Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Reaction Time”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Sources of deactivation during glycerol conversion on Ni/γ-Al 2 O 3

Hydrogenolysis of glycerol was studied using a diluted aqueous solution of glycerol in gas phase and atmospheric pressure on Ni/γ-Al2O3 catalyst. The catalytic transformation of glycerol generates products derived from dehydration, dehydrogenation, hydrogenolysis and condensation reactions. Deep hydrogenolysis route to produce CH4 prevails in the first few hours of reaction. As the reaction time progress, dehydration-dehydrogenation products start to appear. Here, a description of the deactivation sources and its effects on the catalytic performance of Ni catalyst was proposed. The catalyst was characterized before and after the catalytic reaction by high-resolution transmission electron microscopy (HRTEM) and by employing Fourier transformed infrared spectroscopy (FTIR) of adsorbed CO. A source of deactivation was due to carbonaceous deposition. FTIR at low CO dosing pressure reveal bands assignments species essentially due to linear and bridge carbonyls, whereas high pressure CO dosing produces a complex spectra due to polycarbonyls. X-ray absorption near edge structure (XANES) analysis was employed to reveal the initial degree of reduction of the fresh catalyst. The oxidation of metallic Ni in the course of reaction may also be considered as a source of deactivation. Ni oxide species promote dehydration routes. Alumina support facilitates nickel species to be more active toward interacting with glycerol. Dehydration, which takes place on the acid sites, is the mainly route related to the generation of carbon deposition and to the observed catalyst deactivation. Another source of deactivation was due to carbiding of Ni to form Ni3C. The regeneration of used Ni catalyst was achieved by oxidation-reduction steps at 723 K.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Synthesis and Evaluation of Cu@ZnO Core@Shell Nanowires for Use in the Carbon Dioxide Thermal Reduction Reaction

Copper-based core@shell nanomaterials are of interest for the catalytic hydrogenation of carbon dioxide toward value-added products. In this context, we have developed a facile, microwave-based procedure for the reliable and reproducible synthesis of Cu@ZnO core@shell nanowires. A systematic assessment of the effect of rationally varying various reaction conditions on this protocol was completed in order to better evaluate the growth process of these core–shell motifs. We determined that among different reaction parameters, it was the critical role of reaction time which enabled the quantitatively reliable growth of external shells with tunable thicknesses of up to 20 nm. As a demonstration of the material’s practical viability, catalytic testing was subsequently performed for the reverse water–gas shift reaction (CO 2 + H 2 → CO + H 2 O), with the evolution of the process followed with in situ X-ray diffraction and X-ray absorption spectroscopy in order to probe structural changes and gauge stability. These tests found the catalysts to be effective at converting CO 2 to CO, with notable stability detected in the shell layer and no observed alloying between copper and zinc. Furthermore, our studies support the idea that the Cu–ZnO and CuO x –ZnO interfaces are essential for the effective activation of CO 2 and H 2 .

36 MATERIALS SCIENCE↗
DOE OSTI2016

Intracellular Hg(0) Oxidation in Desulfovibrio desulfuricans ND132

The disposal of elemental mercury (Hg(0)) wastes in mining and manufacturing areas has caused serious soil and groundwater contamination issues. Under anoxic conditions, certain anaerobic bacteria can oxidize dissolved elemental mercury and convert the oxidized Hg to neurotoxic methylmercury. In this study, we conducted experiments with the Hg-methylating bacterium Desulfovibrio desulfuricans ND132 to elucidate the role of cellular thiols in anaerobic Hg(0) oxidation. The concentrations of cell-surface and intracellular thiols were measured, and specific fractions of D. desulfuricans ND132 were examined for Hg(0) oxidation activity and analyzed with extended X-ray absorption fine structure (EXAFS) spectroscopy. The experimental data indicate that intracellular thiol concentrations are approximately six times higher than those of the cell wall. Cells reacted with a thiol-blocking reagent were severely impaired in Hg(0) oxidation activity. Spheroplasts lacking cell walls rapidly oxidized Hg(0) to Hg(II), while cell wall fragments exhibited low reactivity toward Hg(0). EXAFS analysis of spheroplast samples revealed that multiple different forms of Hg-thiols are produced by the Hg(0) oxidation reaction and that the local coordination environment of the oxidized Hg changes with reaction time. Here, the results of this study indicate that Hg(0) oxidation in D. desulfuricans ND132 is an intracellular process that occurs by reaction with thiol-containing molecules.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Permeability, porosity, and mineral surface area changes in basalt cores induced by reactive transport of CO 2 -rich brine

