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At least 1,765 records · Page 98

Utilizing TiO 2 amorphous precursors for polymorph selection: An in situ TEM study of phase formation and kinetics

Selective synthesis of metastable polymorphs requires a fundamental understanding of the complex energy landscapes in which these phases form. Recently, the development of in situ high temperature and controlled atmosphere transmission electron microscopy has enabled the direct observation of nucleation, growth, and phase transformations with near atomic resolution. In this work, we directly observe the crystallization behavior of amorphous TiO 2 thin films grown under different pulsed laser deposition conditions and quantify the mechanisms behind metastable crystalline polymorph stabilization. Films deposited at 10 mTorr chamber oxygen pressure crystallize into nanocrystalline Anatase at 325 degrees C, whereas films deposited at 2 mTorr crystallize into significantly larger needle-like grains of Brookite and Anatase at 270 degrees C. Increasing film deposition rate by a factor of 4 results in a 10x increase in the crystalline growth front velocity as well as a decrease in crystallization temperature from 270 degrees C to 225 degrees C. Engineering the amorphous precursor state through deposition conditions therefore provides routes to microstructure control and the accessibility of higher energy metastable phases.

36 MATERIALS SCIENCE↗

The stability of amino acids at submarine hydrothermal vent temperatures

It has been postulated that amino acid stability at hydrothermal vent temperatures is controlled by a metastable thermodynamic equilibrium rather than by kinetics. Experiments reported here demonstrate that the amino acids are irreversibly destroyed by heating at 240 C and that quasi-equilibrium calculations give misleading descriptions of the experimental observations. Equilibrium thermodynamic calculations are not applicable to organic compounds under high-temperature submarine vent conditions.

Bada, Jeffrey L.↗

Ceria Incorporation in Sinter-Resistant Platinum-Based Catalysts

Platinum group metals (PGM) are widely used for exhaust emission abatement. Sintering during the high-temperature emission control conditions decreases noble metal utilization efficiency. Efficient use of scarce noble metals requires sinter-resistant catalysts. Here we extend an approach to synthesize catalysts consisting of platinum nanoparticles encapsulated in a mixture of cerium and aluminum oxides (Pt@Al 2 O 3 -CeO 2 ). We tested the activity of this catalyst toward carbon monoxide, propene, and propane oxidation chosen as model oxidation reactions for emission control catalysts. Pt@Al 2 O 3 -CeO 2 catalysts demonstrated similar activity and stability upon aging as the comparison system without ceria, Pt@Al 2 O 3 , while maintaining small Pt nanoparticles and ceria crystallites. Additionally, we studied the influence of various thermal treatments on CO oxidation activity and determined that a steam treatment can activate low temperature CO oxidation activity of Pt@Al 2 O 3 -CeO 2 . STEM-EDS analysis revealed that thermal treatments led to the co-location of Pt and CeO 2 and temperature programmed-reduction analysis revealed that the steam treatment specifically enhanced CO oxidation activity through surface reduction of the CeO 2 . As a result, we demonstrate the versatility of this encapsulation approach to generate mixed metal-oxide supports with improved metal-support interactions without hindering nanoparticle stability.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Insights into the mechanisms of NH3 inhibition on Cu-CHA SCR catalysts

This work elucidates the atomic-scale mechanism behind ammonia (NH3) inhibition during the selective catalytic reduction (SCR) of NO? on Cu-CHA catalysts, a key issue limiting low-temperature emission control. Using SCR kinetic analysis, operando electron paramagnetic resonance (EPR) spectroscopy, and density functional theory (DFT), we demonstrate that NH3 inhibition primarily slows the oxidation half-cycle (OHC), while the reduction half-cycle (RHC) remains unaffected. DFT simulations reveal that excess NH3 substantially increases the diffusion barrier for CuI ions, hindering formation of essential CuII-oxo dimer intermediates and thus suppressing OHC kinetics. Operando EPR studies confirm that this inhibition strongly depends on operating temperature and catalyst Cu loading. Our findings highlight strategies to counteract NH3 inhibition, including optimizing Cu loading, precisely managing NH3:NO feed ratios, and enhancing CuI ion mobility through tailored catalyst design and operational adjustments, thereby advancing the efficiency of emission control technologies in automotive applications.

