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Results for “differential kinetics”

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 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Increasing Branching and Functionalization Decreases Crystallinity and Crystallization Rate in Linear EVOH

Here, we report the crystallization behavior of a linear poly(ethylene-co-vinyl alcohol) (LEVOH) under isothermal crystallization as a function of both OH incorporation and undercooling, and compare the results to conventional branched EVOH. This LEVOH is synthesized by post-polymerization functionalization of polycyclooctene, and it exhibits a half-crystallization time and primary crystallization rate nearly an order of magnitude faster than branched EVOH at ~ 6 mol% OH incorporation. While the LEVOH obtains approximately twice the extent of crystallization compared to the branched equivalent, as OH incorporation increases, the crystallization kinetics and crystallinity of LEVOH decrease. The crystal structure of LEVOH is orthorhombic at low functionalization (≤ 11 mol% OH), a mixture of orthorhombic and hexagonal at moderate functionalization (17 - 21 mol%), and hexagonal at high functionalization (23 %). The LEVOH crystallizes into plates, with crystallite widths ~ 20 - 60 times the crystallite thickness. Ultimately, we show LEVOH crystallizes faster and to a greater extent than commercial branched EVOH, a potential advantage of post-polymerization functionalization as part of polymer-to-polymer upcycling.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Edge States Drive Exciton Dissociation in Ruddlesden–Popper Lead Halide Perovskite Thin Films

Efficient photovoltaic cells based on thin films of solution-processed 2D Ruddlesden–Popper hybrid perovskites (RPPs) represent an exciting breakthrough due to their enhanced tunability and chemical stability relative to those fabricated from 3D phases. However, reports of efficient charge separation and current collection are in apparent contradiction with the well-known enhancement of the exciton binding energy in multilayered halide perovskites, which should lower the device’s internal quantum efficiency and voltage. This controversy has led to various proposals for the electronic and physical structure of RPP thin films, including phase inhomogeneity as the driving force for exciton dissociation and transport. We address this apparent paradox in high-quality hot-cast RPP films by correlating ultrafast transient absorption spectroscopy with X-ray scattering measurements. We show that a hot-casting fabrication method produces highly phase pure n = 3 (BA) 2 (MA) n-1 Pb n I 3n+1 RPP structures. The high-phase purity and large grain sizes allow us to observe vertical transport of excitons via a diffusive process and allow us to determine that charge separation is primarily driven by dissociation at surface localized subgap electronic states. Furthermore, we analyze the differential absorption kinetics in films of varying thickness to directly determine that the excitonic diffusion constant is ~0.18 cm 2 s –1 . We propose that a surface localized structural distortion, observed using surface selective grazing incidence X-ray scattering measurements, is responsible for the creation of the surface localized defect states. We find that the density and spatial distribution of these defect states is a function of preparation conditions.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
NASA NTRS1977

Energy spectra of cosmic ray nuclei - Z of 4 to 26 and E of 0.3 to 2 GeV/amu

The differential kinetic-energy spectra of cosmic-ray nuclei in the charge range from 4 to 28 are determined using data obtained from a high-altitude balloonborne detector. The data are derived from the response of an acrylic plastic Cerenkov counter and cover the kinetic-energy range from 400 to 2100 MeV/amu. A Cerenkov pulse-height histogram is obtained for each charge, and the kinetic-energy spectra are derived by means of a formal mathematical deconvolution of these histograms. Results of the deconvolution calculation extrapolated to the top of the atmosphere are presented for the most abundant nuclei; it is found that the spectra are not amenable to representation by spectral indices, so the relative spectra of the different elements are compared by evaluating the charge ratios as a function of energy. The results show that secondary/primary ratios decrease with increasing energy, while primary/primary ratios are constant for Z of 6 to 10 and 14 to 26 but vary for Z of 10 to 14. It is concluded that the data seem to indicate more than one cosmic-ray source region.