Four reactive flow–through laboratory experiments (two each at 0.1 mL/min and 0.01 mL/min flow rates) at 150°C and 150 bar (15 MPa) are conducted on intact basalt cores to assess changes in porosity, permeability, and surface area caused by CO 2 –rich fluid–rock interaction. Permeability decreases slightly during the lower flow rate experiments and increases during the higher flow rate experiments. At the higher flow rate, core permeability increases by more than one order of magnitude in one experiment and less than a factor of two in the other due to differences in preexisting flow path structure. X–ray computed tomography (XRCT) scans of pre– and post–experiment cores identify both mineral dissolution and secondary mineralization, with a net decrease in XRCT porosity of ~0.7%–0.8% for the larger pores in all four cores. (Ultra) small–angle neutron scattering ((U)SANS) data sets indicate an increase in both (U)SANS porosity and specific surface area (SSA) over the ~1 nm to 10 µm scale range in post–experiment basalt samples, with differences due to flow rate and reaction time. Net porosity increases from summing porosity changes from XRCT and (U)SANS analyses are consistent with core mass decreases. (U)SANS data suggest an overall preservation of the pore structure with no change in mineral surface roughness from reaction, and the pore structure is unique in comparison to previously published basalt analyses. Altogether, these data sets illustrate changes in physical parameters that arise due to fluid–basalt interaction in relatively low pH environments with elevated CO 2 concentration, with significant implications for flow, transport, and reaction through geologic formations.

(ultra) small‐angle neutron scattering ((U)SANS)↗
DOE OSTI2017

Insights into Azetidine Polymerization for the Preparation of Poly(propylenimine)-Based CO 2 Adsorbents

The cationic ring-opening polymerization of azetidine to form branched poly(propylenimine) (PPI) is investigated for the purpose of evaluating the utility of PPI/silica composite adsorbents for CO 2 capture. The polymerization kinetics and primary:secondary:tertiary amine distribution are monitored with 1H NMR during reaction with varied synthesis conditions (i.e., reaction time 20–150 h), temperature (343–353 K), and monomer to acid initiator (here, HClO 4 ) ratio. It is found that primary amines are converted to tertiary amines with increased polymerization time, while the addition of monomer over the first 6 h of polymerization increases the primary amine content. This suggests a mechanism where the monomer is rapidly consumed, leaving dimers or small oligomers that still contain rings as key reaction centers. The synthesized polymer is neutralized with either NH 4 OH or a basic resin and impregnated into mesoporous silica (SBA-15). The CO 2 capture properties of these composite adsorbents are investigated, giving information about the effectiveness of the acid neutralization processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Leaching Kinetics of Rare Earth Elements from Fire Clay Seam Coal

Recovery of rare earth elements (REEs) from coal samples collected from the Fire Clay coal seam using diluted mineral acid solutions was investigated. The initial processing step was coal recovery using conventional froth flotation which concentrated the REEs in tailing material resulting in an upgrade to values around 700 ppm on a dry whole mass basis. Leaching experiments were performed on the flotation tailings material using a 1.2 M sulfuric acid solution adjusted to a temperature of 75 °C to study the extractability of REEs from coal material. The effect of particle size, leaching time, leaching temperature, and solid concentration on REE leaching recovery were evaluated. The kinetic data obtained from leaching over a range of temperatures suggested that the leaching process follows the shrinking core model with possibly a mixed control mechanism that may be a result of several heterogenous materials leaching simultaneously. Leaching recovery increased rapidly at the beginning of the reaction then slowed as the system reached equilibrium. The apparent activation energy determined from test data obtained over a range of temperatures using 1 M sulfuric acid was 36 kJ/mol for the first 20 min of reaction time and 27 kJ/mol for the leaching period between 20 and 120 min. The leaching of light REEs during the initial stage was determined to be driven by a chemical reaction, followed by the formation of a product layer, which required lower activation energy in the later stage of leaching. In regards to the heavy REEs, the major mechanism for leaching is desorption and the product layer formation does not affect the heavy REEs significantly.

