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Results for “Conditional rate functions”

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At least 1,765 records · Page 98

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DOE OSTI2015

Acidolysis of α-O-4 Aryl-Ether Bonds in Lignin Model Compounds: A Modeling and Experimental Study

Lignocellulosic biomass offers a vast, renewable resource for the sustainable production of fuels and chemicals. To date, a commonly employed approach to depolymerize the polysaccharides in plant cell walls employs mineral acids, and upgrading strategies for the resulting sugars are under intense development. Although the behavior of cellulose and hemicellulose is reasonably well characterized, a more thorough understanding of lignin depolymerization mechanisms in acid environments is necessary to predict the fate of lignin under such conditions and ultimately to potentially make lignin a viable feedstock. To this end, dilute acid hydrolysis experiments were performed on two lignin model compounds containing the a-O-4 ether linkage at two temperatures concomitant with dilute acid pretreatment. Both primary and secondary products were tracked over time, giving insight into the reaction kinetics. The only difference between the two model compounds was the presence or absence of a methyl group on the a-carbon, with the former being typical of native lignin. It was found that methylation of the a-carbon increases the rate of reaction by an order of magnitude. Density functional theory calculations were performed on a proposed mechanism initiated by a nucleophilic attack on the a-carbon by water with a commensurate protonation of the ether oxygen. The values for the thermodynamics and kinetics derived from these calculations were used as the basis for a microkinetic model of the reaction. Results from this model are in good agreement with the experimental kinetic data for both lignin model compounds and provide useful insight into the primary pathways of a-O-4 scission reactions in acid-catalyzed lignin depolymerization. The distribution of primary and secondary products is interpreted as a function of two barriers of formation exhibiting opposite trends upon methylation of the a-carbon (one barrier is lowered while the other is increased). Such insights will be needed to construct a comprehensive model of how lignin behaves in a common deconstruction approach.

14 SOLAR ENERGY↗

DOE OSTI2023

Synergistic effects of mixing and strain in high entropy spinel oxides for oxygen evolution reaction

Developing stable and efficient electrocatalysts is vital for boosting oxygen evolution reaction (OER) rates in sustainable hydrogen production. High-entropy oxides (HEOs) consist of five or more metal cations, providing opportunities to tune their catalytic properties toward high OER efficiency. This work combines theoretical and experimental studies to scrutinize the OER activity and stability for spinel-type HEOs. Density functional theory confirms that randomly mixed metal sites show thermodynamic stability, with intermediate adsorption energies displaying wider distributions due to mixing-induced equatorial strain in active metal-oxygen bonds. The rapid sol-flame method is employed to synthesize HEO, comprising five 3d-transition metal cations, which exhibits superior OER activity and durability under alkaline conditions, outperforming lower-entropy oxides, even with partial surface oxidations. The study highlights that the enhanced activity of HEO is primarily attributed to the mixing of multiple elements, leading to strain effects near the active site, as well as surface composition and coverage.

08 HYDROGEN↗

DOE OSTI2025

Spatially programmed alignment and actuation in printed liquid crystal elastomers

Liquid crystal elastomers (LCEs) exhibit reversible shape morphing behavior when cycled above their nematic-to-isotropic transition temperature. During extrusion-based 3D printing, LCE inks are subjected to coupled shear and extensional flows that can be harnessed to spatially control the alignment of their nematic director along prescribed print paths. Here, we combine experiment and modeling to elucidate the effects of ink composition, nozzle geometry, and printing parameters on director alignment. From rheological measurements, we quantify the dimensionless Weissenberg number ( Wi ) for the flow field each ink experiences as a function of printing conditions and demonstrate that Wi is a strong predictor of LCE alignment. We find that director alignment in LCE filaments printed through a tapered nozzle varies radially when Wi < 1, while it is uniform when Wi ≫ 1. Based on COMSOL simulations and in operando X-ray measurements, we show that LCE inks printed through nozzles with an internal hyperbolic geometry exhibit a more uniform director alignment for a given Wi compared to those through tapered nozzles. Concomitantly, the stiffness along the print direction and actuation strain of printed LCEs increases substantially under such conditions. By varying Wi during printing through adjusting the flow rate “on the fly”, LCE architectures with uniform composition, yet locally encoded shape morphing transitions can be realized.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Towards Mitigating Electron Beam-Induced Damage in MOFs Using Low Dose Electron Microscopy for In-Situ Room-Temperature Measurements

