions (less than 2-3% TiO2) there may be a relation between the spectral ratio and iron content and that some of the reddest mare areas in the Imbrium region may have low iron contents as well as low titanium abundances.

Johnson, T. V.

Remote sensing of potential lunar resources. 2: High spatial resolution mapping of spectral reflectance ratios and implications for nearside mare TiO2 content`

High spatial resolution maps illustrating variations in spectral reflectance 400/560 nm ratio values have been generated for the following mare regions: (1) the border between southern Mare Serenitatis and northern Mare Tranquillitatis (including the MS-2 standard area and Apollo 17 landing site), (2) central Mare Tranquillitatis, (3) Oceanus Procellarum near Seleucus, and (4) southern Oceanus Procellarum and Flamsteed. We have also obtained 320-1000 nm reflectance spectra of several sites relative to MS-2 to facilitate scaling of the images and provide additional information on surface composition. Inferred TiO2 abundances for these mare regions have been determined using an empirical calibration which relates the weight percent TiO2 in mature mare regolith to the observed 400/560 nm ratio. Mare areas with high TiO2 abundances are probably rich in ilmenite (FeTiO3) a potential lunar resource. The highest potential TiO2 concentrations we have identified in the nearside maria occur in central Mare Tranquillitatis. Inferred TiO2 contents for these areas are greater than 9 wt% and are spatially consistent with the highest-TiO2 regions mapped previously at lower spatial resolution. We note that the morphology of surface units with high 400/560 nm ratio values increases in complexity at higher spatial resolutions. Comparisons have been made with previously published geologic maps, Lunar Orbiter IV, and ground-based images, and some possible morphologic correlatins have been found between our mapped 400/560 nm ratio values and volcanic landforms such as lava flows, mare domes, and collapse pits.

Melendrez, David E.

Outstanding Natural Occurrence of TiO2-II at the Chicxulub Crater - Anatomy of A Shock-Produced High-Pressure Polymorph

Scientific drilling of the end-Cretaceous, approximately 180 kilometers-diameter Chicxulub crater (Yucatan Peninsula, Mexico) during IODP–ICDP (Integrated Ocean Drilling Program - International Continental Scientific Drilling Program) Expedition 364 has provided new insights into the formation, shock metamorphism, structural evolution, and thermal history of peak rings in large complex impact craters. An outstanding feature in uplifted granitoid rocks of the Chicxulub peak ring is the preservation of TiO2-II, an orthorhombic high-pressure polymorph of TiO2 with an alpha-PbO2 structure, produced during the impact from rutile and/or anatase at shock pressures of approximately 12.5-17.5 gigapascals. Unlike other mostly micro- and cryptocrystalline occurrences of TiO2-II at terrestrial impact sites, ejecta deposits, and in rare ultra-high pressure metamorphic rocks, TiO2-II at Chicxulub occurs as abundant euhedral crystals greater than or equal to 70 microns in size within aggregates of altered magmatic titanite. This mode of occurrence provides an excellent opportunity to investigate the crystallography and transformation kinetics of the shock-produced high-pressure polymorph using scanning electron microscopic, micro-Raman, electron backscatter diffraction (EBSD), focused ion beam (FIB), as well as transmission-EBSD and transmission electron microscopic (TEM) techniques. Here we present refined microstructural and new crystallographic results for TiO2-II at the Chicxulub crater.

Schmieder, Martin

TiCl4 as a source of TiO2 particles for laser anemometry measurements in hot gas

A method of reacting TiCl4 with water saturated gaseous nitrogen (GN2) at the entrance into a high temperature gas flow is described. The TiO2 particles formed are then entrained in the gas flow and used as seed particles for making laser anemometry (LA) measurements of the flow velocity distribution in the hot gas. Scanning electron microscope photographs of the TiO2 particles are shown. Data rate of the LA processor was measured to determine the amount of TiO2 formed. The TiCl4 and mixing gas flow diagram is shown. This work was performed in an open jet burner.

Weikle, Donald H.

Enhanced TiO2 Photocatalytic Processing of Organic Wastes for Green Space Exploration

The effect of transition metal co-catalysts on the photocatalytic properties of TiO2 was investigated. Ruthenium (Ru), palladium, platinum, copper, silver, and gold, were loaded onto TiO2 powders (anatase and mixed-phase P25) and screened for the decomposition of rhodamine B (RhB) under broad-band irradiation. The morphology and estimated chemical composition of photocatalysts were determined by scanning electron microscopy and energy dispersive spectroscopy, respectively. Brunhauer, Emmett and Teller (BET) analysis measured mass-specific surface area(s). X-ray diffraction analysis was performed to confirm the identity of titania phase(s) present. The BET surface area of anatase TiO2/Ru 1% (9.2 sq m/gm) was one of the highest measured of all photocatalysts prepared in our laboratory. Photolyses conducted under air-saturated and nitrogen-saturated conditions revealed photodegradation efficiencies of 85 and 2 percent, respectively, after 60 min compared to 58 percent with no catalyst. The cause of low photocatalytic activity under an inert atmosphere is discussed. TiO2/Ru 1% showed a superior photocatalytic activity relative to P25-TiO2 under broad-band irradiation. A potential deployment of photocatalytic technologies on a mission could be a reactor with modest enhancement in solar intensity brought about by a trough-style reactor, with reactants and catalyst flowing along the axis of the trough and therefore being illuminated for a controlled duration based on the flow rate.