58 GEOSCIENCES↗
NASA NTRS1974

Design analysis and computer-aided performance evaluation of shuttle orbiter electrical power system. Volume 1: Summary

Studies were conducted to develop appropriate space shuttle electrical power distribution and control (EPDC) subsystem simulation models and to apply the computer simulations to systems analysis of the EPDC. A previously developed software program (SYSTID) was adapted for this purpose. The following objectives were attained: (1) significant enhancement of the SYSTID time domain simulation software, (2) generation of functionally useful shuttle EPDC element models, and (3) illustrative simulation results in the analysis of EPDC performance, under the conditions of fault, current pulse injection due to lightning, and circuit protection sizing and reaction times.

Source record↗
DOE OSTI2022

Chemoselective, osmium-free, dihydroxylation/oxidative cleavage of heteroaryl isoprenes by a contemporary Malaprade reaction

The methyl ketone is a central synthetic building block for the construction of advanced heteroaryl scaffolds and systems. Reactions, including oxidative cyclization strategies, are often predicated on efficient access to this ubiquitous moiety. In the context of arenes, standard approaches leveraging Markovnikov hydration/oxidation or oxidative cleavage of the C–C π bond often afford satisfactory performance. However, when the substrate contains an electron-deficient heteroaryl core, the traditional Malaprade reaction, and related oxidative-cleavage strategies, frequently result in diminished performance over carbon-based arenes. In this work we present the development and application of an oxidative cleavage reaction of various pyridinyl isoprenes towards accessing the downstream methyl ketone for utilization in advanced cyclizations for the preparation of soft-N-donor complexant scaffolds. Further, this efficient protocol parallels the principles of Green chemistry by exchanging KMnO 4 for the toxic OsO 4 and offers the end-user an efficient, more environmentally friendly option for accessing heteroaryl methyl ketones in one hour of reaction time using potassium permanganate and sodium paraperiodate as a synergistically potent oxidative cleavage system. The wide substrate scope defined access to simple, as well as advanced heteroaryl methyl ketones. Method development, optimization, substrate scope, preliminary mechanistic observations, and a scale up reaction are delineated herein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Influence of sequential stimulation practices on geochemical alteration of shale

Water-based hydraulic fracturing fluids (HFFs) can chemically interact with formation shale, resulting in altered porosity and permeability of the host rock. Experimental investigations of spatial and temporal shale-HFF interactions are helpful in interpreting chemical compositions of the injectate, as well as predicting alteration of hydraulic properties in the reservoir due to mineral dissolution and precipitation. Most bench-top experiments designed to study shale-HFF chemical interactions, either using batch reactors or flow-through setups, are carried out assuming that the acid spearhead has already become mixed with neutral HFFs. During operations, however, HFFs are typically injected according to a sequenced pumping schedule, starting with a concentrated acid spearhead, followed by multiple additions of near-neutral pH HFFs containing chemical amendments and proppant. In this study, we use geochemical modeling to consider whether this pre-mixed experimental protocol provides results directly comparable to a sequential discrete fluid-shale interaction protocol. Our results show that for the batch system, the transient evolution in major ion concentrations is faster with the sequential procedure. After 2 h of reaction time, the two protocols converge to the same aqueous concentrations. In a flow-through geometry, the pre-mixed model predicts extensive chemical alteration close to the injection point but negligible alteration downstream. In contrast, the sequential model predicts mineral reactions over hundreds of meters along the flow path. The extent of shale alteration in the sequential model at a given location depends on shale mineralogy and where the acid spearhead resides during the shut-in period. The predictive model developed in this study can help experimentalists to design bench-top tests and operators to better translate the results of laboratory experiments into practical applications.

Li, Qingyun↗
NASA NTRS1980

Turbulent eddy diffusivity and mean eddy lifetimes measured in spray combustion

A quantitative description of the eddy structure that occurs in turbulent combustion processes can be obtained by the use of laser velocimetry, as shown in this work. The mean eddy length scales, eddy lifetimes, and turbulent diffusivity have been determined in a spray combustion flame for the first time. Velocity data was obtained at various locations within the flame, and standard correlation techniques were modified and then applied to reduce the data. In order to assess how the spray burns, the measured eddy lifetimes were compared with the relevant reaction times and drop lifetimes. Conditions that are conducive to group combustion of the droplets, rather than individual droplet combustion, were found to exist in the upstream region of the spray. Local measurements of the hydrocarbon concentration also support the conclusion that the majority of droplets undergo group combustion. However, the data indicate that some of the larger drops can survive the initial burning region and form a dilute spray downstream where conditions favor individual droplet combustion.

