An Isotopic Exchange Kinetic Model to Assess the Speciation of Metal Available Pool in Soil: The Case of Nickel.

PubMed

Zelano, I O; Sivry, Y; Quantin, C; Gélabert, A; Maury, A; Phalyvong, K; Benedetti, M F

2016-12-06

In this study an innovative approach is proposed to predict the relative contribution of each mineral phase to the total metal availability in soils, which, in other words, could be called the available metal fractionation. Through the use of isotopic exchange kinetics (IEK) performed on typical Ni bearing phases (i.e., two types of serpentines, chlorite, smectite, goethite, and hematite) the isotopic exchange and metal-solid interaction processes are connected, considering both the thermodynamic and kinetic aspects. Results of Ni IEK experiments on mineral phases are fitted with a pseudo-first order kinetic model. For each Ni bearing phase, this allows to (i) determine the number and size of exchangeable pools (E Ni(i) ), (ii) assess their corresponding kinetic constants (k (i) ), and (iii) discuss the mechanism of Ni isotopic exchange at mineral surfaces. It is shown that all the phases investigated, with the only exception of hematite, present at least two distinct reactive pools with significantly different k (i) values. Results suggest also that metal involved in outer-sphere complexes would display isotopic exchange between 100 and 1000 times faster than metal involved in inner-sphere complexes, and that the presence of high and low affinity sites may influence the rate of isotopic exchange up to 1 order of magnitude. Moreover, the method developed represents a tool to predict and estimate Ni mobility and availability in natural soil samples on the basis of soil mineral composition, providing information barely obtained with other techniques.

Mechanisms of kinetic trapping in self-assembly and phase transformation

PubMed Central

Hagan, Michael F.; Elrad, Oren M.; Jack, Robert L.

2011-01-01

In self-assembly processes, kinetic trapping effects often hinder the formation of thermodynamically stable ordered states. In a model of viral capsid assembly and in the phase transformation of a lattice gas, we show how simulations in a self-assembling steady state can be used to identify two distinct mechanisms of kinetic trapping. We argue that one of these mechanisms can be adequately captured by kinetic rate equations, while the other involves a breakdown of theories that rely on cluster size as a reaction coordinate. We discuss how these observations might be useful in designing and optimising self-assembly reactions. PMID:21932884

Kinetics of Polydomain Ordering at Second-Order Phase Transitions (by the Example of the AuCu3 Alloy)

NASA Astrophysics Data System (ADS)

Feldman, E. P.; Stefanovich, L. I.; Gumennyk, K. V.

2008-08-01

Kinetics of polydomain spinodal ordering is studied in alloys of AuCu3 type. We introduce four non-conserved long-range order parameters whose sum, however, is conserved and, using the statistical approach, follow the temporal evolution of their random spatial distribution after a rapid temperature quench. A system of nonlinear differential equations for correlators of second and third order is derived. Asymptotical analysis of this system allows to investigate the scaling regime, which develops on the late stages of evolution and to extract additional information concerning the rate of decrease of the specific volume of disordered regions and the rate of decrease of the average thickness of antiphase boundaries. Comparison of these results to experimental data is given. The quench below the spinodal and the onset of long-range order may be separated by the incubation time, whose origin is different from that in first-order phase transitions. Numerical integration of equations for correlators shows also, that it is possible to prepare a sample in such a way that its further evolution will go with formation of transient kinetically slowed polydomain structures different from the final L12 structure.

Kinetic evidence for folding and unfolding intermediates in staphylococcal nuclease.

PubMed

Walkenhorst, W F; Green, S M; Roder, H

1997-05-13

The complex kinetic behavior commonly observed in protein folding studies suggests that a heterogeneous population of molecules exists in solution and that a number of discrete steps are involved in the conversion of unfolded molecules to the fully native form. A central issue in protein folding is whether any of these kinetic events represent conformational steps important for efficient folding rather than side reactions caused by slow steps such as proline isomerization or misfolding of the polypeptide chain. In order to address this question, we used stopped-flow fluorescence techniques to characterize the kinetic mechanism of folding and unfolding for a Pro- variant of SNase in which all six proline residues were replaced by glycines or alanines. Compared to the wild-type protein, which exhibits a series of proline-dependent slow folding phases, the folding kinetics of Pro- SNase were much simpler, which made quantitative kinetic analysis possible. Despite the absence of prolines or other complicating factors, the folding kinetics still contain several phases and exhibit a complex denaturant dependence. The GuHCl dependence of the major observable folding phase and a distinct lag in the appearance of the native state provide clear evidence for an early folding intermediate. The fluorescence of Trp140 in the alpha-helical domain is insensitive to the formation of this early intermediate, which is consistent with a partially folded state with a stable beta-domain and a largely disordered alpha-helical region. A second intermediate is required to model the kinetics of unfolding for the Pro- variant, which shows evidence for a denaturant-induced change in the rate-limiting unfolding step. With the inclusion of these two intermediates, we are able to completely model the major phase(s) in both folding and unfolding across a wide range of denaturant concentrations using a sequential four-state folding mechanism. In order to model the minor slow phase observed for the Pro- mutant, a six-state scheme containing a parallel pathway originating from a distinct unfolded state was required. The properties of this alternate unfolded conformation are consistent with those expected due to the presence of a non-prolyl cis peptide bond. To test the kinetic model, we used simulations based on the six-state scheme and were able to completely reproduce the folding kinetics for Pro- SNase across a range of denaturant concentrations.

A second-order accurate kinetic-theory-based method for inviscid compressible flows

NASA Technical Reports Server (NTRS)

Deshpande, Suresh M.

1986-01-01

An upwind method for the numerical solution of the Euler equations is presented. This method, called the kinetic numerical method (KNM), is based on the fact that the Euler equations are moments of the Boltzmann equation of the kinetic theory of gases when the distribution function is Maxwellian. The KNM consists of two phases, the convection phase and the collision phase. The method is unconditionally stable and explicit. It is highly vectorizable and can be easily made total variation diminishing for the distribution function by a suitable choice of the interpolation strategy. The method is applied to a one-dimensional shock-propagation problem and to a two-dimensional shock-reflection problem.

Fractal reaction kinetics.

PubMed

Kopelman, R

1988-09-23

Classical reaction kinetics has been found to be unsatisfactory when the reactants are spatially constrained on the microscopic level by either walls, phase boundaries, or force fields. Recently discovered theories of heterogeneous reaction kinetics have dramatic consequences, such as fractal orders for elementary reactions, self-ordering and self-unmixing of reactants, and rate coefficients with temporal "memories." The new theories were needed to explain the results of experiments and supercomputer simulations of reactions that were confined to low dimensions or fractal dimensions or both. Among the practical examples of "fractal-like kinetics" are chemical reactions in pores of membranes, excitation trapping in molecular aggregates, exciton fusion in composite materials, and charge recombination in colloids and clouds.

The two-dimensional kinetic ballooning theory for ion temperature gradient mode in tokamak

NASA Astrophysics Data System (ADS)

Xie, T.; Zhang, Y. Z.; Mahajan, S. M.; Hu, S. L.; He, Hongda; Liu, Z. Y.

2017-10-01

The two-dimensional (2D) kinetic ballooning theory is developed for the ion temperature gradient mode in an up-down symmetric equilibrium (illustrated via concentric circular magnetic surfaces). The ballooning transform converts the basic 2D linear gyro-kinetic equation into two equations: (1) the lowest order equation (ballooning equation) is an integral equation essentially the same as that reported by Dong et al., [Phys. Fluids B 4, 1867 (1992)] but has an undetermined Floquet phase variable, (2) the higher order equation for the rapid phase envelope is an ordinary differential equation in the same form as the 2D ballooning theory in a fluid model [Xie et al., Phys. Plasmas 23, 042514 (2016)]. The system is numerically solved by an iterative approach to obtain the (phase independent) eigen-value. The new results are compared to the two earlier theories. We find a strongly modified up-down asymmetric mode structure, and non-trivial modifications to the eigen-value.

Phase-field Model for Interstitial Loop Growth Kinetics and Thermodynamic and Kinetic Models of Irradiated Fe-Cr Alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yulan; Hu, Shenyang Y.; Sun, Xin

2011-06-15

Microstructure evolution kinetics in irradiated materials has strongly spatial correlation. For example, void and second phases prefer to nucleate and grow at pre-existing defects such as dislocations, grain boundaries, and cracks. Inhomogeneous microstructure evolution results in inhomogeneity of microstructure and thermo-mechanical properties. Therefore, the simulation capability for predicting three dimensional (3-D) microstructure evolution kinetics and its subsequent impact on material properties and performance is crucial for scientific design of advanced nuclear materials and optimal operation conditions in order to reduce uncertainty in operational and safety margins. Very recently the meso-scale phase-field (PF) method has been used to predict gas bubblemore » evolution, void swelling, void lattice formation and void migration in irradiated materials,. Although most results of phase-field simulations are qualitative due to the lake of accurate thermodynamic and kinetic properties of defects, possible missing of important kinetic properties and processes, and the capability of current codes and computers for large time and length scale modeling, the simulations demonstrate that PF method is a promising simulation tool for predicting 3-D heterogeneous microstructure and property evolution, and providing microstructure evolution kinetics for higher scale level simulations of microstructure and property evolution such as mean field methods. This report consists of two parts. In part I, we will present a new phase-field model for predicting interstitial loop growth kinetics in irradiated materials. The effect of defect (vacancy/interstitial) generation, diffusion and recombination, sink strength, long-range elastic interaction, inhomogeneous and anisotropic mobility on microstructure evolution kinetics is taken into account in the model. The model is used to study the effect of elastic interaction on interstitial loop growth kinetics, the interstitial flux, and sink strength of interstitial loop for interstitials. In part II, we present a generic phase field model and discuss the thermodynamic and kinetic properties in phase-field models including the reaction kinetics of radiation defects and local free energy of irradiated materials. In particular, a two-sublattice thermodynamic model is suggested to describe the local free energy of alloys with irradiated defects. Fe-Cr alloy is taken as an example to explain the required thermodynamic and kinetic properties for quantitative phase-field modeling. Finally the great challenges in phase-field modeling will be discussed.« less

An atmospheric pressure flow reactor: Gas phase kinetics and mechanism in tropospheric conditions without wall effects

NASA Technical Reports Server (NTRS)

Koontz, Steven L.; Davis, Dennis D.; Hansen, Merrill

1988-01-01

A new type of gas phase flow reactor, designed to permit the study of gas phase reactions near 1 atm of pressure, is described. A general solution to the flow/diffusion/reaction equations describing reactor performance under pseudo-first-order kinetic conditions is presented along with a discussion of critical reactor parameters and reactor limitations. The results of numerical simulations of the reactions of ozone with monomethylhydrazine and hydrazine are discussed, and performance data from a prototype flow reactor are presented.

In situ synchrotron XRD analysis of the kinetics of spodumene phase transitions.

PubMed

L Moore, Radhika; Mann, Jason P; Montoya, Alejandro; Haynes, Brian S

2018-04-25

The phase transition by thermal activation of natural α-spodumene was followed by in situ synchrotron XRD in the temperature range 896 to 940 °C. We observed both β- and γ-spodumene as primary products in approximately equal proportions. The rate of the α-spodumene inversion is first order and highly sensitive to temperature (apparent activation energy ∼800 kJ mol-1). The γ-spodumene product is itself metastable, forming β-spodumene, with the total product mass fraction ratio fγ/fβ decreasing as the conversion of α-spodumene continues. We found the relationship between the product yields and the degree of conversion of α-spodumene to be the same at all temperatures in the range studied. A model incorporating first order kinetics of the α- and γ-phase inversions with invariant rate constant ratio describes the results accurately. Theoretical phonon analysis of the three phases indicates that the γ phase contains crystallographic instabilities, whilst the α and β phases do not.

Higher-order kinetic expansion of quantum dissipative dynamics: mapping quantum networks to kinetic networks.

PubMed

Wu, Jianlan; Cao, Jianshu

2013-07-28

We apply a new formalism to derive the higher-order quantum kinetic expansion (QKE) for studying dissipative dynamics in a general quantum network coupled with an arbitrary thermal bath. The dynamics of system population is described by a time-convoluted kinetic equation, where the time-nonlocal rate kernel is systematically expanded of the order of off-diagonal elements of the system Hamiltonian. In the second order, the rate kernel recovers the expression of the noninteracting-blip approximation method. The higher-order corrections in the rate kernel account for the effects of the multi-site quantum coherence and the bath relaxation. In a quantum harmonic bath, the rate kernels of different orders are analytically derived. As demonstrated by four examples, the higher-order QKE can reliably predict quantum dissipative dynamics, comparing well with the hierarchic equation approach. More importantly, the higher-order rate kernels can distinguish and quantify distinct nontrivial quantum coherent effects, such as long-range energy transfer from quantum tunneling and quantum interference arising from the phase accumulation of interactions.

Investigating the mechanisms of surface-bound functional groups in overcoming kinetic barriers to the precipitation of ordered dolomite at low temperature (Invited)

NASA Astrophysics Data System (ADS)

Kenward, P. A.; Roberts, J.; Fowle, D.; Goldstein, R.; Moore, D.; Gonzalez, L. A.

2013-12-01

The mineral dolomite, while abundant in the geologic record, is scarce in modern environments and limited to specific environments, due to kinetic barriers at low temperature (< 50°C). The microbial mediation of dolomite has been extensively studied using numerous microorganisms and disordered dolomite has been synthesized under abiotic conditions. However these studies either yielded disordered dolomite or failed to elucidate the specific mechanism(s) necessary to achieve the precipitation ordered phases of dolomite. Our work [1,2] demonstrates laboratory synthesis of dolomite at 25 °C using microcosms composed of either microbial biomass or abiotic carboxylated polystyrene micro-spheres and fluids with a range of marine-type compositions. We identify the density of surface-bound carboxyl-groups of organic matter as a primary control in ordered dolomite formation at low temperatures under the conditions studied. We hypothesize that surface-bound carboxyl-groups, such as those associated with organic matter or microbial biomass, overcome slow reaction kinetics for dolomite precipitation by dehydrating Mg2+ in an energetically favorable reaction. The precipitation of solid carbonate phases remains the most effective means of permanently sequestering CO2 from the atmosphere. As such, an increased understanding of dolomite kinetics at low temperature affords us the opportunity to apply this mechanism to engineered systems designed to enhance carbon sequestration in environments which do not kinetically favor the formation of carbonate mineral phases. [1] Kenward et al. (2013) AAPG, in press. [2] Roberts et al. (2013) PNAS, in press.

Continuum theory of phase separation kinetics for active Brownian particles.

PubMed

Stenhammar, Joakim; Tiribocchi, Adriano; Allen, Rosalind J; Marenduzzo, Davide; Cates, Michael E

2013-10-04

Active Brownian particles (ABPs), when subject to purely repulsive interactions, are known to undergo activity-induced phase separation broadly resembling an equilibrium (attraction-induced) gas-liquid coexistence. Here we present an accurate continuum theory for the dynamics of phase-separating ABPs, derived by direct coarse graining, capturing leading-order density gradient terms alongside an effective bulk free energy. Such gradient terms do not obey detailed balance; yet we find coarsening dynamics closely resembling that of equilibrium phase separation. Our continuum theory is numerically compared to large-scale direct simulations of ABPs and accurately accounts for domain growth kinetics, domain topologies, and coexistence densities.

Kinetic modeling of secondary organic aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-08-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Kinetic modeling of Secondary Organic Aerosol formation: effects of particle- and gas-phase reactions of semivolatile products

NASA Astrophysics Data System (ADS)

Chan, A. W. H.; Kroll, J. H.; Ng, N. L.; Seinfeld, J. H.

2007-05-01

The distinguishing mechanism of formation of secondary organic aerosol (SOA) is the partitioning of semivolatile hydrocarbon oxidation products between the gas and aerosol phases. While SOA formation is typically described in terms of partitioning only, the rate of formation and ultimate yield of SOA can also depend on the kinetics of both gas- and aerosol-phase processes. We present a general equilibrium/kinetic model of SOA formation that provides a framework for evaluating the extent to which the controlling mechanisms of SOA formation can be inferred from laboratory chamber data. With this model we examine the effect on SOA formation of gas-phase oxidation of first-generation products to either more or less volatile species, of particle-phase reaction (both first- and second-order kinetics), of the rate of parent hydrocarbon oxidation, and of the extent of reaction of the parent hydrocarbon. The effect of pre-existing organic aerosol mass on SOA yield, an issue of direct relevance to the translation of laboratory data to atmospheric applications, is examined. The importance of direct chemical measurements of gas- and particle-phase species is underscored in identifying SOA formation mechanisms.

Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

PubMed

Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

2016-07-01

Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC. © 2015 SETAC.

Nucleation of ordered solid phases of proteins via a disordered high-density state: Phenomenological approach

NASA Astrophysics Data System (ADS)

Pan, Weichun; Kolomeisky, Anatoly B.; Vekilov, Peter G.

2005-05-01

Nucleation of ordered solid phases of proteins triggers numerous phenomena in laboratory, industry, and in healthy and sick organisms. Recent simulations and experiments with protein crystals suggest that the formation of an ordered crystalline nucleus is preceded by a disordered high-density cluster, akin to a droplet of high-density liquid that has been observed with some proteins; this mechanism allowed a qualitative explanation of recorded complex nucleation kinetics curves. Here, we present a simple phenomenological theory that takes into account intermediate high-density metastable states in the nucleation process. Nucleation rate data at varying temperature and protein concentration are reproduced with high fidelity using literature values of the thermodynamic and kinetic parameters of the system. Our calculations show that the growth rate of the near-critical and supercritical ordered clusters within the dense intermediate is a major factor for the overall nucleation rate. This highlights the role of viscosity within the dense intermediate for the formation of the ordered nucleus. The model provides an understanding of the action of additives that delay or accelerate nucleation and presents a framework within which the nucleation of other ordered protein solid phases, e.g., the sickle cell hemoglobin polymers, can be analyzed.

Wave vector modification of the infinite order sudden approximation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachs, J.G.; Bowman, J.M.

1980-10-15

A simple method is proposed to modify the infinite order sudden approximation (IOS) in order to extend its region of quantitative validity. The method involves modifying the phase of the IOS scattering matrix to include a part calculated at the outgoing relative kinetic energy as well as a part calculated at the incoming kinetic energy. An immediate advantage of this modification is that the resulting S matrix is symmetric. We also present a closely related method in which the relative kinetic energies used in the calculation of the phase are determined from quasiclassical trajectory calculations. A set of trajectories ismore » run with the initial state being the incoming state, and another set is run with the initial state being the outgoing state, and the average final relative kinetic energy of each set is obtained. One part of the S-operator phase is then calculated at each of these kinetic energies. We apply these methods to vibrationally inelastic collinear collisions of an atom and a harmonic oscillator, and calculate transition probabilities P/sub n/1..-->..nf for three model systems. For systems which are sudden, or nearly so, the agreement with exact quantum close-coupling calculations is substantially improved over standard IOS ones when ..delta..n=such thatub f/-n/sub i/ is large, and the corresponding transition probability is small, i.e., less than 0.1. However, the modifications we propose will not improve the accuracy of the IOS transition probabilities for any collisional system unless the standard form of IOS already gives at least qualitative agreement with exact quantal calculations. We also suggest comparisons between some classical quantities and sudden predictions which should help in determining the validity of the sudden approximation. This is useful when exact quantal data is not available for comparison.« less

Wave vector modification of the infinite order sudden approximation

NASA Astrophysics Data System (ADS)

Sachs, Judith Grobe; Bowman, Joel M.

1980-10-01

A simple method is proposed to modify the infinite order sudden approximation (IOS) in order to extend its region of quantitative validity. The method involves modifying the phase of the IOS scattering matrix to include a part calculated at the outgoing relative kinetic energy as well as a part calculated at the incoming kinetic energy. An immediate advantage of this modification is that the resulting S matrix is symmetric. We also present a closely related method in which the relative kinetic energies used in the calculation of the phase are determined from quasiclassical trajectory calculations. A set of trajectories is run with the initial state being the incoming state, and another set is run with the initial state being the outgoing state, and the average final relative kinetic energy of each set is obtained. One part of the S-operator phase is then calculated at each of these kinetic energies. We apply these methods to vibrationally inelastic collinear collisions of an atom and a harmonic oscillator, and calculate transition probabilities Pn1→nf for three model systems. For systems which are sudden, or nearly so, the agreement with exact quantum close-coupling calculations is substantially improved over standard IOS ones when Δn=‖nf-ni‖ is large, and the corresponding transition probability is small, i.e., less than 0.1. However, the modifications we propose will not improve the accuracy of the IOS transition probabilities for any collisional system unless the standard form of IOS already gives at least qualitative agreement with exact quantal calculations. We also suggest comparisons between some classical quantities and sudden predictions which should help in determining the validity of the sudden approximation. This is useful when exact quantal data is not available for comparison.

Kinetics and Equilibrium of Fe3+ Ions Adsorption on Carbon Nanofibers

NASA Astrophysics Data System (ADS)

Alimin; Agusu, La; Ahmad, L. O.; Kadidae, L. O.; Ramadhan, L.; Nurdin, M.; Isdayanti, N.; Asria; Aprilia M, P.; Hasrudin

2018-05-01

Generally, the interaction between metal ions and adsorbent is governed by many factors including; concentration of metal ions, interaction time and solution pH. In this work, we applied liquid phase adsorption for studying the interaction between Fe3+ ions and Carbon Nanofibers (CNFs) irradiated by ultrasonic waves. Kinetics and isotherms model of the Fe3+ ion adsorption was investigated by varying contact time and pH. We found that the Fe3+ ions were efficiently adsorbed on CNFs for 0.5 h in acidic pH of around 5. In order to obtain the best-fitted isotherms model, Langmuir and Freundlich’s isotherms were used in this work. The adsorption equilibrium Fe3+ metal ions on CNFs tend to follow Langmuir. Adsorption kinetics of Fe3+ ions on CNFs were investigated by using both pseudo-first and pseudo-second orders. The adsorption kinetics coincided well with the pseudo-second-order.

A Rate-Theory-Phase-Field Model of Irradiation-Induced Recrystallization in UMo Nuclear Fuels

NASA Astrophysics Data System (ADS)

Hu, Shenyang; Joshi, Vineet; Lavender, Curt A.

2017-12-01

In this work, we developed a recrystallization model to study the effect of microstructures and radiation conditions on recrystallization kinetics in UMo fuels. The model integrates the rate theory of intragranular gas bubble and interstitial loop evolutions and a phase-field model of recrystallization zone evolution. A first passage method is employed to describe one-dimensional diffusion of interstitials with a diffusivity value several orders of magnitude larger than that of fission gas xenons. With the model, the effect of grain sizes on recrystallization kinetics is simulated. The results show that (1) recrystallization in large grains starts earlier than that in small grains, (2) the recrystallization kinetics (recrystallization volume fraction) decrease as the grain size increases, (3) the predicted recrystallization kinetics are consistent with the experimental results, and (4) the recrystallization kinetics can be described by the modified Avrami equation, but the parameters of the Avrami equation strongly depend on the grain size.

Cation ordering/disordering kinetics in Ba3CoNb2O9: An in situ study using synchrotron x-ray powder diffraction

NASA Astrophysics Data System (ADS)

Mallinson, P. M.; Claridge, J. B.; Rosseinsky, M. J.; Ibberson, R. M.; Wright, J. P.; Fitch, A. N.; Price, T.; Iddles, D. M.

2007-11-01

In situ synchrotron x-ray powder diffraction has been used to study the kinetics of cation ordering and disordering in the microwave dielectric electroceramic Ba3CoNb2O9 with a time resolution of 15s. The method enables the order/disorder temperature (To /d) in this material of 1430°C to be directly observed. The changes in the rate and degree of cation ordering and in the growth of ordered domains between samples ordered from standard precursor material and then subsequently reordered following an annealing period above To /d show that small changes in precursor order state and phase assemblage strongly influence the final domain size.

Pathway-engineering for highly-aligned block copolymer arrays

DOE PAGES

Choo, Youngwoo; Majewski, Paweł W.; Fukuto, Masafumi; ...

2017-12-06

While kinetic aspects of self-assembly can hinder ordering, non-equilibirum effects can also be exploited to enforce a particular kind of order. We develop a pathway-engineering approach, using it to select a particular arrangement of a block copolymer cylinder phase.

Pathway-engineering for highly-aligned block copolymer arrays

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choo, Youngwoo; Majewski, Paweł W.; Fukuto, Masafumi

While kinetic aspects of self-assembly can hinder ordering, non-equilibirum effects can also be exploited to enforce a particular kind of order. We develop a pathway-engineering approach, using it to select a particular arrangement of a block copolymer cylinder phase.

Genetic algorithms for GNC settings and DACS design application to an asteroid Kinetic Impactor

NASA Astrophysics Data System (ADS)

Vernis, P.; Oliviero, V.

2018-06-01

This paper deals with an application of Genetic Algorithm (GA) tools in order to perform and optimize the settings phase of the Guidance, Navigation, and Control (GNC) data set for the endgame phase of a Kinetic Impactor (KI) targeting a medium-size Near Earth Object (NEO). A coupled optimization of the GNC settings and of the GC-oriented design of the Divert and Attitude Control System (DACS) is also proposed. The illustration of the developed principles is made considering the NEOShield study frame.

A novel kinetic modeling method for the stabilization phase of the composting process for biodegradation of solid wastes.

PubMed

Ebrahimzadeh, Reza; Ghazanfari Moghaddam, Ahmad; Sarcheshmehpour, Mehdi; Mortezapour, Hamid

2017-12-01

Biomass degradation kinetics of the composting process for kitchen waste, pruned elm tree branches and sheep manure were studied to model changes in volatile solids (VS) over time. Three experimental reactors containing raw mixtures with a carbon to nitrogen (C/N) ratio of 27:1 and a moisture content of 65% were prepared. During the composting process two of the reactors used forced air and the third used natural aeration. The composting stabilization phases in all reactors were completed in 30 days. During this period, composting indexes such as temperature, moisture content and VS changes were recorded. Elementary reactions were used for kinetics modeling of the degradation process. Results showed that the numerical values of rate constant ( k) for zero-order ranged from 0.86 to 1.03 VS×day -1 , for first-order models it ranged from 0.01 to 0.02 day -1 , for second-order the range was from 1.36×10 -5 to 1.78×10 -5 VS -1 ×day -1 and for n-order the rate constant ranged from 0.031 to 0.095 VS (1-n) ×day -1 . The resulting models were validated by comparing statistical parameters. Evaluation of the models showed that, in the aerated reactors, the n-order models (less than 1) successfully estimated the VS changes. In the non-aeration reactor, for the second-order model good agreement was achieved between the simulated and actual quantities of VS. Also, half-life time provided a useful criterion for the estimation of expected time for completion of different phases of composting.

Hydrolysis kinetics in anaerobic degradation of particulate organic material: an overview.