Udom, I.

Visible-Light-Responsive Catalysts Using Quantum Dot-Modified TiO2 for Air and Water Purification

Photocatalysis, the oxidation or reduction of contaminants by light-activated catalysts, utilizing titanium dioxide (TiO2) as the catalytic substrate has been widely studied for trace contaminant control in both air and water applications. The interest in this process is due primarily to its low energy consumption and capacity for catalyst regeneration. Titanium dioxide requires ultraviolet light for activation due to its relatively large band gap energy of 3.2 eV. Traditionally, Hg-vapor fluorescent light sources are used in PCO reactors; however, the use of mercury precludes the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. The development of a visible-light responsive (VLR) TiO2-based catalyst would eliminate the concerns over mercury contamination. Further, VLR development would allow for the use of ambient visible solar radiation or highly efficient LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Though VLR catalyst development has been an active area of research for the past two decades, there are few commercially available VLR catalysts. Those VLR catalysts that are commercially available do not have adequate catalytic activity, in the visible region, to make them competitive with those operating under UV irradiation. This study was initiated to develop more effective VLR catalysts through a novel method in which quantum dots (QD) consisting of narrow band gap semiconductors (e.g., CdS, CdSe, PbS, ZnSe, etc.) are coupled to TiO2 via two preparation methods: 1) photodeposition and 2) mechanical alloying using a high-speed ball mill. A library of catalysts was developed and screened for gas and aqueous phase applications using ethanol and 4-chlorophenol as the target contaminants, respectively. Both target compounds are well studied in photocatalytic systems and served as model contaminants for this research. Synthesized catalysts were compared in terms of preparation method, nature of the quantum dots, and dosage of quantum dots.

visible light

Chemical modification of TiO2 surfaces with methylsilanes and characterization by infrared absorption spectroscopy

Infrared absorption spectra of methylsilanes bonded to a TiO2 powder were obtained. The reacting silanes include Me sub (4-n)SiX sub n (n=1-4; X=Cl, OMe) and hexamethyldisilazane (HMDS). Reactions were performed on hydroxylated-but-anhydrous TiO2 surfaces in the gas phase. IR spectra confirm the presence of a bonded silane layer. Terminal surface OH groups are found to react more readily than bridging OH groups. By-products of the modification adsorp tenaciously to the surface. The various silanes show only small differences in their ability to sequester surface OH groups. Following hydrolysis in moist air, Si-OH groups are observed only for the tetrafunctional silanes.

Finklea, H. O.

A reevaluation of spectral ratios for lunar mare TiO2 mapping

The empirical relation established by Charette et al. (1974) between the 400/560-nm spectral ratio of mature mare soils and weight percent TiO2 has been used extensively to map titanium content in the lunar maria. Relative reflectance spectra of mare regions show that a reference wavelength further into the near-IR, e.g., above 700 nm, could be used in place of the 560-nm band to provide greater contrast (a greater range of ratio values) and hence a more sensitive indicator of titanium content. An analysis of 400/730-nm ratio values derived from both laboratory and telescopic relative reflectance spectra suggests that this ratio provides greater sensitivity to TiO2 content than the 400/560-nm ratio. The increased range of ratio values is manifested in higher contrast 400/730-nm ratio images compared to 400/560-nm ratio images. This potential improvement in sensivity encourages a reevaluation of the original Charette et al. (1974) relation using the 400/730-nm ratio.

Johnson, Jeffrey R.