Maehl, R. C.↗
NASA NTRS1978

Theory of flux anisotropies in a guiding center plasma

The one particle distribution function f on the scale of the bounce motion of particles in a magnetic field B is considered. The Vlasov equation is expanded through O(epsilon) in the adiabatic parameter which is the ratio of particle gyroradius to scale length of the magnetic field. Because f is directly proportional to particle flux differential in kinetic energy and solid angle, f is in principle measurable in space experiments, and the analysis is tailored to be explicitly applicable to space problems. To O(1), f is gyrotropic; its first velocity moment is (if non-vanishing) parallel to B, and hence macroscopic parallel flow is included in this term. The O(epsilon) contribution is non-gyrotropic and macroscopic flow parallel to B plus additional parallel flow results from these terms. The degree of non-gyrotropy and the amount of cross-field macroscopic flow depend on the perpendicular component of the electric field, on curvature and shear in the magnetic field, and on the spatial gradient, pitch angle derivative, and speed derivative of the lowest order distribution function.

Birmingham, T. J.↗
NASA NTRS1979

Theory of flux anisotropies in a guiding center plasma

Assuming time stationarity of the one-particle distribution function f on the scale of the bounce motion of particles in a magnetic field, the paper expands the Vlasov equation through O(epsilon) in the adiabatic parameter epsilon, which is the ratio of particle gyroradius to scale length of the magnetic field. Since f is directly proportional to particle flux differential in kinetic energy and solid angle, f is in principle measurable in space experiments, and the present analysis is tailored to be explicitly applicable to space problems. It is shown that the usual expression for the electric field which produces plasma corotation in an axisymmetric system such as a dipole also holds for any nonaxisymmetric but rigidly rotating magnetic field pattern, provided the observed magnetic field is used in place of the dipole field. The analysis is applied to the electric field in a rigidly corotating magnetosphere.

Birmingham, T. J.↗
NASA NTRS1982

The effect of physical aging on the time-dependent properties of carbon-fiber-reinforced epoxy composites

Annealing in nitrogen below the glass transition temperature T(g) is found to affect the matrix-dominated physical properties of postcured, (+ and -45)2s specimens of Thornel 300 carbon fiber/Fiberite 934 epoxy composite as well as neat Fiberite 934 epoxy resin. The damping behavior, stress-relaxation rate and enthalpic state of the matrix material are found to decrease as functions of annealing time. The time-dependent change in physical properties is explained on the basis of free-volume collapse related to the physical aging of the nonequilibrium glassy network of epoxy. Such physical aging in network epoxy has been demonstrated to be thermoreversible through the monitoring of its kinetics by differential scanning calorimetry, stress relaxation tests, and dynamic mechanical analysis.

Kong, E. S. W.↗
NASA NTRS1988

Kinetics of determination in the differentiation of isolated mesophyll cells of Zinnia elegans to tracheary elements

Mechanically isolated mesophyll cells of Zinnia elegans L. cv Envy differentiate to tracheary elements when cultured in inductive medium containing 0.5 micromolar alpha-naphthaleneacetic acid and 0.5 micromolar benzyladenine. The cells do not differentiate when cultured in medium in which the concentration of auxin and/or cytokinin has been reduced to 0.005 micromolar. Cells require an initial 24-hour exposure to inductive cytokinin and 56-hour exposure to inductive auxin for differentiation at 72 hours of culture. Freshly isolated Zinnia cells can be maintained in medium having low concentrations of both auxin and cytokinin for only 1 day without significant loss of potential to differentiate upon transfer to inductive medium. Initial culture for up to 2 days in medium having high auxin and low cytokinin, or low auxin and high cytokinin, allows full differentiation on the third day after transfer to inductive medium and potentiates the early differentiation of some cells.

Non-NASA Center↗
DOE OSTI2021

CHEMNODE: CHEMICAL KINETICS SOLVER APPROACH BASED ON NEURAL ORDINARY DIFFERENTIAL EQUATIONS

This software contains an algorithm to model and predict the time evolution of chemical kinetics in reacting flow simulations using neural ordinary differential equations (NODEs). The approach works by using artificial neural networks to predict the chemical source terms. It achieves this by using forward-mode automatic differentiation and the Levenberg-Marquardt algorithm to adjust the neural network parameters, such that the discrepancies between the actual and predicted species profiles are minimized.

