Summary report on the induction of water to the inlet air as a means of internal cooling in aircraft-engine cylinders
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Dilute Pd-in-Au alloys are valuable materials for selectively hydrogenating alkynes and isomerizing alkenes. By diluting Pd in a Au host, the selectivity toward semihydrogenated alkene isomers can be significantly enhanced and the unfavorable overhydrogenation to alkanes is suppressed. However, a detailed mechanistic study on the origin of the enhanced alkene selectivity over dilute alloy catalysts is still missing. Here, we combine experiment and theory to unravel the reaction mechanism, identifying rate-limiting and selectivity-controlling steps in 1-hexene hydrogenation over dilute Pd-in-Au catalysts. Using isotope-exchange hydrogenation experiments, we show that 1-hexene and hydrogen over a bimetallic Pd4Au96 in silica catalyst preferentially form 1-hexene isomers, (trans and cis) 2- and 3-hexene and only a small amounts of hexane. The reaction is consistent with a Horiuti–Polanyi mechanism, similar to a monometallic Pd nanoparticle catalyst. Computation of the free-energy profiles for 1-hexene hydrogenation and isomerization over a single Pd atom in a Au surface using first principles calculations indicated that the isomerization of 1-hexene to 2-hexene is energetically favorable due to the relatively large barrier for H2 dissociation preventing hydrogenation to n-hexane. Microkinetic modeling established that H2 dissociation on the single-atom Pd sites and H spillover from these sites onto the Au host are rate-limiting and key in steering the selectivity of dilute Pd-in-Au alloys toward the hexene isomers. Furthermore, the mechanistic insights from this study contribute to the rational design of optimized dilute alloy catalysts for selective alkene isomerization.
The feasibility of making quantitative nonintrusive NO concentration ([NO]) measurements in nonpremixed flames has been assessed by obtaining laser-induced fluorescence (LIF) measurements of [NO] in counterflow diffusion flames at atmospheric and higher pressures. Comparisons at atmospheric pressure between laser-saturated fluorescence (LSF) and linear LIF measurements in four diluted ethane-air counterflow diffusion flames with strain rates from 5 to 48/s yielded excellent agreement from fuel-lean to moderately fuel-rich conditions, thus indicating the utility of a model-based quenching correction technique, which was then extended to higher pressures. Quantitative LIF measurements of [NO] in three diluted methane-air counterflow diffusion flames with strain rates from 5 to 35/s were compared with OPPDIF model predictions using the GRI (version 2.11) chemical kinetic mechanism. The comparisons revealed that the GRI mechanism underpredicts prompt-NO by 30-50% at atmospheric pressure. Based on these measurements, a modified reaction rate coefficient for the prompt-NO initiation reaction was proposed which causes the predictions to match experimental data. Temperature measurements using thin filament pyrometry (TFP) in conjunction with a new calibration method utilizing a near-adiabatic H2-air Hencken burner gave very good comparisons with model predictions in these counterflow diffusion flames. Quantitative LIF measurements of [NO] were also obtained in four methane-air counterflow partially-premixed flames with fuel-side equivalence ratios (phi(sub B)) of 1.45, 1.6, 1.8 and 2.0. The measurements were in excellent agreement with model predictions when accounting for radiative heat loss. Spatial separation between regions dominated by the prompt and thermal NO mechanisms was observed in the phi(sub B) = 1.45 flame. The modified rate coefficient proposed earlier for the prompt-NO initiation reaction improved agreement between code predictions and measurements in the region where prompt-NO dominates. Finally, LIF measurements of NO were obtained in counterflow diffusion flames at 2 to 5 atm. Comparisons between [NO] measurements and predictions show that the GRI mechanism underpredicts prompt-NO by a factor of two to three at all pressures. In general, the results indicate a need for refinement of the CH chemistry, especially the pressure-dependent CH formation and destruction reactions.
To facilitate its vitrification, a portion of the radioactive wastes currently stored at the Hanford Site will be staged and treated using tank-side operations to render their chemistry compliant with the requirements of Hanford’s low-activity waste vitrification facility. Initial sampling of staged feeds indicates that process-water dilution, used to reduce waste feed sodium content to levels acceptable for vitrification (5–6 M Na), may cause precipitation of fine, difficult to settle solids that could affect downstream tank-side filtration and ion-exchange. However, dilution-induced precipitation has not been demonstrated under controlled, rigorous laboratory conditions. This paper presents a set of qualitative and quantitative assessments of dilution-induced precipitation using a nonradioactive, Hanford Tank AP-105 simulated waste. Further, these studies found that dilution of AP-farm waste simulants induced precipitation of up to 150 ppm solids, regardless of whether dilution was done with process water (which contains, among other analytes, naturally occurring Ca and Mg) or deionized water. Naturally occurring process-water analytes appeared to accelerate the rate (and possibly extent) of precipitation. Filtration of diluted waste simulants also found that the precipitated solids challenged prototypic tank-side filter operations; however, the impact to filtration performance was readily managed through waste staging settle/decant operations.
