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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.

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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Barrier-free predictions of short-range ordering/clustering kinetics in binary FCC solid solutions

We present comparisons of kinetic Monte Carlo (kMC) simulations of isothermal short-range ordering (SRO) and clustering (SRC) kinetics in binary FCC alloys with a mean-field concentration wave (CW) model. We find that the CW model is able to give order-of-magnitude agreement with kMC simulations for ordering/clustering relaxation times over a wide range of temperatures and compositions. The advantage of the CW model is that it does not require parameterization of vacancy hopping energy barriers, which, for a concentrated alloy, becomes prohibitive. We assess limits in the accuracy of the model and discuss the effect of cooling rates as well as the extension to multi-component systems. Ultimately, the simplicity and performance of the CW model compared to kMC simulations suggests that it is a useful tool to connect with models of properties dependent on SRO/SRC as well as for designing thermal treatments to control formation of SRO/SRC.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Switching kinetics in ferroelectric zinc magnesium oxide thin films

The switching kinetics of RF-magnetron reactively sputtered ~200 nm thick Zn 1-x Mg x O (ZMO) ferroelectric thin films with x = 0.41 and x = 0.27 prepared on Pt/Ti/SiO 2 /Si substrates were studied at applied fields near the coercive fields, ranging from 3.4 to 5.1 MV cm -1 , and at temperatures ranging from room temperature to 100 °C. Polarization reversal in ZMO followss the Kolmogorov-Avrami-Ishibashi kinetics model for nucleation and growth at applied fields near the coercive field, and obeys an individual column switching (ICS) model at higher applied fields required to switch most of the spontaneous polarization. Switching in the high-applied field regime can be described using either the Gaussian or inverse gamma distribution functions depending on the mole fraction of magnesium in the film. The switching current transients of the high-Mg content ZMO film (x = 0.41) are always bi-modal, whereas the low Mg composition film (x = 0.27) is described by the Gaussian distribution initially following wake-up, and becomes bimodal with continued cycling. Rayleigh-like behavior of the dielectric constant revealed a simultaneous increase of the irreversible and decrease of the reversible contributions to the dielectric constant, which was ascribed to an increase in the density of mobile domain walls with cycling and resulted in faster switching.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2021

Predicting phase transformation kinetics during metal additive manufacturing using non-isothermal Johnson-Mehl-Avrami models: Application to Inconel 718 and Ti-6Al-4V

Here, a computational model was developed to predict solid-state phase transformation kinetics within mechanical parts during metal additive manufacturing processes. This model is a modified version of the Johnson-Mehl-Avrami model for non-isothermal phase transformations that can be applied to various material systems undergoing solid-state phase transformations. Using the thermal history of an additive manufacturing fabricated mechanical part, along with the necessary thermodynamic data and kinetic information as inputs, the model outputs the history of phase fraction evolution during the build process. The model was applied to an Inconel 718 part built by powder bed fusion and a Ti-6Al-4V part built by directed energy deposition. Microstructure characterization and mechanical testing were performed for the validation of the model.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Lie group analysis of the point-reactor neutron kinetics equations for various reactivity models

This work applies Lie Group Theory to the nonlinear point-reactor neutron kinetics equations for several reactivity feedback and reactivity insertion models. The goal of this work is to connect known analytical solutions to their corresponding Lie groups as well as to obtain new analytical solutions and the circumstances from which they arise. The reactivity models we consider are the Nordheim-Fuchs Model, an arbitrary-order polynomial reactivity insertion model, and the Fuchs Ramp-Insertion Model. In all three models, we generalize the analysis when possible and obtain analytical solutions in every case. For the first two models, we succeed in finding the Lie groups corresponding to classical solutions and find additional solutions that were otherwise unknown. Finally, for the final model, we obtain a reduced-order nonlinear kinetics equation which is not analytically solvable, but by applying a second-order truncation, we find a novel closed-form solution and demonstrate its validity with a numerical example.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Generation of localized reactor point kinetics parameters using coupled neutronic and thermal fluid models for pebble-bed reactor transient analysis