OWOYELE, OPEOLUWA↗
NASA NTRS1984

Exponential-fitted methods for integrating stiff systems of ordinary differential equations: Applications to homogeneous gas-phase chemical kinetics

Conventional algorithms for the numerical integration of ordinary differential equations (ODEs) are based on the use of polynomial functions as interpolants. However, the exact solutions of stiff ODEs behave like decaying exponential functions, which are poorly approximated by polynomials. An obvious choice of interpolant are the exponential functions themselves, or their low-order diagonal Pade (rational function) approximants. A number of explicit, A-stable, integration algorithms were derived from the use of a three-parameter exponential function as interpolant, and their relationship to low-order, polynomial-based and rational-function-based implicit and explicit methods were shown by examining their low-order diagonal Pade approximants. A robust implicit formula was derived by exponential fitting the trapezoidal rule. Application of these algorithms to integration of the ODEs governing homogenous, gas-phase chemical kinetics was demonstrated in a developmental code CREK1D, which compares favorably with the Gear-Hindmarsh code LSODE in spite of the use of a primitive stepsize control strategy.

Pratt, D. T.↗
DOE OSTI2022

PolyODENet: Deriving mass-action rate equations from incomplete transient kinetics data

Kinetics of a reaction network that follows mass-action rate laws can be described with a system of ordinary differential equations (ODEs) with polynomial right-hand side. However, it is challenging to derive such kinetic differential equations from transient kinetic data without knowing the reaction network, especially when the data are incomplete due to experimental limitations. We introduce a program, PolyODENet, toward this goal. Based on the machine-learning method Neural ODE, PolyODENet defines a generative model and predicts concentrations at arbitrary time. As such, it is possible to include unmeasurable intermediate species in the kinetic equations. Importantly, we have implemented various measures to apply physical constraints and chemical knowledge in the training to regularize the solution space. Here, using simple catalytic reaction models, we demonstrate that PolyODENet can predict reaction profiles of unknown species and doing so even reveal hidden parts of reaction mechanisms.

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

PolyODENet

Kinetics of a reaction network that follows mass-action rate laws can be described with a system of ordinary differential equations (ODEs) with polynomial right-hand side. However, it is challenging to derive such kinetic differential equations from transient kinetic data without knowing the reaction network, especially when the data are incomplete due to experimental limitations. We introduce a program, PolyODENet, toward this goal. Based on the machine-learning method Neural ODE, PolyODENet defines a generative model and predicts concentrations at arbitrary time. As such, it is possible to include unmeasurable intermediate species in the kinetic equations. Importantly, we have implemented various measures to apply physical constraints and chemical knowledge in the training to regularize the solution space.

Wu, Qin [Brookhaven National Lab. (BNL), Upton, NY↗
DOE OSTI2022

Prediction of curing kinetics of resorcinol‐added resole phenolic resins using differential scanning calorimetry for the fabrication of carbon/carbon composites

Phenolic resins are commonly used as carbon precursors for the fabrication of carbon/carbon composites due to their high carbon yield and aromatic nature. To decrease curing times, acid catalysts are generally used, but the addition of resorcinol was found to have a similar effect while being incorporated into the resin matrix with no contamination or corrosion issues. In this work, the curing kinetics of pure, 10, 20, and 30 wt% resorcinol-added phenolic resins were investigated through differential scanning calorimetry. Heating rates of 0.5, 1, 2.5, and 5°C min -1 were used with several curing models to predict isothermal curing. Averaged mean absolute error (MAE) for the isoconversional mathematical approaches namely Kissinger–Akahira–Sunose (MAE = 12.9 min), Flynn–Wall–Ozawa (15.8 min), and Vyazovkin (14 min) show that these methods provide the best predictions, attributed to their adoption of an activation energy that depends on the extent of cure (E a (α)). The Kissinger method (MAE = 36 min), which depends only on peak temperature with a constant activation energy assumption, and the data noise sensitive Friedman model (MAE = 1144.7 min) provide the least accurate results. Thermogravimetric analysis revealed that resorcinol decreases the curing times by up to 71% without lowering carbon yield.