Our goal has been to investigate the influence of both dilution and radiation on the extinction process of nonpremixed flames at low strain rates. Simulations have been performed by using a counterflow code and three radiation models have been included in it, namely, the optically thin, the narrowband, and discrete ordinate models. The counterflow flame code OPPDIFF was modified to account for heat transfer losses by radiation from the hot gases. The discrete ordinate method (DOM) approximation was first suggested by Chandrasekhar for solving problems in interstellar atmospheres. Carlson and Lathrop developed the method for solving multi-dimensional problem in neutron transport. Only recently has the method received attention in the field of heat transfer. Due to the applicability of the discrete ordinate method for thermal radiation problems involving flames, the narrowband code RADCAL was modified to calculate the radiative properties of the gases. A non-premixed counterflow flame was simulated with the discrete ordinate method for radiative emissions. In comparison with two other models, it was found that the heat losses were comparable with the optically thin and simple narrowband model. The optically thin model had the highest heat losses followed by the DOM model and the narrow-band model.
To study the constitutive behavior of granular materials, the presence of gravity is detrimental. Although empirical relations have been obtained for engineering designs to control granular flows on Earth, it is not known how well these Earthbound relations can be used in another gravity field. Fundamental understanding must be derived to reliably design for granular flows in space exploration. There are two extremes of granular flows of which significant amount of knowledge is available. One deals with a dense and quasi-static situation where the deformation rate nearly vanishes. The other deals with dilute and rapidly fluctuating grain velocities where particle inertia dominates. This project, funded by the NASA Microgravity Fluid Physics Program, aims to study this transitional regime via physical experiments and computer simulations. A conceptual model has been established as described below. There are two natural time scales in a granular flow. One is the travel time between two consecutive collisions and the other is the duration of a collision contact. At a very low shear-rate, the shear-induced particle velocity is low. Hence the travel time between collisions is longer than the contact time between colliding particles. Binary collisions prevail. As the shear-rate increases, the traveling time between collisions reduces and the probability of multiple collisions goes up. These particle groups disperse shortly after and new groups form. When shear-rate is further increased, clusters grow in size due to an increasing chance for free particles to join before groups have the time to disperse. The maximum cluster size may depend on the global concentration and material properties. As the solid concentration approaches zero, the cluster size goes to one particle diameter. The maximum possible cluster size under any condition is the container size, provided that the shear flow is inside a container. The critical shear-rates that dictate the initiation of the multiple contacts, and the size and lifetime of the collision clusters, are functions of the concentration also. A 'regime' theory has been proposed by Babic et al. This theory suggested that both the solid concentration, C, and the non-dimensional shear-rate, B, are important in determining the regimes of the granular constitutive law. Additional information is included in the original extended abstract.
Here, this study investigates the effect of temperature on the heat generation and the associated electrochemical phenomena occurring in IL-based EDLCs. The EDLCs consisted of two identical activated carbon electrodes with neat Pyr14TFSI or Pyr14TFSI diluted in propylene carbonate (PC) as electrolytes. The instantaneous heat generation rate at each electrode was measured by isothermal calorimetry between 5 and 80 °C under constant current cycling and potential window of 2.5 V. First, the instantaneous heat generation rate was similar at each electrode in neat IL. However, it was smaller at the negative electrode in diluted IL and featured endothermic dips growing with increasing temperature > 40 °C due to overscreening effects, ion desolvation, and/or decomposition of PC. The irreversible heat generation was similar in each half-cell and decreased with increasing temperature due to the reduction in internal resistance, particularly with neat IL. The irreversible heat generation exceeded Joule heating in all cases, especially at high temperature and low current. This was attributed to ion desorption and charge redistribution in the porous electrodes. Finally, the reversible heat generation for both electrolytes was larger at the positive than at the negative electrode due to the difference in anion and cation sizes.