The systems analysis of anticipated operating occurrences and design basis accidents for pebble-bed reactor systems requires knowledge of neutron point kinetics equations (PKE) parameters. Typically, the generation of PKE parameters is performed in a global manner using standalone neutronics calculations, without the inclusion of thermal fluid distributions. We utilize Griffin and Pronghorn for generating global and local PKE parameters which includes the use of thermal fluid distributions to account for localized effects. This work establishes a methodology for calculating PKE parameters for a pebble bed reactor with a coupled neutronics/thermal fluids analysis. PKE parameters generated on a global and local basis are compared against a diffusion solve for a typical load-following transient. Locally-generated neutron kinetic parameters are able to reduce the maximum error in the transient power level from 5% to below 1.5%; along with this, bulk temperature errors were reduced from 12 K to 4 K.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Utilization of ACE nuclear data file toolkit ACEtk to calculate relative sensitivity coefficients of point-kinetics parameters

Sensitivity and uncertainty methods are quintessential for nuclear criticality safety and experiment design. This type of analysis relies on calculations of sensitivity coefficients; sensitivity coefficients of the effective neutron multiplication factor with respect to some nuclear data are predominantly calculated and used. As a part of the Laboratory Directed Research & Development project EUCLID (Experiments Underpinned by Computational Learning for Improvements in nuclear Data) at Los Alamos National Laboratory, sensitivity coefficients of many radiation detector measurement responses with respect to nuclear data were investigated. Specifically, this paper outlines a method to calculate point-kinetics parameters relative sensitivity coefficients with respect to nuclear data. Point-kinetics parameters such as the prompt neutron decay constant, effective delayed neutron fraction, and neutron generation time are especially important to experimenters and reactor operators designing systems with dynamic neutron populations. This method couples capabilities of the ACE (A Compact ENDF) nuclear data file toolkit, ACEtk, with the ability to load cross sections into the radiation transport code Monte Carlo N-Particle (MCNP). In conclusion, key aspects of optimizing this method for a particular application and sensitivity profiles of the Jezebel criticality experiment are examined and discussed.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2021

Effect of operating parameters on H 2 /CO 2 conversion to methanol over Cu-Zn oxide supported on ZrO 2 polymorph catalysts: Characterization and kinetics

Kinetic aspects of the operating parameters for the catalytic conversion of H 2 /CO 2 to methanol over two novel catalysts were evaluated to understand the effect of the polymorphic ZrO 2 phase composed of Cu 0/+ -ZnO sites at the atomic level and its impact on the reaction mechanism. The catalysts were characterized by in situ and ex-situ XRD, N 2 adsorption/desorption isotherms, FRX, TPR, TPD-N 2 O, in situ XANES, TPD-CO 2 , and in situ DRIFTS techniques. The influence of different reaction variables such as the GHSV, temperature, pressure, and H 2 /CO 2 ratio were studied using a fixed bed continuous plug flow reactor. The Cu-ZnO catalyst supported on the tetragonal zirconia polymorph exhibited the highest methanol yield due to the lower activation energy when compared to the catalyst with a greater amount of the monoclinic phase. In addition, the catalysts were reused for 8 cycles of 6 hours to evaluate their stability, which can translate into lower costs for large-scale methanol production. As a result, the estimation of the kinetic parameters over Cu-Zn oxide supported on ZrO 2 polymorphs was significant for understanding the reaction mechanism, as well as to provide a pathway for scaling-up of the process.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Theoretical and kinetic modeling study of H 2 S pyrolysis

Hydrogen sulfide pyrolysis was investigated theoretically and through chemical kinetic modeling. Reactions on the SHH potential energy surface, primarily S + H 2 (+Ar) ⇌ H 2 S (+ Ar) (R1) and S + H 2 ⇌ SH + H (R6b) were characterized by ab initio calculations. Results for k 1 were in good agreement with experiment, but deviated strongly below 2000 K from values previously used in modeling. Collider efficiencies for H 2 S, S 2 , and N 2 compared to Ar were calculated for R1. Hydrogen sulfide decomposition experiments reported in literature were re-examined in terms of an updated detailed chemical kinetic model. Concentration profiles for the atomic S at high temperature in shock tubes supported the present value of k 1 and served to constrain the rate constants for reaction of S with SH and H 2 S. To explain results from batch and flow reactors, conducted at high H 2 S concentrations in the 900–1400 K range, a very fast rate constant was required for HSS + H ⇌ SH + SH. Under dilute conditions, the gas-phase chemistry was too slow to compete and the decomposition of H 2 S was controlled by loss on the reactor surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Portable quantitative confocal Raman spectroscopy: Non-destructive approach of the carbonation chemistry and kinetics

