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At least 109 records · Page 6

Thermal-oxidative pretreatment and evaluation of poly(hexafluoropropene oxide) fluids

Two commercial poly(hexafluoropropene oxide) fluids were thermally pretreated at 343 C in pure oxygen. IR and nuclear magnetic resonance(NMR) spectra indicate that this pretreatment was effective in removing hydrogen end-capped impurities. A decrease in the quantity of volatile material produced during thermal oxidative decomposition and increase in the thermal decomposition temperature indicated improvement in the stability of the fluids. However, this pretreatment failed to render the fluids completely stable in oxidizing atmospheres at 316 C in the presence of metal alloys.

Paciorek, K. J. L.↗

New precious metal containing normal spinels: LiRhRu 1-x Ir x O 4 , LiFeIr 1-x Ru x O 4 , and LiCoIr 1-x Ru x O 4

Large spin-orbit-coupled cations in geometrically frustrated crystal structures have the most suitable setting for exploring novel exotic states of matter. Spinel oxides (AM 2 O 4 ) are well-known examples of geometrically frustrated systems. In this study, we report for the first time the synthesis of compositions LiRhRu 1-x Ir x O 4 (x = 0–0.5), LiFeIr 1-x Ru x O 4 (x = 0–0.5), and LiCoIr 1-x Ru x O 4 (x = 0–0.3) containing precious metal cations on edge-sharing octahedral M-sites, and systematically investigate their magnetic and electrical properties. 57 Fe Mössbauer spectroscopy revealed that iron is trivalent in all LiFeIr 1-x Ru x O 4 solid solutions. Magnetic measurements indicate deviations from theoretical spin-only magnetic moment values, indicating the influence of spin-orbit coupling owing to the presence of 4d and 5d block elements. The LiFeIr 1-x Ru x O 4 series shows spin-glass-like freezing behavior with T g ≈ 20 K, and a small frustration index (f ≈ 1-2), indicating that the frustration originates from site disorder. LiRhRu 1-x Ir x O 4 and LiCoIr 1-x Ru x O 4 exhibit strongly geometrically frustrated magnetism. Electrical resistivity measurements as a function of temperature indicate that all phases are semiconducting. Seebeck coefficient measurements show that LiRhRu 1-x Ir x O 4 and LiFeIr 1-x Ru x O 4 are p-type semiconductors with holes as the major charge carriers. A sign reversal of the Seebeck coefficient indicates both holes and electrons as carriers for LiCoIr 1-x RuxO 4 (x = 0–0.2), but only holes as major carriers for x = 0.3. Here, the Seebeck coefficient and power factor increase drastically in the LiRhRu 1-x Ir x O 4 solid solution with Ir substitution, reaching a maximum of ≈ +125 μV/K and ≈2.3×10 -6 W/mK 2 at ∼650 K for x = 0.5.

Charge carriers↗

Thermal Evolution and Core Formation on Asteroid 4 Vesta in the Magma Ocean Regime

Geochemical observations of the eucrite and diogenite meteorites, together with observations made by NASA’s Dawn spacecraft while orbiting asteroid 4 Vesta, indicate that Vesta has differentiated to form a crust, mantle, and core. Eucrite and diogenite petrology is best explained by solidification of the crust from a magma ocean constituting 60-70% of Vesta’s silicates [3], or a temperature of ~1550 °C. The abundances of moderately siderophile elements (Ni, Co, Mo, W, and P) in eucrites require that essentially all of the metallic phase in Vesta segregated to form a core prior to eucrite formation and likely reached a temperature of 1450- 1575 °C. These observations provide important constraints on Vesta’s thermal evolution. The high inferred temperature indicates that convective heat transport must have been important during part of Vesta’s thermal evolution. In this study, we model Vesta’s thermal evolution in the magma ocean regime.

Kiefer, Walter S.↗

Hypervelocity impact testing of L-band truss cable meteoroid shielding on Skylab

A series of tests was performed to determine the protection provided by the L-band truss cable meteoroid shielding installed on Skylab space station at space environment temperatures of minus 180 F. The damage sustained when three test specimens were impacted by spherical projectiles at hypersonic speed was investigated. It is concluded that the L-band truss cable meteoroid shielding provides adequate protection at the indicated temperature.