PubMed

Vavilin, V A; Fernandez, B; Palatsi, J; Flotats, X

2008-01-01

The applicability of different kinetics to the hydrolysis of particulate organic material in anaerobic digestion is discussed. Hydrolysis has traditionally been modelled according to the first-order kinetics. For complex substrate, the first-order kinetics should be modified in order to take into account hardly degradable material. It has been shown that models in which hydrolysis is coupled to the growth of hydrolytic bacteria work well at high or at fluctuant organic loading. In particular, the surface-related two-phase and the Contois models showed good fits to experimental data from a wide range of organic waste. Both models tend to the first-order kinetics at a high biomass-to-waste ratio and, for this reason, they can be considered as more general models. Examples on different inhibition processes that might affect the degradation of solid waste are reported. Acetogenesis or methanogenesis might be the rate-limiting stages in complex waste. In such cases, stimulation of hydrolysis (mechanically, chemically or biologically) may lead to a further inhibition of these stages, which ultimately affects hydrolysis as well. Since the hydrolysis process is characterized by surface and transport phenomena, new developments in spatially distributed models are considered fundamental to provide new insights in this complex process.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weese, Randall K.

In order to calculate the kinetic parameters from DSC data, we have used the generally accepted methods of Bershtein [13]. We have calculated the rate constants for 4 temperatures and the activation energy based on the shift in the transition temperature, β→δ for HMX. The values of E a from this work is 402 kJ/mol compared to previous results by Brill [9] of 204 kJ/mol. Brill and associates measured the phase transition of HMX using FTIR, sodium chloride plates and silicon oil. Given the differences in technique between FTIR and DSC the results found in this work are reasonable. Inmore » this investigation a large sample set (16) proved to be statistically valid for the determinations of k. Linear regressions were performed, observed and good fits were obtained, for each temperature. The enthalpy determination of ΔH o, for the β→δ phase transition was reproducible with in 3 parts in 100 over the range of this experiment. Thus, the data derived from this experiment k, E a, and ΔH o are valid parameters for the solid-solid phase transition. Obtaining pure β phase HMX was very important for this investigation. Related to the phase change is the particle size distribution and is presented in Figure 3. Compared to previous work on HMX, this study utilized very pure β phase material. In addition, the particle size was controlled more rigorously at about 160 μm, giving a more consistent result for α. Thus, these kinetic results should have less scatter than results with less control of HMX purity and particle size. The kinetic basis of the polymorphic conversion is due to the cohesive forces in the HMX crystal lattice [21]. The energy required to bring about change from chair to chair-chair conformation has been reported by Brill [21] as ring torsion and is essentially a normal mode of the molecule that requires about 4 kJ mol -1. For the purpose of this investigation the energy of activation found in this work relates to the disruption of the intermolecular interactions with in the crystal lattice of β phase HMX and is much larger (100X) than that of simple conformational changes. The evidence of a straightforward one step mechanism is not supported by this research. Solid-solid phase transition kinetics is very complexed. There are many factors that contribute to an overall reaction mechanism. The initial assumptions that were chosen to allow simple manipulation of the HMX phase transition data prove to be too limiting. The rate constant by definition should in fact be constant, however, our data reflects it is not (refer to k vs time plot in Appendix 2). The assumption of a first order, simple single step reaction is a good starting point for the study of HMX phase transition kinetics, but further analysis should be done with other reaction orders and multiple step mechanisms. Understanding the kinetics of β phase HMX will clearly help the custodian understand the limitations of storage and use of this compound.« less

Kinetic effects in thermal explosion with oscillating ambient conditions.

PubMed

Novozhilov, Vasily

2018-03-05

Thermal explosion problem for a medium with oscillating ambient temperature at its boundaries is a new problem which was introduced in the preceding publication by the present author. It is directly applicable to a range of practical fire autoignition scenarios (e.g. in the storages of organic matter, explosives, propellants, etc.). Effects of kinetic mechanisms, however, need be further investigated as they are expected to alter critical conditions of thermal explosion. We consider several global kinetic mechanisms: first order reaction, second order reaction, and first order autocatalysis. It is demonstrated that kinetic effects related to reactants consumption do indeed shift respective critical boundaries. Effect of kinetics on oscillatory development of thermal explosion is of particular interest. In line with conclusions of the preceding publication, it is confirmed that temperature oscillations may develop during induction phase of thermal explosion when the effect of reactants consumption is properly taken into account. Moreover, development of thermal explosion instability through the prior oscillations is an inevitable and natural scenario. This fact is confirmed by a number of examples. Besides, effects of the other relevant parameter, Zeldovich number on critical conditions are also investigated.

Interface Reactions and Synthetic Reaction of Composite Systems

PubMed Central

Park, Joon Sik; Kim, Jeong Min

2010-01-01

Interface reactions in composite systems often determine their overall properties, since product phases usually formed at interfaces during composite fabrication processing make up a large portion of the composites. Since most composite materials represent a ternary or higher order materials system, many studies have focused on analyses of diffusion phenomena and kinetics in multicomponent systems. However, the understanding of the kinetic behavior increases the complexity, since the kinetics of each component during interdiffusion reactions need to be defined for interpreting composite behaviors. From this standpoint, it is important to clarify the interface reactions for producing compatible interfaces with desired product phases. A thermodynamic evaluation such as a chemical potential of involving components can provide an understanding of the diffusion reactions, which govern diffusion pathways and product phase formation. A strategic approach for designing compatible interfaces is discussed in terms of chemical potential diagrams and interface morphology, with some material examples.

The Interface Influence in TiN/SiN x Multilayer Nanocomposite Under Irradiation

NASA Astrophysics Data System (ADS)

Uglov, V. V.; Safronov, I. V.; Kvasov, N. T.; Remnev, G. E.; Shimanski, V. I.

2018-01-01

The paper focuses on studying the kinetics of radiation-induced point defects formed in TiN/SiN x multilayer nanocomposites with account of their generation, diffusion recombination, and the influence of sinks functioning as interfaces. In order to describe the kinetics in nanocrystalline TiN and amorphous SiN x phases, a finite-difference method is used to solve the system of balance kinetic equations for absolute defect concentrations depending on the spatiotemporal variables. A model of the disclination-dislocation interface structure is used to study the absorption of radiation-induced point defects on the boundaries in created stress fields. It is shown that the interface effectively absorbs point defects in these phases of TiN/SiN x multilayer nanocomposite, thereby reducing their amount within the space between phases. This behavior of point defects partially explains a mechanism of the radiation resistance in this type of nanocomposites.

Monitoring reactive microencapsulation dynamics using microfluidics

PubMed Central

Brosseau, Quentin; Baret, Jean-Christophe

2015-01-01

We use microfluidic polydimethylsiloxane (PDMS) devices to measure the kinetics of reactive encapsulations occurring at the interface of emulsion droplets. The formation of the polymeric shell is inferred from the droplet deformability measured in a series of expansion–constriction chambers along the microfluidic chip. With this tool we quantify the kinetic processes governing the encapsulation at the very early stage of shell formation with a time resolution of the order of the millisecond for overall reactions occurring in less than 0.5 s. We perform a comparison of monomer reactivities used for the encapsulation. We study the formation of polyurea microcapsules (PUMCs); the shell formation proceeds at the water–oil interface by an immediate reaction of amines dissolved in the aqueous phase and isocyanates dissolved in the oil phase. We observe that both monomers contribute differently to the encapsulation kinetics. The kinetics of the shell formation process at the oil-in-water (O/W) experiments significantly differs from the water-in-oil (W/O) systems; the component dissolved in the continuous phase has the largest impact on the kinetics. In addition, we quantified the retarding effect on the encapsulation kinetics by the interface stabilizing agent (surfactant). Our approach is valuable for quantifying in situ reactive encapsulation processes and provides guidelines to generate microcapsules with soft interfaces of tailored and controllable interfacial properties. PMID:25705975

Assessment of methane biodegradation kinetics in two-phase partitioning bioreactors by pulse respirometry.

PubMed

Ordaz, Alberto; López, Juan C; Figueroa-González, Ivonne; Muñoz, Raúl; Quijano, Guillermo

2014-12-15

Biological methane biodegradation is a promising treatment alternative when the methane produced in waste management facilities cannot be used for energy generation. Two-phase partitioning bioreactors (TPPBs), provided with a non-aqueous phase (NAP) with high affinity for the target pollutant, are particularly suitable for the treatment of poorly water-soluble compounds such as methane. Nevertheless, little is known about the influence of the presence of the NAP on the resulting biodegradation kinetics in TPPBs. In this study, an experimental framework based on the in situ pulse respirometry technique was developed to assess the impact of NAP addition on the methane biodegradation kinetics using Methylosinus sporium as a model methane-degrading microorganism. A comprehensive mass transfer characterization was performed in order to avoid mass transfer limiting scenarios and ensure a correct kinetic parameter characterization. The presence of the NAP mediated significant changes in the apparent kinetic parameters of M. sporium during methane biodegradation, with variations of 60, 120, and 150% in the maximum oxygen uptake rate, half-saturation constant and maximum specific growth rate, respectively, compared with the intrinsic kinetic parameters retrieved from a control without NAP. These significant changes in the kinetic parameters mediated by the NAP must be considered for the design, operation and modeling of TPPBs devoted to air pollution control. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantitative kinetic theory of active matter

NASA Astrophysics Data System (ADS)

Ihle, Thomas; Chou, Yen-Liang

2014-03-01

Models of self-driven agents similar to the Vicsek model [Phys. Rev. Lett. 75 (1995) 1226] are studied by means of kinetic theory. In these models, particles try to align their travel directions with the average direction of their neighbours. At strong alignment a globally ordered state of collective motion forms. An Enskog-like kinetic theory is derived from the exact Chapman-Kolmogorov equation in phase space using Boltzmann's mean-field approximation of molecular chaos. The kinetic equation is solved numerically by a nonlocal Lattice-Boltzmann-like algorithm. Steep soliton-like waves are observed that lead to an abrupt jump of the global order parameter if the noise level is changed. The shape of the wave is shown to follow a novel scaling law and to quantitatively agree within 3 % with agent-based simulations at large particle speeds. This provides a mean-field mechanism to change the second-order character of the flocking transition to first order. Diagrammatic techniques are used to investigate small particle speeds, where the mean-field assumption of Molecular Chaos is invalid and where correlation effects need to be included.

Report on the Implementation of Homogeneous Nucleation Scheme in MARMOT-based Phase Field Simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yulan; Hu, Shenyang Y.; Sun, Xin

2013-09-30

In this report, we summarized our effort in developing mesoscale phase field models for predicting precipitation kinetics in alloys during thermal aging and/or under irradiation in nuclear reactors. The first part focused on developing a method to predict the thermodynamic properties of critical nuclei such as the sizes and concentration profiles of critical nuclei, and nucleation barrier. These properties are crucial for quantitative simulations of precipitate evolution kinetics with phase field models. Fe-Cr alloy was chosen as a model alloy because it has valid thermodynamic and kinetic data as well as it is an important structural material in nuclear reactors.more » A constrained shrinking dimer dynamics (CSDD) method was developed to search for the energy minimum path during nucleation. With the method we are able to predict the concentration profiles of the critical nuclei of Cr-rich precipitates and nucleation energy barriers. Simulations showed that Cr concentration distribution in the critical nucleus strongly depends on the overall Cr concentration as well as temperature. The Cr concentration inside the critical nucleus is much smaller than the equilibrium concentration calculated by the equilibrium phase diagram. This implies that a non-classical nucleation theory should be used to deal with the nucleation of Cr precipitates in Fe-Cr alloys. The growth kinetics of both classical and non-classical nuclei was investigated by the phase field approach. A number of interesting phenomena were observed from the simulations: 1) a critical classical nucleus first shrinks toward its non-classical nucleus and then grows; 2) a non-classical nucleus has much slower growth kinetics at its earlier growth stage compared to the diffusion-controlled growth kinetics. 3) a critical classical nucleus grows faster at the earlier growth stage than the non-classical nucleus. All of these results demonstrated that it is critical to introduce the correct critical nuclei into phase field modeling in order to correctly capture the kinetics of precipitation. In most alloys the matrix phase and precipitate phase have different concentrations as well as different crystal structures. For example, Cu precipitates in FeCu alloys have fcc crystal structure while the matrix Fe-Cu solid solution has bcc structure at low temperature. The WBM model and KimS model, where both concentrations and order parameters are chosen to describe the microstructures, are commonly used to model precipitations in such alloys. The WBM and KimS models have not been implemented into Marmot yet. In the second part of this report, we focused on implementing the WBM and KimS models into Marmot. The Fe-Cu alloys, which are important structure materials in nuclear reactors, was taken as the model alloys to test the models.« less

Radial transport of radiation belt electrons in kinetic field-line resonances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chaston, Christopher C.; Bonnell, J. W.; Wygant, J. R.

A representative case study from the Van Allen Probes during a geomagnetic storm recovery phase reveals enhanced electron fluxes at intermediate pitch angles over energies from ~100 keV to 5 MeV coincident with broadband low-frequency electromagnetic waves. The statistical properties of these waves are used to build a model for radial diffusion via drift-bounce resonances in kinetic Alfvén eigenmodes/kinetic field-line resonances. Estimated diffusion coefficients indicate timescales for radial transport on the order of hours in storm time events at energies from <100 keV to MeVs over equatorial pitch angles from the edge of the loss cone to nearly perpendicular tomore » the geomagnetic field. In conclusion, the correlation of kinetic resonances with electron depletions and enhancements during storm main phase and recovery, and the rapid diffusion these waves drive, suggests that they may modulate the outer radiation belt.« less

Radial transport of radiation belt electrons in kinetic field-line resonances

DOE PAGES

Chaston, Christopher C.; Bonnell, J. W.; Wygant, J. R.; ...

2017-07-25

A representative case study from the Van Allen Probes during a geomagnetic storm recovery phase reveals enhanced electron fluxes at intermediate pitch angles over energies from ~100 keV to 5 MeV coincident with broadband low-frequency electromagnetic waves. The statistical properties of these waves are used to build a model for radial diffusion via drift-bounce resonances in kinetic Alfvén eigenmodes/kinetic field-line resonances. Estimated diffusion coefficients indicate timescales for radial transport on the order of hours in storm time events at energies from <100 keV to MeVs over equatorial pitch angles from the edge of the loss cone to nearly perpendicular tomore » the geomagnetic field. In conclusion, the correlation of kinetic resonances with electron depletions and enhancements during storm main phase and recovery, and the rapid diffusion these waves drive, suggests that they may modulate the outer radiation belt.« less

Development of a fully-consistent reduced order model to study instabilities in boiling water reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dykin, V.; Demaziere, C.

2012-07-01

A simple nonlinear Reduced Order Model to study global, regional and local instabilities in Boiling Water Reactors is described. The ROM consists of three submodels: neutron-kinetic, thermal-hydraulic and heat-transfer models. The neutron-kinetic model allows representing the time evolution of the three first neutron kinetic modes: the fundamental, the first and the second azimuthal modes. The thermal-hydraulic model describes four heated channels in order to correctly simulate out-of-phase behavior. The coupling between the different submodels is performed via both void and Doppler feedback mechanisms. After proper spatial homogenization, the governing equations are discretized in the time-domain. Several modifications, compared to othermore » existing ROMs, have been implemented, and are reported in this paper. One novelty of the ROM is the inclusion of both azimuthal modes, which allows to study combined instabilities (in-phase and out-of-phase), as well as to investigate the corresponding interference effects between them. The second modification concerns the precise estimation of so-called reactivity coefficients or C{sub mn}{sup *V,D} - coefficients by using direct cross-section data from SIMULATE-3 combined with the CORE SIM core simulator in order to calculate Eigenmodes. Furthermore, a non-uniform two-step axial power profile is introduced to simulate the separate heat production in the single and two-phase regions, respectively. An iterative procedure was developed to calculate the solution to the coupled neutron-kinetic/thermal-hydraulic static problem prior to solving the time-dependent problem. Besides, the possibility of taking into account the effect of local instabilities is demonstrated in a simplified manner. The present ROM is applied to the investigation of an actual instability that occurred at the Swedish Forsmark-1 BWR in 1996/1997. The results generated by the ROM are compared with real power plant measurements performed during stability tests and show a good qualitative agreement. The present study provides some insight in a deeper understanding of the physical principles which drive both core-wide and local instabilities. (authors)« less

Formation of metastable phases by spinodal decomposition

PubMed Central

Alert, Ricard; Tierno, Pietro; Casademunt, Jaume

2016-01-01

Metastable phases may be spontaneously formed from other metastable phases through nucleation. Here we demonstrate the spontaneous formation of a metastable phase from an unstable equilibrium by spinodal decomposition, which leads to a transient coexistence of stable and metastable phases. This phenomenon is generic within the recently introduced scenario of the landscape-inversion phase transitions, which we experimentally realize as a structural transition in a colloidal crystal. This transition exhibits a rich repertoire of new phase-ordering phenomena, including the coexistence of two equilibrium phases connected by two physically different interfaces. In addition, this scenario enables the control of sizes and lifetimes of metastable domains. Our findings open a new setting that broadens the fundamental understanding of phase-ordering kinetics, and yield new prospects of applications in materials science. PMID:27713406

Biodegradation kinetics of BTE-OX and MTBE by a diesel-grown biomass.

PubMed

Acuna-Askar, K; de la Torre-Torres, M A; Guerrero-Munoz, M J; Garza-Gonzalez, M T; Chavez-Gomez, B; Rodriguez-Sanchez, I P; Barrera-Saldana, H A

2006-01-01

The biodegradation kinetics of BTE-oX and MTBE, mixed all together in the presence of diesel-grown bioaugmented bacterial populations as high as 885 mg/L VSS, was evaluated. The effect of soil in aqueous samples and the effect of Tergitol NP-10 on substrate biodegradation rates were also evaluated. Biodegradation kinetics was evaluated for 54 h, every 6 h. All BTE-oX chemicals followed a first-order two-phase biodegradation kinetic model, whereas MTBE followed a zero-order removal kinetic model in all samples. BTE-oX removal rates were much higher than those of MTBE in all samples. The presence of soil in aqueous samples retarded BTE-oX and MTBE removal rates. The addition of Tergitol NP-10 to aqueous samples containing soil had a positive effect on substrate removal rate in all samples. Substrate percent removals ranged between 64.8-98.9% for benzene, toluene and ethylbenzene. O-xylene and MTBE percent removals ranged between 18.7-40.8% and 7.2-10.3%, respectively.

Kinetics of Phase Transition from Lamellar to Hexagonally Packed Cylinders for a Triblock Copolymer in a Selective Solvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu,Y.; Li, M.; Bansil, R.

2007-01-01

We examined the kinetics of the transformation from the lamellar (LAM) to the hexagonally packed cylinder (HEX) phase for the triblock copolymer, polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) in dibutyl phthalate (DBP), a selective solvent for polystyrene (PS), using time-resolved small-angle X-ray scattering (SAXS). We observe the HEX phase with the EB block in the cores at a lower temperature than that observed for the LAM phase due to the solvent selectivity of DBP for the PS block. Analysis of the SAXS data for a deep temperature quench well below the LAM-HEX transition shows that the transformation occurs in a one-step process. Wemore » calculate the scattering using a geometric model of rippled layers with adjacent layers totally out of phase during the transformation. The agreement of the calculations with the data further supports the continuous transformation mechanism from the LAM to HEX for a deep quench. In contrast, for a shallow quench close to the order-order transition, we find agreement with a two-step nucleation and growth mechanism.« less

Kinetically Inhibited Order in a Diamond-Lattice Antiferromagnet

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDougall, Gregory J; Gout, Delphine J; Zarestky, Jerel L

2011-01-01

Frustrated magnetic systems exhibit highly degenerate ground states and strong fluctuations, often leading to new physics. An intriguing example of current interest is the antiferromagnet on a diamond lattice, realized physically in the A-site spinel materials. This is a prototypical system in three dimensions where frustration arises from competing interactions rather than purely geometric constraints, and theory suggests the possibility of novel order at low temperature. Here we present a comprehensive single crystal neutron scattering study CoAl2O4, a highly frustrated A-site spinel. We observe strong diffuse scattering that peaks at wavevectors associated with Neel ordering. Below the temperature T*=6.5K, theremore » is a dramatic change in elastic scattering lineshape accompanied by the emergence of well-defined spin-wave excitations. T* had previously been associated with the onset of glassy behavior. Our new results suggest instead that in fact T* signifies a first-order phase transition, but with true long-range order inhibited by the kinetic freezing of domain walls. This scenario might be expected to occur widely in frustrated systems containing first-order phase transitions and is a natural explanation for existing reports of anomalous glassy behavior in other materials.« less

THERMODYNAMICS AND KINETICS OF PHASE TRANSFORMATIONS IN PLUTONIUM ALLOYS - PART I

DOE Office of Scientific and Technical Information (OSTI.GOV)

Turchi, P A; Kaufman, L; Liu, Z

2004-08-18

In this report we investigate order, stability, and phase transformations for a series of actinide-based alloys. The statics and kinetics of precipitation and ordering in this class of alloys are modeled with a scheme that couples fundamental information on the alloy energetics obtained from experimental and assessed thermo-chemical data to the CALPHAD approach commonly used in industry for designing alloys with engineering specificity with the help of the Thermo-Calc software application. The CALPHAD approach is applied to the study of the equilibrium thermodynamic properties of Pu-based alloys, Pu-X, where X=Al, Fe, Ga. The assessment of the equilibrium phase diagrams inmore » the whole range of alloy composition has been performed with the PARROT module of the Thermo-Calc application software. Predictions are made on the low temperature and Pu-rich side of the phase diagrams of Pu-Ga and Pu-Al for which controversy has been noted in the past. The validity of the assessed thermo-chemical database will be discussed by comparing predicted heats of transformation for pure Pu with measured values from differential scanning calorimetry analysis. An overall picture for the stability properties of Pu-Ga and Pu-Al that reconciles the results of past studies carried out on these alloys is proposed. Results on phase stability in the ternary Fe-Ga-Pu and Al-Fe-Pu alloys are discussed. The information collected in this study is then used to model metastability, long-term stability and aging for this class of alloys by coupling Thermo-Calc with DICTRA, a series of modules that allow the analysis of DIffusion Controlled TRAnsformations. Kinetics information is then summarized in so-called TTT (temperature-time-transformations) diagrams for the most relevant phases of actinide alloys. Specifically, results are presented on kinetics of phase transformations associated with the eutectoid-phase decomposition reaction occurring at low temperature, and with the martensitic transformation that takes place at low Ga content in Pu-Ga alloys. Finally, after a summary of the most salient results, suggestions are made for further studies at the micro- and mesoscales.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Shenyang; Joshi, Vineet; Lavender, Curt A.

Experiments showed that recrystallization dramatically speeds up the gas bubble swelling kinetics in metallic UMo fuels. In this work a recrystallization model is developed to study the effect of microstructures and radiation conditions on recrystallization kinetics. The model integrates the rate theory of intra-granular gas bubble and interstitial loop evolution and a phase field model of recrystallization zone evolution. A fast passage method is employed to describe one dimensional diffusion of interstitials which have diffusivity several order magnitude larger than that of the fission gas Xe. With the model, the effect of grain sizes on recrystallization kinetics is simulated.

Morphology and Kinetics of Growth of CaCO3 Precipitates Formed in Saline Water at 30°C

NASA Astrophysics Data System (ADS)

Sui, Xin; Wang, Baohui; Wu, Haiming

2018-02-01

The crystallization kinetics and morphology of CaCO3 crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO3 crystal lattice. The morphology of CaCO3 precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).

Xenon elimination kinetics following brief exposure.

PubMed

Schaefer, Maximilian S; Piper, Thomas; Geyer, Hans; Schneemann, Julia; Neukirchen, Martin; Thevis, Mario; Kienbaum, Peter

2017-05-01

Xenon is a modern inhalative anaesthetic with a very low solubility in tissues providing rapid elimination and weaning from anaesthesia. Besides its anaesthetic properties, Xenon promotes the endogenous erythropoietin biosynthesis and thus has been enlisted as prohibited substance by the World Anti-Doping Agency (WADA). For effective doping controls, knowledge about the elimination kinetics of Xenon and the duration of traceability are of particular importance. Seventy-seven full blood samples were obtained from 7 normal weight patients undergoing routine Xenon-based general anaesthesia with a targeted inspiratory concentration of 60% Xenon in oxygen. Samples were taken before and during Xenon inhalation as well as one, two, 4, 8, 16, 24, 32, 40, and 48 h after exposure. Xenon concentrations were assessed in full blood by gas chromatography and triple quadrupole tandem mass spectrometry with a detection limit of 0.25 µmol/L. The elimination of Xenon was characterized by linear regression of log-transformed Xenon blood concentrations, as well as non-linear regression. Xenon exposure yielded maximum concentrations in arterial blood of 1.3 [1.1; 1.6] mmol/L. Xenon was traceable for 24 to 48 h. The elimination profile was characterized by a biphasic pattern with a rapid alpha phase, followed by a slower beta phase showing a first order kinetics (c[Xe] = 69.1e -0.26x , R 2  = 0.83, t 1/2  = 2.7 h). Time in hours after exposure could be estimated by 50*ln(1.39/c[Xe] 0.077 ). Xenon's elimination kinetics is biphasic with a delayed beta phase following a first order kinetics. Xenon can reliably be detected for at least 24 h after brief exposure. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Energy Index For Aircraft Maneuvers

NASA Technical Reports Server (NTRS)

Chidester, Thomas R. (Inventor); Lynch, Robert E. (Inventor); Lawrence, Robert E. (Inventor); Amidan, Brett G. (Inventor); Ferryman, Thomas A. (Inventor); Drew, Douglas A. (Inventor); Ainsworth, Robert J. (Inventor); Prothero, Gary L. (Inventor); Romanowski, Tomothy P. (Inventor); Bloch, Laurent (Inventor)

2006-01-01

Method and system for analyzing, separately or in combination, kinetic energy and potential energy and/or their time derivatives, measured or estimated or computed, for an aircraft in approach phase or in takeoff phase, to determine if the aircraft is or will be put in an anomalous configuration in order to join a stable approach path or takeoff path. A 3 reference value of kinetic energy andor potential energy (or time derivatives thereof) is provided, and a comparison index .for the estimated energy and reference energy is computed and compared with a normal range of index values for a corresponding aircraft maneuver. If the computed energy index lies outside the normal index range, this phase of the aircraft is identified as anomalous, non-normal or potentially unstable.

Phase Coexistence and Kinetic Arrest in the Magnetostructural Transition of the Ordered Alloy FeRh

DOE PAGES

Keavney, David J.; Choi, Yongseong; Holt, Martin V.; ...