Deka, Dhruba Jyoti↗

Thermal control systems for low-temperature heat rejection on a lunar base

In this report, Rankine-cycle heat pumps and absorption heat pumps (ammonia-water and lithium bromide-water) have been analyzed and optimized for a lunar base cooling load of 100 kW. For the Rankine cycle, a search of several commonly used commercial refrigerants provided R11 and R717 as possible working fluids. Hence, the Rankine-cycle analysis has been performed for both R11 and R717. Two different configurations were considered for the system--one in which the heat pump is directly connected to the rejection loop and another in which a heat exchanger connects the heat pump to the rejection loop. For a marginal increase in mass, the decoupling of the rejection loop and the radiator from the heat pump provides greater reliability of the system and better control. Hence, the decoupled system is the configuration of choice. The optimal TCS mass for a 100 kW cooling load at 270 K was 5940 kg at a radiator temperature of 362 K. R11 was the working fluid in the heat pump, and R717 was the transport fluid in the rejection loop. Two TCS's based on an absorption-cycle heat pump were considered, one with an ammonia-water mixture and the other with a lithium bromide-water mixture as the working fluid. A complete cycle analysis was performed for these systems. The system components were approximated as heat exchangers with no internal pressure drop for the mass estimate. This simple approach underpredicts the mass of the systems, but is a good 'optimistic' first approximation to the TCS mass in the absence of reliable component mass data. The mass estimates of the two systems reveal that, in spite of this optimistic estimate, the absorption heat pumps are not competitive with the Rankine-cycle heat pumps. Future work at the systems level will involve similar analyses for the Brayton- and Stirling-cycle heat pumps. The analyses will also consider the operation of the pump under partial-load conditions. On the component level, a capillary evaporator will be designed, built, and tested in order to investigate its suitability in lunar base TCS and microgravity two-phase applications.

Sridhar, K. R.↗

Consideration of the Impact of the Environmental Conditions when Designing Heat-Receiving Systems of the Solar Cylindrical Parabolic Modules

The aerohydrodynamic and heat exchange characteristics in the cylindrical heat receiver of a solar cylindrical parabolic concentrating module are investigated. The mathematical model is based on the Navier- Stokes equation system for a laminar flow in a channel. The model is implemented using the control volume method. The created computer algorithm allows carrying out parametric studies and revealing the most rational geometric, dynamic, and power parameters of the process. The proposed model describes the general physical outlines of the heat exchange in a cylindrical heat receiver which allows estimating the influence of the environment—wind velocity, ambient temperature, etc.—on it.

14 SOLAR ENERGY↗

Five-Year (2004-2009)Observations of Upper Tropospheric Water Vapor and Cloud Ice from MLS and Comparisons with GEOS-5 Analyses

This paper gives an overview of August 2004 through July 2009 upper tropospheric (UT) water vapor (H2O) and ice water content (IWC) from the Aura Microwave Limb Sounder (MLS) and comparisons with outputs from the NASA Goddard Earth Observing System Version 5 (GEOS-5) data assimilation system. Both MLS and GEOS-5 show that high values of H2O and IWC at 215 to 147 hPa are associated with areas of deep convection. They exhibit good (within approximately 15%) agreement in IWC at these altitudes, but GEOS-5 H2O is approximately 50% (215 hPa) to approximately 30% (147 hPa) larger than MLS, possibility due to its higher temperatures at these altitudes. GOES-5 produces a weaker intertropical convergence zone than MLS, while a seasonally-migrating band of tropical deep convection is clearly evident in both the MLS and GEOS-5 UT H2O and IWC. MLS and GEOS-5 both show spatial anti-correlation between IWC and H2O at 100 hPa, where less H2O is associated with low temperatures in regions of tropical convection. At 100 hPa, GEOS-5 produces 50% less IWC and 15% less H2O in the tropics, and approximately 20% more H2O in the extra-tropics, than does MLS. Behavior of the 100 hPa H2O, which exhibits a quasi-biennial oscillation, appears consistent with it being controlled by temperature. The seasonal cycle in the vertical transport of tropical mean H2O from approximately 147 hPa to approximately 10 hPa appears much stronger in MLS than in GEOS-5. The UT IWC and H2O interannual variations, from both MLS and GEOS-5, show clear imprints of the El Nino-Southern Oscillation.