Jex, D. W.↗

X-Ray Diffraction Study of the Internal Structure of Supercooled Water

A Bragg X-ray spectrometer equipped with a volume-sensitive Geiger counter and Soller slits and employing filtered molybdenum Ka radiation was used to obtain a set of diffracted intensity curves as a Punction of angle for supercooled water. Diffracted intensity curves in the temperature region of 21 to -16 C were obtained. The minimum between the two main diffraction peaks deepened continuously with lowering temperature, indicating a gradual change in the internal structure of the water. No discontinuity in this trend was noted at the melting point. The internal structure of supercooled water was concluded to become progressively more ice-like as the temperature is lowered.

Dorsch, Robert G.↗

Energetics of CO 2 and H 2 O adsorption on alkaline earth metal doped TiO 2

The process of CO 2 and H 2 O adsorption on the surface of nano-oxide semiconductors is important in the overall performance of artificial photosynthesis and other applications. In this study, we explored the thermodynamics of CO 2 and H 2 O adsorption on TiO 2 as a function of surface chemistry. We applied gas adsorption calorimetry to investigate the energetics of adsorption of those molecules on the surface of anatase nanoparticles. In an attempt to increase TiO 2 surface affinity to CO 2 and H 2 O, TiO 2 was doped with alkaline earth metals (MgO, CaO, SrO, and BaO) by manipulating the chemical synthesis. Adsorption studies using diffuse reflectance infrared spectroscopy at different temperatures indicate that due to the segregation of alkaline earth metals on the surface of TiO 2 nanoparticles, both CO 2 and subsequent H2O adsorption amounts could be increased. CO 2 adsorbs in two different manners, forming carbonates which can be removed at temperatures lower than 700 °C, and a more stable linear adsorption that remains even at 700 °C. Additionally to the surface energetic effects, doping also increased specific surface area, resulting in further improvement in net gas adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Validation of Play Fairway Analysis of the geothermal potential of Camas Prairie, south-central Idaho, by an exploration well

Abstract Play Fairway Analysis (PFA) methodology was adapted for geothermal exploration at Camas Prairie, Idaho. Geophysical data, structural and geologic mapping, volcanic rock ages and vent locations, and the distribution of thermal springs and wells all indicated a relatively high geothermal potential along the southern margin of the Prairie. An exploration well (USU Camas-1) was drilled to a depth of 618.3 m to validate the PFA. A permeable zone was encountered at ~ 357.5 m with a maximum measured temperature of ~ 80 °C, which was suppressed following the injection of cold water. A moderate transmissivity of ~ 0.25–1 cm 2 /s estimated from an injection test as well a seasonal artesian flow at ~ 0.7 L/s corroborate the presence of a permeable zone. The existence of a lacustrine clay seal was confirmed near the bottom of the basin-fill sediment occupying the upper 314 m of the well. Geothermometers suggest the USU Camas-1 well water equilibrated at a reservoir temperature of ~ 120 °C. Based on the locations of both thermal and cold wells, geothermal fluids appear to be flowing upward along one or both of two fault systems. The presence of young basalts and elevated helium isotope ratios suggest that the heat source of Camas Prairie is magmatic. However, the faults may be acting as a conduit for geothermal fluids to rise from great depth without a shallow magmatic source being present. Camas Prairie is a promising area for geothermal development, but the relatively low reservoir temperatures indicate this resource may not be suitable for electric generation. Perhaps the best use would be for heating.

Lachmar, Thomas E. (ORCID:0000000249640119)↗

Near-Field Passive Wireless Sensor for High-Temperature Metal Corrosion Monitoring

This work focuses on the fabrication and evaluation of a passive wireless sensor for the monitoring of the temperature and corrosion of a metal material at high temperatures. An inductor–capacitor (LC) resonator sensor was fabricated through the screen printing of Ag-based inks on dense polycrystalline Al 2 O 3 substrates. The LC design was modeled using the ANSYS HFSS modeling package, with the LC passive wireless sensors operating at frequencies from 70 to 100 MHz. The wireless response of the LC was interrogated and received by a radio frequency signal generator and spectrum analyzer at temperatures from 50 to 800 °C in real time. The corrosion kinetics of the Cu 110 was characterized through thermogravimetric (TGA) analysis and microscopy images, and the oxide thickness growth was then correlated to the wireless sensor signal under isothermal conditions at 800 °C. The results showed that the wireless signal was consistent with the corrosion kinetics and temperature, indicating that these two characteristics can be further deconvoluted in the future. In addition, the sensor also showed a magnitude- and frequency-dependent response to crack/spallation events in the oxide corrosion layer, permitting the in situ wireless identification of these catastrophic events on the metal surface at high temperatures.