Metal-Organic Frameworks (MOFs) have emerged as a versatile class of materials with applications in gas storage and separation, catalysis, and drug delivery [1]. Understanding their damage mechanisms in under various environmental conditions is crucial for optimizing performance and stability [2]. This study employs a combination of Length Structural Coherence (LSC) analysis in electron scattering and Electron Energy Loss Spectroscopy (EELS) to elucidate the damage mechanisms in two representative MOFs. MIL101(Fe), and MIL101(Cr). Here, the primary objective is to reveal structural and chemical changes that occur under electron beam irradiation in Scanning Transmission Electron Microscopy (STEM), both in the pristine state and during in-situ CO and CO 2 adsorption. By combining LSC in Radial Distribution Function (RDF) analysis with EELS, comprehensive insights into the nanoscale alterations are obtained and correlated to the electron dose rate.

dos Santos, Gabriel T. [Northwestern University, E↗

DOE OSTI2020

Mechanisms underlying leaf photosynthetic acclimation to warming and elevated CO 2 as inferred from least‐cost optimality theory

Abstract The mechanisms responsible for photosynthetic acclimation are not well understood, effectively limiting predictability under future conditions. Least‐cost optimality theory can be used to predict the acclimation of photosynthetic capacity based on the assumption that plants maximize carbon uptake while minimizing the associated costs. Here, we use this theory as a null model in combination with multiple datasets of C 3 plant photosynthetic traits to elucidate the mechanisms underlying photosynthetic acclimation to elevated temperature and carbon dioxide (CO 2 ). The model‐data comparison showed that leaves decrease the ratio of the maximum rate of electron transport to the maximum rate of Rubisco carboxylation ( J max / V cmax ) under higher temperatures. The comparison also indicated that resources used for Rubisco and electron transport are reduced under both elevated temperature and CO 2 . Finally, our analysis suggested that plants underinvest in electron transport relative to carboxylation under elevated CO 2 , limiting potential leaf‐level photosynthesis under future CO 2 concentrations. Altogether, our results show that acclimation to temperature and CO 2 is primarily related to resource conservation at the leaf level. Under future, warmer, high CO 2 conditions, plants are therefore likely to use less nutrients for leaf‐level photosynthesis, which may impact whole‐plant to ecosystem functioning.

Smith, Nicholas G.↗

NASA NTRS1972

Experimental and Analytical Investigation of the Coolant Flow Characteristics in Cooled Turbine Airfoils

The flow characteristics of turbine airfoil cooling system components were experimentally investigated. Flow models representative of leading edge impingement, impingement with crossflow (midchord cooling), pin fins, feeder supply tube, and a composite model of a complete airfoil flow system were tested. Test conditions were set by varying pressure level to cover the Mach number and Reynolds number range of interest in advanced turbine applications. Selected geometrical variations were studied on each component model to determine these effects. Results of these tests were correlated and compared with data available in the literature. Orifice flow was correlated in terms of discharge coefficients. For the leading edge model this was found to be a weak function of hole Mach number and orifice-to-impinged wall spacing. In the impingement with crossflow tests, the discharge coefficient was found to be constant and thus independent of orifice Mach number, Reynolds number, crossflow rate, and impingement geometry. Crossflow channel pressure drop showed reasonable agreement with a simple one-dimensional momentum balance. Feeder tube orifice discharge coefficients correlated as a function of orifice Mach number and the ratio of the orifice-to-approach velocity heads. Pin fin data was correlated in terms of equivalent friction factor, which was found to be a function of Reynolds number and pin spacing but independent of pin height in the range tested.

