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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 1,189 records · Page 66
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Transition of electron kinetics in weakly magnetized inductively coupled plasmas

Transition of the electron kinetics from nonlocal to local regime was studied in weakly magnetized solenoidal inductively coupled plasma from the measurement of the electron energy probability function (EEPF). Without DC magnetic field, the discharge property was governed by nonlocal electron kinetics at low gas pressure. The electron temperatures were almost same in radial position, and the EEPFs in total electron energy scale were radially coincided. However, when the DC magnetic field was applied, radial non-coincidence of the EEPFs in total electron energy scale was observed. The electrons were cooled at the discharge center where the electron heating is absent, while the electron temperature was rarely changed at the discharge boundary with the magnetic field. These changes show the transition from nonlocal to local electron kinetics and the transition is occurred when the electron gyration diameter was smaller than the skin depth. The nonlocal to local transition point almost coincided with the calculation results by using nonlocal parameter and collision parameter.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2014

General theory of multistage geminate reactions of isolated pairs of reactants. I. Kinetic equations

General matrix approach to the consideration of multistage geminate reactions of isolated pairs of reactants depending on reactant mobility is formulated on the basis of the concept of “effective” particles. Various elementary reactions (stages of multistage reaction including physicochemical processes of internal quantum state changes) proceeding with the participation of isolated pairs of reactants (or isolated reactants) are taken into account. Investigation has been made in terms of kinetic approach implying the derivation of general (matrix) kinetic equations for local and mean probabilities of finding any of the reaction species in the sample under study (or for local and mean concentrations). The recipes for the calculation of kinetic coefficients of the equations for mean quantities in terms of relative coordinates of reactants have been formulated in the general case of inhomogeneous reacting systems. Important specific case of homogeneous reacting systems is considered.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Role of filament annealing in the kinetics and thermodynamics of nucleated polymerization

The formation of nanoscale protein filaments from soluble precursor molecules through nucleated polymerization is a common form of supra-molecular assembly phenomenon. This process underlies the generation of a range of both functional and pathological structures in nature. Filament breakage has emerged as a key process controlling the kinetics of the growth reaction since it increases the number of filament ends in the system that can act as growth sites. In order to ensure microscopic reversibility, however, the inverse process of fragmentation, end-to-end annealing of filaments, is a necessary component of a consistent description of such systems. Here, we combine Smoluchowski kinetics with nucleated polymerization models to generate a master equation description of protein fibrillization, where filamentous structures can undergo end-to-end association, in addition to elongation, fragmentation, and nucleation processes. We obtain self-consistent closed-form expressions for the growth kinetics and discuss the key physics that emerges from considering filament fusion relative to current fragmentation only models. Furthermore, we study the key time scales that describe relaxation to equilibrium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Measuring kinetic energy changes in the mesoscale with low acquisition rates

We report on the measurement of the average kinetic energy changes in isothermal and non-isothermal quasistatic processes in the mesoscale, realized with a Brownian particle trapped with optical tweezers. Our estimation of the kinetic energy change allows to access to the full energetic description of the Brownian particle. Kinetic energy estimates are obtained from measurements of the mean square velocity of the trapped bead sampled at frequencies several orders of magnitude smaller than the momentum relaxation frequency. The velocity is tuned applying a noisy electric field that modulates the amplitude of the fluctuations of the position and velocity of the Brownian particle, whose motion is equivalent to that of a particle in a higher temperature reservoir. Additionally, we show that the dependence of the variance of the time-averaged velocity on the sampling frequency can be used to quantify properties of the electrophoretic mobility of a charged colloid. Our method could be applied to detect temperature gradients in inhomogeneous media and to characterize the complete thermodynamics of biological motors and of artificial micro and nanoscopic heat engines.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Periodic and stochastic thermal modulation of protein folding kinetics

Chemical reactions are usually observed either by relaxation of a bulk sample after applying a sudden external perturbation, or by intrinsic fluctuations of a few molecules. Here we show that the two ideas can be combined to measure protein folding kinetics, either by periodic thermal modulation, or by creating artificial thermal noise that greatly exceeds natural thermal fluctuations. We study the folding reaction of the enzyme phosphoglycerate kinase driven by periodic temperature waveforms. As the temperature waveform unfolds and refolds the protein, its fluorescence color changes due to FRET (Förster resonant Energy Transfer) of two donor/acceptor fluorophores labeling the protein. We adapt a simple model of periodically driven kinetics that nicely fits the data at all temperatures and driving frequencies: The phase shifts of the periodic donor and acceptor fluorescence signals as a function of driving frequency reveal reaction rates. We also drive the reaction with stochastic temperature waveforms that produce thermal fluctuations much greater than natural fluctuations in the bulk. Such artificial thermal noise allows the recovery of weak underlying signals due to protein folding kinetics. This opens up the possibility for future detection of a stochastic resonance for protein folding subject to noise with controllable amplitude.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Kinetics of solid-gas reactions characterized by scanning AC nano-calorimetry with application to Zr oxidation