36 MATERIALS SCIENCE↗

The Solar Flare 4: 10 keV X-ray Spectrum

The 4-10 keV solar flare spectrum includes highly excited lines of stripped Ca, Fe, and Ni ions as well as a continuum steeply falling with energy. Groups of lines at approximately 7 keV and approximately 8 keV, observed during flares by the broad-band RHESSI spectrometer and called here the Fe-line and Fe/Ni-line features, are formed mostly of Fe lines but with Ni lines contributing to the approximately 8 keV feature. Possible temperature indicators of these line features are discussed - the peak or centroid energies of the Fe-line feature, the line ratio of the Fe-line to the Fe/Ni-line features, and the equivalent width of the Fe-line feature. The equivalent width is by far the most sensitive to temperature. However, results will be confused if, as is commonly believed, the abundance of Fe varies from flare to flare, even during the course of a single flare. With temperature determined from the thermal continuum, the Fe-line feature becomes a diagnostic of the Fe abundance in flare plasmas. These results are of interest for other hot plasmas in coronal ionization equilibrium such as stellar flare plasmas, hot gas in galaxies, and older supernova remnants.

Phillips, K. J. H.↗

Studies of noble-metal thermocouple stability at high temperatures

Two investigatory studies on performance characteristics of noble-metal thermocouples are described. (1) thermoelectric stability as affected by preferential oxidation of iridium in the system iridium-40% rhodium versus iridium, and (2) the effects of temperature gradients on the emf stability of the systems platinum-13% rhodium versus platinum and iridium-40% rhodium versus iridium, operating in air. The stability investigation was carried out at three temperatures - 1700, 1850, and 2000 C - by comparing the output of the test thermocouple in air with the output of an identically constructed reference thermocouple in nitrogen. The results show that no calibration shift was observed producing a change in output greater than that corresponding to a 2.0% change in the indicated temperature for all samples tested. The investigation of gradient effects was carried out by subjecting test thermocouples to both severe and mild gradients for periods up to 200 hours. For the platinum system, the operating temperature was 1500 C with gradients of 1475 and 700 C/cm; for the iridium system, 2000 C with gradients of 700, 1500, and 1975 C/cm. Exposure to temperature gradients was found to introduce significant changes in calibration for both systems. In both investigations, the thermoelements were examined by means of electron-probe analysis and by metallographic methods to detect chemical and structural changes. Data and micrographs are presented.

Freeze, P.↗

Monitoring Temperatures Indirectly in Cooled Combustors

Noninvasive monitoring of temperatures on inner surface of combustion liner of cooled combustor increases liner life, thereby increasing combustor reliability and performance. Technique used in furnaces, reactors, jet engines, rocket engines, stationary turbines, combustors, and heat exchangers. Growth of internal overheating streaks monitored using output from array of thermocouples on outside wall of combustor. Computer analysis of output indicates temperature pattern on combustor lining. Use of data enables timely liner maintenance or overhaul.

Wagner, W.↗

Thermalization of Fluorescent Protein Exciton–Polaritons at Room Temperature

Fluorescent proteins (FPs) have recently emerged as a serious contender for realizing ultralow threshold room temperature exciton–polariton condensation and lasing. Here, this contribution investigates the thermalization of FP microcavity exciton–polaritons upon optical pumping under ambient conditions. Polariton cooling is realized using a new FP molecule, called mScarlet, coupled strongly to the optical modes in a Fabry–Pérot cavity. Interestingly, at the threshold excitation energy (fluence) of ≈9 nJ per pulse (15.6 mJ cm –2 ), an effective temperature is observed, T eff ≈ 350 ± 35 K close to the lattice temperature indicative of strongly thermalized exciton–polaritons at equilibrium. This efficient thermalization results from the interplay of radiative pumping facilitated by the energetics of the lower polariton branch and the cavity Q-factor. Direct evidence for dramatic switching from an equilibrium state into a metastable state is observed for the organic cavity polariton device at room temperature via deviation from the Maxwell–Boltzmann statistics at k || = 0 above the threshold. Thermalized polariton gases in organic systems at equilibrium hold substantial promise for designing room temperature polaritonic circuits, switches, and lattices for analog simulation.