Damerow, W. P.↗

NASA NTRS1992

Venusian sinuous rilles

After a preliminary assessment of venusian channels, it now seems to be clear that the channels have distinctive classes, which imply a wide range of formation parameters and formation mechanisms. They include outflow channels mainly formed by mechanical erosion from very high discharge flow, and canali-type channels requiring either constructional process or mechanical erosion by rather exotic low-viscosity lava such as carbonatite or sulfur. Here we focus on venusian sinuous rilles. Venusian sinuous rilles are generally simple, and originate from a collapsed source. They are shallow and narrow downstream. The venusian sinuous rilles are distinct from canali-type channels, which exhibit almost constant morphologies throughout their entire length, and from outflow channels, which are characterized by wide anastomosing reaches. The lunar sinuous rilles could have been formed initially as constructional channels. However, incision was caused by the long flow duration and high temperatures of eruption, along with relatively large discharge rates, possibly assisted by a low viscosity of the channel-forming lava. Channel narrowing and levee formation suggest relatively fast cooling. The venusian channels could have had a similar sequence of formation including rapid cooling. Assuming the substrate is typical tholeiitic lava, the flowing lavas' temperatures have to be higher than the melting temperature of the substrate. The flow should have a low viscosity to cause turbulence and keep a high Reynolds number to sustain efficient thermal erosion. Determining eruption conditions also provide insights to estimate lava composition. Assuming a channel is formed mostly by thermal erosion, the channel's length and longitudinal profile are functions of lava properties. The depth profiles of the channel are measured by radar foreshortening methods and stereo images. Eruption conditions of channel forming lava can be estimated by the methods developed by Hulme.

Komatsu, G.↗

NASA NTRS1995

P-polarized reflectance spectroscopy: A high sensitive real-time monitoring technique to study surface kinetics under steady state epitaxial deposition conditions

This paper describes the results of real-time optical monitoring of epitaxial growth processes by p-polarized reflectance spectroscopy (PRS) using a single wavelength application under pulsed chemical beam epitaxy (PCBE) condition. The high surface sensitivity of PRS allows the monitoring of submonolayer precursors coverage on the surface as shown for GaP homoepitaxy and GaP on Si heteroepitaxy as examples. In the case of heteroepitaxy, the growth rate and optical properties are revealed by PRS using interference oscillations as they occur during growth. Super-imposed on these interference oscillations, the PRS signal exhibits a fine structure caused by the periodic alteration of the surface chemistry by the pulsed supply of chemical precursors. This fine structure is modeled under conditions where the surface chemistry cycles between phosphorus supersaturated and phosphorus depleted surfaces. The mathematical model describes the fine structure using a surface layer that increases during the tertiarybutyl phosphine (TBP) supply and decreases during and after the triethylgallium (TEG) pulse, which increases the growing GaP film thickness. The imaginary part of the dielectric function of the surface layer is revealed from the turning points in the fine structure, where the optical response to the first precursor pulse in the cycle sequence changes sign. The amplitude of the fine structure is determined by the surface layer thickness and the complex dielectric functions for the surface layer with the underlying bulk film. Surface kinetic data can be obtained by analyzing the rise and decay transients of the fine structure.

Dietz, Nikolaus↗

NASA NTRS1995

Cascade Optimization Strategy Maximizes Thrust for High-Speed Civil Transport Propulsion System Concept

The design of a High-Speed Civil Transport (HSCT) air-breathing propulsion system for multimission, variable-cycle operations was successfully optimized through a soft coupling of the engine performance analyzer NASA Engine Performance Program (NEPP) to a multidisciplinary optimization tool COMETBOARDS that was developed at the NASA Lewis Research Center. The design optimization of this engine was cast as a nonlinear optimization problem, with engine thrust as the merit function and the bypass ratios, r-values of fans, fuel flow, and other factors as important active design variables. Constraints were specified on factors including the maximum speed of the compressors, the positive surge margins for the compressors with specified safety factors, the discharge temperature, the pressure ratios, and the mixer extreme Mach number. Solving the problem by using the most reliable optimization algorithm available in COMETBOARDS would provide feasible optimum results only for a portion of the aircraft flight regime because of the large number of mission points (defined by altitudes, Mach numbers, flow rates, and other factors), diverse constraint types, and overall poor conditioning of the design space. Only the cascade optimization strategy of COMETBOARDS, which was devised especially for difficult multidisciplinary applications, could successfully solve a number of engine design problems for their flight regimes. Furthermore, the cascade strategy converged to the same global optimum solution even when it was initiated from different design points. Multiple optimizers in a specified sequence, pseudorandom damping, and reduction of the design space distortion via a global scaling scheme are some of the key features of the cascade strategy. HSCT engine concept, optimized solution for HSCT engine concept. A COMETBOARDS solution for an HSCT engine (Mach-2.4 mixed-flow turbofan) along with its configuration is shown. The optimum thrust is normalized with respect to NEPP results. COMETBOARDS added value in the design optimization of the HSCT engine.