2018-01-29

In materials where two or more ordering degrees of freedom are closely matched in their free energies, coupling between them, or multiferroic behavior can occur. These phenomena can produce a very rich phase behavior, as well as emergent phases that offer useful properties and opportunities to reveal novel phenomena in phase transitions. The ordered alloy FeRh undergoes an antiferromagnetic to ferromagnetic phase transition at ~375 K, which illustrates the interplay between structural and magnetic order mediated by a delicate energy balance between two configurations. We have examined this transition using a combination of high-resolution x-ray structural and magnetic imaging andmore » comprehensive x-ray magnetic circular dichroism spectroscopy. We find that the transition proceeds via a defect-driven domain nucleation and growth mechanism, with significant return point memory in both the structural and magnetic domain configurations. In conclusion, the domains show evidence of inhibited growth after nucleation, resulting in a quasi- 2nd order temperature behavior.« less

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

NASA Technical Reports Server (NTRS)

Pratt, D. T.

1984-01-01

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.

Transition and Damping of Collective Modes in a Trapped Fermi Gas between BCS and Unitary Limits near the Phase Transition

PubMed Central

Dong, Hang; Zhang, Wenyuan; Zhou, Li; Ma, Yongli

2015-01-01

We investigate the transition and damping of low-energy collective modes in a trapped unitary Fermi gas by solving the Boltzmann-Vlasov kinetic equation in a scaled form, which is combined with both the T-matrix fluctuation theory in normal phase and the mean-field theory in order phase. In order to connect the microscopic and kinetic descriptions of many-body Feshbach scattering, we adopt a phenomenological two-fluid physical approach, and derive the coupling constants in the order phase. By solving the Boltzmann-Vlasov steady-state equation in a variational form, we calculate two viscous relaxation rates with the collision probabilities of fermion’s scattering including fermions in the normal fluid and fermion pairs in the superfluid. Additionally, by considering the pairing and depairing of fermions, we get results of the frequency and damping of collective modes versus temperature and s-wave scattering length. Our theoretical results are in a remarkable agreement with the experimental data, particularly for the sharp transition between collisionless and hydrodynamic behaviour and strong damping between BCS and unitary limits near the phase transition. The sharp transition originates from the maximum of viscous relaxation rate caused by fermion-fermion pair collision at the phase transition point when the fermion depair, while the strong damping due to the fast varying of the frequency of collective modes from BCS limit to unitary limit. PMID:26522094

Nonequilibrium Statistical Mechanics in One Dimension

NASA Astrophysics Data System (ADS)

Privman, Vladimir

2005-08-01

Part I. Reaction-Diffusion Systems and Models of Catalysis; 1. Scaling theories of diffusion-controlled and ballistically-controlled bimolecular reactions S. Redner; 2. The coalescence process, A+A->A, and the method of interparticle distribution functions D. ben-Avraham; 3. Critical phenomena at absorbing states R. Dickman; Part II. Kinetic Ising Models; 4. Kinetic ising models with competing dynamics: mappings, correlations, steady states, and phase transitions Z. Racz; 5. Glauber dynamics of the ising model N. Ito; 6. 1D Kinetic ising models at low temperatures - critical dynamics, domain growth, and freezing S. Cornell; Part III. Ordering, Coagulation, Phase Separation; 7. Phase-ordering dynamics in one dimension A. J. Bray; 8. Phase separation, cluster growth, and reaction kinetics in models with synchronous dynamics V. Privman; 9. Stochastic models of aggregation with injection H. Takayasu and M. Takayasu; Part IV. Random Sequential Adsorption and Relaxation Processes; 10. Random and cooperative sequential adsorption: exactly solvable problems on 1D lattices, continuum limits, and 2D extensions J. W. Evans; 11. Lattice models of irreversible adsorption and diffusion P. Nielaba; 12. Deposition-evaporation dynamics: jamming, conservation laws and dynamical diversity M. Barma; Part V. Fluctuations In Particle and Surface Systems; 13. Microscopic models of macroscopic shocks S. A. Janowsky and J. L. Lebowitz; 14. The asymmetric exclusion model: exact results through a matrix approach B. Derrida and M. R. Evans; 15. Nonequilibrium surface dynamics with volume conservation J. Krug; 16. Directed walks models of polymers and wetting J. Yeomans; Part VI. Diffusion and Transport In One Dimension; 17. Some recent exact solutions of the Fokker-Planck equation H. L. Frisch; 18. Random walks, resonance, and ratchets C. R. Doering and T. C. Elston; 19. One-dimensional random walks in random environment K. Ziegler; Part VII. Experimental Results; 20. Diffusion-limited exciton kinetics in one-dimensional systems R. Kroon and R. Sprik; 21. Experimental investigations of molecular and excitonic elementary reaction kinetics in one-dimensional systems R. Kopelman and A. L. Lin; 22. Luminescence quenching as a probe of particle distribution S. H. Bossmann and L. S. Schulman; Index.

Degradation kinetics of di-(2-ethylhexyl) phthalate (DEHP) and organic matter of sewage sludge during composting.

PubMed

Cheng, Hsiao-Fen; Kumar, Mathava; Lin, Jih-Gaw

2008-06-15

The potential degradation of di-(2-ethylhexyl) phthalate (DEHP) and organic matter of sewage sludge by composting was investigated using laboratory reactor at different operating conditions (E-1, E-2 and E-3). In all conditions, single stage thermophilic phase was observed within 2 days and almost, 60% of DEHP was degraded under this phase. At the end of composting, total DEHP degradation of more than 85% was observed in all conditions and total carbon reduction was 11.8% in E-1, 7.6% in E-2 and 10.8% in E-3. Similar trend was observed in the degradation of total nitrogen. The reduction of volatile solids (VS) in the composting reactors was 5.4% in E-1 (18 days), 5.5% in E-2 (12 days) and 4.3% in E-3 (18 days). The degradation kinetics of DEHP in thermophilic phase (including initial mesophilic phase) and the phase there after were determined by first order and fractional power kinetics, respectively. The significance of experimental parameters in DEHP degradation was assessed by Pearson correlation approach. Elevated temperature produced during composting was effective for the rapid degradation of DEHP from sewage sludge compared to mesophilic treatment.

Proline 54 trans-cis isomerization is responsible for the kinetic partitioning at the last-step photocycle of photoactive yellow protein

PubMed Central

Lee, Byoung-Chul; Hoff, Wouter D.

2008-01-01

Photoactive yellow protein (PYP), a blue-light photoreceptor for Ectothiorhodospira halophila, has provided a unique system for studying protein folding that is coupled with a photocycle. Upon receptor activation by blue light, PYP proceeds through a photocycle that includes a partially folded signaling state. The last-step photocycle is a thermal recovery reaction from the signaling state to the native state. Bi-exponential kinetics had been observed for the last-step photocycle; however, the slow phase of the bi-exponential kinetics has not been extensively studied. Here we analyzed both fast and slow phases of the last-step photocycle in PYP. From the analysis of the denaturant dependence of the fast and slow phases, we found that the last-step photocycle proceeds through parallel channels of the folding pathway. The burial of the solvent-accessible area was responsible for the transition state of the fast phase, while structural rearrangement from the compact state to the native state was responsible for the transition state of the slow phase. The photocycle of PYP was linked to the thermodynamic cycle that includes both unfolding and refolding of the fast- and slow-phase intermediates. In order to test the hypothesis of proline-limited folding for the slow phase, we constructed two proline mutants: P54A and P68A. We found that only a single phase of the last-step photocycle was observed in P54A. This suggests that there is a low energy barrier between trans to cis conformation in P54 in the light-induced state of PYP, and the resulting cis conformation of P54 generates a slow-phase kinetic trap during the photocycle-coupled folding pathway of PYP. PMID:18794212

Molecular salt effects in the gas phase: tuning the kinetic basicity of [HCCLiCl]⁻ and [HCCMgCl₂]⁻ by LiCl and MgCl₂.

PubMed

Khairallah, George N; da Silva, Gabriel; O'Hair, Richard A J

2014-10-06

A combination of gas-phase ion-molecule reaction experiments and theoretical kinetic modeling is used to examine how a salt can influence the kinetic basicity of organometallates reacting with water. [HC≡CLiCl](-) reacts with water more rapidly than [HC≡CMgCl2](-), consistent with the higher reactivity of organolithium versus organomagnesium reagents. Addition of LiCl to [HC≡CLiCl](-) or [HC≡CMgCl2](-) enhances their reactivity towards water by a factor of about 2, while addition of MgCl2 to [HC≡CMgCl2](-) enhances its reactivity by a factor of about 4. Ab initio calculations coupled with master equation/RRKM theory kinetic modeling show that these reactions proceed via a mechanism involving formation of a water adduct followed by rearrangement, proton transfer, and acetylene elimination as either discrete or concerted steps. Both the energy and entropy requirements for these elementary steps need to be considered in order to explain the observed kinetics. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamics of polymerization induced phase separation in reactive polymer blends

NASA Astrophysics Data System (ADS)

Lee, Jaehyung

Mechanisms and dynamics of phase decomposition following polymerization induced phase separation (PIPS) of reactive polymer blends have been investigated experimentally and theoretically. The phenomenon of PIPS is a non-equilibrium and non-linear dynamic process. The mechanism of PIPS has been thought to be a nucleation and growth (NG) type originally, however, newer results indicate spinodal decomposition (SD). In PIPS, the coexistence curve generally passes through the reaction temperature at off-critical compositions, thus phase separation has to be initiated first in the metastable region where nucleation occurs. When the system farther drifts from the metastable to unstable region, the NG structure transforms to the SD bicontinuous morphology. The crossover behavior of PIPS may be called nucleation initiated spinodal decomposition (NISD). The formation of newer domains between the existing ones is responsible for the early stage of PIPS. Since PIPS is non- equilibrium kinetic process, it would not be surprising to discern either or both structures. The phase separation dynamics of DGEBA/CTBN mixtures having various kinds of curing agents from low reactivity to high reactivity and various amount of curing agents were examined at various reaction temperatures. The phase separation behavior was monitored by a quantity of scattered light intensity experimentally and by a quantity of collective structure factor numerically. Prior to the study of phase separation dynamics, a preliminary investigation on the isothermal cure behavior of the mixtures were executed in order to determine reaction kinetics parameters. The cure behavior followed the overall second order reaction kinetics. Next, based on the knowledge obtained from the phase separation dynamics study of DGEBA/CTBN mixtures, the phase separation dynamics of various composition of DGEBA/R45EPI mixtures having MDA as a curing agent were investigated. The phase separation behavior was quite dependent upon the composition variation. R45EPI itself can react with itself or with DGEBA without curing, therefore three-component system was considered in this mixture. For the numerical studies of this three- component mixture, a system that is composed of a reactive component-1 that is miscible with its growing molecules and another reactive component-2 that is not miscible with its growing molecules was considered with crosslinking reaction kinetics of the each component.

Noncollisional kinetic model for non-neutral plasmas in a Penning trap: General properties and stationary solutions

NASA Astrophysics Data System (ADS)

Coppa, G. G.; Ricci, Paolo

2002-10-01

This work deals with a noncollisional kinetic model for non-neutral plasmas in a Penning trap. Using the spatial coordinates r, θ, z and the axial velocity vz as phase-space variables, a kinetic model is developed starting from the kinetic equation for the distribution function f(r,θ,z,vz,t). In order to reduce the complexity of the model, the kinetic equations are integrated along the axial direction by assuming an ergodic distribution in the phase space (z,vz) for particles of the same axial energy ɛ and the same planar position. In this way, a kinetic equation for the z-integrated electron distribution F(r,θ,ɛ,t) is obtained taking into account implicitly the three-dimensionality of the problem. The general properties of the model are discussed, in particular the conservation laws. The model is also related to the fluid model that was introduced by Finn et al. [Phys. Plasmas 6, 3744 (1999); Phys. Rev. Lett. 84, 2401 (2000)] and developed by Coppa et al. [Phys. Plasmas 8, 1133 (2001)]. Finally, numerical investigations are presented regarding the stationary solutions of the model.

Correlation functions in first-order phase transitions

NASA Astrophysics Data System (ADS)

Garrido, V.; Crespo, D.

1997-09-01

Most of the physical properties of systems underlying first-order phase transitions can be obtained from the spatial correlation functions. In this paper, we obtain expressions that allow us to calculate all the correlation functions from the droplet size distribution. Nucleation and growth kinetics is considered, and exact solutions are obtained for the case of isotropic growth by using self-similarity properties. The calculation is performed by using the particle size distribution obtained by a recently developed model (populational Kolmogorov-Johnson-Mehl-Avrami model). Since this model is less restrictive than that used in previously existing theories, the result is that the correlation functions can be obtained for any dependence of the kinetic parameters. The validity of the method is tested by comparison with the exact correlation functions, which had been obtained in the available cases by the time-cone method. Finally, the correlation functions corresponding to the microstructure developed in partitioning transformations are obtained.

Rarefied gas flow simulations using high-order gas-kinetic unified algorithms for Boltzmann model equations

NASA Astrophysics Data System (ADS)

Li, Zhi-Hui; Peng, Ao-Ping; Zhang, Han-Xin; Yang, Jaw-Yen

2015-04-01

This article reviews rarefied gas flow computations based on nonlinear model Boltzmann equations using deterministic high-order gas-kinetic unified algorithms (GKUA) in phase space. The nonlinear Boltzmann model equations considered include the BGK model, the Shakhov model, the Ellipsoidal Statistical model and the Morse model. Several high-order gas-kinetic unified algorithms, which combine the discrete velocity ordinate method in velocity space and the compact high-order finite-difference schemes in physical space, are developed. The parallel strategies implemented with the accompanying algorithms are of equal importance. Accurate computations of rarefied gas flow problems using various kinetic models over wide ranges of Mach numbers 1.2-20 and Knudsen numbers 0.0001-5 are reported. The effects of different high resolution schemes on the flow resolution under the same discrete velocity ordinate method are studied. A conservative discrete velocity ordinate method to ensure the kinetic compatibility condition is also implemented. The present algorithms are tested for the one-dimensional unsteady shock-tube problems with various Knudsen numbers, the steady normal shock wave structures for different Mach numbers, the two-dimensional flows past a circular cylinder and a NACA 0012 airfoil to verify the present methodology and to simulate gas transport phenomena covering various flow regimes. Illustrations of large scale parallel computations of three-dimensional hypersonic rarefied flows over the reusable sphere-cone satellite and the re-entry spacecraft using almost the largest computer systems available in China are also reported. The present computed results are compared with the theoretical prediction from gas dynamics, related DSMC results, slip N-S solutions and experimental data, and good agreement can be found. The numerical experience indicates that although the direct model Boltzmann equation solver in phase space can be computationally expensive, nevertheless, the present GKUAs for kinetic model Boltzmann equations in conjunction with current available high-performance parallel computer power can provide a vital engineering tool for analyzing rarefied gas flows covering the whole range of flow regimes in aerospace engineering applications.

Stochastic cooling of bunched beams from fluctuation and kinetic theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chattopadhyay, S.

1982-09-01

A theoretical formalism for stochastic phase-space cooling of bunched beams in storage rings is developed on the dual basis of classical fluctuation theory and kinetic theory of many-body systems in phase-space. The physics is that of a collection of three-dimensional oscillators coupled via retarded nonconservative interactions determined by an electronic feedback loop. At the heart of the formulation is the existence of several disparate time-scales characterizing the cooling process. Both theoretical approaches describe the cooling process in the form of a Fokker-Planck transport equation in phase-space valid up to second order in the strength and first order in the auto-correlationmore » of the cooling signal. With neglect of the collective correlations induced by the feedback loop, identical expressions are obtained in both cases for the coherent damping and Schottky noise diffusion coefficients. These are expressed in terms of Fourier coefficients in a harmonic decomposition in angle of the generalized nonconservative cooling force written in canonical action-angle variables of the particles in six-dimensional phase-space. Comparison of analytic results to a numerical simulation study with 90 pseudo-particles in a model cooling system is presented.« less

Nucleation of stoichiometric compounds from liquid: Role of the kinetic factor

DOE PAGES

Song, H.; Sun, Y.; Zhang, F.; ...

2018-02-02

The nucleation rate depends on the free-energy barrier and the kinetic factor. While the role of the free energy barrier is a text-book subject, the importance of the kinetic factor is frequently underestimated. Here in this study, we applied the mean first-passage time method, to obtain the free-energy landscape and kinetic factor directly from the molecular dynamics (MD) simulations of the nucleation of the face-centered cubic (fcc) phase in the pure Ni and the B2 phases in the Ni 50Al 50 and Cu 50Zr 50 alloys. The obtained data show that while the free-energy barrier for nucleation is higher inmore » pure Ni the nucleation rate is considerably lower in the Ni 50Al 50 alloy. This result can be explained by the slow attachment kinetics in the N i 50 A l 50 alloy, which was related to the ordered nature of the B2 phase. Even smaller fraction of the antisite defects in the C u 50 Z r 50 alloy leads to such a slow attachment kinetics that the nucleation is never observed for this alloy in the course of the MD simulation. Finally, this is consistent with the experimental facts that the Cu 50Zr 50 alloy is a good glass forming alloy and the Ni 50Al 50 alloy is not. Thus the present study demonstrates that the atom attachment rate can be the critical factor that controls the nucleation process under certain conditions.« less

Nucleation of stoichiometric compounds from liquid: Role of the kinetic factor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Song, H.; Sun, Y.; Zhang, F.

The nucleation rate depends on the free-energy barrier and the kinetic factor. While the role of the free energy barrier is a text-book subject, the importance of the kinetic factor is frequently underestimated. Here in this study, we applied the mean first-passage time method, to obtain the free-energy landscape and kinetic factor directly from the molecular dynamics (MD) simulations of the nucleation of the face-centered cubic (fcc) phase in the pure Ni and the B2 phases in the Ni 50Al 50 and Cu 50Zr 50 alloys. The obtained data show that while the free-energy barrier for nucleation is higher inmore » pure Ni the nucleation rate is considerably lower in the Ni 50Al 50 alloy. This result can be explained by the slow attachment kinetics in the N i 50 A l 50 alloy, which was related to the ordered nature of the B2 phase. Even smaller fraction of the antisite defects in the C u 50 Z r 50 alloy leads to such a slow attachment kinetics that the nucleation is never observed for this alloy in the course of the MD simulation. Finally, this is consistent with the experimental facts that the Cu 50Zr 50 alloy is a good glass forming alloy and the Ni 50Al 50 alloy is not. Thus the present study demonstrates that the atom attachment rate can be the critical factor that controls the nucleation process under certain conditions.« less

Kinetics and Mechanism of the Oxidation of Cyclic Methylsiloxanes by Hydroxyl Radical in the Gas Phase: An Experimental and Theoretical Study.

PubMed

Xiao, Ruiyang; Zammit, Ian; Wei, Zongsu; Hu, Wei-Ping; MacLeod, Matthew; Spinney, Richard

2015-11-17

The ubiquitous presence of cyclic volatile methylsiloxanes (cVMS) in the global atmosphere has recently raised environmental concern. In order to assess the persistence and long-range transport potential of cVMS, their second-order rate constants (k) for reactions with hydroxyl radical ((•)OH) in the gas phase are needed. We experimentally and theoretically investigated the kinetics and mechanism of (•)OH oxidation of a series of cVMS, hexamethylcyclotrisiloxane (D3), octamethycyclotetrasiloxane (D4), and decamethycyclopentasiloxane (D5). Experimentally, we measured k values for D3, D4, and D5 with (•)OH in a gas-phase reaction chamber. The Arrhenius activation energies for these reactions in the temperature range from 313 to 353 K were small (-2.92 to 0.79 kcal·mol(-1)), indicating a weak temperature dependence. We also calculated the thermodynamic and kinetic behaviors for reactions at the M06-2X/6-311++G**//M06-2X/6-31+G** level of theory over a wider temperature range of 238-358 K that encompasses temperatures in the troposphere. The calculated Arrhenius activation energies range from -2.71 to -1.64 kcal·mol(-1), also exhibiting weak temperature dependence. The measured k values were approximately an order of magnitude higher than the theoretical values but have the same trend with increasing size of the siloxane ring. The calculated energy barriers for H-atom abstraction at different positions were similar, which provides theoretical support for extrapolating k for other cyclic siloxanes from the number of abstractable hydrogens.

Catalytic Effect of Pd Clusters in the Poly( N-vinyl-2-pyrrolidone) Combustion

NASA Astrophysics Data System (ADS)

Schiavo, L.; De Nicola, S.; Carotenuto, G.

2018-01-01

Pd(0) is able to catalyze oxygen-involving reactions because of its capability to convert molecular oxygen to the very reactive atomic form. Consequently, the embedding of a little amount of Pd(0) clusters in polymeric phases can be technologically exploited to enhance the incineration kinetic of these polymers. The effect of nanostructuration on the Pd(0) catalytic activity in the polymer incineration reaction has been studied using poly( N-vinyl-2-pyrrolidone) ( \\overline{Mw} = 10,000 gmol-1) as polymeric model system. A change in the PVP incineration kinetic mechanism with significant increase in the reaction rate was experimentally found. The kinetic of the Pd(0)-catalyzed combustion has been studied by isothermal thermogravimetric analysis. After a short induction time, the combustion in presence of Pd(0) clusters shifted to a zero-order kinetic from a second-order kinetic control, which is operative in pure PVP combustion reaction. In addition, the activation energy resulted much lowered compared to the pure PVP incineration case (from 300 to 260 kJ/mol).

Kinetics of SiHCl3 chemical vapor deposition and fluid dynamic simulations.

PubMed

Cavallotti, Carlo; Masi, Maurizio

2011-09-01

Though most of the current silicon photovoltaic technology relies on trichlorosilane (SiHCl3) as a precursor gas to deposit Si, only a few studies have been devoted to the investigation of its gas phase and surface kinetics. In the present work we propose a new kinetic mechanism apt to describe the gas phase and surface chemistry active during the deposition of Si from SiHCl3. Kinetic constants of key reactions were either taken from the literature or determined through ab initio calculations. The capability of the mechanism to reproduce experimental data was tested through the implementation of the kinetic scheme in a fluid dynamic model and in the simulation of both deposition and etching of Si in horizontal reactors. The results of the simulations show that the reactivity of HCl is of key importance in order to control the Si deposition rate. When HCl reaches a critical concentration in the gas phase it starts etching the Si surface, so that the net deposition rate is the net sum of the adsorption rate of the gas phase precursors and the etching rate due to HCl. In these conditions the possibility to further deposit Si is directly related to the rate of consumption of HCl through its reaction with SiHCl3 to give SiCl4. The proposed reaction mechanism was implemented in a 3D fluid dynamic model of a simple Siemens reactor. The simulation results indicate that the proposed interpretation of the growth process applies also to this class of reactors, which operate in what can be defined as a mixed kinetic-transport controlled regime.

Cs{sup +} ion exchange kinetics in complex electrolyte solutions using hydrous crystalline silicotitanates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, D.; Nguyen, L.; Philip, C.V.

1997-12-01

TAM-5 is a hydrous crystalline sodium silicotitanate inorganic ion exchanger with a high selectivity for Cs{sup +}. The kinetics of Cs{sup +}-Na{sup +} ion exchange using TAM-5 in multicomponent electrolyte solutions were determined using batch experiments. For the powder, which is composed of crystals, a single-phase, homogeneous model fit the data best. For the granules, which were prepared from the powder, a two-phase, heterogeneous model resulted in an excellent fit of the data. Macropore and crystal diffusivities were determined by fitting the model to experimental data collected on the powder and the granules. Intracrystalline diffusivities were concentration dependent and weremore » on the order of 10{sup {minus}19} m{sup 2}/s. Macropore diffusivities were on the order of 10{sup {minus}10} m{sup 2}/s. Resistance to diffusion in the macropores was not significant for granules with diameters less than 15 {micro}m. A two-phase, homogeneous model, where liquid within the pores is in equilibrium with the solid, was also evaluated for the granules. Surprisingly, for the granules, an excellent fit of the data was obtained; however, the effective macropore diffusivity was 1.1 {times} 10{sup {minus}11} m{sup 2}/s, an order of magnitude smaller than the macropore diffusivity found using the two-phase, heterogeneous model.« less

Development of high performance particle in cell code for the exascale age

NASA Astrophysics Data System (ADS)

Lapenta, Giovanni; Amaya, Jorge; Gonzalez, Diego; Deep-Est H2020 Consortium Collaboration

2017-10-01

Magnetized plasmas are most effectively described by magneto-hydrodynamics, MHD, a fluid theory based on describing some fields defined in space: electromagnetic fields, density, velocity and temperature of the plasma. However, microphysics processes need kinetic theory, where statistical distributions of particles are governed by the Boltzmann equation. While fluid models are based on the ordinary space and time, kinetic models require a six dimensional space, called phase space, besides time. The two methods are not separated but rather interact to determine the system evolution. Arriving at a single self-consistent model is the goal of our research. We present a new approach developed with the goal of extending the reach of kinetic models to the fluid scales. Kinetic models are a higher order description and all fluid effects are included in them. However, the cost in terms of computing power is much higher and it has been so far prohibitively expensive to treat space weather events fully kinetically. We have now designed a new method capable of reducing that cost by several orders of magnitude making it possible for kinetic models to study macroscopic systems. H2020 Deep-EST consortium (European Commission).

Transformation kinetics for the shock wave induced phase transition in cadmium sulfide crystals

NASA Astrophysics Data System (ADS)

Knudson, M. D.; Gupta, Y. M.

2002-06-01

Initial stage kinetics of the cadmium sulfide (CdS) phase transition was investigated using picosecond time-resolved electronic spectroscopy in plate-impact shock wave experiments. Real-time changes in the electronic spectra were observed, with 100 ps time resolution, in CdS single crystals shocked along a and c axes to stresses ranging between 35 and 90 kbar, which is above the phase-transition threshold stress of approximately 30 kbar. Significant difference in the transformation kinetics was observed for the two crystal orientations. At sufficiently high instantaneous stress, above approximately 60 to 70 kbar for a axis and 50 kbar for c axis, transformation to a metastable state appears to reach a constant state within the 100 ps time resolution. At lower instantaneous stresses, an incubation period on the order of several nanoseconds is observed prior to the onset of electronic changes that mark the onset of the structural change. The subsequent increase in absorbance was quite rapid, with a constant state being reached within the first few nanoseconds after the onset of the structural changes. These results suggest that the nucleation process determines the transformation rate. This insight into transformation kinetics, along with the transformation mechanism obtained from the high-stress experiments, was used to develop a phenomenological model, incorporating ideas of nucleation and growth in martensitic transformations, to simulate the time-dependent extinction of light observed in our experiments. The calculational results incorporating both extinction due to light absorption by the daughter phase volumes and scattering of light by small volumes of the daughter phase were in good agreement with experimental observations. Finally, the orientational differences observed in the transformation kinetics were interpreted in terms of the differences in the elastic-plastic response for the two orientations.

Kinetics of pulse photothermal surface deformation as a method of studying the phase interface movement in a first-order phase transition

NASA Astrophysics Data System (ADS)

Vintzentz, S. V.; Kiselev, V. F.; Levshin, N. L.; Sandomirskii, V. B.