36 MATERIALS SCIENCE↗

A Miniature Mineralogical Instrument for In-Situ Characterization of Ices and Hydrous Minerals at the Lunar Poles

Lunar missions over the past few years have provided new evidence that water may be present at the lunar poles in the form of cold-trapped ice deposits, thereby rekindling interest in sampling the polar regions. Robotic landers fitted with mineralogical instrumentation for in-situ analyses could provide unequivocal answers on the presence of crystalline water ice and/or hydrous minerals at the lunar poles. Data from Lunar Prospector suggest that any surface exploration of the lunar poles should include the capability to drill to depths of more than 40 cm. Limited data on the lunar geotherm indicate temperatures of approximately 245-255 K at regolith depths of 40 cm, within a range where water may exist in the liquid state as brine. A relevant terrestrial analog occurs in Antarctica, where the zeolite mineral chabazite has been found at the boundary between ice-free and ice-cemented regolith horizons, and precipitation from a regolith brine is indicated. Soluble halogens and sulfur in the lunar regolith could provide comparable brine chemistry in an analogous setting. Regolith samples collected by a drilling device could be readily analyzed by CheMin, a mineralogical instrument that combines X-ray diffraction (XRD) and X-ray fluorescence (XRF) techniques to simultaneously characterize the chemical and mineralogical compositions of granular or powdered samples. CheMin can unambiguously determine not only the presence of hydrous alteration phases such as clays or zeolites, but it can also identify the structural variants or types of clay or zeolite present (e.g., well-ordered versus poorly ordered smectite; chabazite versus phillipsite). In addition, CheMin can readily measure the abundances of key elements that may occur in lunar minerals (Na, Mg, Al, Si, K, Ca, Fe) as well as the likely constituents of lunar brines (F, Cl, S). Finally, if coring and analysis are done during the lunar night or in permanent shadow, CheMin can provide information on the chemistry and structure of any crystalline ices that might occur in the regolith samples.

Sarrazin, P.↗

Thermal implications of metamorphism in greenstone belts and the hot asthenosphere-thick continental lithoshere paradox

From considerations of secular cooling of the Earth and the slow decay of radiogenic heat sources in the Earth with time, the conclusion that global heat loss must have been higher in the Archean than at present seems inescapable. The mechanism by which this additional heat was lost and the implications of higher heat low for crustal temperatures are fundamental unknowns in our current understanding of Archean tectonics and geological processes. Higher heat loss implies that the average global geothermal gradient was higher in the Archean than at present, and the restriction of ultramafic komatiites to the Archean and other considerations suggests that the average temperature of the mantle was several hundred degrees hotter during the Archean than today. In contrast, there is little petrologic evidence that the conditions of metamorphism or crustal thickness (including maximum crustal thickness under mountains) were different in archean continental crust from the Phanerozoic record. Additionally, Archean ages have recently been determined for inclusions in diamonds from Cretaceous kimeberlites in South Africa, indicating temperatures of 900 to 1300 at depths of 150 to 215 km (45 to 65 kbar) in the Archean mantle, again implying relatively low geothermal gradients at least locally in the Archean. The thermal implications of metamorphism are examined, with special reference to greenstone belts, and a new thermal model of the continental lithosphere is suggested which is consistent with thick continental lithosphere and high asthenosphere temperatures in the Archean.

Morgan, P.↗

Time-resolved CO 2 , CO, and N 2 vibrational population measurements in Ns pulse discharge plasmas

Abstract Time-resolved CO 2 and N 2 vibrational populations and translational-rotational temperature are measured in a CO 2 –N 2 plasma sustained by a ns pulse discharge burst in plane-to-plane geometry. Time-resolved, absolute number density of CO generated in the plasma is also inferred from the experimental data. CO 2 and CO vibrational populations are measured by mid-IR, tunable quantum cascade laser absorption spectroscopy, and N 2 vibrational populations are measured by the ns broadband vibrational CARS. Transient excitation of N 2 and CO 2 asymmetric stretch vibrational energy modes is detected during the discharge burst. The time-resolved rate of CO generation does not correlate with N 2 or CO 2 ( ν 3 ) vibrational temperatures, indicating that CO 2 dissociation via the vibrational excitation is insignificant at the present conditions. The rate of CO generation decreases gradually during the discharge burst. The estimated specific energy cost of the CO product is close to that of N atoms in pure nitrogen, measured previously at similar operating conditions. Comparison of the experimental data with the kinetic modeling analysis indicates that CO 2 dissociation in collisions with electronically excited N 2 molecules is the dominant channel of CO generation at the present conditions, although the inferred CO yield in these processes is significantly lower than 1. The effect of vibrational energy transfer between N 2 and CO 2 on the plasma chemical processes is insignificant. The kinetic model underpredicts a rapid reduction of the N 2 and CO 2 ( ν 3 ) vibrational temperatures during the later half of the discharge burst and in the afterglow. V–T relaxation of N 2 by N and O atoms generated in the ns pulse discharge plasma does not affect the vibrational relaxation rate in a significant way. However, rapid V–T relaxation of CO 2 by O atoms has a significant effect on the relaxation rate. The difference between the experimental data and the modeling predictions may be due to the unknown scaling of the CO 2 –O V–T rates with the vibrational quantum number.