Jiang, Jonathan H.↗

Evaluating bloom potential of the green-tide forming alga Ulva ohnoi under ocean acidification and warming

Herein we discuss the occurrence of green-tides, whose bloom potential may be increased by various human activities and biogeochemical process, results in enormous economic losses and ecosystem collapse. In this study, we investigated the ecophysiology of the subtropical green-tide forming alga, Ulva ohnoi complex (hereafter: U. ohnoi), under simulated future ocean conditions in order to predict its bloom potential using photosynthesis and growth measurements, and stable isotope analyses. Our mesocosm system included four experimental conditions that simulated the individual and combined effects of elevated CO 2 and temperature, namely control (450 μatm CO 2 & 20 °C), acidification (900 μatm CO 2 & 20 °C), warming (450 μatm CO 2 & 25 °C), and greenhouse (900 μatm CO 2 & 25 °C). Photosynthetic electron transport rates (rETR) increased significantly under acidification conditions, but net photosynthesis and growth were not affected. In contrast, rETR, net photosynthesis, and growth all decreased significantly under elevated temperature conditions (i.e. both warming and greenhouse). These results represent the imbalance of energy metabolism between electron transport and O 2 production that may be expected under ocean acidification conditions. This imbalance appears to be related to carbon and nitrogen assimilation by U. ohnoi. In particular, 13 C and 15 N discrimination data suggest U. ohnoi prefers CO 2 and NH 4 + over HCO 3 - and NO 3 - as sources of carbon and nitrogen, respectively, and this results in increased N content in the thallus under ocean acidification conditions. Together, our results suggest a trade-off in which the bloom potential of U. ohnoi could increase under ocean acidification due to greater N accumulation and through the saving of energy during carbon and nitrogen metabolism, but that elevated temperatures could decrease U. ohnoi's bloom potential through a decrease in photosynthesis and growth.

54 ENVIRONMENTAL SCIENCES↗

Features of the Electron Mobility in the n-InSe Layered Semiconductor

The dependences of the Hall electron mobility of n-InSe single crystals grown by the Bridgman method on a sample’s technological history, temperature, electric field, doping, and illumination are experimentally investigated. It is established that at temperatures below room temperature, the dependences of the electron mobility on external factors, initial resistivity, and doping are anomalous, i.e., do not obey the theory of free carrier mobility in quasi-ordered crystalline semiconductors. The observed anomalies are attributed to partial disordering and fluctuation of the potential of free energy bands of the n-InSe single crystals and can be controlled by temperature, electric field, doping, and illumination.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Methane-cycling microbial communities from Amazon floodplains and upland forests respond differently to simulated climate change scenarios

Seasonal floodplains in the Amazon basin are important sources of methane (CH 4 ), while upland forests are known for their sink capacity. Climate change effects, including shifts in rainfall patterns and rising temperatures, may alter the functionality of soil microbial communities, leading to uncertain changes in CH 4 cycling dynamics. To investigate the microbial feedback under climate change scenarios, we performed a microcosm experiment using soils from two floodplains (i.e., Amazonas and Tapajós rivers) and one upland forest. We employed a two-factorial experimental design comprising flooding (with non-flooded control) and temperature (at 27 °C and 30 °C, representing a 3 °C increase) as variables. We assessed prokaryotic community dynamics over 30 days using 16S rRNA gene sequencing and qPCR. These data were integrated with chemical properties, CH 4 fluxes, and isotopic values and signatures. In the floodplains, temperature changes did not significantly affect the overall microbial composition and CH 4 fluxes. CH 4 emissions and uptake in response to flooding and non-flooding conditions, respectively, were observed in the floodplain soils. By contrast, in the upland forest, the higher temperature caused a sink-to-source shift under flooding conditions and reduced CH 4 sink capability under dry conditions. The upland soil microbial communities also changed in response to increased temperature, with a higher percentage of specialist microbes observed. Floodplains showed higher total and relative abundances of methanogenic and methanotrophic microbes compared to forest soils. Isotopic data from some flooded samples from the Amazonas river floodplain indicated CH 4 oxidation metabolism. This floodplain also showed a high relative abundance of aerobic and anaerobic CH 4 oxidizing Bacteria and Archaea. Taken together, our data indicate that CH 4 cycle dynamics and microbial communities in Amazonian floodplain and upland forest soils may respond differently to climate change effects. We also highlight the potential role of CH 4 oxidation pathways in mitigating CH 4 emissions in Amazonian floodplains.