This study aims to investigate the effect of the potential window on heat generation in carbon-based electrical double layer capacitors (EDLCs) with ionic-liquid (IL)-based electrolytes using in operando calorimetry. The EDLCs consisted of two identical activated-carbon electrodes with either neat 1-butyl-1-methylpyrrolidinium bis(trifluoromethane-sulfonyl)imide ([Pyr 14 ][TFSI]) electrolyte or 1.0 m [Pyr 14 ][TFSI] in propylene carbonate (PC) as electrolyte. The instantaneous heat generation rate at each electrode was measured under galvanostatic cycling for different potential windows ranging from 1 to 4 V. First, the heat generation rates at the positive and negative electrodes differed significantly in neat IL owing to the differences in the ion sizes and diffusion coefficients. However, these differences were minimized when the IL was diluted in PC. Second, for EDLC in neat [Pyr 14 ][TFSI] at high potential window (4 V), a pronounced endothermic peak was observed at the beginning of the charging step at the positive electrode owing to TFSI - intercalation in the activated carbon. On the other hand, for EDLC in 1.0 m [Pyr 14 ][TFSI] in PC at potential window above 3 V, an endothermic peak was observed only at the negative electrode owing to the decomposition of PC. Third, for both neat and diluted [Pyr 14 ][TFSI] electrolytes, the irreversible heat generation rate increased with increasing potential window and exceeded Joule heating. This was attributed to the effect of potential-dependent charge redistribution resistance. Additionally, a further increase in the irreversible heat generation rate was observed for the largest potential windows owing to the degradation of the PC solvent. Finally, for both types of electrolyte, the reversible heat generation rate increased with increasing potential window because of the increase in the amount of ion adsorbed/desorbed at the electrode/electrolyte interface.
The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.
This paper aims to investigate the influences of high Portland cement substitutions (>60 wt%) by low-grade calcined clay (CC) and limestone (LF) on 3D concrete printability, stiffness evolution and early-age hydration. Results show that, with the same dosage of admixtures (superplasticizer and viscosity modifier), increasing LF and CC content reduced the slump, flowability and initial material flow rate, and significantly improved the buildability of fresh mixtures, which can be attributed to the reduced water film thickness (WFT). Furthermore, the stiffness evolution and SSA{sub total} development up to the first 3 h were accelerated by increasing CC content, which can also be linked to the change of WFT, and consumption of superplasticizer for the dispersion induced by hydration products. Additionally, the dilution effect on compressive strength and hydration caused by the high cement replacement was observed.
The effect of shear velocity gradients on the size (L) of rodlike micelles in dilute and semidilute solution is considered. A kinetic equation is introduced for the time-dependent concentration of aggregates of length L, consisting of 'bimolecular' combination processes L + L-prime yield (L + L-prime) and unimolecular fragmentations L yield L + (L - L-prime). The former are described by a generalization (from spheres to rods) of the Smoluchowski mechanism for shear-induced coalesence of emulsions, and the latter by incorporating the tension-deformation effects due to flow. Steady-state solutions to the kinetic equation are obtained, with the corresponding mean micellar size evaluated as a function of the Peclet number P (i.e., the dimensionless ratio of the flow rate and the rotational diffusion coefficient). For sufficiently dilute solutions, only a weak dependence of the micellar size on P is found. In the semidilute regime, however, an apparent divergence in the micellar size at P of about 1 suggests a flow-induced first-order gelation phenomenon.
This final technical report details the successful design, construction, and operational validation of an innovative dual-loop CO 2 capture technology designed to achieve deep decarbonization (>99%) from Natural Gas Combined Cycle (NGCC) power plants that results in the electricity with carbon intensity of approximate 42 kg CO 2 -eq/MWh, less than the electricity produced by solar PV. The integrated process couples a primary aqueous solvent (in this project, a water lean solvent – WLS) absorption loop for bulk CO 2 removal with a secondary potassium hydroxide (KOH) polishing loop featuring electrochemical regeneration. This architecture leverages the higher exergy efficiency of the primary loop while utilizing the fastest kinetic of the secondary loop to capture dilute residual CO 2 , achieving an overall capture rate of 99.9% and co-producing pure hydrogen after moisture being condensed and dehydrated. Technical feasibility was established through a comprehensive 2,000-hour experimental campaign on a bench-scale fully-integrated unit (using 4” absorber and 4” stripper) with the feeding flue gas flowrate in the range of 8-20 cfm, confirming the attainment of Technology Readiness Level (TRL) 4. The project executed extensive parametric testing followed by 1,000 hours of continuous steady-state testing, demonstrating exceptional process stability with the electrochemical regenerator exhibiting less than a 10% reduction in electrical conductivity over the duration of the campaign. Operational characterization gathering on the bench unit revealed distinct energy profiles for the hybrid system: the primary loop required approximately 280 kJ mol -1 for bulk removal, while the polishing loop required approximately 1,600 kJ mol -1 specifically when reducing dilute CO 2 concentrations from ~740 ppm down to <50 ppm. (Please note those energy values/numbers can only be viewed as relative relationship and should not be extrapolated as absolute values required for CO 2 capture). Furthermore, dynamic testing validated the system’s flexibility for utility applications, demonstrating a rapid process response time of <30 minutes to changes in flue gas flowrate. Emission monitoring confirmed that the dual-loop architecture effectively mitigates solvent losses, utilizing a water wash to remove entrained aerosols to <1 ppm. The Techno-Economic Analysis (TEA) indicates a cost of capture of $\$$59.3/tonne and a Levelized Cost of Electricity (LCOE) of 71.7 $\$$/MWh at the overall capture efficiency of 99.8% of total carbon in the flue gas stream, with sensitivity analysis identifying an economic optimum when the primary loop captures 97% of the total CO 2 . A Life Cycle Assessment (LCA) confirms the technology’s potential for net-negative emissions, determining a Global Warming Potential (GWP) of 52 kg CO 2 -eq/MWh—significantly lower than the baseline—which further decreases to 42 kg CO 2 -eq/MWh when crediting the displacement of conventional hydrogen production.