Scanning AC nano-calorimetry is a recently developed experimental technique capable of measuring the heat capacity of thin-film samples of a material over a wide range of temperatures and heating rates. Here, we describe how this technique can be used to study solid-gas phase reactions by measuring the change in heat capacity of a sample during reaction. We apply this approach to evaluate the oxidation kinetics of thin-film samples of zirconium in air. The results confirm parabolic oxidation kinetics with an activation energy of 0.59 ± 0.03 eV. The nano-calorimetry measurements were performed using a device that contains an array of micromachined nano-calorimeter sensors in an architecture designed for combinatorial studies. We demonstrate that the oxidation kinetics can be quantified using a single sample, thus enabling high-throughput mapping of the composition-dependence of the reaction rate.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Geodesic acoustic mode in anisotropic plasmas using double adiabatic model and gyro-kinetic equation

Geodesic acoustic mode in anisotropic tokamak plasmas is theoretically analyzed by using double adiabatic model and gyro-kinetic equation. The bi-Maxwellian distribution function for guiding-center ions is assumed to obtain a self-consistent form, yielding pressures satisfying the magnetohydrodynamic (MHD) anisotropic equilibrium condition. The double adiabatic model gives the dispersion relation of geodesic acoustic mode (GAM), which agrees well with the one derived from gyro-kinetic equation. The GAM frequency increases with the ratio of pressures, p{sub ⊥}/p{sub ∥}, and the Landau damping rate is dramatically decreased by p{sub ⊥}/p{sub ∥}. MHD result shows a low-frequency zonal flow existing for all p{sub ⊥}/p{sub ∥}, while according to the kinetic dispersion relation, no low-frequency branch exists for p{sub ⊥}/p{sub ∥}≳ 2.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Different singularities in the functions of extended kinetic theory at the origin of the yield stress in granular flows

We use previous results from discrete element simulations of simple shear flows of rigid, identical spheres in the collisional regime to show that the volume fraction-dependence of the stresses is singular at the shear rigidity. Here, we identify the shear rigidity, which is a decreasing function of the interparticle friction, as the maximum volume fraction beyond which a random collisional assembly of grains cannot be sheared without developing force chains that span the entire domain. In the framework of extended kinetic theory, i.e., kinetic theory that accounts for the decreasing in the collisional dissipation due to the breaking of molecular chaos at volume fractions larger than 0.49, we also show that the volume fraction-dependence of the correlation length (measure of the velocity correlation) is singular at random close packing, independent of the interparticle friction. The difference in the singularities ensures that the ratio of the shear stress to the pressure at shear rigidity is different from zero even in the case of frictionless spheres: we identify that with the yield stress ratio of granular materials, and we show that the theoretical predictions, once the different singularities are inserted into the functions of extended kinetic theory, are in excellent agreement with the results of numerical simulations.

42 ENGINEERING↗
DOE OSTI2015

Note: Proton microbeam formation with continuously variable kinetic energy using a compact system for three-dimensional proton beam writing

A compact focused gaseous ion beam system has been developed to form proton microbeams of a few hundreds of keV with a penetration depth of micrometer range in 3-dimensional proton beam writing. Proton microbeams with kinetic energies of 100-140 keV were experimentally formed on the same point at a constant ratio of the kinetic energy of the object side to that of the image side. The experimental results indicate that the beam diameters were measured to be almost constant at approximately 6 μm at the same point with the kinetic energy range. These characteristics of the system were experimentally and numerically demonstrated to be maintained as long as the ratio was constant.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2015

On the dimensionally correct kinetic theory of turbulence for parallel propagation