Highlights: • Raman spectroscopy was used to monitor carbonation of portlandite • The approach was non-destructive, continuous, and performed within the material • Carbonation was identified coupling Raman spectroscopy and chemometrics • Kinetics was calculated for one portlandite thickness at different CO{sub 2}-percentages Carbonation is one major alteration process of cementitious materials. It can be monitored through several methods, all destructive. In this study, some preliminary investigations were conducted to monitor the carbonation process of pure portlandite with an in situ and non-destructive spectroscopic method. This complementary approach was motivated by a literature review indicating the benefits of Raman spectroscopy, but requiring innovative approaches for data acquisition and analysis. The material was selected to validate this spectroscopic monitoring, coupled with chemometrics tools to allowing an early detection of the carbonation reaction through a structure identified in the spectra data population. The carbonation occurred abruptly, and spectra analysis indicated the occurrence of phases synonymous of microstructural evolutions. Varying the atmospheric percentage of CO{sub 2} (0.04% - 4%) conducted to an appreciation of the kinetics of the carbonation front through the same thickness of portlandite.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Atomistic thermodynamics and kinetics of dicalcium silicate dissolution

Low-temperature cement manufacturing has garnered academic and industrial attention for its low environmental footprints. However, the sluggish hydration kinetics of the resultant cement affects their early-age strength development. This motivates fundamental studies to unravel the mechanistic picture of the dissolution process and discover science-informed pathways to accelerate hydration. Standard atomistic simulations seldomly exceed a microsecond making them impractical to study slow dissolution processes. We are using rare event sampling techniques, we provide the mechanistic picture of Ca 2+ ion dissolution from a kink site on the dicalcium silicate surface. The Ca 2+ ion dissolution is comprised of two sequential stages: breaking restraints from the kink sites to form a ledge adatom and detaching from the ledge/terrace adatom sites into the solution. The first and second stages feature free energy barriers of ~63 kJ/mol and ~ 29 kJ/mol respectively, making the first stage the rate-limiting step of the entire Ca 2+ dissolution kinetics. Using the reactive flux method, the rate and equilibrium constants for each reaction step are calculated, which yield the Ca 2+ ion activity of ~1.03 × 10 -5 . The diffusion calculations indicate that the surface effects lower the self-diffusion coefficient of Ca 2+ ions at the solid-water interface.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Thermodynamics and kinetics of solution combustion synthesis: Ni(NO 3 ) 2 + fuels systems

Solution combustion synthesis (SCS) utilizes exothermic self-propagating reactions to prepare nanoscale materials that can be used widely in energy, electronics, and biomedical technologies and other applications. SCS is a specific variety of a more general combustion synthesis (CS) method. Investigations of the thermodynamics, kinetics, and the mechanisms of SCS reactions, are not as well studied as the other CS processes. This work reports on a systematic study of the thermodynamics and kinetics of SCS reactions involving Ni(NO 3 ) 2 , an oxidizer, and either glycine (C 2 H 5 NO 2 ) or hexamethylenetetramine (HMT, C 6 H 12 N 4 ) as fuels. A thermodynamic modeling approach, based on the Gibbs free energy minimization principle, is applied to the simultaneous calculations of the adiabatic temperatures and compositions of the equilibrium products. Our calculations reveal the influence of fuel-to-oxidizer ratio, amount of water, and the oxygen in air on the combustion temperature under adiabatic conditions and the composition of the resulting products. We have, in turn, measured the combustion temperature and phase composition of products and compared them with the calculations. Variations of drying times for the solutions yield precursor gels with varying water contents. This approach enables the manipulation of combustion parameters and confirms the use of calculated activation energies for reactions using the Merzhanov-Khaikin method. Here, the results show that SCS reactions in fuel-lean solutions producing NiO have higher activation energy in contrast to reactions with fuel-rich solutions that form Ni. Reduction of activation energies due to the increase in the fuel-to-oxidizer ratio could be related to the observed change of the rate-limiting stages of the endothermic decomposition of the individual reactants to the exothermic decomposition of coordinate compounds formed between the reactants.