1991-01-01

The photothermal surface deformation (PTSD) method is used for characterization of the first-order phase transition (PT) for the first time. The advantages of the method are demonstrated experimentally for the well known metal-to-semiconductor PT in VO 2. It is found that near the PT temperature the PTSD pulse in a VO 2 film has a sign opposite to that of the thermoelastic response. The conclusion is drawn that this phenomenon is determined primarily by the contribution of the decrease in the specific volume (Δ V/ V) of the substance involved in the semiconductor-to-metal PT. The sign of Δ V/ V for a submicron polycrystalline VO 2 film is determined. Besides, analysis shows that in the PTSD kinetics measured as a whole we can "separate" a law for the metal-semicon- ductor interface movement (i.e. the interface moves towards the interior of the film when the latter is heated and back towards the surface when it is cooling down). The relative density change due to the PT is estimated based on this law.

Ordering kinetics in the long-period superlattice alloy Cu0.79 Pd0.21

NASA Astrophysics Data System (ADS)

Wang, X.; Mainville, J.; Ludwig, K.; Flament, X.; Finel, A.; Caudron, R.

2005-07-01

The kinetics of long-period superlattice (LPS) formation from the disordered state has been examined in a Cu0.79Pd0.21 alloy that exhibits a one-dimensional LPS ordered state. Time-resolved x-ray scattering shows that, following a rapid temperature quench from the disordered state into the LPS region of the phase diagram, the satellite peaks initially grow more quickly than do the central integer-order superlattice peaks. During this process, the satellite peak position, which is inversely related to the average modulation wavelength 2M , initially decreases rapidly, then reaches a minimum and relaxes slowly back toward its new equilibrium position. In the later stages of the LPS formation process, the satellite and central integer-order superlattice peaks narrow in a manner consistent with t1/2 domain coarsening. A simple stochastic model of the partially ordered structure was developed to better understand the relationships between peak widths.

Microstructural Evolution during the Dynamic Deformation of High Strength Navy Steels

DTIC Science & Technology

2008-05-19

phase particles (Figures 23d,e). These include carbides as well as copper precipitates that are of the order of 10 nm or less in size. These particles ...Microstructure and kinetics of martensite transformations in splat-quenched Fe and Fe-Ni alloys - I pure Fe: Acta Metallurgica 30(1982)323. 22. Y. Inokuti...and B. Cantor, Microstructure and kinetics of martensite transformations in splat-quenched Fe and Fe-Ni alloys - II Fe-Ni alloys : Acta

Economical and technical efficiencies evaluation of full scale piggery wastewater treatment BNR plants.

PubMed

Oa, S W; Choi, E; Kim, S W; Kwon, K H; Min, K S

2009-01-01

A method evaluating the economic efficiency of piggery waste treatment plant based on kinetics for nitrogen removal performances is executed in this study and five full scale plants were evaluated, monitored intensively during one year under steady-state conditions. The performance data from those surveyed plants were recalculated by first-order kinetic equation instead of the Monod's equation, and the nitrogen removal kinetics related with COD/TKN ratios. Two plants adapting two extreme strategies for pre treatment, 'excess phase separation', and 'minimum phase separation', were evaluated by the assessment of life cycle cost (LCC). Although the compared two plants use an opposite strategy to each other, similar evaluation results are deduced by nitrogen removal efficiencies and operational and construction costs. But the proportions of constituent elements are as different as two opposite strategies, so electrical and construction costs are inversely proportional to chemical costs and operational costs respectively.

Approach for discrimination and quantification of electroactive species: kinetics difference revealed by higher harmonics of Fourier transformed sinusoidal voltammetry.

PubMed

Fang, Yishan; Huang, Xinjian; Wang, Lishi

2015-01-06

Discrimination and quantification of electroactive species are traditionally realized by a potential difference which is mainly determined by thermodynamics. However, the resolution of this approach is limited to tens of millivolts. In this paper, we described an application of Fourier transformed sinusoidal voltammetry (FT-SV) that provides a new approach for discrimination and quantitative evaluation of electroactive species, especially thermodynamic similar ones. Numerical simulation indicates that electron transfer kinetics difference between electroactive species can be revealed by the phase angle of higher order harmonics of FT-SV, and the difference can be amplified order by order. Thus, even a very subtle kinetics difference can be amplified to be distinguishable at a certain order of harmonics. This method was verified with structurally similar ferrocene derivatives which were chosen as the model systems. Although these molecules have very close redox potential (<10 mV), discrimination and selective detection were achieved by as high as the thirteenth harmonics. The results demonstrated the feasibility and reliability of the method. It was also implied that the combination of the traditional thermodynamic method and this kinetics method can form a two-dimension resolved detection method, and it has the potential to extend the resolution of voltammetric techniques to a new level.

Understanding Performance Limitations to Enable High Performance Magnesium-Ion Batteries

DOE PAGES

Kim, Sun Ung; Perdue, Brian; Apblett, Christopher A.; ...

2016-05-18

We developed a mathematical model in order to investigate the performance limiting factors of Mg-ion battery with a Chevrel phase (Mg xMo 6S 8) cathode and a Mg metal anode. Furthermore, the model was validated using experimental data from the literature [Cheng et al., Chem. Mater., 26, 4904 (2014)]. Two electrochemical reactions of the Chevrel phase with significantly different kinetics and solid diffusion were included in the porous electrode model, which captured the physics sufficiently well to generate charge curves of five rates (0.1C–2C) for two different particle sizes. Limitation analysis indicated that the solid diffusion and kinetics in themore » higher-voltage plateau limit the capacity and increase the overpotential in the Cheng et al.’s thin (20-μm) electrodes. The model reveals that the performance of the cells with reasonable thickness would also be subject to electrolyte-phase limitations. Finally, the simulation also suggested that the polarization losses on discharge will be lower than that on charge, because of the differences in the kinetics and solid diffusion between the two reactions of the Chevrel phase.« less

Crystallization kinetics of GeTe phase-change thin films grown by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Sun, Xinxing; Thelander, Erik; Gerlach, Jürgen W.; Decker, Ulrich; Rauschenbach, Bernd

2015-07-01

Pulsed laser deposition was employed to the growth of GeTe thin films on Silicon substrates. X-ray diffraction measurements reveal that the critical crystallization temperature lies between 220 and 240 °C. Differential scanning calorimetry was used to investigate the crystallization kinetics of the as-deposited films, determining the activation energy to be 3.14 eV. Optical reflectivity and in situ resistance measurements exhibited a high reflectivity contrast of ~21% and 3-4 orders of magnitude drop in resistivity of the films upon crystallization. The results show that pulsed laser deposited GeTe films can be a promising candidate for phase-change applications.

Linear dispersion relation for the mirror instability in context of the gyrokinetic theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Porazik, Peter; Johnson, Jay R.

2013-10-15

The linear dispersion relation for the mirror instability is discussed in context of the gyrokinetic theory. The objective is to provide a coherent view of different kinetic approaches used to derive the dispersion relation. The method based on gyrocenter phase space transformations is adopted in order to display the origin and ordering of various terms.

Nonequilibrium magnetic properties in a two-dimensional kinetic mixed Ising system within the effective-field theory and Glauber-type stochastic dynamics approach.

PubMed

Ertaş, Mehmet; Deviren, Bayram; Keskin, Mustafa

2012-11-01

Nonequilibrium magnetic properties in a two-dimensional kinetic mixed spin-2 and spin-5/2 Ising system in the presence of a time-varying (sinusoidal) magnetic field are studied within the effective-field theory (EFT) with correlations. The time evolution of the system is described by using Glauber-type stochastic dynamics. The dynamic EFT equations are derived by employing the Glauber transition rates for two interpenetrating square lattices. We investigate the time dependence of the magnetizations for different interaction parameter values in order to find the phases in the system. We also study the thermal behavior of the dynamic magnetizations, the hysteresis loop area, and dynamic correlation. The dynamic phase diagrams are presented in the reduced magnetic field amplitude and reduced temperature plane and we observe that the system exhibits dynamic tricritical and reentrant behaviors. Moreover, the system also displays a double critical end point (B), a zero-temperature critical point (Z), a critical end point (E), and a triple point (TP). We also performed a comparison with the mean-field prediction in order to point out the effects of correlations and found that some of the dynamic first-order phase lines, which are artifacts of the mean-field approach, disappeared.

Vapor Wall Deposition in Chambers: Theoretical Considerations

NASA Astrophysics Data System (ADS)

McVay, R.; Cappa, C. D.; Seinfeld, J.

2014-12-01

In order to constrain the effects of vapor wall deposition on measured secondary organic aerosol (SOA) yields in laboratory chambers, Zhang et al. (2014) varied the seed aerosol surface area in toluene oxidation and observed a clear increase in the SOA yield with increasing seed surface area. Using a coupled vapor-particle dynamics model, we examine the extent to which this increase is the result of vapor wall deposition versus kinetic limitations arising from imperfect accommodation of organic species into the particle phase. We show that a seed surface area dependence of the SOA yield is present only when condensation of vapors onto particles is kinetically limited. The existence of kinetic limitation can be predicted by comparing the characteristic timescales of gas-phase reaction, vapor wall deposition, and gas-particle equilibration. The gas-particle equilibration timescale depends on the gas-particle accommodation coefficient αp. Regardless of the extent of kinetic limitation, vapor wall deposition depresses the SOA yield from that in its absence since vapor molecules that might otherwise condense on particles deposit on the walls. To accurately extrapolate chamber-derived yields to atmospheric conditions, both vapor wall deposition and kinetic limitations must be taken into account.

A KINETIC ANALYSIS OF THE ENDOGENOUS RESPIRATION OF BAKERS' YEAST

PubMed Central

Stier, T. J. B.; Stannard, J. N.

1936-01-01

The process of endogenous respiration of two strains of bakers' yeast, Saccharomyces cerevisiae, was examined kinetically. The rate of respiration with respect to time in a non-nutrient medium was found to exhibit two phases: (a) a period of constant rate of O2 consumption and CO2 production (R.Q. = 1) characteristic of cells with ample concentrations of stored material; (b) a first order decline in rate of respiration with respect to time, where the rate was proportional to the concentration of some substrate, S. (R.Q. = 1 throughout second phase.) The nature of this substrate was reexamined and the evidence summarized confirms the notion that it is a carbohydrate, probably glycogen. These phases of endogenous respiration were shown to depend upon the age of the culture and the amount of substrate available. PMID:19872942

In-situ laser ultrasonic measurement of the hcp to bcc transformation in commercially pure titanium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shinbine, A., E-mail: alyssa.shinbine@gmail.com; Garcin, T.; Sinclair, C.

2016-07-15

Using a novel in-situ laser ultrasonic technique, the evolution of longitudinal velocity was used to measure the α − β transformation during cyclic heating and cooling in commercially pure titanium. In order to quantify the transformation kinetics, it is shown that changes in texture can not be ignored. This is particularly important in the case of titanium where significant grain growth occurs in the β-phase leading to the ultrasonic wave sampling a decreasing number of grains on each thermal treatment cycle. Electron backscatter diffraction measurements made postmortem in the region where the ultrasonic pulse traveled were used to obtain anmore » estimate of such local texture and grain size changes. An analysis technique for including the anisotropy of wave velocity depending on local texture is presented and shown to give self consistent results for the transformation kinetics. - Highlights: • Laser ultrasound and EBSD interpret the hcp/bcc phase transformation in cp-Ti. • Grain growth and texture produced variation in velocity during similar treatments. • Texture was deconvoluted from phase addition to obtain transformation kinetics.« less

Quatenary structure of methemoglobin II. Pulse radiolysis study of the binding of oxygen to the valence-hybrid. Progress report, December 1, 1978-November 30, 1979

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chevion, M; Ilan, Y A; Samuni, A

1979-01-01

The pulse-radiolysis of solutions of adult human methemoglobin was used in order to reduce a single heme-iron within the protein tetramers. The valence-hybrids thus formed were reacted with oxygen. Kinetics of the reactions were studied. The effects of pH and inositol-hexaphosphate were examined. The kinetics of the ligation of oxygen to stripped valence-hybrids showed a single-phase behavior at the pH range 6.5 to 9. As the pH was lowered below 6.5 a second, slower phase became apparent. In the presence of IHP, above pH 8, the kinetics of oxygem binding was of a single phase. As the pH was loweredmore » a transition to a second, slower phase was noticed. Below pH 7 the slower phase was the only detectable one. The analysis of the relative contribution of the faster phase to the total reaction as a function of the pH showed a typical transition curve characterized by a pK = 7.5 and a Hill parameter n =2.9. On the basis it is concluded that human adult stripped methemoglobin resides in an R quarternary structure while the presence of IHP stabilizes the T structure at pH below 7.5.« less

Measurement of collective dynamical mass of Dirac fermions in graphene.

PubMed

Yoon, Hosang; Forsythe, Carlos; Wang, Lei; Tombros, Nikolaos; Watanabe, Kenji; Taniguchi, Takashi; Hone, James; Kim, Philip; Ham, Donhee

2014-08-01

Individual electrons in graphene behave as massless quasiparticles. Unexpectedly, it is inferred from plasmonic investigations that electrons in graphene must exhibit a non-zero mass when collectively excited. The inertial acceleration of the electron collective mass is essential to explain the behaviour of plasmons in this material, and may be directly measured by accelerating it with a time-varying voltage and quantifying the phase delay of the resulting current. This voltage-current phase relation would manifest as a kinetic inductance, representing the reluctance of the collective mass to accelerate. However, at optical (infrared) frequencies, phase measurements of current are generally difficult, and, at microwave frequencies, the inertial phase delay has been buried under electron scattering. Therefore, to date, the collective mass in graphene has defied unequivocal measurement. Here, we directly and precisely measure the kinetic inductance, and therefore the collective mass, by combining device engineering that reduces electron scattering and sensitive microwave phase measurements. Specifically, the encapsulation of graphene between hexagonal boron nitride layers, one-dimensional edge contacts and a proximate top gate configured as microwave ground together enable the inertial phase delay to be resolved from the electron scattering. Beside its fundamental importance, the kinetic inductance is found to be orders of magnitude larger than the magnetic inductance, which may be utilized to miniaturize radiofrequency integrated circuits. Moreover, its bias dependency heralds a solid-state voltage-controlled inductor to complement the prevalent voltage-controlled capacitor.

Nanoscale Properties of Rocks and Subduction Zone Rheology: Inferences for the Mechanisms of Deep Earthquakes

NASA Astrophysics Data System (ADS)

Riedel, M. R.

2007-12-01

Grain boundaries are the key for the understanding of mineral reaction kinetics. More generally, nanometer scale processes involved in breaking and establishing bonds at reaction sites determine how and at which rate bulk rock properties change in response to external tectonic forcing and possibly feed back into various geodynamic processes. A particular problem is the effects of grain-boundary energy on the kinetics of the olivine-spinel phase transformation in subducting slabs. Slab rheology is affected in many ways by this (metastable) mineral phase change. Sluggish kinetics due to metastable hindrance is likely to cause particular difficulties, because of possible strong non-linear feedback loops between strain-rate and change of creep properties during transformation. In order to get these nanoscale properties included into thermo-mechanical models, reliable kinetic data is required. The measurement of grain-boundary energies is, however, a rather difficult problem. Conventional methods of grain boundary surface tension measurement include (a) equilibrium angles at triple junction (b) rotating ball method (c) thermal groove method, and others (Gottstein & Shvindlerman, 1999). Here I suggest a new method that allows for the derivation of grain-boundary energies for an isochemical phase transformation based on experimental (in-situ) kinetic data in combination with a corresponding dynamic scaling law (Riedel and Karato, 1997). The application of this method to the olivine-spinel phase transformation in subducting slabs provides a solution to the extrapolation problem of measured kinetic data: Any kinetic phase boundary measured at the laboratory time scale can be "scaled" to the correct critical isotherm at subduction zones, under experimentelly "forbidden" conditions (Liou et al., 2000). Consequences for the metastability hypothesis that relates deep seismicity with olivine metastability are derived and discussed. References: Gottstein G, Shvindlerman LS (1999) Grain Boundary Migration in Metals, CRC Press, 385 pp., New York. Riedel MR, Karato S (1997) Grain-Size Evolution in Subducted Oceanic Lithosphere Associated with the Olivine- Spinel Transformation and Its Effects on Rheology. EPSL 148: 27-43. Liou JG, Hacker BR, Zhang RY (2000) Into the forbidden zone. Science 287, 1215-1216.

Kinetics and mechanism of the pressure-induced lamellar order/disorder transition in phosphatidylethanolamine: a time-resolved X-ray diffraction study.

PubMed

Mencke, A P; Caffrey, M

1991-03-05

By using synchrotron radiation, a movie was made of the X-ray scattering pattern from a biological liquid crystal undergoing a phase transition induced by a pressure jump. The system studied includes the fully hydrated phospholipid dihexadecylphosphatidylethanolamine in the lamellar gel (L beta') phase at a temperature of 68 degrees C and a pressure of 9.7 MPa (1400 psig). Following the rapid release of pressure to atmospheric the L beta' phase transforms slowly into the lamellar liquid crystal (L alpha) phase. The pressure perturbation is applied with the intention of producing a sudden phase disequilibrium followed by monitoring the system as it relaxes to its new equilibrium condition. Remarkably, the proportion of sample in the L alpha phase grows linearly with time, taking 37 s to totally consume the L beta' phase. The time dependencies of radius, peak intensity, and width of the powder diffraction ring of the low-angle (001) lamellar reflections were obtained from the movie by image processing. The concept of an "effective pressure" is introduced to account for the temperature variations that accompany the phase transition and to establish that the observed large transit time is indeed intrinsic to the sample and not due to heat exchange with the environment. The reverse transformation, L alpha to L beta', induced by a sudden jump from atmospheric pressure to 9.7 MPa, is complete in less than 13 s. These measurements represent a new approach for studying the kinetics of lipid phase transitions and for gaining insights into the mechanism of the lamellar order/disorder transition.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Nucleation of stoichiometric compounds from liquid: Role of the kinetic factor

NASA Astrophysics Data System (ADS)

Song, H.; Sun, Y.; Zhang, F.; Wang, C. Z.; Ho, K. M.; Mendelev, M. I.

2018-02-01

The nucleation rate depends on the free-energy barrier and the kinetic factor. While the role of the free energy barrier is a text-book subject, the importance of the kinetic factor is frequently underestimated. In this study, we applied the mean first-passage time method, to obtain the free-energy landscape and kinetic factor directly from the molecular dynamics (MD) simulations of the nucleation of the face-centered cubic (fcc) phase in the pure Ni and the B2 phases in the N i50A l50 and C u50Z r50 alloys. The obtained data show that while the free-energy barrier for nucleation is higher in pure Ni the nucleation rate is considerably lower in the N i50A l50 alloy. This result can be explained by the slow attachment kinetics in the N i50A l50 alloy, which was related to the ordered nature of the B2 phase. Even smaller fraction of the antisite defects in the C u50Z r50 alloy leads to such a slow attachment kinetics that the nucleation is never observed for this alloy in the course of the MD simulation. This is consistent with the experimental facts that the C u50Z r50 alloy is a good glass forming alloy and the N i50A l50 alloy is not. Thus the present study demonstrates that the atom attachment rate can be the critical factor that controls the nucleation process under certain conditions.

Theoretical study of the gas-phase structures of sodiated and cesiated leucine and isoleucine: zwitterionic structure disfavored in kinetic method experiments.

PubMed

Rozman, Marko

2005-10-01

The most stable charge-solvated (CS) and zwitterionic (ZW) structures of sodiated and cesiated leucine and isoleucine were studied by density functional theory methods. According to the Boltzmann distribution in gas phase, both forms of LeuNa+ and IleNa+ exist, but in LeuCs+ and IleCs+, the ZW forms are dominant. Results for the sodiated compounds are consistent with the relationship found between decrease in relative stability of CS versus ZW form and aliphatic amino acid side chain length. The observed degeneracy in energy for IleNa+ conformers is at odds with kinetic method results. Additional calculations showed that kinetic method structural determinations for IleNa+ do not reflect relative order of populations in the lowest energy conformers. Since complexation of cationized amino acids into ion-bound dimers disfavors ZW structure by approximately 8 kJ mol(-1), it is suggested that for energy close conformers of sodium-cationized amino acids, the kinetic method may not be reliable for structural determinations. Copyright (c) 2005 John Wiley & Sons, Ltd.

Kinetics studies of d-glucose hydrogenation over activated charcoal supported platinum catalyst

NASA Astrophysics Data System (ADS)

Ahmed, Muthanna J.

2012-02-01

The kinetics of the catalytic hydrogenation of d-glucose to produce d-sorbitol was studied in a three-phase laboratory scale reactor. The hydrogenation reactions were performed on activated charcoal supported platinum catalyst in the temperature range 25-65°C and in a constant pressure of 1 atm. The kinetic data were modeled by zero, first and second-order reaction equations. In the operating regimes studied, the results show that the hydrogenation reaction was of a first order with respect to d-glucose concentration. Also the activation energy of the reaction was determined, and found to be 12.33 kJ mole-1. A set of experiment was carried out to test the deactivation of the catalyst, and the results show that the deactivation is slow with the ability of using the catalyst for several times with a small decrease in product yield.

Extensional Flow-Induced Dynamic Phase Transitions in Isotactic Polypropylene.

PubMed

Ju, Jianzhu; Wang, Zhen; Su, Fengmei; Ji, Youxin; Yang, Haoran; Chang, Jiarui; Ali, Sarmad; Li, Xiangyang; Li, Liangbin

2016-09-01

With a combination of fast extension rheometer and in situ synchrotron radiation ultra-fast small- and wide-angle X-ray scattering, flow-induced crystallization (FIC) of isotactic polypropylene (iPP) is studied at temperatures below and above the melting point of α crystals (Tmα). A flow phase diagram of iPP is constructed in strain rate-temperature space, composing of melt, non-crystalline shish, α and α&β coexistence regions, based on which the kinetic and dynamic competitions among these four phases are discussed. Above Tmα , imposing strong flow reverses thermodynamic stabilities of the disordered melt and the ordered phases, leading to the occurrence of FIC of β and α crystals as a dynamic phase transition. Either increasing temperature or stain rate favors the competiveness of the metastable β over the stable α crystals, which is attributed to kinetic rate rather than thermodynamic stability. The violent competitions among four phases near the boundary of crystal-melt may frustrate crystallization and result in the non-crystalline shish winning out. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation.

PubMed

Birch, Heidi; Hammershøj, Rikke; Comber, Mike; Mayer, Philipp

2017-10-01

Biodegradation is a dominant removal process for many organic pollutants, and biodegradation tests serve as tools for assessing their environmental fate within regulatory risk assessment. In simulation tests, the inoculum is not standardized, varying in microbial quantity and quality, thereby potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng-μg/L levels. Automated Headspace Solid Phase Microextraction coupled to GC-MS was applied directly to these test systems to determine substrate depletion relative to abiotic controls. Lag phases were generally less than 8 days. First order rate constants were within one order of magnitude for each hydrocarbon in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter than or within one order of magnitude of BioHCwin predictions for 8 of 9 hydrocarbons. These results showed that location choice is important for biodegradation kinetics and can provide a relevant input to aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

Pharmacokinetics of insulin following intravenous and subcutaneous administration in canines.

PubMed

Ravis, W R; Comerci, C; Ganjam, V K

1986-01-01

Studies were conducted to examine the absorption and disposition kinetics of insulin in dogs following intravenous (IV) and subcutaneous (SC) administration of commercial preparations. After IV and SC dosing, the plasma levels were described by models which considered basal insulin level contributions. Intersubject variation in the disposition kinetics was small with half-lives of 0.52 +/- 0.05 h and total body clearances of 16.21 +/- 2.08 ml min-1 kg-1. Calculated insulin plasma secretion rates in the canines were 14.4 +/- 3.3 mUh-1 kg-1. Following SC injection of regular insulin, the rate and extent of absorption were noted to be quite variable. The absorption process appeared first-order with half-life values of 2.3 +/- 1.3 h and extents of absorption of 78 +/- 15 per cent with a range of 55-101 per cent. Insulin absorption from SC NPH preparations was evaluated as being composed of two zero-order release phases, a rapid and a slow release phase. With a dose of 1.65 U kg-1, the rapid release phase had an average duration of 1.5 h and a rate of 580 +/- 269 mUh-1 (4.2 per cent of dose) while the slow phase had a zero-order rate of 237 +/- 92 mU h-1 which continued beyond 12 h. The extent of absorption from the NPH preparation was 23.6 +/- 5.1 per cent and was significantly lower than that for the regular injection.

Hierarchical Freezing in a Lattice Model

NASA Astrophysics Data System (ADS)

Byington, Travis W.; Socolar, Joshua E. S.

2012-01-01

A certain two-dimensional lattice model with nearest and next-nearest neighbor interactions is known to have a limit-periodic ground state. We show that during a slow quench from the high temperature, disordered phase, the ground state emerges through an infinite sequence of phase transitions. We define appropriate order parameters and show that the transitions are related by renormalizations of the temperature scale. As the temperature is decreased, sublattices with increasingly large lattice constants become ordered. A rapid quench results in a glasslike state due to kinetic barriers created by simultaneous freezing on sublattices with different lattice constants.

Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.

Core–shell PdPb@Pd aerogels with multiply-twinned intermetallic nanostructures: facile synthesis with accelerated gelation kinetics and their enhanced electrocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang

Delicately engineering the well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported one-pot and facile method for synthesizing core-shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 hrs, far faster than the previous reports. Owe to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performancemore » towards ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.Core–shell PdPb@Pd aerogels with multiply-twinned grains and an ordered intermetallic phase was synthesized, which exhibited good electrocatalytic activity towards ethanol oxidation.« less

Nematic-like stable glasses without equilibrium liquid crystal phases

DOE Data Explorer

Gomez, Jaritza [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Gujral, Ankit [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Huang, Chengbin [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Bishop, Camille [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA; Yu, Lian [School of Pharmacy, University of Wisconsin-Madison, 777 Highland Avenue, Madison, Wisconsin 53705-2222, USA; Ediger, Mark [Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin 53706, USA

2017-02-01

We report the thermal and structural properties of glasses of posaconazole, a rod-like molecule, prepared using physical vapor deposition (PVD). PVD glasses of posaconazole can show substantial molecular orientation depending upon the choice of substrate temperature, Tsubstrate, during deposition.Ellipsometry and IR measurements indicate that glasses prepared at Tsubstrate very near the glass transition temperature (Tg) are highly ordered. For these posaconazole glasses, the orientation order parameter is similar to that observed in macroscopically aligned nematic liquid crystals, indicating that the molecules are mostly parallel to one another and perpendicular to the interface. To our knowledge, these are the most anisotropic glasses ever prepared by PVD from a molecule that does not form equilibrium liquid crystal phases. These results are consistent with a previously proposed mechanism in which molecular orientation in PVD glasses is inherited from the orientation present at the free surface of the equilibrium liquid. This mechanism suggests that molecular orientation at the surface of the equilibrium liquid of posaconazole is nematic-like. Posaconazole glasses can show very high kinetic stability; the isothermal transformation of a 400 nm glass into the supercooled liquid occurs via a propagating front that originates at the free surface and requires ~105 times the structural relaxation time of the liquid (τα). We also studied the kinetic stability of PVD glasses of itraconazole, which is a structurally similar molecule with equilibrium liquid crystal phases. While itraconazole glasses can be even more anisotropic than posaconazole glasses, they exhibit lower kinetic stability.