The purpose of the model provides a method to analyze some of the events that could account for the decrease in red cell mass observed in crewmen returning from space missions. The model is based on the premise that erythrocyte production is governed by the balance between oxygen supply and demand at a renal sensing site. Oxygen supply is taken to be a function of arterial oxygen tension, mean corpuscular hemoglobin concentration, oxy-hemoglobin carrying capacity, hematocrit, and blood flow. Erythrocyte destruction is based on the law of mass action. The instantaneous hematocrit value is derived by integrating changes in production and destruction rates and accounting for the degree of plasma dilution.
Thin-film, single-crystal gallium arsenide (GaAs) solar cells could exhibit a specific power approaching 700 W/kg including coverglass. A simple process has been described whereby epitaxial GaAs layers are peeled from a reusable substrate. This process takes advantage of the extreme selectivity of the etching rate of aluminum arsenide (AlAs) over GaAs in dilute hydrofluoric acid. The feasibility of using the peeled film technique to fabricate high-efficiency, low-mass GaAs solar cells is presently demonstrated. A peeled film GaAs solar cell was successfully produced. The device, although fractured and missing the aluminum gallium arsenide window and antireflective coating, had a Voc of 874 mV and a fill factor of 68 percent under AM0 illumination.
The Burning and Suppression of Solids (BASS) experiment was performed on the International Space Station. Microgravity combustion tests burning thin and thick flat samples, acrylic spheres, and candles were conducted. The samples were mounted inside a small wind tunnel which could impose air flow speeds up to 40 cms. The wind tunnel was installed in the Microgravity Science Glovebox which supplied power, imaging, and a level of containment. The effects of air flow speed, fuel thickness, fuel preheating, and nitrogen dilution on flame appearance, flame growth, and spread rates were determined in both the opposed and concurrent flow configuration. In some cases, a jet of nitrogen was introduced to attempt to extinguish the flame. Microgravity flames were found to be especially sensitive to air flow speed in the range 0 to 5 cms. The gas phase response is much faster compared to the solid and so as the flow speed is changed, the flame responds with almost no delay. At the lowest speeds examined (less than 1 cms) all the flames tended to become dim blue and very stable. However, heat loss at these very low convective rates is small so the flames can burn for a long time. At moderate flow speeds (between about 1 and 5 cms) the flame continually heats the solid fuel resulting in an increasing fuel temperature, higher rate of fuel vaporization, and a stronger, more luminous flame as time progresses. Only the smallest flames burning acrylic slabs appeared to be adversely influenced by solid conductive heat loss, but even these burned for over 5 minutes before self-extinguishing. This has implications for spacecraft fire safety since a tiny flame might be undetected for a long time. While the small flame is not particularly hazardous if it remains small, the danger is that it might flare up if the air convection is suddenly increased or if the flame spreads into another fuel source.
Thiophene and several of its derivatives (2-methylthiophene, 3methylthiophene) have been detected on the surface of Mars in lacustrine mudstones using the pyrolysis-GC-MS instrument onboard NASA’s Curiosity Rover. The biosynthesis of thiophenes is considered an important production pathway on Earth, suggesting that thiophenes could serve as a secondary chemical biosignature on Mars. However, Mars lacks a global magnetic field allowing GCRs to readily penetrate the thin CO 2 atmosphere and several meters into the regolith. GCRs can destroy the organic molecules present (i.e., chemical biosignatures). To date, the radiation-driven decomposition of these thiophenes has not been examined and their destruction rates constants have not been measured. Here, we provide radiolytic decomposition rates for thiophene as a neat ice and diluted in water ice to provide additional astrochemical context to the recent detections on Mars.