16S rRNA sequencing↗

Further Investigations of High Temperature Knitted Spring Tubes for Advanced Control Surface Seal Applications

Knitted metallic spring tubes are the structural backbones that provide resiliency in control surface seals for use on current and future reusable space launch vehicles. Control surface seals fill the space between movable control surfaces such as body flaps, rudders and elevons, and the static body structures to which they are attached. These seals must remain in continuous contact with opposing surfaces to prevent the ingestion of damaging hot gases encountered during atmospheric re-entry. The Inconel X-750 (Special Metals Corporation) spring tube utilized in the baseline control surface seal shows significant resiliency loss when compressed at temperatures as low as 1200 F. High temperature compression testing and microstructural analysis show that creep is the dominant deformation mechanism leading to permanent set and resiliency loss in tested spring tube samples. Additional evaluation using a structured design of experiments approach shows that spring tube performance, primarily high temperature resiliency, can be enhanced through material substitution of Rene 41 (Allvac) alloy (for the baseline Inconel X-750 material) when coupled with specialized thermal processing.

Taylor, Shawn C.↗

Creep fatigue life prediction for engine hot section materials (isotropic)

A series of high temperature strain controlled fatigue tests have been completed to study the effects of thermomechanical fatigue, multiaxial loading, reactive environments, and imposed mean stresses. The baseline alloy used in these tests was cast B1900+Hf (with and without coatings); a small number of tests of wrought INCO 718 are also included. A strong path dependence was demonstrated during the thermomechanical fatigue testing, using in-phase, out-phase, and non-proportional (elliptical and 'dogleg') strain-temperature cycles. The multiaxial tests also demonstrated cycle path to be a significant variable, using both proportional and non-proportional tension-torsion loading. Environmental screening tests were conducted in moderate pressure oxygen and purified argon; the oxygen reduced the specimen lives by two, while the argon testing produced ambiguous data. Both NiCoCrAlY overlay and diffusion aluminide coatings were evaluated under isothermal and TMF conditions; in general, the lives of the coated specimens were higher that those of uncoated specimens. Controlled mean stress TMF tests showed that small mean stress changes could change initiation lives by orders of magnitude; these results are not conservatively predicted using traditional linear damage summation rules. Microstructures were evaluated using optical, SEM and TEM methods.

Nelson, R. S.↗

Accelerated Synthesis of Ordered Mesoporous Carbons Using Plasma

Conventional ordered mesoporous carbon (OMC) production usually requires long processing times in the carbonization step to achieve desired temperatures through controlled ramps. To enable expedited materials discovery, developing advanced manufacturing capability with significantly improved throughput is highly desired. Current approaches for accelerating the synthesis of OMCs include using microwave and Joule heating. However, both methods rely on the introduction of additional components, such as microwave absorbers and electrically conductive agents, within the bulk materials to impart the ability to reach high carbonization temperatures. This work demonstrates accelerated synthesis and functionalization of OMCs through the use of a dielectric barrier discharge plasma, where carbonization can be accomplished within 15 min using 30 W plasma sources, representing more than an order of magnitude increase in polymer-to-carbon conversion kinetics compared to that of a traditionally pyrolyzed analogue. Particularly, the ability of performing rapid carbonization without the use of additional substrates within the OMC precursor systems is advantageous. A systematic investigation of how plasma power, time, and gas atmosphere impact the resulting OMC pore textures and properties is performed, demonstrating the broad applicability of plasma-enabled carbonization methods. Furthermore, we demonstrate that the plasma treatment strategy can be extended to incorporate heteroatoms into the carbon framework by introducing ammonia gas, resulting in OMCs with a nitrogen content up to 4.7 at %, as well as non-Pluronic templating systems for synthesizing OMC with pore sizes larger than 10 nm. As employing a plasma source for materials pyrolysis is an industrially relevant approach, our system can be extended toward scaled synthesis of OMCs with much faster production rates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A multi-zone muffle furnace design

A Multi-Zone Muffle-Tube Furnace was designed, built, and tested for the purpose of providing an in-house experience base with tubular furnaces for materials processing in microgravity. As such, it must not only provide the desired temperatures and controlled thermal gradients at several discrete zones along its length but must also be capable of sustaining the rigors of a Space Shuttle launch. The furnace is insulated to minimize radial and axial heat losses. It is contained in a water-cooled enclosure for purposes of dissipating un-wanted residual heat, keeping the outer surfaces of the furnace at a 'touch-safe' temperature, and providing a rugged housing. This report describes the salient features of the furnace, testing procedures and results, and concluding remarks evaluating the overall design.