Source record↗

NASA NTRS2003

System for Testing Thermal Insulation of Pipes

An apparatus and method have been developed for measuring the rates of leakage of heat into pipes carrying liquids, the purpose of the measurements being to quantify the thermal performance of the insulation system. The apparatus is designed primarily for testing pipes used to carry cryogenic liquids, but can also be used for measuring the thermal performance of other insulated pipes or piping systems. The basic measurement principle is straightforward: The outer surface of the pipe insulation is maintained at a fixed warmer temperature. The interior of the pipe is maintained in a narrow fixed lower-temperature range by means of a regular liquid (e.g., water) that is pumped through the pipe at a known flow rate or a cryogenic liquid (e.g., nitrogen) that is saturated at atmospheric pressure and replenished until steady-state conditions are achieved. In the case of water or another liquid pumped through, the inlet and outlet temperatures are measured and heat-leak power is calculated as the mass flow rate of the liquid multiplied by the specific heat of the liquid multiplied by the inlet-to-outlet temperature rise of the liquid. In the case of liquid nitrogen or another low-temperature boiling liquid, the heat-leak power is calculated as the rate of boil-off multiplied by the latent heat of vaporization of the liquid. Then the thermal-insulation performance of the pipe system can be calculated as a function of the measured heat-leak power, the inner and outer boundary temperatures, and the dimensions of the pipe. The apparatus can test as many as three pipes simultaneously. The pipes can have inner diameters up to .15 cm and outer diameters up to .20 cm. The lengths of the pipes may vary; typical lengths are of the order of 18 m. Two thermal guard boxes . one for each end of the pipe(s) under test . are used to make the inlet and outlet fluid connections to the pipe(s) (see figure). The connections include bellows that accommodate thermal expansion and contraction of the pipes. The guard boxes and pipe(s) are positioned so that the pipe(s) slope upward from the upstream to the downstream end at an angle of at least 2 . The upward slope allows vapor bubbles to accumulate at the downstream end. The thermal guard boxes keep the ends of the pipes at the lower interior temperature to prevent spurious lengthwise leakage of heat into the pipes. It is important to prevent this spurious heat leakage because, if it were allowed to occur, it could contribute a large error in the measured heat-leak power. The upstream thermal guard box includes a heat exchanger through which liquid flowing into the pipe(s) is subcooled to the saturation temperature corresponding to the ambient pressure. Conversely, this heat exchanger can also be used to warm the flowing liquid to a desired fixed temperature. The apparatus includes a temperature control device that is placed around each pipe under test. Each device is operated under thermostatic control to maintain the outer surface of the pipe insulation at the specified test temperature. All measurements are recorded on a portable data-acquisition system.

Fesmire, James E.↗

NASA NTRS2017

Relationship Between Unusual High-Temperature Fatigue Crack Growth Threshold Behavior in Superalloys and Sudden Failure Mode Transitions

An investigation of high temperature cyclic fatigue crack growth (FCG) threshold behavior of two advanced nickel disk alloys was conducted. The focus of the study was the unusual crossover effect in the near-threshold region of these type of alloys where conditions which produce higher crack growth rates in the Paris regime, produce higher resistance to crack growth in the near threshold regime. It was shown that this crossover effect is associated with a sudden change in the fatigue failure mode from a predominant transgranular mode in the Paris regime to fully intergranular mode in the threshold fatigue crack growth region. This type of a sudden change in the fracture mechanisms has not been previously reported and is surprising considering that intergranular failure is typically associated with faster crack growth rates and not the slow FCG rates of the near-threshold regime. By characterizing this behavior as a function of test temperature, environment and cyclic frequency, it was determined that both the crossover effect and the onset of intergranular failure are caused by environmentally driven mechanisms which have not as yet been fully identified. A plausible explanation for the observed behavior is proposed.