Lithium-Sulfur (Li-S) batteries have become a promising candidate to meet the current energy storage demand, with its natural abundance of materials, high theoretical capacity of 1672 mAhg-1, high energy density of 2600 Whkg-1, low cost and lower environmental impact. Sulfide based solid state electrolytes (SSEs) have received greater attention due to their higher ionic conductivity, compatible interface with sulfur-based cathodes, and lower grain boundary resistance. However, the interface between SSEs and cathodes has become a challenge in all solid-state Li-S batteries due to the rigidity of the participating surfaces. A hybrid electrolyte containing SSE coupled with a small amount of ionic liquid, was essential to improve the interface contact of the SSE with the electrodes. Coating-based cathodes were successfully fabricated using water-based carboxymethyl cellulose (CMC) solution and Styrene butadiene rubber (SBR) as the binder with low sulfur loading (0.70 mgcm-2) as well as high sulfur loading (4.0 mgcm-2). Solid-state composite powder-based cathodes pressed onto SSE (loading 4.0 mgcm-2) with enhanced electronic and ionic conductivity were fabricated with Super P: Sulfur (SP:S) and SSE. Ionic Liquids (IL) prepared using Lithium bis(trifluoromethyl sulfonyl)imide (LiTFSI) as salt, with premixed pyrrolidinium bis(trifluoromethyl sulfonyl)imide (PYR) as solvent and 1,3-dioxolane (DOL) as diluent were used to wet both SSE-electrode interfaces. The effect of IL dilution, co-solvent amount, LiTFSI concentration, C rate at which the batteries are tested and the effect of SSE inside the cathode, were systematically studied and optimized to develop a quasi-solid-state electrolyte Li-S battery (QSSLSB) with higher capacity retention and cyclability. LiTFSI (2M) dissolved in PYR:DOL(1:1) found to be optimum IL combination for low sulfur loading QSSLSBs reaching 500 mAh/g after 100 cycles while LiTFSI (3M) in PYR:DOL(1:3) was the optimum IL concentration for higher loading QSSLSBs reaching 400 mAh/g after 100 cycles. This work reports promising results of QSSLSB based on novel Li6PS5F0.5Cl0.5 Li-argyrodite solid-state electrolyte (SSE) with minute amount of IL, Super P-Sulfur (SP:S) cathode, and Li-anode. It also offers a new insight into the intimate interfacial contacts between the SSE and carbon-sulfur cathodes, which will be critical for improved electrochemical performance of quasi-solid-state lithium-sulfur batteries with high sulfur loading in the future.
Approximately 9 L of supernatant from Hanford waste tank 241-AW-105 was delivered by Hanford Tank Waste Operations and Closure (H2C) to the Radiochemical Processing Laboratory (RPL) at Pacific Northwest National Laboratory (PNNL). The thirty-six 241-AW-105 sample bottles consisted of four sets of nine samples, with each set pulled from a unique tank sampling level. Prior to testing, samples from each level were composited and diluted to 5.5 M Na to provide nominally level-independent feed for dead-end filtration and ion exchange testing. The composited 241-AW-105 supernatant was chilled to 16 °C for 1 week prior to testing. Filtration testing was then conducted using a backpulse dead-end filter (BDEF) system equipped with a feed vessel and a Mott inline filter (Model 6610, Media Grade 5) in the hot cells of the RPL. The purpose of this testing was to (a) demonstrate dead-end filtration (DEF) of 241-AW-105 feed at reduced temperature to obtain prototypic Tank Side Cesium Removal (TSCR) flux rates and identify issues that may impact filtration after dilution to 5.5 M Na, and (b) provide feed for follow-on ion exchange unit operation. The feed was filtered through the BDEF system at a targeted flux of 0.065 gpm/ft2. For most of the filtration campaign, the differential pressure required to effect filtration at 0.065 gpm/ft2 was slow to increase. After all the feed bottles had been pumped into the slurry reservoir, the bottoms of the bottles were added to the reservoir and transmembrane pressure (TMP) reached 2.0 psid (the TSCR action limit). A backpulse was performed after >50 hours of filtration to remove fouled solids and reduce the TMP. The filter was cleaned after completing filtration of the 241-AW-105 feed, and clean water flux tests showed filter performance was effectively restored. Solids concentrated from the backpulse solutions were composed of steel-like particles, uranium-bearing phases, Mn-Fe phases, a Ce-bearing phase, Zr phases, and some smaller Ca-bearing particles. The Ca-bearing and U bearing phases were identified as calcite and clarkeite, respectively.