Rowe, Neil D.↗

Advances in Solid State Joining of High Temperature Alloys

Many of the metals used in the oil and gas industry are difficult to fusion weld including Titanium and its alloys. Solid state joining processes are being pursued as an alternative process to produce robust structures more amenable to high pressure applications. Various solid state joining processes include friction stir welding (FSW) and a patented modification termed thermal stir welding (TSW). The configuration of TSWing utilizes an induction coil to preheat the material minimizing the burden on the weld tool extending its life. This provides the ability to precisely select and control the temperature to avoid detrimental changes to the microstructure. The work presented in this presentation investigates the feasibility of joining various titanium alloys using the solid state welding processes of FSW and TSW. Process descriptions and attributes of each weld process will be presented. Weld process set ]up and welding techniques will be discussed leading to the challenges experienced. Mechanical property data will also be presented.

Ding, Jeff↗

Thermomechanical deformation testing and modeling in the presence of metallurgical instabilities

A number of viscoplastic constitutive models were developed to describe deformation behavior under complex combinations of thermal and mechanical loading. Questions remain, however, regarding the validity of procedures used to characterize these models for specific structural alloys. One area of concern is that the majority of experimental data available for this purpose are determined under isothermal conditions. This experimental study is aimed at determining whether viscoplastic constitutive theories characterized using an isothermal data base can adequately model material response under the complex thermomechanical loading conditions typical of power generation service. The approach adopted was to conduct a series of carefully controlled thermomechanical experiments on a nickel-based superalloy, Hastelloy Alloy X. Previous investigations had shown that this material experiences metallurgical instabilities leading to complex hardening behavior, termed dynamic strain aging. Investigating this phenomenon under full thermomechanical conditions leads to a number of challenging experimental difficulties which up to the present work were unresolved. To correct this situation, a number of advances were made in thermomechanical testing techniques. Advanced methods for dynamic temperature gradient control, phasing control and thermal strain compensation were developed and incorporated into real time test control software. These advances allowed the thermomechanical data to be analyzed with minimal experimental uncertainty. The thermomechanical results were evaluated on both a phenomenological and microstructural basis. Phenomenological results revealed that the thermomechanical hardening trends were not bounded by those displayed under isothermal conditions. For the case of Hastelloy Alloy X (and similar dynamic strain aging materials), this strongly suggests that some form of thermomechanical testing is necessary when characterizing a thermoviscoplastic deformation model. Transmission electron microscopy was used to study the microstructural physics, and analyze the unique phenomenological behavior.

Castelli, Michael G.↗

Development of joining technology using local heating for SiC fuel cladding

Silicon carbide (SiC) is an attractive material for an accident-tolerant fuel in light water reactors because of its lower hydrogen-generation rate and lower heat of reaction than conventional Zircaloy. On the other hand, practical application of SiC fuel cladding faces a lot of critical issues, one of which is end-plug joining. The objective of this study is to clarify the feasibility of end-plug joining by silicon brazing using local heating by evaluating the shear strength of joint specimens and producing a circumferential joint experimentally. Silicon is thought to be a compatible joining material with SiC because as well as being a constituent of SiC, its thermal-expansion coefficient is close to that of SiC. Local heating using processes such as laser irradiation and a resistance-heating element needs to be applied for end-plug joining. Brazing is expected to seal a cladding with an end plug by using brief heating without a strong compression force. Shear strength was evaluated using specimens with silicon-brazing joints processed using laser irradiation. The joint sections without defects showed shear strengths higher than or equal to 59 MPa at temperatures from normal room temperature to 1473 K. The average shear strength of the joint (99 MPa) is comparable to that of a diffusion-bonding joint using titanium or molybdenum foil. A tube and a plug were circumferentially joined with silicon brazing using laser irradiation or a graphite heating element. A defocused laser beam was effective for joining without cracking during laser irradiation. Although local heating using a resistance-heating element can more easily control the temperature of the joint, it took longer processing time than that using laser irradiation due to limited temperature-increase rate in order to avoid thermal shock damage. (authors)

36 MATERIALS SCIENCE↗