Driscoll, J. F.↗
DOE OSTI2015

Dynamics of Magnesite Formation at Low-Temperature and High pCO2 in Aqueous Solution

Like many metal carbonate minerals, despite conditions of supersaturation, precipitation of magnesite from aqueous solution is kinetically hindered at low temperatures, for reasons that remain poorly understood. The present study examines precipitation products from reaction of Mg(OH)2 in aqueous solutions saturated with supercritical CO2 at high pressures (90 atm and 110 atm) and low temperatures (35 °C and 50 °C). Traditional bulk characterization (X-ray diffraction) of the initial solid formed indicated the presence of hydrated magnesium carbonates (hydromagnesite and nesquehonite), thermodynamically metastable phases that were found to slowly react during ageing to the more stable anhydrous form, magnesite, at temperatures as low as 35 °C (135-140 days) and at a faster rate at 50 °C (56 days). Undetected by bulk measurements, detailed examination of the precipitates by scanning electron microscopy (SEM) showed that magnesite is present as a minor component at relatively early reaction times (7 days) at 50 °C. In addition to magnesite dominating the solid phases over time, we find that mangesite nucleation and growth occurs more quickly with increasing partial pressure of CO2, and in electrolyte solutions with high bicarbonate content. Furthermore, formation of magnesite was found to be enhanced in sulfate-rich solutions, compared to chloride-rich solutions. We speculate that much of this behavior is possibly due to sulfate serving as sink of protons generated during carbonation reactions. These results support the importance of integrating magnesite as an equilibrium phase in reactive transport calculations of the effects of carbon dioxide sequestration on subsurface formations at long time scales.

Qafoku, Odeta↗
DOE OSTI2019

Aerobic oxidation of glycerol catalyzed by M salts of PMo 12 O 40 3- (M = K + , Zn 2+ , Cu 2+ , Al 3+ , Cr 3+ , Fe 3+ )

Glycerol is a co-product in the manufacture of biodiesel from vegetable oil and animal fat. A significant increase in biodiesel production results in adramatic overproduction of glycerol. The oxidation of glycerol to lactic acid (LA) by O 2 is considered to be a promising technology to increase the value of glycerol. Studies on the fundamental reaction mechanism vary for different catalytic systems. Here in this work we have chosen Keggin polyoxometalates (POMs) as an exemplary family of water-soluble hydrolytically and oxidatively-stable, fully-inorganic complexes with transition-metal and non-transition-metal counter-cations (M in the formula, MPMo 12 O 40 , where M = H + , K + , Zn 2+ , Cu 2+ , Al 3+ , Cr 3+ , Fe 3+ in appropriate number to counterbalance the 3- charge of PMo 12 O 40 3- ). Reactions involving hydrogen peroxide, an intermediate during glycerol oxidation, produce free radicals. A kinetic analysis reveals that the radical chain length under typical conditions is about 20–30. After minimal optimization, the yield of LA was 88% at glycerol conversion > 97% (1.0 M aqueous solution of glycerol, 4.0 mM of the Al salt of PMo 12 O 40 3- , henceforth “AlPMo”, 10 bar O 2 at 60 °C, reaction time 6.0 h).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Simulation of biochemical reactions with time-dependent rates by the rejection-based algorithm

We address the problem of simulating biochemical reaction networks with time-dependent rates and propose a new algorithm based on our rejection-based stochastic simulation algorithm (RSSA) [Thanh et al., J. Chem. Phys. 141(13), 134116 (2014)]. The computation for selecting next reaction firings by our time-dependent RSSA (tRSSA) is computationally efficient. Furthermore, the generated trajectory is exact by exploiting the rejection-based mechanism. We benchmark tRSSA on different biological systems with varying forms of reaction rates to demonstrate its applicability and efficiency. We reveal that for nontrivial cases, the selection of reaction firings in existing algorithms introduces approximations because the integration of reaction rates is very computationally demanding and simplifying assumptions are introduced. The selection of the next reaction firing by our approach is easier while preserving the exactness.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1972

Effect of set size, age, and mode of stimulus presentation on information-processing speed.