Revisiting thermodynamics and kinetic diffusivities of uranium–niobium with Bayesian uncertainty analysis

DOE PAGES

Duong, Thien C.; Hackenberg, Robert E.; Landa, Alex; ...

2016-09-20

In this paper, thermodynamic and kinetic diffusivities of uranium–niobium (U–Nb) are re-assessed by means of the CALPHAD (CALculation of PHAse Diagram) methodology. In order to improve the consistency and reliability of the assessments, first-principles calculations are coupled with CALPHAD. In particular, heats of formation of γ -U–Nb are estimated and verified using various density-functional theory (DFT) approaches. These thermochemistry data are then used as constraints to guide the thermodynamic optimization process in such a way that the mutual-consistency between first-principles calculations and CALPHAD assessment is satisfactory. In addition, long-term aging experiments are conducted in order to generate new phase equilibriamore » data at the γ 2/α+γ 2 boundary. These data are meant to verify the thermodynamic model. Assessment results are generally in good agreement with experiments and previous calculations, without showing the artifacts that were observed in previous modeling. The mutual-consistent thermodynamic description is then used to evaluate atomic mobility and diffusivity of γ-U–Nb. Finally, Bayesian analysis is conducted to evaluate the uncertainty of the thermodynamic model and its impact on the system's phase stability.« less

Kinetics from Replica Exchange Molecular Dynamics Simulations.

PubMed

Stelzl, Lukas S; Hummer, Gerhard

2017-08-08

Transitions between metastable states govern many fundamental processes in physics, chemistry and biology, from nucleation events in phase transitions to the folding of proteins. The free energy surfaces underlying these processes can be obtained from simulations using enhanced sampling methods. However, their altered dynamics makes kinetic and mechanistic information difficult or impossible to extract. Here, we show that, with replica exchange molecular dynamics (REMD), one can not only sample equilibrium properties but also extract kinetic information. For systems that strictly obey first-order kinetics, the procedure to extract rates is rigorous. For actual molecular systems whose long-time dynamics are captured by kinetic rate models, accurate rate coefficients can be determined from the statistics of the transitions between the metastable states at each replica temperature. We demonstrate the practical applicability of the procedure by constructing master equation (Markov state) models of peptide and RNA folding from REMD simulations.

Curing kinetics of visible light curing dental resin composites investigated by dielectric analysis (DEA).

PubMed

Steinhaus, Johannes; Hausnerova, Berenika; Haenel, Thomas; Großgarten, Mandy; Möginger, Bernhard

2014-03-01

During the curing process of light curing dental composites the mobility of molecules and molecule segments is reduced leading to a significant increase of the viscosity as well as the ion viscosity. Thus, the kinetics of the curing behavior of 6 different composites was derived from dielectric analysis (DEA) using especially redesigned flat sensors with interdigit comb electrodes allowing for irradiation at the top side and measuring the ion viscosity at the bottom side. As the ion viscosities of dental composites change 1-3 orders of magnitude during the curing process, DEA provides a sensitive approach to evaluate their curing behavior, especially in the phase of undisturbed chain growth. In order to determine quantitative kinetic parameters a kinetic model is presented and examined for the evaluation of the ion viscosity curves. From the obtained results it is seen that DEA might be employed in the investigation of the primary curing process, the quality assurance of ingredients as well as the control of processing stability of the light curing dental composites. Copyright © 2014 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A kinetic rate model for crystalline basalt dissolution at temperature and pressure conditions relevant for geologic CO2 sequestration

NASA Astrophysics Data System (ADS)

Pollyea, R.; Rimstidt, J. D.

2016-12-01

Geologic carbon sequestration in terrestrial basalt reservoirs is predicated on permanent CO2 trapping through CO2-water-rock dissolution reactions followed by carbonate precipitation. Bench-scale experiments have shown these reaction paths to be rapid, occurring on a timescale 100 - 102 years. Moreover, recent results from the CarbFix basalt sequestration pilot project in Iceland demonstrate >95% CO2 isolation two years after a small-scale injection. In order to assess the viability of basalt sequestration worldwide (e.g., Deccan Traps, Columbia Plateau, etc.), flexible simulation tools are required that distill the dissolution reactions into a user-friendly format that is readily transmissible to existing reactive transport numerical simulators. In the present research, we combine experimental results extant in the literature for Icelandic basalt to develop kinetic rate models describing the pH-dependent dissolution of (1) basaltic glass and (2) an aggregate mineral assemblage for crystalline basalt comprising olivine, pyroxene, and plagioclase phases. In order to utilize these kinetic rate models with numerical simulation, a thermodynamic solubility model for each phase is developed for use with the reactive transport simulation code, TOUGHREACT. We use reactive transport simulation in a simple 1-D reactor to compare dissolution of the aggregate crystalline basalt phase with the traditional formulation comprising individual mineral phases for the crystalline basalt. Simulation results are in general agreement, illustrating the efficacy of this simplified approach for modeling basalt dissolution at temperature and pressure conditions typical of geologic CO2 reservoirs. Moreover, this approach may be of value to investigators seeking dissolution models for crystalline basalt in other mafic provinces.

Effects of Transition-Metal Mixing on Na Ordering and Kinetics in Layered P 2 Oxides

NASA Astrophysics Data System (ADS)

Zheng, Chen; Radhakrishnan, Balachandran; Chu, Iek-Heng; Wang, Zhenbin; Ong, Shyue Ping

2017-06-01

Layered P 2 oxides are promising cathode materials for rechargeable sodium-ion batteries. In this work, we systematically investigate the effects of transition-metal (TM) mixing on Na ordering and kinetics in the NaxCo1 -yMnyO2 model system using density-functional-theory (DFT) calculations. The DFT-predicted 0-K stability diagrams indicate that Co-Mn mixing reduces the energetic differences between Na orderings, which may account for the reduction of the number of phase transformations observed during the cycling of mixed-TM P 2 layered oxides compared to a single TM. Using ab initio molecular-dynamics simulations and nudged elastic-band calculations, we show that the TM composition at the Na(1) (face-sharing) site has a strong influence on the Na site energies, which in turn impacts the kinetics of Na diffusion towards the end of the charge. By employing a site-percolation model, we establish theoretical upper and lower bounds for TM concentrations based on their effect on Na(1) site energies, providing a framework to rationally tune mixed-TM compositions for optimal Na diffusion.

Effect of liquid droplets on turbulence in a round gaseous jet

NASA Technical Reports Server (NTRS)

Mostafa, A. A.; Elghobashi, S. E.

1986-01-01

The main objective of this investigation is to develop a two-equation turbulence model for dilute vaporizing sprays or in general for dispersed two-phase flows including the effects of phase changes. The model that accounts for the interaction between the two phases is based on rigorously derived equations for turbulence kinetic energy (K) and its dissipation rate epsilon of the carrier phase using the momentum equation of that phase. Closure is achieved by modeling the turbulent correlations, up to third order, in the equations of the mean motion, concentration of the vapor in the carrier phase, and the kinetic energy of turbulence and its dissipation rate for the carrier phase. The governing equations are presented in both the exact and the modeled formes. The governing equations are solved numerically using a finite-difference procedure to test the presented model for the flow of a turbulent axisymmetric gaseous jet laden with either evaporating liquid droplets or solid particles. The predictions include the distribution of the mean velocity, volume fractions of the different phases, concentration of the evaporated material in the carrier phase, turbulence intensity and shear stress of the carrier phase, droplet diameter distribution, and the jet spreading rate. The predictions are in good agreement with the experimental data.

Theoretical Studies of the Kinetics of First-Order Phase Transitions.

NASA Astrophysics Data System (ADS)

Zheng, Qiang

This thesis involves theoretical studies of the kinetics of orderings in three classes of systems. The first class involves problems of phase separation in which the order parameter is conserved, such as occurs in the binary alloy Al-Zn. A theory is developed for the late stages of phase separation in the droplet regime for two -dimensional systems, namely, Ostwald ripening in two dimensions. The theory considers droplet correlations, which was neglected before, by a proper treatment of the screening effect of the correlations. This correlation effect is found that it does not alert the scaling features of phase separation, but significantly changes the shape of droplet-size distribution function. Further experiments and computer simulations are needed before this long-time subject may be closed. A second class of problem involves a study of the finite-size effects on domain growth described by the Allen-Cahn dynamics. Based on a theoretical approach of Ohta, Jasnow, and Kawasaki the explicit scaling functions for the scattering intensity for hypercubes and films are obtained. These results are for the cases in which the order-parameter is not conserved, such as in an order-disorder transition in alloys. These studies will be relevant to the experimental and computer simulation research projects currently being carried out in the United States and Europe. The last class of problems involves orderings in strong correlated systems, namely, the growth of Breath Figures. A special feature of this class of problems is that the coalescence effect. A theoretical model is proposed which can handle the two growth mechanisms, the individual droplet growth and coalescence simultaneously. Under certain approximations, the droplet-size distribution function is obtained analytically, and is in qualitative agreement with computer simulations. Our model also suggests that there may be an interesting relationship between the growth of Breath Figures and a geometric structure (ultrametricity) of general complex systems.

Kinetics of Cr/Mo-rich precipitates formation for 25Cr-6.9Ni-3.8Mo-0.3N super duplex stainless steel

NASA Astrophysics Data System (ADS)

Byun, Sang-Ho; Kang, Namhyun; Lee, Tae-Ho; Ahn, Sang-Kon; Lee, Hae Woo; Chang, Woong-Seong; Cho, Kyung-Mox

2012-04-01

The amount and composition of Cr-rich (σ) and Mo-rich (χ) precipitates in super duplex stainless steels was analyzed. An isothermal heat treatment was conducted at temperatures ranging from 700 °C to 1000 °C for up to 10 days. A time-temperature transformation (TTT) diagram was constructed for the mixture of σ and χ phases. The mixture of the σ and χ phases exhibited the fastest rate of formation at approximately 900 °C. Minor phases, such as Cr2N, M23C6, and M7C3, were also detected using a transmission electron microscopy (TEM). Also, a continuous cooling transformation (CCT) diagram was constructed for the mixture of σ and χ phases using the Johnson-Mehl-Avrami equation. Compared with the known CCT diagram of the σ phase, this study revealed faster kinetics with an order of magnitude difference and a new CCT diagram was also developed for a mixture of σ and χ phases. The calculated fraction of σ and χ phases obtained at a cooling speed of 0.5 °C/s was in good agreement with the experimental data.

Modeling of batch sorber system: kinetic, mechanistic, and thermodynamic modeling

NASA Astrophysics Data System (ADS)

Mishra, Vishal

2017-10-01

The present investigation has dealt with the biosorption of copper and zinc ions on the surface of egg-shell particles in the liquid phase. Various rate models were evaluated to elucidate the kinetics of copper and zinc biosorptions, and the results indicated that the pseudo-second-order model was more appropriate than the pseudo-first-order model. The curve of the initial sorption rate versus the initial concentration of copper and zinc ions also complemented the results of the pseudo-second-order model. Models used for the mechanistic modeling were the intra-particle model of pore diffusion and Bangham's model of film diffusion. The results of the mechanistic modeling together with the values of pore and film diffusivities indicated that the preferential mode of the biosorption of copper and zinc ions on the surface of egg-shell particles in the liquid phase was film diffusion. The results of the intra-particle model showed that the biosorption of the copper and zinc ions was not dominated by the pore diffusion, which was due to macro-pores with open-void spaces present on the surface of egg-shell particles. The thermodynamic modeling reproduced the fact that the sorption of copper and zinc was spontaneous, exothermic with the increased order of the randomness at the solid-liquid interface.

Metastable Superconductivity in Two-Dimensional IrTe2 Crystals.

PubMed

Yoshida, Masaro; Kudo, Kazutaka; Nohara, Minoru; Iwasa, Yoshihiro

2018-05-09

Two-dimensional (2D) materials exhibit unusual physical and chemical properties that are attributed to the thinning-induced modification of their electronic band structure. Recently, reduced thickness was found to dramatically impact not only the static electronic structure, but also the dynamic ordering kinetics. The ordering kinetics of first-order phase transitions becomes significantly slowed with decreasing thickness, and metastable supercooled states can be realized by thinning alone. We therefore focus on layered iridium ditelluride (IrTe 2 ), a charge-ordering system that is transformed into a superconductor by suppressing its first-order transition. Here, we discovered a persistent superconducting zero-resistance state in mechanically exfoliated IrTe 2 thin flakes. The maximum superconducting critical temperature ( T c ) was identical to that which is chemically optimized, and the emergent superconductivity was revealed to have a metastable nature. The discovered robust metastable superconductivity suggests that 2D material is a new platform to induce, control, and functionalize metastable electronic states that are inaccessible in bulk crystals.

Toward a Multi-scale Phase Transition Kinetics Methodology: From Non-Equilibrium Statistical Mechanics to Hydrodynamics

NASA Astrophysics Data System (ADS)

Belof, Jonathan; Orlikowski, Daniel; Wu, Christine; McLaughlin, Keith

2013-06-01

Shock and ramp compression experiments are allowing us to probe condensed matter under extreme conditions where phase transitions and other non-equilibrium aspects can now be directly observed, but first principles simulation of kinetics remains a challenge. A multi-scale approach is presented here, with non-equilibrium statistical mechanical quantities calculated by molecular dynamics (MD) and then leveraged to inform a classical nucleation and growth kinetics model at the hydrodynamic scale. Of central interest is the free energy barrier for the formation of a critical nucleus, with direct NEMD presenting the challenge of relatively long timescales necessary to resolve nucleation. Rather than attempt to resolve the time-dependent nucleation sequence directly, the methodology derived here is built upon the non-equilibrium work theorem in order to bias the formation of a critical nucleus and thus construct the nucleation and growth rates. Having determined these kinetic terms from MD, a hydrodynamics implementation of Kolmogorov-Johnson-Mehl-Avrami (KJMA) kinetics and metastabilty is applied to the dynamic compressive freezing of water and compared with recent ramp compression experiments [Dolan et al., Nature (2007)] Lawrence Livermore National Laboratory is operated by Lawrence Livermore National Security, LLC, for the U.S. Department of Energy, National Nuclear Security Administration under Contract DE-AC52-07NA27344.

On the Nonequilibrium Interface Kinetics of Rapid Coupled Eutectic Growth

NASA Astrophysics Data System (ADS)

Dong, H.; Chen, Y. Z.; Shan, G. B.; Zhang, Z. R.; Liu, F.

2017-08-01

Nonequilibrium interface kinetics (NEIK) is expected to play an important role in coupled growth of eutectic alloys, when solidification velocity is high and intermetallic compound or topologically complex phases form in the crystallized product. In order to quantitatively evaluate the effect of NEIK on the rapid coupled eutectic growth, in this work, two nonequilibrium interface kinetic effects, i.e., atom attachment and solute trapping at the solid-liquid interface, were incorporated into the analyses of the coupled eutectic growth under the rapid solidification condition. First, a coupled growth model incorporating the preceding two nonequilibrium kinetic effects was derived. On this basis, an expression of kinetic undercooling (Δ T k), which is used to characterize the NEIK, was defined. The calculations based on the as-derived couple growth model show good agreement with the reported experimental results achieved in rapidly solidified eutectic Al-Sm alloys consisting of a solid solution phase ( α-Al) and an intermetallic compound phase (Al11Sm3). In terms of the definition of Δ T k defined in this work, the role of NEIK in the coupled growth of the Al-Sm eutectic system was analyzed. The results show that with increasing the coupled growth velocity, Δ T k increases continuously, and its ratio to the total undercooling reaches 0.32 at the maximum growth velocity for coupled eutectic growth. Parametric analyses on two key alloy parameters that influence Δ T k, i.e., interface kinetic parameter ( μ i ) and solute distribution coefficient ( k e ), indicate that both μ i and k e influence the NEIK significantly and the decrease of either these two parameters enhances the NEIK effect.

Kinetic Defects Induced by Melittin in Model Lipid Membranes: A Solution Atomic Force Microscopy Study.

PubMed

Pan, Jianjun; Khadka, Nawal K

2016-05-26

Quantitative characterization of membrane defects (pores) is important for elucidating the molecular basis of many membrane-active peptides. We study kinetic defects induced by melittin in vesicular and planar lipid bilayers. Fluorescence spectroscopy measurements indicate that melittin induces time-dependent calcein leakage. Solution atomic force microscopy (AFM) is used to visualize melittin-induced membrane defects. After initial equilibration, the most probable defect radius is ∼3.8 nm in 1,2-dilauroyl-sn-glycero-3-phosphocholine (DLPC) bilayers. Unexpectedly, defects become larger with longer incubation, accompanied by substantial shape transformation. The initial defect radius is ∼4.7 nm in 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayers. Addition of 30 mol % cholesterol to DOPC bilayers suppresses defect kinetics, although the inhibitory impact is negated by longer incubation. Overall, the kinetic rate of defect development follows DLPC > DOPC > DOPC/cholesterol. Kinetic defects are also observed when anionic lipids are present. Based on the observation that defects can occupy as large as 40% of the bilayer surface, we propose a kinetic defect growth model. We also study the effect of melittin on the phase behavior of DOPC/egg-sphingomyelin/cholesterol bilayers. We find that melittin initially suppresses or eliminates liquid-ordered (Lo) domains; Lo domains gradually emerge and become the dominant species with longer incubation; and defects in phase-coexisting bilayers have a most probable radius of ∼5 nm and are exclusively localized in the liquid-disordered (Ld) phase. Our experimental data highlight that melittin-induced membrane defects are not static; conversely, spontaneous defect growth is intrinsically associated with membrane permeabilization exerted by melittin.

Indistinguishability and identifiability of kinetic models for the MurC reaction in peptidoglycan biosynthesis.

PubMed

Hattersley, J G; Pérez-Velázquez, J; Chappell, M J; Bearup, D; Roper, D; Dowson, C; Bugg, T; Evans, N D

2011-11-01

An important question in Systems Biology is the design of experiments that enable discrimination between two (or more) competing chemical pathway models or biological mechanisms. In this paper analysis is performed between two different models describing the kinetic mechanism of a three-substrate three-product reaction, namely the MurC reaction in the cytoplasmic phase of peptidoglycan biosynthesis. One model involves ordered substrate binding and ordered release of the three products; the competing model also assumes ordered substrate binding, but with fast release of the three products. The two versions are shown to be distinguishable; however, if standard quasi-steady-state assumptions are made distinguishability cannot be determined. Once model structure uniqueness is ensured the experimenter must determine if it is possible to successfully recover rate constant values given the experiment observations, a process known as structural identifiability. Structural identifiability analysis is carried out for both models to determine which of the unknown reaction parameters can be determined uniquely, or otherwise, from the ideal system outputs. This structural analysis forms an integrated step towards the modelling of the full pathway of the cytoplasmic phase of peptidoglycan biosynthesis. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Rapid removal of bisphenol A on highly ordered mesoporous carbon.

PubMed

Sui, Qian; Huang, Jun; Liu, Yousong; Chang, Xiaofeng; Ji, Guangbin; Deng, Shubo; Xie, Tao; Yu, Gang

2011-01-01

Bisphenol A (BPA) is of global concern due to its disruption of endocrine systems and ubiquity in the aquatic environment. It is important, therefore, that efforts are made to remove it from the aqueous phase. A novel adsorbent, mesoporous carbon CMK-3, prepared from hexagonal SBA-15 mesoporous silica was studied for BPA removal from aqueous phase, and compared with conventional powdered activated carbon (PAC). Characterization of CMK-3 by transmission electron microscopy (TEM), X-ray diffraction, and nitrogen adsorption indicated that prepared CMK-3 had an ordered mesoporous structure with a high specific surface area of 920 m2/g and a pore-size of about 4.9 nm. The adsorption of BPA on CMK-3 followed a pseudo second-order kinetic model. The kinetic constant was 0.00049 g/(mg x min), much higher than the adsorption of BPA on PAC. The adsorption isotherm fitted slightly better with the Freundlich model than the Langmuir model, and adsorption capacity decreased as temperature increased from 10 to 40 degrees C. No significant influence of pH on adsorption was observed at pH 3 to 9; however, adsorption capacity decreased dramatically from pH 9 to 13.

Magnetostructural Transition Kinetics in Shocked Iron

DOE PAGES

Surh, Michael P.; Benedict, Lorin X.; Sadigh, Babak

2016-08-15

Here, a generalized Heisenberg model is implemented to study the effect of thermal magnetic disorder on kinetics of the Fe α–ε transition. The barrier to bulk martensitic displacement remains large in α-Fe shocked well past the phase line but is much reduced in the [001] α–ε boundary. The first result is consistent with observed overdriving to metastable α, while the second suggests structural instability, as implied by observation of a [001] shock transformation front without plastic relaxation. Reconciling both behaviors may require concurrent treatment of magnetic and structural order.

Simulation of 2D Kinetic Effects in Plasmas using the Grid Based Continuum Code LOKI

NASA Astrophysics Data System (ADS)

Banks, Jeffrey; Berger, Richard; Chapman, Tom; Brunner, Stephan

2016-10-01

Kinetic simulation of multi-dimensional plasma waves through direct discretization of the Vlasov equation is a useful tool to study many physical interactions and is particularly attractive for situations where minimal fluctuation levels are desired, for instance, when measuring growth rates of plasma wave instabilities. However, direct discretization of phase space can be computationally expensive, and as a result there are few examples of published results using Vlasov codes in more than a single configuration space dimension. In an effort to fill this gap we have developed the Eulerian-based kinetic code LOKI that evolves the Vlasov-Poisson system in 2+2-dimensional phase space. The code is designed to reduce the cost of phase-space computation by using fully 4th order accurate conservative finite differencing, while retaining excellent parallel scalability that efficiently uses large scale computing resources. In this poster I will discuss the algorithms used in the code as well as some aspects of their parallel implementation using MPI. I will also overview simulation results of basic plasma wave instabilities relevant to laser plasma interaction, which have been obtained using the code.

Kinetic modeling of n-hexane oxyfunctionalization by hydrogen peroxide on titanium silicalites of MEL structure (TS-2)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gallot, J.E.; Fu, H.; Kapoor, M.P.

The authors present mathematical models of catalytic oxyfunctionalization of n-hexane over titanium silicalites. The model showed second-order reaction rates with respect to H{sub 2}O{sub 2} concentration in the aqueous phase. 56 refs., 7 figs., 3 tabs.

Interlayer Communication in Aurivillius Vanadate to Enable Defect Structures and Charge Ordering.

PubMed

Zhang, Yaoqing; Yamamoto, Takafumi; Green, Mark A; Kageyama, Hiroshi; Ueda, Yutaka

2015-11-16

The fluorite-like [Bi2O2](2+) layer is a fundamental building unit in a great variety of layered compounds. Here in this contribution, we presented a comprehensive study on an unusual Aurivillius phase Bi3.6V2O10 with respect to its defect chemistry and polymorphism control as well as implications for fast oxide ion transport at lower temperatures. The bismuth oxide layer in Bi4V2O11 is found to tolerate a large number of Bi vacancies without breaking the high temperature prototype I4/mmm structure (γ-phase). On cooling, an orthorhombic distortion occurs to the γ-phase, giving rise to a different type of phase (B-phase) in the intermediate temperature region. Cooling to room temperature causes a further transition to an oxygen-vacancy ordered A-phase, which is accompanied by the charge ordering of V(4+) and V(5+) cations, providing magnetic (d(1)) and nonmagnetic (d(0)) chains along the a axis. This is a novel charge ordering transition in terms of the concomitant change of oxygen coordination. Interestingly, upon quenching, both the γ- and B-phase can be kinetically trapped, enabling the structural probing of the two phases at ambient temperature. Driven by the thermodynamic forces, the oxide anion in the γ-phase undergoes an interlayer diffusion process to reshuffle the compositions of both Bi-O and V-O layers.

Phase transformation mechanism in lithium manganese nickel oxide revealed by single-crystal hard X-ray microscopy

DOE PAGES

Kuppan, Saravanan; Xu, Yahong; Liu, Yijin; ...

2017-02-01

Understanding the reaction pathway and kinetics of solid-state phase transformation is critical in designing advanced electrode materials with better performance and stability. Despite the first-order phase transition with a large lattice mismatch between the involved phases, spinel LiMn 1.5Ni 0.5O 4 is capable of fast rate even at large particle size, presenting an enigma yet to be understood. The present study uses advanced two-dimensional and three-dimensional nano-tomography on a series of well-formed LixMn 1.5Ni 0.5O 4 (0 ≤ x ≤ 1) crystals to visualize the mesoscale phase distribution, as a function of Li content at the sub-particle level. Inhomogeneity alongmore » with the coexistence of Li-rich and Li-poor phases are broadly observed on partially delithiated crystals, providing direct evidence for a concurrent nucleation and growth process instead of a shrinking-core or a particle-by-particle process. As a result, superior kinetics of (100) facets at the vertices of truncated octahedral particles promote preferential delithiation, whereas the observation of strain-induced cracking suggests mechanical degradation in the material.« less

The Influence of Annealing Temperature and Time on the Formation of δ-Phase in Additively-Manufactured Inconel 625

NASA Astrophysics Data System (ADS)

Stoudt, M. R.; Lass, E. A.; Ng, D. S.; Williams, M. E.; Zhang, F.; Campbell, C. E.; Lindwall, G.; Levine, L. E.

2018-07-01

This research evaluated the kinetics of δ-phase growth in laser powder bed additively-manufactured (AM) Inconel 625 during post-build stress-relief heat treatments. The temperatures ranged between 650 °C and 1050 °C, and the times from 0.25 to 168 hours. The presence of δ-phase was verified for each temperature/time combination through multiple techniques. A conventional time-temperature-transformation diagram was constructed from the time-temperature data. Comparison to the growth in wrought IN625 with a similar nominal composition revealed that δ-phase formation occurred at least two orders of magnitude faster in the AM IN625. The results of this study also revealed that the segregated microstructure in the as-built condition has a strong influence on the kinetics of δ-phase formation in AM IN625 as compared to a homogenized material. Since control of the δ-phase growth is essential for reliable prediction of the performance of IN625 components in service, avoiding heat treatments that promote the formation of δ-phase in AM components that are not homogenized is highly recommended. This will be particularly true at elevated temperatures where the microstructural stability and the consistency of mechanical properties are more likely to be affected by the presence of δ-phase.