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

Klettlinger, Jennifer Lindsey Suder

Visible-Light-Responsive Photocatalysis: Ag-Doped TiO2 Catalyst Development and Reactor Design Testing

In recent years, the alteration of titanium dioxide to become visible-light-responsive (VLR) has been a major focus in the field of photocatalysis. Currently, bare titanium dioxide requires ultraviolet light for activation due to its band gap energy of 3.2 eV. Hg-vapor fluorescent light sources are used in photocatalytic oxidation (PCO) reactors to provide adequate levels of ultraviolet light for catalyst activation; these mercury-containing lamps, however, hinder the use of this PCO technology in a spaceflight environment due to concerns over crew Hg exposure. VLR-TiO2 would allow for use of ambient visible solar radiation or highly efficient visible wavelength LEDs, both of which would make PCO approaches more efficient, flexible, economical, and safe. Over the past three years, Kennedy Space Center has developed a VLR Ag-doped TiO2 catalyst with a band gap of 2.72 eV and promising photocatalytic activity. Catalyst immobilization techniques, including incorporation of the catalyst into a sorbent material, were examined. Extensive modeling of a reactor test bed mimicking air duct work with throughput similar to that seen on the International Space Station was completed to determine optimal reactor design. A bench-scale reactor with the novel catalyst and high-efficiency blue LEDs was challenged with several common volatile organic compounds (VOCs) found in ISS cabin air to evaluate the system's ability to perform high-throughput trace contaminant removal. The ultimate goal for this testing was to determine if the unit would be useful in pre-heat exchanger operations to lessen condensed VOCs in recovered water thus lowering the burden of VOC removal for water purification systems.

Photocatalysis

Microstructural Characterization of TiO2-II in the Chicxulub Peak Ring

The peak ring of the approximately 180 kilometer-diameter Chicxulub impact crater on the Yucatan Peninsula, Mexico, was recently drilled during IODP-ICDP (International Ocean Discovery Program-International Continental Scientific Drilling Program) Expedition 364, producing core M0077A. The new core provides insights into the anatomy, composition, tectonic deformation, shock metamorphism, and post-impact overprint of crater-filling impactites and crystalline basement rocks. The basement rocks were shocked to approximately 12.5-17.5 gigapascals, uplifted, and hydrothermally altered. This study presents a combined Raman spectroscopic and electron backscatter diffraction (EBSD) study of TiO2-II, a high-pressure polymorph of TiO2 with an alpha-PbO2 structure (orthorhombic; space group Pbcn; density 4.34 grams per cubic centimeter, in shocked granitoid rock of the Chicxulub peak ring.

Schmieder, Martin

TiO2 film properties as a function of processing temperature, volume 3

Thin film TiO2 was produced at 150 C by chemical vapor deposition using hydrolysis of tetraisopropyl titanate. Films were amorphous as grown, but annealing in air caused crystallization, with anatase formed beginning at 350 C and rutile at 700 C. Density and index of refraction increased substantially with increasing anneal temperature, while etch susceptibility in HF and H2SO4 decreased. Comparison with literature data showed two groups of processes. One group yields films having properties that gradually approach those of rutile with increasing process temperature. The other group gives rutile directly at moderate temperatures. Deposition of amorphous film followed by etching and annealing is suggested as a means for pattern definition.

Fitzgibbons, E. T.

Near-uv photon efficiency in a TiO2 electrode - Application to hydrogen production from solar energy

An n-type (001) TiO2 electrode irradiated at 365 nm was tested under anodic polarization. A saturation current independent of pH and proportional to light intensity has been observed. Accurate measurements of the incident power lead to a 60 per cent photon efficiency. A photoelectrochemical cell built with such an electrode, operated under solar irradiation without concentration, produced an electrolysis current of 0.7 mA/sq cm without applied voltage.

Desplat, J.-L.

Liquid-solid equilibria involving spinel, ilmenite, and ferropseudobrookite in the system 'FeO'-Al2O3-TiO2 in contact with metallic iron

Phase relations in the liquidus temperature region of the system 'FeO'-Al2O3-TiO2 in contact with metallic iron, at a total pressure below 1 atm, have been determined by the quenching technique. Four invariant points have been located, with phase assemblages and temperatures as follows; wuestite, ulvoespinel, nercynite and liquid, 1306 C; ulvoespinel, ilmenite, ferropseudobrookite and liquid, 1340 C; ulvoespinel, hercynite, ferropseudobrookite and liquid, 1367 C; hercynite, ferropseudobrookite, corundum and liquid, 1465 C. The data obtained confirm the presence of a miscibility gap between titanate and aluminate spinels, and provide quantitative data for the effect of Al2O3 on mutual stability relations among spinel, ilmenite, and ferropseudobrookite phases in the presence of liquid at high temperatures and strongly reducing conditions. It is shown that Al2O3 has a strong stabilizing effect on the phase assemblage ferropseudobrookite and spinel relative to ilmenite.

Schreifels, W. A.

The solubility of sulfur in high-TiO2 mare basalts

The present paper deals with an experimental investigation of the solubility of sulfur of the high-TiO2 mare basalt 74275 at 1 atm, 1250 C. The data indicate that at saturation, 74275 is capable of dissolving 3400 ppm sulfur at 10 to 15 degrees below its liquidus. The analyzed samples of 74275 show sulfur contents of 1650 ppm S, which indicates that 74275 was 50% undersaturated at the time of eruption.

Danckwerth, P. A.