Physics↗

Multidisciplinary Constraints on the Thermal‐Chemical Boundary Between Earth's Core and Mantle

Abstract Heat flux from the core to the mantle provides driving energy for mantle convection thus powering plate tectonics, and contributes a significant fraction of the geothermal heat budget. Indirect estimates of core‐mantle boundary heat flow are typically based on petrological evidence of mantle temperature, interpretations of temperatures indicated by seismic travel times, experimental measurements of mineral melting points, physical mantle convection models, or physical core convection models. However, previous estimates have not consistently integrated these lines of evidence. In this work, an interdisciplinary analysis is applied to co‐constrain core‐mantle boundary heat flow and test the thermal boundary layer (TBL) theory. The concurrence of TBL models, energy balance to support geomagnetism, seismology, and review of petrologic evidence for historic mantle temperatures supports Q CMB ∼15 TW, with all except geomagnetism supporting as high as ∼20 TW. These values provide a tighter constraint on core heat flux relative to previous work. Our work describes the seismic properties consistent with a TBL, and supports a long‐lived basal mantle molten layer through much of Earth's history.

58 GEOSCIENCES↗

Differential credibility assessment for statistical downscaling

Climate science is increasingly using (i) ensembles of climate projections from multiple models derived using different assumptions and/or scenarios and (ii) process-oriented diagnostics of model fidelity. Efforts to assign differential credibility to projections and/or models are also rapidly advancing. A framework to quantify and depict the credibility of statistically downscaled model output is presented and demonstrated. Here, the approach employs transfer functions in the form of robust and resilient generalized linear models applied to downscale daily minimum and maximum temperature anomalies at 10 locations using predictors drawn from ERA-Interim reanalysis and two global climate models (GCM; GFDL-ESM2M and MPI-ESM-LR). The downscaled time series are used to derive several impact relevant CLIMDEX temperature indices that are assigned credibility based on (1) the reproduction of relevant large-scale predictors by the GCMs (i.e. fraction of regression beta-weights derived from predictors that are well-reproduced) and (2) the degree of variance in the observations reproduced in the downscaled series following application of a new variance inflation technique. Credibility of the downscaled predictands varies across locations, between the two GCM and is generally higher for minimum temperature than maximum temperature. The differential credibility assessment framework demonstrated here is easy to use and flexible. It can be applied as is to inform decision makers regarding projection confidence, and/or extended to include other components of the transfer functions, and/or used to weight members of a statistically downscaled ensemble.

54 ENVIRONMENTAL SCIENCES↗

Elastomer Reinforced with Carbon Nanotubes

Elastomers are reinforced with functionalized, single-walled carbon nanotubes (SWNTs) giving them high-breaking strain levels and low densities. Cross-linked elastomers are prepared using amine-terminated, poly(dimethylsiloxane) (PDMS), with an average molecular weight of 5,000 daltons, and a functionalized SWNT. Cross-link densities, estimated on the basis of swelling data in toluene (a dispersing solvent) indicated that the polymer underwent cross-linking at the ends of the chains. This thermally initiated cross-linking was found to occur only in the presence of the aryl alcohol functionalized SWNTs. The cross-link could have been via a hydrogen-bonding mechanism between the amine and the free hydroxyl group, or via attack of the amine on the ester linage to form an amide. Tensile properties examined at room temperature indicate a three-fold increase in the tensile modulus of the elastomer, with rupture and failure of the elastomer occurring at a strain of 6.5.

Hudson, Jared L.↗