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

An experimental and kinetic modeling study of cyclopentane and dimethyl ether blends

Cyclopentane is a suitable naphthene, or cycloalkane, in a palette for multi-component gasoline surrogate fuels due to its presence in market fuels and its relevance to alkyl substituted cyclopentanes also present. However, the previous oxidation studies of cyclopentane have primarily focused on neat mixtures. Blending cyclopentane with dimethyl ether in this work therefore serves to inform our understanding of, and improve predictive models for, multi-component mixtures. Here, the auto-ignition of cyclopentane/dimethyl ether blends was studied in a high-pressure shock tube and in a rapid compression machine. A wide range of temperatures (650 – 1350 K) and elevated pressures of 20 and 40 bar were studied at equivalence ratios of 0.5, 1.0 and 2.0 in air for two blending ratios (30/70 and 70/30 mole% cyclopentane/di-methyl ether mixtures). A detailed kinetic model for cyclopentane was revised to capture the measured ignition delay times and apparent heat release rates in this study. Literature ignition delay time, jet-stirred reactor, and laminar burning velocity measurements of neat cyclopentane were used as additional validation. Improvements to the kinetic model were based on recent literature studies related to sub-models including cyclopentene and cyclopentadiene which allowed the removal of previous local rate-constant optimizations. Low temperature reactivity of cyclopentane was found to be controlled by the branching ratio between concerted elimination of HO͘ 2 and the strained formation of Q&#775OOH radicals in agreement with previous studies. In this study, the low branching ratio of Q&#775OOH formation increases the influence of a competing consumption pathway for cyclopentyl-peroxy (CPTO͘ 2 J) radicals. The sensitivity of the simulated ignition delay times to the formation of cyclopentyl hydroperoxide (CPTO 2 H), from CPTO͘ 2 J and HO͘ 2 , is discussed. The current model is used to analyze the influence of dimethyl ether on the reactivity of cyclopentane in the context of previous literature studies of dimethyl ether binary blends with ethanol and toluene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Chemical insights into the multi-regime low-temperature oxidation of di-n-propyl ether: Jet-stirred reactor experiments and kinetic modeling

To further understand the combustion characteristics and the reaction pathways of acyclic ethers, in this work the oxidation of di-n-propyl ether (DPE) was investigated in a jet-stirred reactor (JSR) combined with a photoionization molecular-beam mass spectrometer. The experiments were carried out at near-atmospheric pressure (700 Torr) and over a temperature range of 425–850 K. Based on the experimental data and previous studies on ether oxidation, a new kinetic model was constructed and used to interpret the oxidation chemistry of DPE. In DPE oxidation, a high reactivity at low temperatures and two negative temperature coefficient (NTC) zones were observed. These behaviors are explained in this work by taking advantage of the obtained species information and the modeling analyses: the two NTC zones are caused by the competition of chain branching and termination reactions of the fuel itself and specific oxidation intermediates, respectively. Furthermore, the general requirements to have double-NTC behavior are discussed. A variety of crucial fuel-specific C 6 species, such as ketohydroperoxides and diones, were detected in the species pool of DPE oxidation. Their formation pathways are illuminated based on rate-of-production (ROP) analyses. Propanal was identified as the most abundant small molecule intermediate, and its related reactions have an important impact on the oxidation process of DPE. Both acetic acid and propionic acid were detected in high concentrations. A new formation pathway of propionic acid is proposed and incorporated into the kinetic model to achieve a more accurate prediction for propionic acid mole fractions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

An experimental and kinetic modeling study of NO x sensitization on methane autoignition and oxidation