36 MATERIALS SCIENCE↗
NASA NTRS1977

A multiscale numerical study into the cascade of kinetic energy leading to severe local storms

The cascade of kinetic energy from macro- through mesoscales is studied on the basis of a nested grid system used to solve a set of nonlinear differential equations. The kinetic energy cascade and the concentration of vorticity through the hydrodynamic spectrum provide a means for predicting the location and intensity of severe weather from large-scale data sets. A mechanism described by the surface pressure tendency equation proves to be important in explaining how initial middle-tropospheric mass-momentum imbalances alter the low-level pressure field.

Paine, D. A.↗
NASA NTRS1997

Physiological Response of Plants Grown on Porous Ceramic Tubes

This research involves the manipulation of the root-zone water potential for the purposes of discriminating the rate limiting step in the inorganic nutrient uptake mechanism utilized by higher plants. This reaction sequence includes the pathways controlled by the root-zone conditions such as water tension and gradient concentrations. Furthermore, plant based control mechanisms dictated by various protein productions are differentiated as well. For the nutrients limited by the environmental availability, the kinetics were modeled using convection and diffusion equations. Alternatively, for the nutrients dependent upon enzyme manipulations, the uptakes are modeled using Michaelis-Menten kinetics. In order to differentiate between these various mechanistic steps, an experimental apparatus known as the Porous Ceramic Tube - Nutrient Delivery System (PCT-NDS) was used. Manipulation of the applied suction pressure circulating a nutrient solution through this system imposes a change in the matric component of the water potential. This compensates for the different osmotic components of water potential dictated by nutrient concentration. By maintaining this control over the root-zone conditions, the rate limiting steps in the uptake of the essential nutrients into tomato plants (Lycopersicon esculentum cv. Cherry Elite) were differentiated. Results showed that the uptake of some nutrients were mass transfer limited while others were limited by the enzyme kinetics. Each of these were adequately modeled with calculations and discussions of the parameter estimations provided.

Tsao, David↗
DOE OSTI2022

Plastic Scintillators via Rapid Photoinitiated Cationic Polymerization of Vinyltoluene

Cationic photopolymerization is applied for the rapid curing of a vinyltoluene and fluorophore solution into an efficient plastic scintillator. A hard solid is obtained via UV light-initiated polymerization of vinyltoluene, diaryliodonium salt, 9,9-dimethyl-2-phenylfluorene (PhF), and 9,9-dimethyl-2,7-distyrlfluorene (SFS) at ambient conditions with high conversion rates under a range of cationic photoinitiator concentrations, fluorophore concentrations, and light intensities. Insight into photopolymerization kinetics via photo differential scanning calorimetry (photoDSC) revealed photocuring time scales similar to those achieved in a commercial 3D printing resin. Furthermore, scintillator samples prepared cationically performed well compared to samples of equivalent compositions prepared by a lengthy thermally initiated radical polymerization.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Therapeutic efficacy of a potent anti-Venezuelan equine encephalitis virus antibody is contingent on Fc effector function

The development of specific, safe, and potent monoclonal antibodies (Abs) has led to novel therapeutic options for infectious disease. In addition to preventing viral infection through neutralization, Abs can clear infected cells and induce immunomodulatory functions through engagement of their crystallizable fragment (Fc) with complement proteins and Fc receptors on immune cells. Little is known about the role of Fc effector functions of neutralizing Abs in the context of encephalitic alphavirus infection. To determine the role of Fc effector function in therapeutic efficacy against Venezuelan equine encephalitis virus (VEEV), we compared the potently neutralizing anti-VEEV human IgG F5 (hF5) Ab with intact Fc function (hF5-WT) or containing the loss of function Fc mutations L234A and L235A (hF5-LALA) in the context of VEEV infection. We observed significantly reduced binding to complement and Fc receptors, as well as differential in vitro kinetics of Fc-mediated cytotoxicity for hF5-LALA compared to hF5-WT. The in vivo efficacy of hF5-LALA was comparable to hF5-WT at -24 and + 24 h post infection, with both Abs providing high levels of protection. However, when hF5-WT and hF5-LALA were administered + 48 h post infection, there was a significant decrease in the therapeutic efficacy of hF5-LALA. Together these results demonstrate that optimal therapeutic Ab treatment of VEEV, and possibly other encephalitic alphaviruses, requires neutralization paired with engagement of immune effectors via the Fc region.

59 BASIC BIOLOGICAL SCIENCES↗