Fatigue Crack Growth Thresholds; Grain boundary ox↗

NASA NTRS2017

Relationship Between Unusual High-Temperature Fatigue Crack Growth Threshold Behavior in Superalloys and Sudden Failure Mode Transitions

Fatigue Crack Growth Thresholds; Grain boundary ox↗

DOE OSTI2014

Solution of relativistic quantum optics problems using clusters of graphical processing units

Numerical solution of relativistic quantum optics problems requires high performance computing due to the rapid oscillations in a relativistic wavefunction. Clusters of graphical processing units are used to accelerate the computation of a time dependent relativistic wavefunction in an arbitrary external potential. The stationary states in a Coulomb potential and uniform magnetic field are determined analytically and numerically, so that they can used as initial conditions in fully time dependent calculations. Relativistic energy levels in extreme magnetic fields are recovered as a means of validation. The relativistic ionization rate is computed for an ion illuminated by a laser field near the usual barrier suppression threshold, and the ionizing wavefunction is displayed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2018

Potentiostatic and Potential Cycling Dissolution of Polycrystalline Platinum and Platinum Nano-Particle Fuel Cell Catalysts

The dissolution of Pt in aqueous electrolytes has been studied for over forty years, most recently in the context of understanding the observed loss in electrochemically-active surface area (ECA) of cathode electrocatalysts in polymer electrolyte fuel cells. Despite extensive research, there are many unresolved issues regarding the dissolution of nano-particle Pt, such as the source of the observed potential dependence of potentiostatic and potential cycling dissolution rates. To help resolve these issues, in this paper we present results of measurements of the concentration of dissolved Pt and Pt dissolution rates for carbon-supported platinum nano-particles (Pt/C) in dilute perchloric acid, as a mimic of the PEFC cathode environment, as a function of potential and upper potential limit of potential cycling. Also presented, for comparison, are results of similar studies on polycrystalline platinum. In situ Pt L III X-ray absorption spectroscopy was used to determine the extent of oxidation, the coordination environment, and loss of Pt from the Pt nano-particles to elucidate the mechanism of Pt dissolution. Finally, based on the correlation of these studies with those presented in the literature, mechanisms for Pt dissolution under potentiostatic and potential cycling conditions are proposed.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Field-Scale Testing of a High-Efficiency Membrane Reactor (MR)—Adsorptive Reactor (AR) Process for H2 Generation and Pre-Combustion CO2 Capture

The study objective was to field-validate the technical feasibility of a membrane- and adsorption-enhanced water gas shift reaction process employing a carbon molecular sieve membrane (CMSM)-based membrane reactor (MR) followed by an adsorptive reactor (AR) for pre-combustion CO2 capture. The project was carried out in two different phases. In Phase I, the field-scale experimental MR-AR system was designed and constructed, the membranes, and adsorbents were prepared, and the unit was tested with simulated syngas to validate functionality. In Phase II, the unit was installed at the test site, field-tested using real syngas, and a technoeconomic analysis (TEA) of the technology was completed. All project milestones were met. Specifically, (i) high-performance CMSMs were prepared meeting the target H2 permeance (>1 m3/(m2.hbar) and H2/CO selectivity of >80 at temperatures of up to 300 °C and pressures of up to 25 bar with a <10% performance decline over the testing period; (ii) pelletized adsorbents were prepared for use in relevant conditions (250 °C < T < 450 °C, pressures up to 25 bar) with a working capacity of >2.5 wt.% and an attrition rate of <0.2; (iii) TEA showed that the MR-AR technology met the CO2 capture goals of 95% CO2 purity at a cost of electricity (COE) 30% less than baseline approaches.