The Influence of Annealing Temperature and Time on the Formation of δ-Phase in Additively-Manufactured Inconel 625

NASA Astrophysics Data System (ADS)

Stoudt, M. R.; Lass, E. A.; Ng, D. S.; Williams, M. E.; Zhang, F.; Campbell, C. E.; Lindwall, G.; Levine, L. E.

2018-05-01

This research evaluated the kinetics of δ-phase growth in laser powder bed additively-manufactured (AM) Inconel 625 during post-build stress-relief heat treatments. The temperatures ranged between 650 °C and 1050 °C, and the times from 0.25 to 168 hours. The presence of δ-phase was verified for each temperature/time combination through multiple techniques. A conventional time-temperature-transformation diagram was constructed from the time-temperature data. Comparison to the growth in wrought IN625 with a similar nominal composition revealed that δ-phase formation occurred at least two orders of magnitude faster in the AM IN625. The results of this study also revealed that the segregated microstructure in the as-built condition has a strong influence on the kinetics of δ-phase formation in AM IN625 as compared to a homogenized material. Since control of the δ-phase growth is essential for reliable prediction of the performance of IN625 components in service, avoiding heat treatments that promote the formation of δ-phase in AM components that are not homogenized is highly recommended. This will be particularly true at elevated temperatures where the microstructural stability and the consistency of mechanical properties are more likely to be affected by the presence of δ-phase.

On-Line Analysis and Kinetic Behavior of Arsenic Release during Coal Combustion and Pyrolysis.

PubMed

Shen, Fenghua; Liu, Jing; Zhang, Zhen; Dai, Jinxin

2015-11-17

The kinetic behavior of arsenic (As) release during coal combustion and pyrolysis in a fluidized bed was investigated by applying an on-line analysis system of trace elements in flue gas. This system, based on inductively coupled plasma optical emission spectroscopy (ICP-OES), was developed to measure trace elements concentrations in flue gas quantitatively and continuously. Obvious variations of arsenic concentration in flue gas were observed during coal combustion and pyrolysis, indicating strong influences of atmosphere and temperature on arsenic release behavior. Kinetic laws governing the arsenic release during coal combustion and pyrolysis were determined based on the results of instantaneous arsenic concentration in flue gas. A second-order kinetic law was determined for arsenic release during coal combustion, and the arsenic release during coal pyrolysis followed a fourth-order kinetic law. The results showed that the arsenic release rate during coal pyrolysis was faster than that during coal combustion. Thermodynamic calculations were carried out to identify the forms of arsenic in vapor and solid phases during coal combustion and pyrolysis, respectively. Ca3(AsO4)2 and Ca(AsO2)2 are the possible species resulting from As-Ca interaction during coal combustion. Ca(AsO2)2 is the most probable species during coal pyrolysis.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

PubMed

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Direct high-performance liquid chromatography method with refractometric detection designed for stability studies of treosulfan and its biologically active epoxy-transformers.

PubMed

Główka, Franciszek K; Romański, Michał; Teżyk, Artur; Żaba, Czesław

2013-01-01

Treosulfan (TREO) is an alkylating agent registered for treatment of advanced platin-resistant ovarian carcinoma. Nowadays, TREO is increasingly applied iv in high doses as a promising myeloablative agent with low organ toxicity in children. Under physiological conditions it undergoes pH-dependent transformation into epoxy-transformers (S,S-EBDM and S,S-DEB). The mechanism of this reaction is generally known, but not its kinetic details. In order to investigate kinetics of TREO transformation, HPLC method with refractometric detection for simultaneous determination of the three analytes in one analytical run has been developed for the first time. The samples containing TREO, S,S-EBDM, S,S-DEB and acetaminophen (internal standard) were directly injected onto the reversed phase column. To assure stability of the analytes and obtain their complete resolution, mobile phase composed of acetate buffer pH 4.5 and acetonitrile was applied. The linear range of the calibration curves of TREO, S,S-EBDM and S,S-DEB spanned concentrations of 20-6000, 34-8600 and 50-6000 μM, respectively. Intra- and interday precision and accuracy of the developed method fulfilled analytical criteria. The stability of the analytes in experimental samples was also established. The validated HPLC method was successfully applied to the investigation of the kinetics of TREO activation to S,S-EBDM and S,S-DEB. At pH 7.4 and 37 °C the transformation of TREO followed first-order kinetics with a half-life 1.5h. Copyright © 2012 Elsevier B.V. All rights reserved.

A comparison of G2 phase radiation-induced chromatid break kinetics using calyculin-PCC with those obtained using colcemid block.

PubMed

Bryant, Peter E; Mozdarani, Hossein

2007-09-01

To study the possible influence of cell-cycle delay on cells reaching mitosis during conventional radiation-induced chromatid break experiments using colcemid as a blocking agent, we have compared the chromatid break kinetics following a single dose of gamma rays (0.75 Gy) in metaphase CHO cells using calyculin-induced premature chromosome condensation (PCC), with those using colcemid block. Calyculin-induced PCC causes very rapid condensation of G2 cell chromosomes without the need for a cell to progress to mitosis, hence eliminating any effect of cell-cycle checkpoint on chromatid break frequency. We found that the kinetics of the exponential first-order decrease in chromatid breaks with time after irradiation was similar (not significantly different) between the two methods of chromosome condensation. However, use of the calyculin-PCC technique resulted in a slightly increased rate of disappearance of chromatid breaks and thus higher frequencies of breaks at 1.5 and 2.5 h following irradiation. We also report on the effect of the nucleoside analogue ara A on chromatid break kinetics using the two chromosome condensation techniques. Ara A treatment of cells abrogated the decrease in chromatid breaks with time, both using the calyculin-PCC and colcemid methods. We conclude that cell-cycle delay may be a factor determining the absolute frequency of chromatid breaks at various times following irradiation of cells in G2 phase but that the first-order disappearance of chromatid breaks with time and its abrogation by ara A are not significantly influenced by the G2 checkpoint.

Spiral magnetic order and pressure-induced superconductivity in transition metal compounds.

PubMed

Wang, Yishu; Feng, Yejun; Cheng, J-G; Wu, W; Luo, J L; Rosenbaum, T F

2016-10-06

Magnetic and superconducting ground states can compete, cooperate and coexist. MnP provides a compelling and potentially generalizable example of a material where superconductivity and magnetism may be intertwined. Using a synchrotron-based non-resonant X-ray magnetic diffraction technique, we reveal a spiral spin order in MnP and trace its pressure evolution towards superconducting order via measurements in a diamond anvil cell. Judging from the magnetostriction, ordered moments vanish at the quantum phase transition as pressure increases the electron kinetic energy. Spins remain local in the disordered phase, and the promotion of superconductivity is likely to emerge from an enhanced coupling to residual spiral spin fluctuations and their concomitant suppression of phonon-mediated superconductivity. As the pitch of the spiral order varies across the 3d transition metal compounds in the MnP family, the magnetic ground state switches between antiferromagnet and ferromagnet, providing an additional tuning parameter in probing spin-fluctuation-induced superconductivity.

Dynamo onset as a first-order transition: lessons from a shell model for magnetohydrodynamics.

PubMed

Sahoo, Ganapati; Mitra, Dhrubaditya; Pandit, Rahul

2010-03-01

We carry out systematic and high-resolution studies of dynamo action in a shell model for magnetohydrodynamic (MHD) turbulence over wide ranges of the magnetic Prandtl number PrM and the magnetic Reynolds number ReM. Our study suggests that it is natural to think of dynamo onset as a nonequilibrium first-order phase transition between two different turbulent, but statistically steady, states. The ratio of the magnetic and kinetic energies is a convenient order parameter for this transition. By using this order parameter, we obtain the stability diagram (or nonequilibrium phase diagram) for dynamo formation in our MHD shell model in the (PrM-1,ReM) plane. The dynamo boundary, which separates dynamo and no-dynamo regions, appears to have a fractal character. We obtain a hysteretic behavior of the order parameter across this boundary and suggestions of nucleation-type phenomena.

Lead and vanadium removal from a real industrial wastewater by gravitational settling/sedimentation and sorption onto Pinus sylvestris sawdust.

PubMed

Kaczala, F; Marques, M; Hogland, W

2009-01-01

Batch sorption with untreated Pinus sylvestris sawdust after settling/sedimentation phase to remove vanadium and lead from a real industrial wastewater was investigated using different adsorbent doses, initial pH, and contact time. The development of pH along the sorption test and a parallel investigation of metals release from sawdust in distilled water were carried out. In order to evaluate kinetic parameters and equilibrium isotherms, Lagergren first-order, pseudo-second-order, intra-particle diffusion and Freundlich models were explored. When the initial pH was reduced from 7.4 to 4.0, the sorption efficiency increased from 32% to 99% for Pb and from 43% to 95% for V. Whereas, V removal was positively correlated with the adsorbent dose, Pb removal was not. The sorption process was best described by pseudo-second-order kinetics. According to Freundlich parameters (K(f) and n) sawdust presented unfavourable intensity for sorption of V.

Kinetics and mechanism of electron transfer reaction of single and double chain surfactant cobalt(III) complex by Fe2+ ions in liposome (dipalmitoylphosphotidylcholine) vesicles: effects of phase transition

NASA Astrophysics Data System (ADS)

Nagaraj, Karuppiah; Senthil Murugan, Krishnan; Thangamuniyandi, Pilavadi

2015-05-01

In this study, we report the kinetics of reduction reactions of single and double chain surfactant cobalt(III) complexes of octahedral geometry, cis-[Co(en)2(4AMP)(DA)](ClO4)3 and cis-[Co(dmp)2(C12H25NH2)2](ClO4)3 (en = ethylenediamine, dmp = 1,3-diaminopropane, 4AMP = 4-aminopropane, C12H25NH2 = dodecylamine) by Fe2+ ion in dipalmitoylphosphotidylcholine (DPPC) vesicles at different temperatures under pseudo first-order conditions. The kinetics of these reactions is followed by spectrophotometry method. The reactions are found to be second order and the electron transfer is postulated as outer sphere. The remarkable findings in the present investigation are that, below the phase transition temperature of DPPC, the rate decreases with an increase in the concentration of DPPC, while above the phase transition temperature the rate increases with an increase in the concentration of DPPC. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes. Besides, comparing the values of rate constants of these outer-sphere electron transfer reactions in the absence and in the presence of DPPC, the rate constant values in the presence of DPPC are always found to be greater than in the absence of DPPC. This is ascribed to the double hydrophobic fatty acid chain in the DPPC that gives the molecule an overall tubular shape due to the intervesicular hydrophobic interaction between vesicles surface and hydrophobic part of the surfactant complexes more suitable for vesicle aggregation which facilitates lower activation energy, and consequently higher rate is observed in the presence of DPPC. The activation parameters (ΔS# and ΔH#) of the reactions at different temperatures have been calculated which corroborate the kinetics of the reaction.

Sex differences in kinetic and neuromuscular control during jumping and landing

PubMed Central

Márquez, G.; Alegre, L.M.; Jaén, D.; Martin-Casado, L.; Aguado, X.

2017-01-01

In the present study, we analysed the kinetic profile together with the lower limb EMG activation pattern during a countermovement jump and its respective landing phase in males and females. Twenty subjects (10 males and 10 females) took part in the study. One experimental session was conducted in order to record kinetic and electromyographic (EMG) parameters during a countermovement jump (CMJ) and the subsequent landing phase. During the CMJ, males recorded a higher (p<0.001) performance than females in terms of jump height and power production. Stiffness values were lower in males than females due to greater centre of mass displacement during the countermovement (p<0.01). According to the EMG activity, males demonstrated greater (p<0.05) activation during the concentric phase of the jump. However, females revealed a higher co-contraction ratio in the plantar flexors during the push-off phase. During landings males showed higher (p<0.01) peak ground reaction forces (Fpeak), greater (p<0.05) stiffness and a higher maximal displacement of the CoM (p<0.05) than females. EMG analysis revealed greater EMG activity in the tibialis anterior (p<0.05) and rectus femoris (p=0.05) muscles in males. Higher plantar flexor co-activation during landing has also been found in males. Our findings demonstrated different neuromuscular control in males and females during jumping and landing. PMID:28250245

Sex differences in kinetic and neuromuscular control during jumping and landing.

PubMed

Márquez, G; Alegre, L M; Jaén, D; Martin-Casado, L; Aguado, X

2017-03-01

In the present study, we analysed the kinetic profile together with the lower limb EMG activation pattern during a countermovement jump and its respective landing phase in males and females. Twenty subjects (10 males and 10 females) took part in the study. One experimental session was conducted in order to record kinetic and electromyographic (EMG) parameters during a countermovement jump (CMJ) and the subsequent landing phase. During the CMJ, males recorded a higher (p<0.001) performance than females in terms of jump height and power production. Stiffness values were lower in males than females due to greater centre of mass displacement during the countermovement (p<0.01). According to the EMG activity, males demonstrated greater (p<0.05) activation during the concentric phase of the jump. However, females revealed a higher co-contraction ratio in the plantar flexors during the push-off phase. During landings males showed higher (p<0.01) peak ground reaction forces (F peak ), greater (p<0.05) stiffness and a higher maximal displacement of the CoM (p<0.05) than females. EMG analysis revealed greater EMG activity in the tibialis anterior (p<0.05) and rectus femoris (p=0.05) muscles in males. Higher plantar flexor co-activation during landing has also been found in males. Our findings demonstrated different neuromuscular control in males and females during jumping and landing.

Theory of chemical kinetics and charge transfer based on nonequilibrium thermodynamics.

PubMed

Bazant, Martin Z

2013-05-21

Advances in the fields of catalysis and electrochemical energy conversion often involve nanoparticles, which can have kinetics surprisingly different from the bulk material. Classical theories of chemical kinetics assume independent reactions in dilute solutions, whose rates are determined by mean concentrations. In condensed matter, strong interactions alter chemical activities and create variations that can dramatically affect the reaction rate. The extreme case is that of a reaction coupled to a phase transformation, whose kinetics must depend not only on the order parameter but also on its gradients at phase boundaries. Reaction-driven phase transformations are common in electrochemistry, when charge transfer is accompanied by ion intercalation or deposition in a solid phase. Examples abound in Li-ion, metal-air, and lead-acid batteries, as well as metal electrodeposition-dissolution. Despite complex thermodynamics, however, the standard kinetic model is the Butler-Volmer equation, based on a dilute solution approximation. The Marcus theory of charge transfer likewise considers isolated reactants and neglects elastic stress, configurational entropy, and other nonidealities in condensed phases. The limitations of existing theories recently became apparent for the Li-ion battery material LixFePO4 (LFP). It has a strong tendency to separate into Li-rich and Li-poor solid phases, which scientists believe limits its performance. Chemists first modeled phase separation in LFP as an isotropic "shrinking core" within each particle, but experiments later revealed striped phase boundaries on the active crystal facet. This raised the question: What is the reaction rate at a surface undergoing a phase transformation? Meanwhile, dramatic rate enhancement was attained with LFP nanoparticles, and classical battery models could not predict the roles of phase separation and surface modification. In this Account, I present a general theory of chemical kinetics, developed over the past 7 years, which is capable of answering these questions. The reaction rate is a nonlinear function of the thermodynamic driving force, the free energy of reaction, expressed in terms of variational chemical potentials. The theory unifies and extends the Cahn-Hilliard and Allen-Cahn equations through a master equation for nonequilibrium chemical thermodynamics. For electrochemistry, I have also generalized both Marcus and Butler-Volmer kinetics for concentrated solutions and ionic solids. This new theory provides a quantitative description of LFP phase behavior. Concentration gradients and elastic coherency strain enhance the intercalation rate. At low currents, the charge-transfer rate is focused on exposed phase boundaries, which propagate as "intercalation waves", nucleated by surface wetting. Unexpectedly, homogeneous reactions are favored above a critical current and below a critical size, which helps to explain the rate capability of LFP nanoparticles. Contrary to other mechanisms, elevated temperatures and currents may enhance battery performance and lifetime by suppressing phase separation. The theory has also been extended to porous electrodes and could be used for battery engineering with multiphase active materials. More broadly, the theory describes nonequilibrium chemical systems at mesoscopic length and time scales, beyond the reach of molecular simulations and bulk continuum models. The reaction rate is consistently defined for inhomogeneous, nonequilibrium states, for example, with phase separation, large electric fields, or mechanical stresses. This research is also potentially applicable to fluid extraction from nanoporous solids, pattern formation in electrophoretic deposition, and electrochemical dynamics in biological cells.

Gradual Ordering in Red Abalone Nacre

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gilbert, P. U. P. A.; Metzler, Rebecca A.; Zhou, Dong

2008-09-03

Red abalone (Haliotis rufescens) nacre is a layered composite biomineral that contains crystalline aragonite tablets confined by organic layers. Nacre is intensely studied because its biologically controlled microarchitecture gives rise to remarkable strength and toughness, but the mechanisms leading to its formation are not well understood. Here we present synchrotron spectromicroscopy experiments revealing that stacks of aragonite tablet crystals in nacre are misoriented with respect to each other. Quantitative measurements of crystal orientation, tablet size, and tablet stacking direction show that orientational ordering occurs not abruptly but gradually over a distance of 50 {micro}m. Several lines of evidence indicate thatmore » different crystal orientations imply different tablet growth rates during nacre formation. A theoretical model based on kinetic and gradual selection of the fastest growth rates produces results in qualitative and quantitative agreement with the experimental data and therefore demonstrates that ordering in nacre is a result of crystal growth kinetics and competition either in addition or to the exclusion of templation by acidic proteins as previously assumed. As in other natural evolving kinetic systems, selection of the fastest-growing stacks of tablets occurs gradually in space and time. These results suggest that the self-ordering of the mineral phase, which may occur completely independently of biological or organic-molecule control, is fundamental in nacre formation.« less

Analyses of kinetic glass transition in short-range attractive colloids based on time-convolutionless mode-coupling theory.

PubMed

Narumi, Takayuki; Tokuyama, Michio

2017-03-01

For short-range attractive colloids, the phase diagram of the kinetic glass transition is studied by time-convolutionless mode-coupling theory (TMCT). Using numerical calculations, TMCT is shown to recover all the remarkable features predicted by the mode-coupling theory for attractive colloids: the glass-liquid-glass reentrant, the glass-glass transition, and the higher-order singularities. It is also demonstrated through the comparisons with the results of molecular dynamics for the binary attractive colloids that TMCT improves the critical values of the volume fraction. In addition, a schematic model of three control parameters is investigated analytically. It is thus confirmed that TMCT can describe the glass-glass transition and higher-order singularities even in such a schematic model.

Two-phase anaerobic digestion of source sorted OFMSW (organic fraction of municipal solid waste): performance and kinetic study.

PubMed

Pavan, P; Battistoni, P; Cecchi, F; Mata-Alvarez, J

2000-01-01

The results of a two-phase system operated in different conditions, treating the source-sorted organic fraction of municipal solid waste (SS-OFMSW), coming mainly from fruit and vegetable markets, are presented. Hydraulic retention time (HRT) in the hydrolytic reactor and in the methanogenic reactor and also the temperature in the hydrolytic reactor (mesophilic and thermophilic conditions) are varied in order to evaluate the effect of these factors. The methanogenic reactor is always operated within the thermophilic range. Optimum operating conditions are found to be around 12 days (total system) using the mesophilic range of temperature in the first reactor. Specific gas production (SGP) in these conditions is around 0.6 m3/kg TVS. A kinetic study is also carried out, using the first and the step diffusional models. The latter gives much better results, with fitted constants comparable to other studies. Finally, a comparison with a one-phase system is carried out, showing that a two-phase system is much more appropriate for the digestion of this kind of highly biodegradable substrate in thermophilic conditions.

Effect of duty-cycles on the air plasma gas-phase of dielectric barrier discharges

NASA Astrophysics Data System (ADS)

Barni, R.; Biganzoli, I.; Dell'Orto, E. C.; Riccardi, C.

2015-10-01

An experimental investigation concerning the effects of a duty-cycle in the supply of a dielectric barrier discharge in atmospheric pressure air has been performed. Electrical characteristics of the discharge have been measured, focusing mainly on the statistical properties of the current filaments and on dielectric surface charging, both affected by the frequent repetition of breakdown imposed by the duty-cycle. Information on the gas-phase composition was gathered too. In particular, a strong enhancement in the ozone formation rate is observed when suitable long pauses separate the active discharge phases. A simulation of the chemical kinetics in the gas-phase, based on a simplified discharge modeling, is briefly described in order to shed light on the observed increase in ozone production. The effect of a duty-cycle on surface modification of polymeric films in order to increase their wettability has been investigated too.

Motility-Induced Phase Separation

NASA Astrophysics Data System (ADS)

Cates, Michael E.; Tailleur, Julien

2015-03-01

Self-propelled particles include both self-phoretic synthetic colloids and various microorganisms. By continually consuming energy, they bypass the laws of equilibrium thermodynamics. These laws enforce the Boltzmann distribution in thermal equilibrium: The steady state is then independent of kinetic parameters. In contrast, self-propelled particles tend to accumulate where they move more slowly. They may also slow down at high density for either biochemical or steric reasons. This creates positive feedback, which can lead to motility-induced phase separation (MIPS) between dense and dilute fluid phases. At leading order in gradients, a mapping relates variable-speed, self-propelled particles to passive particles with attractions. This deep link to equilibrium phase separation is confirmed by simulations but generally breaks down at higher order in gradients: New effects, with no equilibrium counterpart, then emerge. We give a selective overview of the fast-developing field of MIPS, focusing on theory and simulation but including a brief speculative survey of its experimental implications.

Saponification reaction system: a detailed mass transfer coefficient determination.

PubMed

Pečar, Darja; Goršek, Andreja

2015-01-01

The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

Tachyon condensation due to domain-wall annihilation in Bose-Einstein condensates.

PubMed

Takeuchi, Hiromitsu; Kasamatsu, Kenichi; Tsubota, Makoto; Nitta, Muneto

2012-12-14

We show theoretically that a domain-wall annihilation in two-component Bose-Einstein condensates causes tachyon condensation accompanied by spontaneous symmetry breaking in a two-dimensional subspace. Three-dimensional vortex formation from domain-wall annihilations is considered a kink formation in subspace. Numerical experiments reveal that the subspatial dynamics obey the dynamic scaling law of phase-ordering kinetics. This model is experimentally feasible and provides insights into how the extra dimensions influence subspatial phase transition in higher-dimensional space.

Origin of Spinel Nanocheckerboards via First Principles

NASA Astrophysics Data System (ADS)

Kornbluth, Mordechai; Marianetti, Chris A.

2015-06-01

Self-organizing nanocheckerboards have been experimentally fabricated in Mn-based spinels but have not yet been explained with first principles. Using density-functional theory, we explain the phase diagram of the ZnMnxGa2 -xO4 system and the origin of nanocheckerboards. We predict total phase separation at zero temperature and then show the combination of kinetics, thermodynamics, and Jahn-Teller physics that generates the system's observed behavior. We find that the {011 } surfaces are strongly preferred energetically, which mandates checkerboard ordering by purely geometrical considerations.

Application of a hybrid Electrocoagulation-Fenton process in yarn dye wastewater: Kinetic study

NASA Astrophysics Data System (ADS)

Riadi, L.; Sapei, L.; Lidiawati, T.; Agustin, Y. E.

2016-11-01

Reactive dyes contain a significant portion of colorants used in yarn dying process and also in textile industry. Since the COD content is usually high in such wastewater,we conducted a hybrid electrocoagulation-fenton method to treat the wastewater. This work describes the application of the hybrid system to the removal of chemical oxygen demand and color from the wastewater in a batch reactor. Having worked with initial pH of 3,0; temperature at 30°C, molar ratio of Fe2+/H2O2 =1/10 and the mol ratio H2O2/COD = 4, we got 88.3% COD conversion and 88.5% color removal. The COD degradation process can be explained in two phases, the first phase is instantaneous reaction and the second phase is first order reaction. The kinetic constant was 0.0053 minute-1 and the rate of COD degradation was 0.0053[COD] mg/L minute.

4-wave dynamics in kinetic wave turbulence

NASA Astrophysics Data System (ADS)

Chibbaro, Sergio; Dematteis, Giovanni; Rondoni, Lamberto

2018-01-01

A general Hamiltonian wave system with quartic resonances is considered, in the standard kinetic limit of a continuum of weakly interacting dispersive waves with random phases. The evolution equation for the multimode characteristic function Z is obtained within an ;interaction representation; and a perturbation expansion in the small nonlinearity parameter. A frequency renormalization is performed to remove linear terms that do not appear in the 3-wave case. Feynman-Wyld diagrams are used to average over phases, leading to a first order differential evolution equation for Z. A hierarchy of equations, analogous to the Boltzmann hierarchy for low density gases is derived, which preserves in time the property of random phases and amplitudes. This amounts to a general formalism for both the N-mode and the 1-mode PDF equations for 4-wave turbulent systems, suitable for numerical simulations and for investigating intermittency. Some of the main results which are developed here in detail have been tested numerically in a recent work.

Effect of grain morphology on gas bubble swelling in UMo fuels – A 3D microstructure dependent Booth model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, Shenyang; Burkes, Douglas; Lavender, Curt A.

2016-11-01

A three dimensional microstructure dependent swelling model is developed for studying the fission gas swelling kinetics in irradiated nuclear fuels. The model is extended from the Booth model [1] in order to investigate the effect of heterogeneous microstructures on gas bubble swelling kinetics. As an application of the model, the effect of grain morphology, fission gas diffusivity, and spatial dependent fission rate on swelling kinetics are simulated in UMo fuels. It is found that the decrease of grain size, the increase of grain aspect ratio for the grain having the same volume, and the increase of fission gas diffusivity (fissionmore » rate) cause the increase of swelling kinetics. Other heterogeneities such as second phases and spatial dependent thermodynamic properties including diffusivity of fission gas, sink and source strength of defects could be naturally integrated into the model to enhance the model capability.« less

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations

DOE PAGES

Ji, Ho-Il; Davenport, Timothy C.; Gopal, Chirranjeevi Balaji; ...

2016-07-18

The redox kinetics of undoped ceria (CeO 2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO 2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant k chem is found to obey the correlation log(k chem/cm s -1) = (0.84 ± 0.02) × log(pO 2/atm) - (0.99 ± 0.05) and increases withmore » oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.« less

Extreme high temperature redox kinetics in ceria: exploration of the transition from gas-phase to material-kinetic limitations.