An experimental and kinetic modeling study of the influence of NO x (i.e. NO 2 , NO and N 2 O) addition on the ignition behavior of methane/‘air’ mixtures is performed. Ignition delay time measurements are taken in a rapid compression machine (RCM) and in a shock tube (ST) at temperatures and pressures ranging from 900–1500 K and 1.5–3.0 MPa, respectively for equivalence ratios of 0.5–2.0 in ‘air’. The conditions chosen are relevant to spark ignition and homogeneous charge compression ignition engine operating conditions where exhaust gas recirculation can potentially add NO x to the premixed charge. The RCM measurements show that the addition of 200 ppm NO 2 to the stoichiometric CH 4 /oxidizer mixture results in a factor of three increase in reactivity compared to the baseline case without NOx for temperatures in the range 600–1000 K. However, adding up to 1000 ppm N 2 O does not show any appreciable effect on the measurements. The promoting effect of NO 2 was found to increase with temperature in the range 950–1150 K, while the sensitization effect decreases at higher pressures. The experimental results measured are simulated using NUIGMech1.2 comprising an updated NO x sub-chemistry in this work. A kinetic analysis indicates that the competition between the reactions ĊH 3 + NO 2 ↔ CH 3 Ȯ + NO and ĊH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M), the former being a propagation reaction and the latter being a termination reaction governs NO x sensitization on CH 4 ignition. Recent calculations by Matsugi and Shiina (A. Matsugi, H. Shiina, J. Phys. Chem. A. 121 (2017) 4218–4224) for the nitromethane formation reaction CH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M), together with the recently calculated rate constants for HONO/HNO 2 reactions significantly improve ignition delay time predictions in the temperature range 600–1000 K. Furthermore, the experiments with NO addition reveal a non-monotonous sensitization impact on CH 4 ignition at lower temperatures with NO initially acting as an inhibitor at low NO concentrations and then as a promoter as NO concentrations increase in the mixture. This non-monotonous trend is attributed to the role of the chain-termination reaction ĊH 3 + NO 2 (+M) ↔ CH 3 NO 2 (+M) and the impact of NO on the transition to the chain-branching steps CH 2 O + HȮ 2 ↔ HĊO + H 2 O 2 , H 2 O 2 (+M) ↔ ȮH + ȮH (+M), HĊO ↔ CO + Ḣ followed by CO + O 2 ↔ CO 2 + Ö and Ḣ + O 2 ↔ Ö + ȮH. NUIGMech1.2 is systematically validated against the new ignition delay measurements taken here together with species measurements and high temperature ignition delay time data available in the literature for CH 4 /oxidizer mixtures diluted with NO 2 /N 2 O/NO and is observed to accurately capture the sensitization trends.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A wide range experimental and kinetic modeling study of the oxidation of 2,3-dimethyl-2-butene: Part 1

2,3-Dimethyl-2-butene (TME) is a potential fuel additive with high research octane number (RON) and octane sensitivity (S), which can improve internal combustion engine performance and efficiency. However, the combustion characteristics of TME have not been comprehensively investigated. Thus, it is essential to study the combustion characteristics of TME and construct a detailed chemical kinetic model to describe its combustion. In this paper, two high-pressure shock tubes and a constant-volume reactor are used to measure ignition delay times and laminar flame speeds of TME oxidation. Further, the ignition delay times were measured at equivalence ratios of 0.5, 1.0, and 2.0 in “air”, at pressures of 5 and 10 bar, in the temperature range of 950 – 1500 K. Flame speeds of the TME/ “air” mixtures were measured at atmospheric pressure, at a temperature of 325 K, for equivalence ratios ranging from 0.78 to 1.31. Two detailed kinetic mechanisms were constructed independently using different methodologies; the KAUST TME mechanism was constructed based on NUIGMech1.1, and the MIT TME mechanism was built using the Reaction Mechanism Generator (RMG). Both mechanisms were used to simulate the experimental results using Chemkin Pro. In the present work, reaction flux and sensitivity analyses were performed using the KAUST mechanism to determine the critical reactions controlling TME oxidation at the conditions studied.

33 ADVANCED PROPULSION SYSTEMS↗
DOE OSTI2023

Effect of the ..beta..-Hydroxy Group on Ester Reactivity: Combustion Kinetics of Methyl Hexanoate and Methyl 3-Hydroxyhexanoate

One of the major biofuels used today is biodiesel, composed of fatty acid methyl esters. The fats and oils feedstocks used to make biodiesel are in relatively short supply. To meet increasing global demand, engineered microorganisms have been developed to catalyze conversion of sugar to fatty acid esters that contain unique ..beta..-hydroxy-esters. This study investigated the effect of a hydroxyl group on the combustion characteristics of methyl esters by comparing the chemical behavior of methyl hexanoate (MHx) and methyl 3-hydroxyhexanoate (M3OHHx) - used as surrogates for diesel-boiling-range esters with longer fatty acid chains. The oxidation of these esters was studied experimentally in a flow reactor at 0.84 and 10 bar, 600 to 1,100 K, and stoichiometric conditions; and in a constant volume combustion chamber at 5 and 10 bar, 600 to 900 K, and equivalence ratios of 0.3 and 0.6. MHx was more reactive in the constant volume chamber at temperatures below 800 K at 10 bar and equivalence ratio of 0.6. MHx also exhibited a higher indicated cetane number (16.4) than M3OHHx (8.1). We investigated this reactivity trend using an updated MHx kinetic model and M3OHHx model developed as part of this work. The kinetic models predicted that radicals formed from MHx were consumed by low-temperature chemistry reactions, whereas the M3OHHx reactivity was significantly governed by the ..beta..-radical (on the same carbon as the OH group) chemistry which mainly terminated via the less reactive chain propagation pathway to methyl-3-oxohexanoate + HO2. This study extends our understanding of structural effects on ester reactivity, which will allow for accurate surrogate formulation and performance simulations.

