Anharmonic TiO2 Phonons
Single Crystal ARCS data of TiO2 at several temperatures
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Single Crystal ARCS data of TiO2 at several temperatures
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.
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.
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.
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.
A computational investigation of the ground 1A1 and lowest energy B2 states of the titanium dioxide molecule has been carried out. The treatment utilized SCF calculations in an extended basis followed by a CI treatment for each geometry. The ground state geometry agrees well with experiment, while the agreement between the computed vibrational frequency nu1 and the experimental value for a matrix isolated TiO2 is less satisfactory. Population analysis for the ground state indicates less than one excess electron on each oxygen atom. The first excited state has a linear geometry and the singlet and triplet are essentially degenerate.
High TiO2 mare picritic glasses are derived from cumulate source regions that are only modestly endowed with ilmenite-enriched crystallization products. These sources are mobilized by the heat derived from the primitive interior and evolve into diapirs which rise adiabatically from depths in excess of 700 km. As these diapirs undergo pressure-release melting, they also stir in significant portions of the surrounding mantle.
The indentation microhardness of stoichiometric and reduced single crystal rutile (TiO2) from 25 to 800 C is presented in this paper. The results serve two main purposes. One is to assess the effect of rutile's stoichiometry on its hardness. The other is to test recently suggested theory on solid lubrication with sub Stoichiometric rutile in an effort to better understand shear controlled phenomenon. Microhardness was measured using a Vickers diamond indentor on both vacuum and hydrogen reduced single crystal rutile from 25 to 800 C. The results indicate that stoichiometry and temperature have a pronounced effect on rutile's hardness. The measured effects lend support to theory on solid lubrication by enhanced crystallographic slip and suggest that solid lubricant materials may be produced by careful atomic level tailoring (stoichiometry control).
The vibrational frequencies of several states of CaO2, ScO2, and TiO2 are computed at using density functional theory (DFT), the Hatree-Fock approach, second order Moller-Plesset perturbation theory (MP2), and the complete-active-space self-consistent-field theory. Three different functionals are used in the DFT calculations, including two hybrid functionals. The coupled cluster singles and doubles approach including the effect of unlinked triples, determined using perturbation theory, is applied to selected states. The Becke-Perdew 86 functional appears to be the cost effective method of choice, although even this functional does not perform well for one state of CaO2. The MP2 approach is significantly inferior to the DFT approaches.
Ribbonlike magnetoelastic sensors can be considered the magnetic analog of an acoustic bell; in response to an externally applied magnetic field impulse the sensors emit magnetic flux with a characteristic resonant frequency. The magnetic flux can be detected external to the test area using a pick-up coil, enabling query remote monitoring of the sensor. The characteristic resonant frequency of a magnetoelastic sensor changes in response to mass loads. [L.D. Landau and E. M. Lifshitz, Theory of Elasticity, 3rd ed. (Pergamon, New York, 1986). p. 100].Therefore, remote query chemical sensors can be fabricated by combining the magnetoelastic sensors with a mass changing, chemically responsive layer. In this work magnetoelastic sensors are coated with humidity-sensitive thin films of ceramic, nanodimensionally porous TiO2 to make remote query humidity sensors. c2000 American Institute of Physics.
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.
INS (ARCS) Data at 300, 850, and 1400 K DFT calculations at 0, 4, and 6 GPa (Force constants and phonopy.yaml files)
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We applied X-ray photoelectron emission microscopy (XPEEM) to visualize the surface distribution of photocatalytic activity at the anatase/rutile (A/R) interface of titanium dioxide. Acetic acid was adsorbed on the surface, and its decomposition and desorption reactions under ultraviolet light irradiation were monitored by observing C 1s spectra, enabling direct observation of the spatial distribution of photocatalytic activity. Complementary crystal structure information was obtained using spatially resolved low-energy electron diffraction, low-energy electron microscopy, X-ray absorption spectroscopy, and micro-focused Raman spectroscopy. Comparison with these structural data allowed for the evaluation of the photocatalytic activity as a function of the distance from the A/R interface. The activity is enhanced in the vicinity of the interface and gradually decreases toward both the anatase and rutile regions. These results demonstrate that XPEEM is an effective technique for spatially resolved mapping of photocatalytic activity, which has\\r\\npreviously been inaccessible using conventional characterization techniques.
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