PubMed

Ji, Ho-Il; Davenport, Timothy C; Gopal, Chirranjeevi Balaji; Haile, Sossina M

2016-08-03

The redox kinetics of undoped ceria (CeO2-δ) are investigated by the electrical conductivity relaxation method in the oxygen partial pressure range of -4.3 ≤ log(pO2/atm) ≤ -2.0 at 1400 °C. It is demonstrated that extremely large gas flow rates, relative to the mass of the oxide, are required in order to overcome gas phase limitations and access the material kinetic properties. Using these high flow rate conditions, the surface reaction rate constant kchem is found to obey the correlation log(kchem/cm s(-1)) = (0.84 ± 0.02) × log(pO2/atm) - (0.99 ± 0.05) and increases with oxygen partial pressure. This increase contrasts the known behavior of the dominant defect species, oxygen vacancies and free electrons, which decrease in concentration with increasing oxygen partial pressure. For the sample geometries employed, diffusion was too fast to be detected. At low gas flow rates, the relaxation process becomes limited by the capacity of the sweep gas to supply/remove oxygen to/from the oxide. An analytical expression is derived for the relaxation in the gas-phase limited regime, and the result reveals an exponential decay profile, identical in form to that known for a surface reaction limited process. Thus, measurements under varied gas flow rates are required to differentiate between surface reaction limited and gas flow limited behavior.

Effect of concentration dependence of the diffusion coefficient on homogenization kinetics in multiphase binary alloy systems

NASA Technical Reports Server (NTRS)

Tenney, D. R.; Unnam, J.

1978-01-01

Diffusion calculations were performed to establish the conditions under which concentration dependence of the diffusion coefficient was important in single, two, and three phase binary alloy systems. Finite-difference solutions were obtained for each type of system using diffusion coefficient variations typical of those observed in real alloy systems. Solutions were also obtained using average diffusion coefficients determined by taking a logarithmic average of each diffusion coefficient variation considered. The constant diffusion coefficient solutions were used as reference in assessing diffusion coefficient variation effects. Calculations were performed for planar, cylindrical, and spherical geometries in order to compare the effect of diffusion coefficient variations with the effect of interface geometries. In most of the cases considered, the diffusion coefficient of the major-alloy phase was the key parameter that controlled the kinetics of interdiffusion.

Activation energy for diamond growth from the carbon-hydrogen gas system at low substrate temperatures

NASA Astrophysics Data System (ADS)

Stiegler, J.; Lang, T.; von Kaenel, Y.; Michler, J.; Blank, E.

1997-01-01

The growth kinetics of diamond films deposited at low substrate temperatures (600-400 °C) from the carbon-hydrogen gas system have been studied. When the substrate temperature alone was varied, independently of all other process parameters in the microwave plasma reactor, an activation energy in the order of 7 kcal/mol was observed. This value did not change with different carbon concentrations in hydrogen. It is supposed that growth kinetics in this temperature range are controlled by a single chemical reaction, probably the abstraction of surface bonded hydrogen by gas phase atomic hydrogen.

Critical analysis of nitramine decomposition data: Activation energies and frequency factors for HMX and RDX decomposition

NASA Technical Reports Server (NTRS)

Schroeder, M. A.

1980-01-01

A summary of a literature review on thermal decomposition of HMX and RDX is presented. The decomposition apparently fits first order kinetics. Recommended values for Arrhenius parameters for HMX and RDX decomposition in the gaseous and liquid phases and for decomposition of RDX in solution in TNT are given. The apparent importance of autocatalysis is pointed out, as are some possible complications that may be encountered in interpreting extending or extrapolating kinetic data for these compounds from measurements carried out below their melting points to the higher temperatures and pressure characteristic of combustion.

Kinetics of the cellular decomposition of supersaturated solid solutions

NASA Astrophysics Data System (ADS)

Ivanov, M. A.; Naumuk, A. Yu.

2014-09-01

A consistent description of the kinetics of the cellular decomposition of supersaturated solid solutions with the development of a spatially periodic structure of lamellar (platelike) type, which consists of alternating phases of precipitates on the basis of the impurity component and depleted initial solid solution, is given. One of the equations, which determines the relationship between the parameters that describe the process of decomposition, has been obtained from a comparison of two approaches in order to determine the rate of change in the free energy of the system. The other kinetic parameters can be described with the use of a variational method, namely, by the maximum velocity of motion of the decomposition boundary at a given temperature. It is shown that the mutual directions of growth of the lamellae of different phases are determined by the minimum value of the interphase surface energy. To determine the parameters of the decomposition, a simple thermodynamic model of states with a parabolic dependence of the free energy on the concentrations has been used. As a result, expressions that describe the decomposition rate, interlamellar distance, and the concentration of impurities in the phase that remain after the decomposition have been derived. This concentration proves to be equal to the half-sum of the initial concentration and the equilibrium concentration corresponding to the decomposition temperature.

Hydrogenation properties of KSi and NaSi Zintl phases.

PubMed

Tang, Wan Si; Chotard, Jean-Noël; Raybaud, Pascal; Janot, Raphaël

2012-10-14

The recently reported KSi-KSiH(3) system can store 4.3 wt% of hydrogen reversibly with slow kinetics of several hours for complete absorption at 373 K and complete desorption at 473 K. From the kinetics measured at different temperatures, the Arrhenius plots give activation energies (E(a)) of 56.0 ± 5.7 kJ mol(-1) and 121 ± 17 kJ mol(-1) for the absorption and desorption processes, respectively. Ball-milling with 10 wt% of carbon strongly improves the kinetics of the system, i.e. specifically the initial rate of absorption becomes about one order of magnitude faster than that of pristine KSi. However, this fast absorption causes a disproportionation into KH and K(8)Si(46), instead of forming the KSiH(3) hydride from a slow absorption. This disproportionation, due to the formation of stable KH, leads to a total loss of reversibility. In a similar situation, when the pristine Zintl NaSi phase absorbs hydrogen, it likewise disproportionates into NaH and Na(8)Si(46), indicating a very poorly reversible reaction.

Preliminary investigation of the kinetics of primary creep of a two phase gamma TiAl alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hayes, R.W.

1993-11-01

It is the intent of this communication to present and discuss some data regarding the kinetics of primary creep of a two phase gamma TiAl alloy which had been studied previously to determine the mechanisms giving rise to the minimum strain rate. In order to study the kinetics of primary creep of the present gamma TiAl alloy an approach previously taken by Dorn et al and also recently employed by Argon and Bhattacharya was taken. Dorn et al demonstrated that at a given constant stress, the strain rate during primary creep is governed by a combined time-temperature parameter [Theta] =more » t exp([minus]Q/RT) where Q is the activation energy for self diffusion which many times also governs the process of steady-state creep. It was shown that at the same constant stress level all primary creep curves were found to collapse on one another when the primary creep strain is plotted as a function of [Theta][sup (9)].« less

Modified Gompertz equation for electrotherapy murine tumor growth kinetics: predictions and new hypotheses.

PubMed

Cabrales, Luis E Bergues; Nava, Juan J Godina; Aguilera, Andrés Ramírez; Joa, Javier A González; Ciria, Héctor M Camué; González, Maraelys Morales; Salas, Miriam Fariñas; Jarque, Manuel Verdecia; González, Tamara Rubio; Mateus, Miguel A O'Farril; Brooks, Soraida C Acosta; Palencia, Fabiola Suárez; Zamora, Lisset Ortiz; Quevedo, María C Céspedes; Seringe, Sarah Edward; Cuitié, Vladimir Crombet; Cabrales, Idelisa Bergues; González, Gustavo Sierra

2010-10-28

Electrotherapy effectiveness at different doses has been demonstrated in preclinical and clinical studies; however, several aspects that occur in the tumor growth kinetics before and after treatment have not yet been revealed. Mathematical modeling is a useful instrument that can reveal some of these aspects. The aim of this paper is to describe the complete growth kinetics of unperturbed and perturbed tumors through use of the modified Gompertz equation in order to generate useful insight into the mechanisms that underpin this devastating disease. The complete tumor growth kinetics for control and treated groups are obtained by interpolation and extrapolation methods with different time steps, using experimental data of fibrosarcoma Sa-37. In the modified Gompertz equation, a delay time is introduced to describe the tumor's natural history before treatment. Different graphical strategies are used in order to reveal new information in the complete kinetics of this tumor type. The first stage of complete tumor growth kinetics is highly non linear. The model, at this stage, shows different aspects that agree with those reported theoretically and experimentally. Tumor reversibility and the proportionality between regions before and after electrotherapy are demonstrated. In tumors that reach partial remission, two antagonistic post-treatment processes are induced, whereas in complete remission, two unknown antitumor mechanisms are induced. The modified Gompertz equation is likely to lead to insights within cancer research. Such insights hold promise for increasing our understanding of tumors as self-organizing systems and, the possible existence of phase transitions in tumor growth kinetics, which, in turn, may have significant impacts both on cancer research and on clinical practice.

A kinetic model for beta-amyloid adsorption at the air/solution interface and its implication to the beta-amyloid aggregation process.

PubMed

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis C; Zhang, Yi; Su, Lei; Land, Donald P; Zhou, Feimeng

2009-03-12

At the air/buffer solution interface the kinetics of adsorption of amyloid beta peptide, Abeta(1-42), whose bulk concentration (submicromolar) is more than 2 orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure-time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Abeta adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Abeta bulk concentration and the solution temperature. A large activation energy (62.2 +/- 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Abeta bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Abeta transferred to a solid substrate and circular dichroism measurements of Abeta in the solution layer near the interface reveal that the natively unstructured Abeta in the bulk undergo a conformation change (folding) to mainly the alpha-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Abeta conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Abeta adsorption is kinetically controlled and the apparent rate constant is proportional to the Abeta bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Abeta aggregation/ fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial A/beta conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Abeta fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Abeta misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate.

A Kinetic Model for β-Amyloid Adsorption at the Air/Solution Interface and Its Implication to the β-Amyloid Aggregation Process

PubMed Central

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis; Zhang, Yi; Su, Lei; Land, Donald; Zhou, Feimeng

2011-01-01

The kinetics of adsorption at the air/buffer solution interface of amyloid beta peptide, Aβ(1–42), whose bulk concentration (submicromolar) is more than two orders of magnitude lower than that typically used in other in vitro aggregation studies, has been studied using a Langmuir-Blodgett trough. The pressure–time curves exhibit a lag phase, wherein the surface pressure essentially remains at zero, and a rising phase, corresponding to the Aβ adsorption at the interface. The duration of the lag phase was found to be highly dependent on both the Aβ bulk concentration and the solution temperature. A large activation energy (62.2 ± 4.1 KJ/mol) was determined and the apparent adsorption rate constant was found to be linearly dependent on the Aβ bulk concentration. Attenuated total reflection-IR spectra of the adsorbed Aβ transferred to a solid substrate and circular dichroism measurements of Aβ in the solution layer near the interface reveal that the natively unstructured Aβ in the bulk undergo a conformation change (folding) to mainly the α-helical structure. The results suggest that, prior to the adsorption step, an equilibrium between Aβ conformations is established within the subsurface. The kinetic equation derived from this model confirms that the overall Aβ adsorption is kinetically controlled and the apparent rate constant is proportional to the Aβ bulk concentration. This model also indicates that interfaces such as cell membranes and lipid bilayers may facilitate Aβ aggregation/fibrillation by providing a thin hydrophobic layer adjacent to the interface for the initial Aβ conformation change (misfolding) and accumulation. Such a preconcentration effect offers a plausible explanation of the fact that Aβ fibrillation occurs in vivo at nanomolar concentrations. Another important biological implication from our work is that Aβ misfolding may occur before its adsorption onto a cell membrane. This general kinetic model should also find applications in adsorption studies of other types of biomolecules whose overall kinetics exhibits a lag phase that is dependent on the bulk concentration of the adsorbate. PMID:19260715

Force generation and temperature-jump and length-jump tension transients in muscle fibers.

PubMed Central

Davis, J S; Rodgers, M E

1995-01-01

Muscle tension rises with increasing temperature. The kinetics that govern the tension rise of maximally Ca(2+)-activated, skinned rabbit psoas fibers over a temperature range of 0-30 degrees C was characterized in laser temperature-jump experiments. The kinetic response is simple and can be readily interpreted in terms of a basic three-step mechanism of contraction, which includes a temperature-sensitive rapid preequilibrium(a) linked to a temperature-insensitive rate-limiting step and followed by a temperature-sensitive tension-generating step. These data and mechanism are compared and contrasted with the more complex length-jump Huxley-Simmons phases in which all states that generate tension or bear tension are perturbed. The rate of the Huxley-Simmons phase 4 is temperature sensitive at low temperatures but plateaus at high temperatures, indicating a change in rate-limiting step from a temperature-sensitive (phase 4a) to a temperature-insensitive reaction (phase 4b); the latter appears to correlate with the slow, temperature-insensitive temperature-jump relaxation. Phase 3 is absent in the temperature-jump, which excludes it from tension generation. We confirm that de novo tension generation occurs as an order-disorder transition during phase 2slow and the equivalent, temperature-sensitive temperature-jump relaxation. PMID:7612845

Dependence of pesticide degradation on sorption: nonequilibrium model and application to soil reactors

NASA Astrophysics Data System (ADS)

Guo, Lei; Jury, William A.; Wagenet, Robert J.; Flury, Markus

2000-04-01

The effect of sorption on degradation of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in a soil amended with various amounts of activated carbon (AC). The relationship between sorption and decay of 2,4-D was analyzed using analytical solutions for equilibrium sorption and to a two-site nonequilibrium adsorption model coupled with two first-order degradation terms for the dissolved and sorbed pesticide, respectively. The sorption parameters in the latter model were determined based on data obtained from batch sorption experiments, while those for degradation were obtained from incubation experiments. The adsorption coefficients, ranging from 0.811 to >315 ml g -1, increased at higher AC, and were negatively related to degradation as measured by the first-order rate constant, implying that degradation is faster from the liquid phase than from the sorbed phase. A nonlinear fit of the decay curves to the nonequilibrium model revealed that degradation rate constants were 0.157 and 0.00243 day -1 for the liquid and sorbed phases, respectively, differing by a factor of 65. Similar results were also obtained using the equilibrium model. A parameter sensitivity analysis of the nonequilibrium model indicates that nonequilibrium sorption will initially favor degradation; however, over the long term, will decrease degradation when desorption kinetics becomes the limiting factor in the degradation process. In the presence of a lag phase that allows appreciable amounts of chemical to diffuse into kinetic sorption sites, nonequilibrium sorption will only impede degradation.

Ammonium Removal from Aqueous Solutions by Clinoptilolite: Determination of Isotherm and Thermodynamic Parameters and Comparison of Kinetics by the Double Exponential Model and Conventional Kinetic Models

PubMed Central

Tosun, İsmail

2012-01-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R2) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients. PMID:22690177

Ammonium removal from aqueous solutions by clinoptilolite: determination of isotherm and thermodynamic parameters and comparison of kinetics by the double exponential model and conventional kinetic models.

PubMed

Tosun, Ismail

2012-03-01

The adsorption isotherm, the adsorption kinetics, and the thermodynamic parameters of ammonium removal from aqueous solution by using clinoptilolite in aqueous solution was investigated in this study. Experimental data obtained from batch equilibrium tests have been analyzed by four two-parameter (Freundlich, Langmuir, Tempkin and Dubinin-Radushkevich (D-R)) and four three-parameter (Redlich-Peterson (R-P), Sips, Toth and Khan) isotherm models. D-R and R-P isotherms were the models that best fitted to experimental data over the other two- and three-parameter models applied. The adsorption energy (E) from the D-R isotherm was found to be approximately 7 kJ/mol for the ammonium-clinoptilolite system, thereby indicating that ammonium is adsorbed on clinoptilolite by physisorption. Kinetic parameters were determined by analyzing the nth-order kinetic model, the modified second-order model and the double exponential model, and each model resulted in a coefficient of determination (R(2)) of above 0.989 with an average relative error lower than 5%. A Double Exponential Model (DEM) showed that the adsorption process develops in two stages as rapid and slow phase. Changes in standard free energy (∆G°), enthalpy (∆H°) and entropy (∆S°) of ammonium-clinoptilolite system were estimated by using the thermodynamic equilibrium coefficients.

Multiorbital kinetic effects on charge ordering of frustrated electrons on the triangular lattice

NASA Astrophysics Data System (ADS)

Février, C.; Fratini, S.; Ralko, A.

2015-06-01

The role of the multiorbital effects on the emergence of frustrated electronic orders on the triangular lattice at half filling is investigated through an extended spinless fermion Hubbard model. By using two complementary approaches, unrestricted Hartree-Fock and exact diagonalizations, we unravel a very rich phase diagram controlled by the strength of both local and off-site Coulomb interactions and by the interorbital hopping anisotropy ratio t'/t . Three robust unconventional electronic phases, a pinball liquid, an inverse pinball liquid, and a large-unit-cell √{12 }×√{12 } droplet phase, are found to be generic in the triangular geometry, being controlled by the band structure parameters. The latter are also stabilized in the isotropic limit of our microscopic model, which recovers the standard SU(2) spinful extended single-band Hubbard model.

Aqueous oxidation of green leaf volatiles by hydroxyl radical as a source of SOA: Kinetics and SOA yields

NASA Astrophysics Data System (ADS)

Richards-Henderson, Nicole K.; Hansel, Amie K.; Valsaraj, Kalliat T.; Anastasio, Cort

2014-10-01

Green leaf volatiles (GLVs) are a class of oxygenated hydrocarbons released from vegetation, especially during mechanical stress or damage. The potential for GLVs to form secondary organic aerosol (SOA) via aqueous-phase reactions is not known. Fog events over vegetation will lead to the uptake of GLVs into water droplets, followed by aqueous-phase reactions with photooxidants such as the hydroxyl radical (OH). In order to determine if the aqueous oxidation of GLVs by OH can be a significant source of secondary organic aerosol, we studied the partitioning and reaction of five GLVs: cis-3-hexen-1-ol, cis-3-hexenyl acetate, methyl salicylate, methyl jasmonate, and 2-methyl-3-butene-2-ol. For each GLV we measured the kinetics of aqueous oxidation by OH, and the corresponding SOA mass yield. The second-order rate constants for GLVs with OH were all near diffusion controlled, (5.4-8.6) × 109 M-1 s-1 at 298 K, and showed a small temperature dependence, with an average activation energy of 9.3 kJ mol-1 Aqueous-phase SOA mass yields ranged from 10 to 88%, although some of the smaller values were not statistically different from zero. Methyl jasmonate was the most effective aqueous-phase SOA precursor due to its larger Henry's law constant and high SOA mass yield (68 ± 8%). While we calculate that the aqueous-phase SOA formation from the five GLVs is a minor source of aqueous-phase SOA, the availability of other GLVs, other oxidants, and interfacial reactions suggest that GLVs overall might be a significant source of SOA via aqueous reactions.

Impact of Harness Attachment Point on Kinetics and Kinematics During Sled Towing.

PubMed

Bentley, Ian; Atkins, Steve J; Edmundson, Christopher J; Metcalfe, John; Sinclair, Jonathan K

2016-03-01

Resisted sprint training is performed in a horizontal direction and involves similar muscles, velocities, and ranges of motion (ROM) to those of normal sprinting. Generally, sleds are attached to the athletes through a lead (3 m) and harness; the most common attachment points are the shoulder or waist. At present, it is not known how the different harness point's impact on the kinematics and kinetics associated with sled towing (ST). The aim of the current investigation was to examine the kinetics and kinematics of shoulder and waist harness attachment points in relation to the acceleration phase of ST. Fourteen trained men completed normal and ST trials, loaded at 10% reduction of sprint velocity. Sagittal plane kinematics from the trunk, hip, knee, and ankle were measured, together with stance phase kinetics (third footstrike). Kinetic and kinematic parameters were compared between harness attachments using one-way repeated-measures analysis of variance. The results indicated that various kinetic differences were present between the normal and ST conditions. Significantly greater net horizontal mean force, net horizontal impulses, propulsive mean force, and propulsive impulses were measured (p < 0.05). Interestingly, the waist harness also led to greater net horizontal impulse when compared with the shoulder attachment (p < 0.001). In kinematic terms, ST conditions significantly increased peak flexion in hip, knee, and ankle joints compared with the normal trials (p < 0.05). Results highlighted that the shoulder harness had a greater impact on trunk and knee joint kinematics when compared with the waist harness (p < 0.05). In summary, waist harnesses seem to be the most suitable attachment point for the acceleration phase of sprinting. Sled towing with these attachments resulted in fewer kinematic alterations and greater net horizontal impulse when compared with the shoulder harness. Future research is necessary in order to explore the long-term adaptations of these acute changes.

THE ROLE OF METASTABLE STATES IN POLYMER PHASE TRANSITIONS: Concepts, Principles, and Experimental Observations

NASA Astrophysics Data System (ADS)

Cheng, Stephen Z. D.; Keller, Andrew

1998-08-01

Polymer phases can be described in the same way as phases in other condensed matter using a number density operator and its correlation functions. This description requires the understanding of symmetry operations and order at different atomic and molecular levels. Statistical mechanics provides a link between the microscopic description of the structure and motion and the macroscopic thermodynamic properties. Within the limits of the laws of thermodynamics, polymers exhibit a rich variety of phase transition behaviors. By definition, a first-order phase transition describes a transformation that involves a sudden change of thermodynamic properties at its transition temperature, whereas higher-order phase transitions are classified as critical phenomena. Of special interest is the role of metastability in phase and phase transition behaviors. Although a metastable state possesses a local free energy minimum, it is not at the global equilibrium. Furthermore, metastable states can also be associated with phase sizes. Metastable behavior is also observed in phase transformations that are impeded by kinetic limitations along the pathway to thermodynamic equilibrium. This is illustrated in structural and morphological investigations of crystallization and mesophase transitions, liquid-liquid phase separation, vitrification, and gel formation, as well as combinations of transformation processes. In these cases, the metastable state often becomes the dominant state for the entire system and is observed over a range of time and size scales. This review describes the general principles of metastability in polymer phases and phase transitions and provides illustrations from current experimental works in selected areas.

Some characteristics of intense geomagnetic storms and their energy budget

NASA Astrophysics Data System (ADS)

Vichare, Geeta; Alex, S.; Lakhina, G. S.

2005-03-01

The present study analyses nine intense geomagnetic storms (∣Dst∣ > 175 nT) with the aid of ACE satellite measurements and ground magnetic field values at Alibag Magnetic Observatory. The study confirms the crucial role of southward IMF in triggering the storm main phase as well as controlling the magnitude of the storm. The main phase interval shows clear dependence on the duration of southward IMF. An attempt is made to identify the multipeak signature in the ring current energy injection rate during main phase of the storm. In order to quantify the energy budget of magnetic storms, the present paper computes the solar wind energies, magnetospheric coupling energies, auroral and Joule heating energies, and the ring current energies for each storm under examination. Computation of the solar wind- magnetosphere coupling function considers the variation of the size of the magnetosphere by using the measured solar wind ram pressure. During the main phase of the storm, the solar wind kinetic energy ranges from 9 × 1017 to 72 × 1017 J with an average of 30 × 1017 J; the total energy dissipated in the auroral ionosphere varies between 2 × 1015 and 9 × 1015 J, whereas ring current energies range from 8 × 1015 to 19 × 1015 J. For the total storm period, about 3.5% of total solar wind kinetic energy is available for the redistribution in the magnetosphere, and around 20% of this goes into the inner magnetosphere and in the auroral ionosphere of both the hemispheres. It is found that during main phase of the storm, almost 5% of the total solar wind kinetic energy is available for the redistribution in the magnetosphere, whereas during the recovery phase the percentage becomes 2.3%.

Metastable phase formation in undercooled Fe-Co melts under terrestrial and parabolic flight conditions

NASA Astrophysics Data System (ADS)

Hermann, R.; Löser, W.; Lindenkreuz, H. G.; Yang-Bitterlich, W.; Mickel, Ch.; Diefenbach, A.; Schneider, S.; Dreier, W.

2007-12-01

Soft magnetic Fe-Co alloys display primary fcc phase solidification for>19,5 at% Co in conventional near-equilibrium solidification processes. Undercooled Fe-Co melt drops within the composition range of 30 to 50 at% Co have been investigated with the electromagnetic levitation technique. The solidification kinetics was measured in situ using a high-resolution Siphotodiode. Melt drops were undercooled up to 263 K below the liquidus temperature and subsequently quenched onto a chill substrate in order to characterize the solidification sequence and microstructure. The transition from stable fcc phase to metastable bcc primary phase solidification has been observed after reaching a critical undercooling level. The critical undercooling increases with rising Co content. The growth velocity drops obviously after transition to metastable bcc phase formation. Parabolic flight experiments were performed in order to study the phase selection under reduced gravity conditions. Under microgravity conditions, a much smaller critical undercooling and an increased life time of the metastable bcc phase were obtained. This result was validated with TEM investigations. The appearance of Fe-O particles gives an indirect hint for an intermediate fcc phase formation from the metastable bcc phase at elevated temperature.

Combined Effect of Heating Rate and Microalloying Elements on Recrystallization During Annealing of Dual-Phase Steels

NASA Astrophysics Data System (ADS)

Bellavoine, Marion; Dumont, Myriam; Drillet, Josée; Hébert, Véronique; Maugis, Philippe

2018-05-01

Adjusting ferrite recrystallization kinetics during annealing is a way to control the final microstructure and thus the mechanical properties of advanced cold-rolled high-strength steels. Two strategies are commonly used for this purpose: adjusting heating rates and/or adding microalloying elements. The present work investigates the effect of heating rate and microalloying elements Ti, Nb, and Mo on recrystallization kinetics during annealing in various cold-rolled Dual-Phase steel grades. The use of combined experimental and modeling approaches allows a deeper understanding of the separate influence of heating rate and the addition of microalloying elements. The comparative effect of Ti, Nb, and Mo as solute elements and as precipitates on ferrite recrystallization is also clarified. It is shown that solute drag has the largest delaying effect on recrystallization in the present case and that the order of solute drag effectiveness of microalloying elements is Nb > Mo > Ti.

Combined Effect of Heating Rate and Microalloying Elements on Recrystallization During Annealing of Dual-Phase Steels

NASA Astrophysics Data System (ADS)

Bellavoine, Marion; Dumont, Myriam; Drillet, Josée; Hébert, Véronique; Maugis, Philippe

2018-07-01

Adjusting ferrite recrystallization kinetics during annealing is a way to control the final microstructure and thus the mechanical properties of advanced cold-rolled high-strength steels. Two strategies are commonly used for this purpose: adjusting heating rates and/or adding microalloying elements. The present work investigates the effect of heating rate and microalloying elements Ti, Nb, and Mo on recrystallization kinetics during annealing in various cold-rolled Dual-Phase steel grades. The use of combined experimental and modeling approaches allows a deeper understanding of the separate influence of heating rate and the addition of microalloying elements. The comparative effect of Ti, Nb, and Mo as solute elements and as precipitates on ferrite recrystallization is also clarified. It is shown that solute drag has the largest delaying effect on recrystallization in the present case and that the order of solute drag effectiveness of microalloying elements is Nb > Mo > Ti.