42 ENGINEERING↗

NASA NTRS2001

Indomethacin attenuates post-suspension hypotension in Sprague-Dawley rats

Orthostatic hypotension is a serious condition that is sometimes manifested in astronauts during standing postflight. These observations may be related to impairment of autonomic function and/or excessive production of endothelium-dependent relaxing factors. To evaluate the role of the cyclooxygenase inhibitor indomethacin as a countermeasure against the post-suspension reduction in mean arterial pressure (MAP), we examined the cardiovascular responses to 7-day 30 degrees tail-suspension and a subsequent 6-hr post-suspension period in conscious male Sprague-Dawley rats. Indomethacin (2 mg/kg) or saline were administered intravenously prior to release from suspension and at 2 and 4 hrs post-suspension. Direct MAP and heart rate were determined prior to suspension, daily and every 2 hrs post-suspension. During suspension, MAP did not change, in contrast, during post-suspension; it decreased compared to parallel non-suspended, untreated animals. There were no significant changes in heart rate. The reduction in MAP post-suspension was associated with significant increases in plasma prostacyclin. Indomethacin attenuated the observed post-suspension reduction in MAP and reduced plasma prostacyclin levels. Also, the baroreflex sensitivity for heart rate was modified by indomethacin--the MAP threshold for baroreflex activation was raised and the effective MAP range expanded. Thus, the post suspension reduction in mean arterial pressure may be due to overproduction of vasodilatory prostaglandins and/or other endothelium-dependent relaxing factors and alteration in baroreflex activity.

NASA Discipline Cardiopulmonary↗

DOE OSTI2019

Experimental and Theoretical Study of Cyclopentanone as a Catalyst for Low Temperature Alkene Oxidation: Preprint

Cyclopentanone was evaluated for spark-ignition fuel properties to determine potential as a bio-blendstock. Although key properties such as octane numbers and energy density are promising, when blended with commercial gasoline the oxidation stability was significantly reduced. Oxidation stability determination exposes fuel to mild oxidative conditions of 700 kPa oxygen followed by temperature increase to 100 degrees C, resulting in a final pressure of ~ 900 kPa. Oxygen consumption is determined by monitoring for decrease in pressure over time - the results evaluate potential for autoxidation during storage. An increase in oxidation rate from cyclopentanone was not anticipated given the relatively low reactivity of this compound. Detailed hydrocarbon analysis of blends before and after oxidation revealed cyclopentanone was not consumed, but alkenes were oxidized to a significantly higher degree with this compound present. Experiments with surrogate blends of isooctane, cyclopentanone, and linear isomers of hexene demonstrated that cyclopentanone catalyzes alkene oxidation to form epoxides under mild oxidative conditions. This unexpected behavior observed may have implications in low temperature combustion of alkenes when ketone fuels are present, as well as epoxidation chemistry. This study proposes a detailed mechanism for a catalytic cycle evaluated with quantum chemical calculations performed with density functional theory.

09 BIOMASS FUELS↗

DOE OSTI2025

Cooling-Rate-Driven Polymorphism and Vacancy Ordering in Ce 2 MnGe 6 Intergrowth Phases

Intergrowth phases in intermetallic systems provide a compelling framework for investigating structure–property relationships as a function of crystallographic subunit stacking. In this study, we examine the influence of Mn vacancy ordering on subunit stacking and reassign the structure of Ce 2 MnGe 6 to a monoclinic C2/m space group (a = 8.3486(17) Å, b = 8.6181(18) Å, c = 10.778(2) Å, β = 101.17(2)°). Additionally, we report a monoclinic polymorph of the Ln 2 MGe 6 family characterized as a tripled c-axis supercell derivative of monoclinic Ce 2 MnGe 6 , 3×c-Ce 2 MnGe 6 (a = 8.3482(16) Å, b = 8.6179(18) Å, c = 31.813(6) Å, β = 93.763(7)°). This polymorph emerges under rapid cooling conditions during the synthesis and offers insight into the structural relationship between the orthorhombic and monoclinic variants of the Ln 2 MGe 6 phases. Notably, the supercell form of Ce 2 MnGe 6 (3×c-Ce 2 MnGe 6 ) exhibits increased electrical resistivity and suggests enhanced Zintl-like behavior, potentially indicating greater thermodynamic stability relative to the parent monoclinic phase.

36 MATERIALS SCIENCE↗