Yoon and Fang [Phys. Plasmas 15, 122312 (2008)] formulated a second-order nonlinear kinetic theory that describes the turbulence propagating in directions parallel/anti-parallel to the ambient magnetic field. Their theory also includes discrete-particle effects, or the effects due to spontaneously emitted thermal fluctuations. However, terms associated with the spontaneous fluctuations in particle and wave kinetic equations in their theory contain proper dimensionality only for an artificial one-dimensional situation. The present paper extends the analysis and re-derives the dimensionally correct kinetic equations for three-dimensional case. The new formalism properly describes the effects of spontaneous fluctuations emitted in three-dimensional space, while the collectively emitted turbulence propagates predominantly in directions parallel/anti-parallel to the ambient magnetic field. As a first step, the present investigation focuses on linear wave-particle interaction terms only. A subsequent paper will include the dimensionally correct nonlinear wave-particle interaction terms.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Vapor-deposited non-crystalline phase vs ordinary glasses and supercooled liquids: Subtle thermodynamic and kinetic differences

Vapor deposition of molecules on a substrate often results in glassy materials of high kinetic stability and low enthalpy. The extraordinary properties of such glasses are attributed to high rates of surface diffusion during sample deposition, which makes it possible for constituents to find a configuration of much lower energy on a typical laboratory time scale. However, the exact nature of the resulting phase and the mechanism of its formation are not completely understood. Using fast scanning calorimetry technique, we show that out-of-equilibrium relaxation kinetics and possibly the enthalpy of vapor-deposited films of toluene and ethylbenzene, archetypical fragile glass formers, are distinct from those of ordinary supercooled phase even when the deposition takes place at temperatures above the ordinary glass softening transition temperatures. These observations along with the absolute enthalpy dependences on deposition temperatures support the conjecture that the vapor-deposition may result in formation of non-crystalline phase of unique structural, thermodynamic, and kinetic properties.

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

Perspective: Spectroscopy and kinetics of small gaseous Criegee intermediates

The Criegee intermediates, carbonyl oxides proposed by Criegee in 1949 as key intermediates in the ozonolysis of alkenes, play important roles in many aspects of atmospheric chemistry. Because direct detection of these gaseous intermediates was unavailable until recently, previous understanding of their reactions, derived from indirect experimental evidence, had great uncertainties. Recent laboratory detection of the simplest Criegee intermediate CH{sub 2}OO and some larger members, produced from ultraviolet irradiation of corresponding diiodoalkanes in O{sub 2}, with various methods such as photoionization, ultraviolet absorption, infrared absorption, and microwave spectroscopy opens a new door to improved understanding of the roles of these Criegee intermediates. Their structures and spectral parameters have been characterized; their significant zwitterionic nature is hence confirmed. CH{sub 2}OO, along with other products, has also been detected directly with microwave spectroscopy in gaseous ozonolysis reactions of ethene. The detailed kinetics of the source reaction, CH{sub 2}I + O{sub 2}, which is critical to laboratory studies of CH{sub 2}OO, are now understood satisfactorily. The kinetic investigations using direct detection identified some important atmospheric reactions, including reactions with NO{sub 2}, SO{sub 2}, water dimer, carboxylic acids, and carbonyl compounds. Efforts toward the characterization of larger Criegee intermediates and the investigation of related reactions are in progress. Some reactions of CH{sub 3}CHOO are found to depend on conformation. This perspective examines progress toward the direct spectral characterization of Criegee intermediates and investigations of the associated reaction kinetics, and indicates some unresolved problems and prospective challenges for this exciting field of research.

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

Quantification of protein interaction kinetics in a micro droplet

Characterization of protein interactions is essential to the discovery of disease biomarkers, the development of diagnostic assays, and the screening for therapeutic drugs. Conventional flow-through kinetic measurements need relative large amount of sample that is not feasible for precious protein samples. We report a novel method to measure protein interaction kinetics in a single droplet with sub microliter or less volume. A droplet in a humidity-controlled environmental chamber is replacing the microfluidic channels as the reactor for the protein interaction. The binding process is monitored by a surface plasmon resonance imaging (SPRi) system. Association curves are obtained from the average SPR image intensity in the center area of the droplet. The washing step required by conventional flow-through SPR method is eliminated in the droplet method. The association and dissociation rate constants and binding affinity of an antigen-antibody interaction are obtained by global fitting of association curves at different concentrations. The result obtained by this method is accurate as validated by conventional flow-through SPR system. This droplet-based method not only allows kinetic studies for proteins with limited supply but also opens the door for high-throughput protein interaction study in a droplet-based microarray format that enables measurement of many to many interactions on a single chip.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2015