AFIDA↗
DOE OSTI2024

An experimental, theoretical, and kinetic modeling study of post-flame oxidation of ammonia

The post -flame oxidation rate of ammonia was investigated in a novel atmospheric pressure flow reactor at temperatures of 1280 ± 16 K and as a function of residence time and mixture composition (1-10% O 2 , dry and moist). The experimental results, as well as selected data from literature, were analyzed using an updated detailed chemical kinetic model. The medium temperature, very lean conditions enhance the importance of reactions of the nitroxyl (HNO) intermediate. High-level theory was used to calculate the rate constant for HNO + NH 2 , indicating that this step is significantly faster than values used in literature. Furthermore, a trajectory based approach was used to determine collision efficiencies for selected bath gases for HNO + M. The experimental results show that the NH 3 oxidation rate increases with temperature and O 2 concentration, while the presence of water vapor slightly inhibits reaction. Formation of NO and N 2 O was strongly promoted at higher levels of O 2 . Modeling results agreed well with the measurements, except at the lowest level of O 2 . The predicted oxidation rate of NH 3 was shown to result from a delicate balance between chain branching and terminating steps involving NH 2 , H 2 NO, and HNO. Recent theoretical work on reactions of these species by Klippenstein and coworkers and Stagni et al. was instrumental in improving modeling predictions. After initiation, NO reached a pseudo -steady-state level, where the pathways to NO were largely balanced by the NH 2 + NO reaction. Nitric oxide was partly oxidized to NO 2 , with the NH 2 + NO 2 reaction responsible for most of the N 2 O formation. Novelty and significance statement: This study provides the first detailed kinetic analysis of the lean postflame oxidation of ammonia, based on time -resolved flow reactor data in a novel reactor. In addition to the post -flame oxidation rate of ammonia, data for formation of NO and N 2 O were compared with modeling predictions. The medium temperature, very lean conditions enhance the importance of reactions of the HNO and H 2 NO intermediates. Inclusion in the model of results from recent high-level theoretical work, including present calculations for HNO + NH 2 and HNO + M, was crucial for capturing the observed behavior. It is argued that the post -initiation steady-state NH 3 oxidation rates constitute important data for model validation, along with ignition delays and laminar flame speeds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Growth-induced Donnan exclusion influences swelling kinetics in highly charged dynamic polymerization hydrogels

Polymeric gels crosslinked by DNA sequences can exploit DNA strand-displacement reactions to promote swelling through dynamic polymerization. The degree of swelling and the rate of swelling must be directly tunable to achieve the promise of programmable soft matter. Though the kinetics of the strand-displacement reaction provide insertion rates up to 10 4 /Molar/second as measured in bulk solution, DNA hydrogel swelling can take upwards of 30 h to complete. Computational modeling of the reaction-induced swelling of these gels with our recently-developed reactive electrochemomechanical theory (Zimmerman et al., 2024) suggests that their extraordinarily slow swelling is partly due to a scaling mismatch between the addition of charge and the addition of fluid volume, leading to a large transient increase in the fixed charge density. The significant increase in the gel’s fixed charge density, due to the binding of negatively charged DNA, sharply restricts the concentration of mobile hairpins through the phenomenon of Donnan charge exclusion, an effect commonly exploited in nanofiltration applications using polymeric membranes. The scaling problem is overcome when the mean additional swelling provided to the hydrogel by addition of a crosslink is above a critical value, thus the swelling outpaces the charge accumulation, leading the fixed charge density to drop and significantly accelerating the swelling process. This study shows that Donnan exclusion can explain the kinetics of DNA hydrogel swelling, and studies ways to modulate the reaction speed by either modifying the salt concentration or increasing or decreasing the number of base pairs in each DNA sequence.

42 ENGINEERING↗