First, second, and third grade pupils served as subjects in an experiment designed to show the effect of age, mode of stimulus presentation, and information value on recognition time. Stimuli were presented in picture and printed word form and in groups of 2, 4, and 8. The results of the study indicate that first graders are slower than second and third graders who are nearly equal. There is a gross shift in reaction time as a function of mode of stimulus presentation with increase in age. The first graders take much longer to identify words than pictures, while the reverse is true of the older groups. With regard to set size, a slope appears in the pictures condition in the older groups, while for first graders, a large slope occurs in the words condition and only a much smaller one for pictures.

Norton, J. C.↗
NASA NTRS2003

Mechanistic Studies Of Combustion And Structure Formation During Combustion Synthesis Of Advanced Materials: Phase Separation Mechanism For Bio-Alloys

Among all implant materials, Co-Cr-Mo alloys demonstrate perhaps the most useful balance of resistance to corrosion, fatigue and wear, along with strength and biocompatibility [1]. Currently, these widely used alloys are produced by conventional furnace technology. Owing to high melting points of the main alloy elements (e.g. Tm.p.(Co) ~1768 K), high-temperature furnaces and long process times (several hours) are required. Therefore, attempts to develop more efficient and flexible methods for production of such alloys with superior properties are of great interest. The synthesis of materials using combustion phenomena is an advanced approach in powder metallurgy [2]. The process is characterized by unique conditions involving extremely fast heating rates (up to 10(exp 6 K/s), high temperatures (up to 3500 K), and short reaction times (on the order of seconds). As a result, combustion synthesis (CS) offers several attractive advantages over conventional metallurgical processing and alloy development technologies. The foremost is that solely the heat of chemical reaction (instead of an external source) supplies the energy for the synthesis. Also, simple equipment, rather than energy-intensive high-temperature furnaces, is sufficient. This work was devoted to experiments on CS of Co-based alloys by utilizing thermite (metal oxide-reducing metal) reactions, where phase separation subsequently produces materials with tailored compositions and properties. Owing to high reaction exothermicity, the CS process results in a significant increase of temperature (up to 3000 C), which is higher than melting points of all products. Since the products differ in density, phase separation may be a gravitydriven process: the heavy (metallic phase) settles while the light (slag) phase floats. The goal was to determine if buoyancy is indeed the major mechanism that controls phase segregation.

Varma, A.↗
DOE OSTI2021

In Situ Growth and Interlayer Modulation of Layered Double Hydroxide Thin Films from a Transparent Conducting Oxide Precursor

Layered double hydroxides (LDHs) are a class of cationic-layered solids that can be synthetically designed for a variety of advanced functions. Facile thin film growth of LDHs is an important requisite for a variety of applications including functional coatings, displays, and sensing. In this work we demonstrate, for the first time, an in-situ and patternable thin film synthesis of interconnected Zn-Cr LDH particles from a transparent conducting oxide (TCO) precursor, aluminum-doped zinc oxide (AZO), at room temperature within minutes. Synthetic parameters such as chromium (III) nitrate concentration, solvent composition, and reaction time were found to significantly affect the thickness and morphology of the resulting LDH films. These LDH thin films can undergo interlayer anion exchange, which modulates the interlayer distance of the LDH sheets and surface energy of the thin film. Replacement of the interlayer anion with perfluorooctanoate increases the interlayer sheet distance from 0.9 nm to 2.8 nm and induces a super-hydrophobic thin film that is capable of adsolubilizing and retaining organic guest molecules. The synthetic method and structural analysis of the LDH thin films introduced in this work opens new avenues of application for LDH films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Time Projection Chamber (TPC) detectors for nuclear astrophysics studies with gamma beams

Gamma-Beams at the HIS facility in the USA and anticipated at the ELI-NP facility, now constructed in Romania, present unique new opportunities to advance research in nuclear astrophysics; not the least of which is resolving open questions in oxygen formation during stellar helium burning via a precise measurement of the 12C() reaction. Time projection chamber (TPC) detectors operating with low pressure gas (as an active target) are ideally suited for such studies. We look over the progress of the current research program and plans for the future at the HIS facility with the optical readout TPC (O-TPC) and the development of an electronic readout TPC for the ELI-NP facility (ELITPC).

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