Kinetic model of force-free current sheets with non-uniform temperature

The kinetic model of a one-dimensional force-free current sheet (CS) developed recently by Harrison and Neukirch [Phys. Rev. Lett. 102(13), 135003 (2009)] predicts uniform distributions of the plasma temperature and density across the CS. However, in realistic physical systems, inhomogeneities of these plasma parameters may arise quite naturally due to the boundary conditions or local plasma heating. Moreover, as the CS spatial scale becomes larger than the characteristic kinetic scales (the regime often referred to as the MHD limit), it should be possible to set arbitrary density and temperature profiles. Thus, an advanced model has to allow for inhomogeneities of the macroscopic plasma parameters across the CS, to be consistent with the MHD limit. In this paper, we generalise the kinetic model of a force-free current sheet, taking into account the inhomogeneity of the density and temperature across the CS. In the developed model, the density may either be enhanced or depleted in the CS central region. The temperature profile is prescribed by the density profile, keeping the plasma pressure uniform across the CS. All macroscopic parameters, as well as the distribution functions for the protons and electrons, are determined analytically. Applications of the developed model to current sheets observed in space plasmas are discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Accelerating quantum instanton calculations of the kinetic isotope effects

Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high computational cost. Here, we demonstrate that the efficiency of quantum instanton calculations of the kinetic isotope effects can be increased by orders of magnitude by combining two approaches: The convergence to the quantum limit is accelerated by employing high-order path integral factorizations of the Boltzmann operator, while the statistical convergence is improved by implementing virial estimators for relevant quantities. After deriving several new virial estimators for the high-order factorization and evaluating the resulting increase in efficiency, using ⋅H{sub α} + H{sub β}H{sub γ} → H{sub α}H{sub β} + ⋅ H{sub γ} reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on CH{sub 4} + ⋅ H ⇌ ⋅ CH{sub 3} + H{sub 2} forward and backward reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N{sub 2} and 20% O{sub 2}) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 10{sup 13 }cm{sup −3} is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the flash application, the electrons are thermalized and their concentration has decreased from about 10{sup 13 }cm{sup −3} down to about 10{sup 12 }cm{sup −3} leaving positive and negative ionised species and atomic radicals whose recombination characteristic times are much longer.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

A global reaction route mapping-based kinetic Monte Carlo algorithm

We propose a new on-the-fly kinetic Monte Carlo (KMC) method that is based on exhaustive potential energy surface searching carried out with the global reaction route mapping (GRRM) algorithm. Starting from any given equilibrium state, this GRRM-KMC algorithm performs a one-step GRRM search to identify all surrounding transition states. Intrinsic reaction coordinate pathways are then calculated to identify potential subsequent equilibrium states. Harmonic transition state theory is used to calculate rate constants for all potential pathways, before a standard KMC accept/reject selection is performed. The selected pathway is then used to propagate the system forward in time, which is calculated on the basis of 1st order kinetics. The GRRM-KMC algorithm is validated here in two challenging contexts: intramolecular proton transfer in malonaldehyde and surface carbon diffusion on an iron nanoparticle. We demonstrate that in both cases the GRRM-KMC method is capable of reproducing the 1st order kinetics observed during independent quantum chemical molecular dynamics simulations using the density-functional tight-binding potential.

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

Coupling solidification kinetics with phase-behavior computations in hydrodynamic simulations of high-pressure, dynamic-compression processes

In this study, we report a numerical scheme to integrate models for the kinetics of solidification processes together with phase-behavior computations in the context of continuum-scale hydrodynamic simulations. The objective of the phase-behavior computations is to determine the pressure and temperature, given the following three sets of inputs: (1) an appropriate equation of state to describe our system, (2) the phase fraction(s) produced by the kinetic models, (3) and the volume and internal energy obtained by solving the conservation equations that govern the hydrodynamic behavior. The kinetics are assumed to be governed by the Kolmogorov–Johnson–Mehl–Avrami equation, and the nucleation and growth rates that enter into that equation are functions of the pressure and temperature produced by the phase-behavior computations. Our formulation allows for the fluid and solid phases to be at different temperatures (thermal nonequilibrium) and pressures (arising from surface-tension-induced Laplace contributions). The formulation is presented in a fairly general setting that is independent of any particular material, although we demonstrate it in some examples related to high-energy-density science applications where materials are rapidly compressed to pressures exceeding several gigapascals in less than a microsecond. We conclude with a critical evaluation of our approach and provide suggestions for future work to improve the predictive capabilities and generality of the models.

42 ENGINEERING↗