KEEN Wave Simulations: Comparing various PIC to various fixed grid Vlasov to Phase-Space Adaptive Sparse Tiling & Effective Lagrangian (PASTEL) Techniques

NASA Astrophysics Data System (ADS)

Afeyan, Bedros; Larson, David; Shadwick, Bradley; Sydora, Richard

2017-10-01

We compare various ways of solving the Vlasov-Poisson and Vlasov-Maxwell equations on rather demanding nonlinear kinetic phenomena associated with KEEN and KEEPN waves. KEEN stands for Kinetic, Electrostatic, Electron Nonlinear, and KEEPN, for electron-positron or pair plasmas analogs. Because these self-organized phase space structures are not steady-state, or single mode, or fluid or low order moment equation limited, typical techniques with low resolution or too much noise will distort the answer too much, too soon, and fail. This will be shown via Penrose criteria triggers for instability at the formation stage as well as particle orbit statistics in fully formed KEEN waves and KEEN-KEEN and KEEN-EPW interacting states. We will argue that PASTEL is a viable alternative to traditional methods with reasonable chances of success in higher dimensions. Work supported by a Grant from AFOSR PEEP.

Influence of sodium polyacrylate on the rheology of aqueous Laponite dispersions.

PubMed

Labanda, Jordi; Llorens, Joan

2005-09-01

Aqueous Laponite dispersions containing a sodium polyacrylate were analyzed, at fixed ionic strength and pH, by rheometric and electroacoustic (for zeta-potential determinations) techniques at 7 days after their preparation. The rheological behavior of these dispersions was determined by oscillatory and flow experiments. Addition of sodium polyacrylate modifies the interactions between Laponite particles and therefore the physical state of the dispersion. The phase diagram of Laponite dispersion as a function of sodium polyacrylate concentration shows different sol-gel transitions for a specific Laponite concentration as a function of the polyacrylate concentration. Under equilibrium flow conditions the Laponite dispersions fit the pseudoplastic Oswald-de Waele power law model. At the same time, these dispersions show thixotropy, which was analyzed using a second-order kinetic equation. The kinetic processes were characterized by breakdown and build-up parameters, which were found to depend on shear rate. This kinetic equation was modified by a power law exponent of viscosity with shear rate that takes into account the viscosity variations when the shear rates are suddenly changed, in order to fit the hysteresis loops.

Mechanism of alpha-amino acids decomposition in the gas phase. experimental and theoretical study of the elimination kinetics of N-benzyl glycine ethyl ester.

PubMed

Tosta, Maria; Oliveros, Jhenny C; Mora, Jose R; Córdova, Tania; Chuchani, Gabriel

2010-02-25

The gas-phase elimination kinetics of N-benzylglycine ethyl ester was examined in a static system, seasoned with allyl bromide, and in the presence of the free chain radical suppressor toluene. The working temperature and pressure range were 386.4-426.7 degrees C and 16.7-40.0 torr, respectively. The reaction showed to be homogeneous, unimolecular, and obeys a first-order rate law. The elimination products are benzylglycine and ethylene. However, the intermediate benzylglycine is unstable under the reaction conditions decomposing into benzyl methylamine and CO(2) gas. The variation of the rate coefficients with temperature is expressed by the following Arrhenius equation: log k(1) (s(-1)) = (11.83 +/- 0.52) - (190.3 +/- 6.9) kJ mol(-1) (2.303RT)(-1). The theoretical calculation of the kinetic parameters and mechanism of elimination of this ester were performed at B3LYP/6-31G*, B3LYP/6-31+G**, MPW1PW91/6-31G*, and MPW1PW91/6-31+G** levels of theory. The calculation results suggest a molecular mechanism of a concerted nonsynchronous six-membered cyclic transition state process. The analysis of bond order and natural bond orbital charges implies that the bond polarization of C(=O)O-C, in the sense of C(=O)O(delta-)...C(delta+), is rate determining. The experimental and theoretical parameters have been found to be in reasonable agreement.

Comparison of orthorhombic and alpha-two titanium aluminides as matrices for continuous SiC-reinforced composites

NASA Astrophysics Data System (ADS)

Smith, P. R.; Graves, J. A.; Rhodes, Cg.

1994-06-01

The attributes of an orthorhombic Ti aluminide alloy, Ti-21Al-22Nb (at. pct), and an alpha-two Ti aluminide alloy, Ti-24Al-11Nb (at. pct), for use as a matrix with continuous SiC (SCS-6) fiber reinforcement have been compared. Foil-fiber-foil processing was used to produce both unreinforced (“neat”) and unidirectional “SCS-6” reinforced panels. Microstructure of the Ti-24A1-11Nb matrix consisted of ordered Ti3Al ( α 2) + disordered beta (β), while the Ti-21 Al-22Nb matrix contained three phases: α2, ordered beta ( β 0), and ordered orthorhombic (O). Fiber/ matrix interface reaction zone growth kinetics at 982 °C were examined for each composite system. Although both systems exhibited similar interface reaction products (i.e., mixed Ti carbides, silicides, and Ti-Al carbides), growth kinetics in the α 2 + β matrix composite were much more rapid than in the O + β 0 + α 2 matrix composite. Additionally, interfacial reaction in the α 2 + β} composite resulted in a relatively large brittle matrix zone, depleted of beta phase, which was not present in the O + β 0+ α 2 matrix composite. Mechanical property measurements included room and elevated temperature tensile, thermal stability, thermal fatigue, thermo-mechanical fatigue (TMF), and creep. The three-phase orthorhombic-based alloy outperformed the α2+ β alloy in all of these mechanical behavioral areas, on both an absolute and a specific (i.e., density corrected) basis.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anggita, R. K. Wardani, E-mail: anggita14@mhs.chem.its.ac.id; Yuniar, V. T. P., E-mail: yuniar11@mhs.chem.its.ac.id; Aini, W. T., E-mail: aini11@mhs.chem.its.ac.id

In this study, the influence of hydrothermal temperature and time at zeolite X supported on glasswool were investigated. The results of characterization using XRD showed that a single phase zeolite X with highest crystallinity was obtained when hydrothermal temperature and time at 100°C during 24 hours (ZXF100-24H). The CO{sub 2} adsorption capacity of ZXF100-24H has reached up to 10.15 wt. %. Kinetics of CO{sub 2} adsorption onto zeolite X supported on glasswool was investigated using pseudo-first-order, pseudo-second-order and intra-particle diffusion kinetic models. After evaluating three kinetic models for CO{sub 2} adsorption at adsorption temperatures of 30°C, 40°C and 50°C, itmore » was found that intra-particle diffusion kinetic model provided the best fitting for the adsorption data. Furthermore, the thermodynamic parameters of CO{sub 2} adsorption were obtained as follows, Gibbs free energy change (ΔG°) are −0.409 kJ/mol at 30°C, −0.274 kJ/mol at 40°C and −0.138 kJ/mol at 50 °C, whereas the enthalpy change (ΔH°) is −4.53 kJ/mol and the entropy change (ΔS°) is −0.0135 kJ/(mol K).« less

From MDF and PB wastes to adsorbents for the removal of pollutants

NASA Astrophysics Data System (ADS)

Gomes, J. A. F. L.; Azaruja, B. A.; Mourão, P. A. M.

2016-09-01

The production of activated carbons in powder and monolith forms, by physical activation with CO2, with specific surface areas between 804 and 1469 m2 g-1, porous volume between 0.33 and 0.59 cm3 g-1, with basic nature (PZC ∼ 9.6-10.6) was achieved in our lab, from medium density fibreboard (MDF) and particleboard (PB), engineered wood composites wastes. These highly porous adsorbents were applied in kinetic and equilibrium adsorption studies, in batch and dynamic modes, in powder and monolith forms, of specific adsorptives, considered pollutants, namely phenol (P), p-nitrophenol (PNP) and neutral red (NR). In batch the maximum adsorbed amount was 267, 162 and 92 mg g-1, for PNP, P and NR, respectively. The application of different kinetic models (pseudo-first order, pseudo-second order and intraparticle diffusion model) leads to a better knowledge of the adsorption mechanisms of those adsorptives. The results obtained in the kinetic and equilibrium tests show that the combination of the structural features and the surface chemistry nature of the adsorbents, with the adsorptives properties, establish the kinetic performance, the type and amount adsorbed for each system. This work confirms the potential of these types of wastes in the production of activated carbons and its application in adsorption from liquid phase.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reiche, Helmut Matthias; Vogel, Sven C.

New in situ data for the U-C system are presented, with the goal of improving knowledge of the phase diagram to enable production of new ceramic fuels. The none quenchable, cubic, δ-phase, which in turn is fundamental to computational methods, was identified. Rich datasets of the formation synthesis of uranium carbide yield kinetics data which allow the benchmarking of modeling, thermodynamic parameters etc. The order-disorder transition (carbon sublattice melting) was observed due to equal sensitivity of neutrons to both elements. This dynamic has not been accurately described in some recent simulation-based publications.

Theories of binary fluid mixtures: from phase-separation kinetics to active emulsions

NASA Astrophysics Data System (ADS)

Cates, Michael E.; Tjhung, Elsen

2018-02-01

Binary fluid mixtures are examples of complex fluids whose microstructure and flow are strongly coupled. For pairs of simple fluids, the microstructure consists of droplets or bicontinuous demixed domains and the physics is controlled by the interfaces between these domains. At continuum level, the structure is defined by a composition field whose gradients which are steep near interfaces drive its diffusive current. These gradients also cause thermodynamic stresses which can drive fluid flow. Fluid flow in turn advects the composition field, while thermal noise creates additional random fluxes that allow the system to explore its configuration space and move towards the Boltzmann distribution. This article introduces continuum models of binary fluids, first covering some well-studied areas such as the thermodynamics and kinetics of phase separation, and emulsion stability. We then address cases where one of the fluid components has anisotropic structure at mesoscopic scales creating nematic (or polar) liquid-crystalline order; this can be described through an additional tensor (or vector) order parameter field. We conclude by outlining a thriving area of current research, namely active emulsions, in which one of the binary components consists of living or synthetic material that is continuously converting chemical energy into mechanical work.

Phase-change memory function of correlated electrons in organic conductors

NASA Astrophysics Data System (ADS)

Oike, H.; Kagawa, F.; Ogawa, N.; Ueda, A.; Mori, H.; Kawasaki, M.; Tokura, Y.

2015-01-01

Phase-change memory (PCM), a promising candidate for next-generation nonvolatile memories, exploits quenched glassy and thermodynamically stable crystalline states as reversibly switchable state variables. We demonstrate PCM functions emerging from a charge-configuration degree of freedom in strongly correlated electron systems. Nonvolatile reversible switching between a high-resistivity charge-crystalline (or charge-ordered) state and a low-resistivity quenched state, charge glass, is achieved experimentally via heat pulses supplied by optical or electrical means in organic conductors θ -(BEDT-TTF)2X . Switching that is one order of magnitude faster is observed in another isostructural material that requires faster cooling to kinetically avoid charge crystallization, indicating that the material's critical cooling rate can be useful guidelines for pursuing a faster correlated-electron PCM function.

Numerical tests of local scale invariance in ageing q-state Potts models

NASA Astrophysics Data System (ADS)

Lorenz, E.; Janke, W.

2007-01-01

Much effort has been spent over the last years to achieve a coherent theoretical description of ageing as a non-linear dynamics process. Long supposed to be a consequence of the slow dynamics of glassy systems only, ageing phenomena could also be identified in the phase-ordering kinetics of simple ferromagnets. As a phenomenological approach Henkel et al. developed a group of local scale transformations under which two-time autocorrelation and response functions should transform covariantly. This work is to extend previous numerical tests of the predicted scaling functions for the Ising model by Monte Carlo simulations of two-dimensional q-state Potts models with q=3 and 8, which, in equilibrium, undergo temperature-driven phase transitions of second and first order, respectively.

Mercury removal from aqueous streams utilizing microemulsion liquid membranes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larson, K.A.; Wiencek, J.M.

1994-11-01

The goal of this work is the removal of mercury ion from wastewater using thermodynamically stable microemulsions as liquid membranes. The research focuses on identification and modeling of the appropriate aqueous and organic phase equilibrium reactions for mercury extraction and stripping, comparison of extraction kinetics between coarse emulsions and microemulsions, and demulsification and recovery of the emulsion components. An oleic acid microemulsion liquid membrane (water-in-oil) containing sulfuric acid as the internal phase reduces the feed phase mercury concentration from 460 mg/l to 0.84 mg/l in a single contacting. This compares favorably with a control extraction (oleic acid/no internal phase) whichmore » results in a final concentration of 20 mg/l Hg{sup +2}. Microemulsions can be demulsified using butanol as an additive. The demulsification kinetics are proportional to butanol concentration and temperature and inversely proportional to surfactant concentration. The demulsification rate is second order with respect to water concentration which implies that the rate-limiting step in the process is the rate of internal phase droplet encounters. Proof-of-principle experiments demonstrate the ability to extract mercury ion using microemulsions formulated with recycled organic phase, albeit at a somewhat reduced efficiency. The reduced efficiency is attributed to increased internal phase leakage due to residual butanol in the oil phase. Finally, the cycle is brought around full circle by recovering metallic mercury from the internal phase by electroplating. 27 refs., 11 figs., 1 tab.« less

Initial dissolution kinetics of cocrystal of carbamazepine with nicotinamide.

PubMed

Hattori, Yusuke; Sato, Maiko; Otsuka, Makoto

2015-11-01

Objectives of this study are investigating the initial dissolution kinetics of the cocrystal of carbamazepine (CBZ) with nicotinamide (NIC) and understanding its initial dissolution process. Cocrystal solids of CBZ with NIC were prepared by co-milling and solvent evaporation methods. The formation of cocrystal solid was verified via X-ray diffraction measurement. Dissolution tests of the solids were performed using an original flow cell and ultraviolet-visible spectroscopic detector. The spectra monitored in situ were analyzed to determine the dissolved compounds separately using the classical least squares regression method. The initial dissolution profiles were interpreted using simultaneous model of dissolution and phase changes. In the initial dissolution, CBZ in the cocrystal structure dissolved in water and it was suggested that CBZ reached a metastable intermediate state simultaneously with dissolution. The cocrystal solid prepared by solvent evaporation provided a higher rate constant of the phase change than that prepared by co-milling. Our results thus support the use of evaporation as the method of choice to produce ordered cocrystal structures. We suggest that CBZ forms dihydrate during the dissolution process; however, during the initial phase of dissolution, CBZ changes to a metastable intermediate phase. © 2015 Royal Pharmaceutical Society.

Potential for Non-Contact ACL Injury Between Step-Close-Jump and Hop-Jump Tasks.

PubMed

Wang, Li-I; Gu, Chin-Yi; Chen, Wei-Ling; Chang, Mu-San

2010-01-01

This study aimed to compare the kinematics and kinetics during the landing of hop-jump and step-close-jump movements in order to provide further inferring that the potential risk of ACL injuries. Eleven elite male volleyball players were recruited to perform hop-jump and step-close-jump tasks. Lower extremity kinematics and ground reaction forces during landing in stop-jump tasks were recorded. Lower extremity kinetics was calculated by using an inverse dynamic process. Step-close-jump tasks demonstrated smaller peak proximal tibia anterior shear forces during the landing phase. In step-close-jump tasks, increasing hip joint angular velocity during initial foot-ground contact decreased peak posterior ground reaction force during the landing phase, which theoretically could reduce the risk of ACL injury. Key pointsThe different landing techniques required for these two stop-jump tasks do not necessarily affect the jump height.Hop-jump decreased the hip joint angular velocity at initial foot contact with ground, which could lead to an increasing peak posterior GRF during the landing phase.Hop-jump decreased hip and knee joint angular flexion displacement during the landing, which could increase the peak vertical loading rate during the landing phase.

Chlorine decay and bacterial inactivation kinetics in drinking water in the tropics.

PubMed

Thøgersen, J; Dahi, E

1996-09-01

The decay of free chlorine (Cl2) and combined chlorine (mostly monochloramine: NH2Cl) and the inactivation of bacteria was examined in Dar es Salaam, Tanzania. Batch experiments, pilot-scale pipe experiments and full-scale pipe experiments were carried out to establish the kinetics for both decay and inactivation, and to compare the two disinfectants for use under tropical conditions. The decay of both disinfectants closely followed first order kinetics, with respect to the concentration of both disinfectant and disinfectant-consuming substances. Bacterial densities exhibited a kinetic pattern consisting of first order inactivation with respect to the density of the bacteria and the concentration of the disinfectant, and first order growth with respect to the bacterial density. The disinfection kinetic model takes the decaying concentration of the disinfectant into account. The decay rate constant for free chlorine was 114 lg(-1)h(-1), while the decay rate constant for combined chlorine was 1.84 lg(-1)h(-1) (1.6% of the decay rate for free chlorine). The average concentration of disinfectant consuming substances in the water phase was 2.6 mg Cl2/l for free chlorine and 5.6 mg NH2Cl/l for combined chlorine. The decay rate constant and the concentration of disinfectant consuming substances when water was pumped through pipes, depended on whether or not chlorination was continuous. Combined chlorine especially could clean the pipes of disinfectant consuming substances. The inactivation rate constant λ, was estimated at 3.06×10(4) lg(-1)h(-1). Based on the inactivation rate constant, and a growth rate constant determined in a previous study, the critical concentration of free chlorine was found to be 0.08 mg Cl2/l. The critical concentration is a value below which growth rates dominate over inactivation.

Modified Gompertz equation for electrotherapy murine tumor growth kinetics: predictions and new hypotheses

PubMed Central

2010-01-01

Background Electrotherapy effectiveness at different doses has been demonstrated in preclinical and clinical studies; however, several aspects that occur in the tumor growth kinetics before and after treatment have not yet been revealed. Mathematical modeling is a useful instrument that can reveal some of these aspects. The aim of this paper is to describe the complete growth kinetics of unperturbed and perturbed tumors through use of the modified Gompertz equation in order to generate useful insight into the mechanisms that underpin this devastating disease. Methods The complete tumor growth kinetics for control and treated groups are obtained by interpolation and extrapolation methods with different time steps, using experimental data of fibrosarcoma Sa-37. In the modified Gompertz equation, a delay time is introduced to describe the tumor's natural history before treatment. Different graphical strategies are used in order to reveal new information in the complete kinetics of this tumor type. Results The first stage of complete tumor growth kinetics is highly non linear. The model, at this stage, shows different aspects that agree with those reported theoretically and experimentally. Tumor reversibility and the proportionality between regions before and after electrotherapy are demonstrated. In tumors that reach partial remission, two antagonistic post-treatment processes are induced, whereas in complete remission, two unknown antitumor mechanisms are induced. Conclusion The modified Gompertz equation is likely to lead to insights within cancer research. Such insights hold promise for increasing our understanding of tumors as self-organizing systems and, the possible existence of phase transitions in tumor growth kinetics, which, in turn, may have significant impacts both on cancer research and on clinical practice. PMID:21029411

Enthalpy and high temperature relaxation kinetics of stable vapor-deposited glasses of toluene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharya, Deepanjan; Sadtchenko, Vlad, E-mail: vlad@gwu.edu

Stable non-crystalline toluene films of micrometer and nanometer thicknesses were grown by vapor deposition at distinct rates and probed by fast scanning calorimetry. Fast scanning calorimetry is shown to be extremely sensitive to the structure of the vapor-deposited phase and was used to characterize simultaneously its kinetic stability and its thermodynamic properties. According to our analysis, transformation of vapor-deposited samples of toluene during heating with rates in excess 10{sup 5} K s{sup −1} follows the zero-order kinetics. The transformation rate correlates strongly with the initial enthalpy of the sample, which increases with the deposition rate according to sub-linear law. Analysismore » of the transformation kinetics of vapor-deposited toluene films of various thicknesses reveal a sudden increase in the transformation rate for films thinner than 250 nm. The change in kinetics seems to correlate with the surface roughness scale of the substrate. The implications of these findings for the formation mechanism and structure of vapor-deposited stable glasses are discussed.« less

Microstructure and hydrogenation properties of a melt-spun non-stoichiometric Zr-based Laves phase alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Tiebang, E-mail: tiebangzhang@nwpu.edu.cn; Zhang, Yunlong; Li, Jinshan

2016-01-15

Alloy with composition of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} off normal stoichiometric proportion is selected to investigate the effect of defects introduced by non-stoichiometry on hydrogenation kinetics of Zr–Ti–V Laves phase alloys. Microstructure and phase constituent of melt-spun ribbons have been investigated in this work. The activation process, hydrogenation kinetics, thermodynamics characteristics and hydride phase constituent of as-cast alloy and melt-spun ribbons are also compared. Comparing with the as-cast alloy, the dominant Laves phase ZrV{sub 2} is preserved, V-BCC phase is reduced and α-Zr phase is replaced by a small amount of Zr{sub 3}V{sub 3}O phase in melt-spun ribbons. Melt-spun ribbonsmore » exhibit easy activation and fast initial hydrogen absorption on account of the increased specific surface area. However, the decrease in unit cell volume of the dominant phase leads to the decrease in hydrogen absorption capacity. Melt-spinning technique raises the equilibrium pressure and decreases the stability of hydride due to the decrease of unit cell volume and the elimination of α-Zr phase, respectively. Melt-spun ribbons with fine grains show improved hydrogen absorption kinetics comparing with that of the as-cast alloy. Meanwhile, the prevalent micro twins observed within melt-spun ribbons are believed to account for the improved hydrogen absorption kinetics. - Highlights: • Role of defects on hydrogenation kinetics of Zr-based alloys is proposed. • Microstructure and hydrogenation properties of as-cast/melt-spun alloy are compared. • Melt-spinning technique improves the hydrogenation kinetics of Zr{sub 0.9}Ti{sub 0.1}V{sub 1.7} alloy. • Refined grains and twin defects account for improved hydrogen absorption kinetics.« less

Gyrokinetic and kinetic particle-in-cell simulations of guide-field reconnection. I. Macroscopic effects of the electron flows

DOE Office of Scientific and Technical Information (OSTI.GOV)

Muñoz, P. A., E-mail: munozp@mps.mpg.de; Kilian, P.; Büchner, J.

In this work, we compare gyrokinetic (GK) with fully kinetic Particle-in-Cell (PIC) simulations of magnetic reconnection in the limit of strong guide field. In particular, we analyze the limits of applicability of the GK plasma model compared to a fully kinetic description of force free current sheets for finite guide fields (b{sub g}). Here, we report the first part of an extended comparison, focusing on the macroscopic effects of the electron flows. For a low beta plasma (β{sub i} = 0.01), it is shown that both plasma models develop magnetic reconnection with similar features in the secondary magnetic islands if a sufficientlymore » high guide field (b{sub g} ≳ 30) is imposed in the kinetic PIC simulations. Outside of these regions, in the separatrices close to the X points, the convergence between both plasma descriptions is less restrictive (b{sub g} ≳ 5). Kinetic PIC simulations using guide fields b{sub g} ≲ 30 reveal secondary magnetic islands with a core magnetic field and less energetic flows inside of them in comparison to the GK or kinetic PIC runs with stronger guide fields. We find that these processes are mostly due to an initial shear flow absent in the GK initialization and negligible in the kinetic PIC high guide field regime, in addition to fast outflows on the order of the ion thermal speed that violate the GK ordering. Since secondary magnetic islands appear after the reconnection peak time, a kinetic PIC/GK comparison is more accurate in the linear phase of magnetic reconnection. For a high beta plasma (β{sub i} = 1.0) where reconnection rates and fluctuations levels are reduced, similar processes happen in the secondary magnetic islands in the fully kinetic description, but requiring much lower guide fields (b{sub g} ≲ 3)« less

Kinetics of corneal thermal shrinkage

NASA Astrophysics Data System (ADS)

Borja, David; Manns, Fabrice; Lee, William E.; Parel, Jean-Marie

2004-07-01

Purpose: The purpose of this study was to determine the effects of temperature and heating duration on the kinetics of thermal shrinkage in corneal strips using a custom-made shrinkage device. Methods: Thermal shrinkage was induced and measured in corneal strips under a constant load placed while bathed in 25% Dextran irrigation solution. A study was performed on 57 Florida Lions Eye Bank donated human cadaver eyes to determine the effect of temperature on the amount and rate of thermal shrinkage. Further experiments were performed on 20 human cadaver eyes to determine the effects of heating duration on permanent shrinkage. Data analysis was performed to determine the effects of temperature, heating duration, and age on the amount and kinetics of shrinkage. Results: Shrinkage consisted of two phases: a shrinkage phase during heating and a regression phase after heating. Permanent shrinkage increased with temperature and duration. The shrinkage and regression time constants followed Arrhenius type temperature dependence. The shrinkage time constants where calculated to be 67, 84, 121, 560 and 1112 (s) at 80, 75, 70, 65, and 60°C respectively. At 65°C the permanent shrinkage time constant was calculated to be 945s. Conclusion: These results show that shrinkage treatments need to raise the temperature of the tissue above 75°C for several seconds in order to prevent regression of the shrinkage effect immediately after treatment and to induce the maximum amount of permanent irreversible shrinkage.

Sequential anaerobic/aerobic digestion of waste activated sludge: analysis of the process performance and kinetic study.

PubMed

Tomei, M Concetta; Rita, Sara; Mininni, Giuseppe

2011-12-15

Sequential anaerobic-aerobic digestion was applied to waste activated sludge (WAS) of a full scale wastewater treatment plant. The study was performed with the objective of testing the sequential digestion process on WAS, which is characterized by worse digestibility in comparison with the mixed sludge. Process performance was evaluated in terms of biogas production, volatile solids (VS) and COD reduction, and patterns of biopolymers (proteins and polysaccharides) in the subsequent digestion stages. VS removal efficiency of 40%, in the anaerobic phase, and an additional removal of 26%, in the aerobic one, were observed. For total COD removal efficiencies of 35% and 25% for anaerobic and aerobic stage respectively, were obtained. Kinetics of VS degradation process was analyzed by assuming a first order equation with respect to VS concentration. Evaluated kinetic parameters were 0.44 ± 0.20 d(-1) and 0.25 ± 0.15 d(-1) for the anaerobic stage and aerobic stage, respectively. With regard to biopolymers, in the anaerobic phase the content of proteins and polysaccharides increased to 50% and 69%, respectively, whereas in the subsequent aerobic phase, a decrease of 71% for proteins and 67% for polysaccharides was observed. The average specific biogas production 0.74 m(3)/(kg VS destroyed), was in the range of values reported in the specialized literature for conventional anaerobic mesophilic WAS digestion. Copyright © 2011 Elsevier B.V. All rights reserved.

Search for dark photons using data from CRESST-II Phase 2

NASA Astrophysics Data System (ADS)

Gütlein, A.; Angloher, G.; Bento, A.; Bucci, C.; Canonica, L.; Defay, X.; Erb, A.; Feilitzsch, F. v.; Ferreiro Iachellini, N.; Gorla, P.; Hauff, D.; Jochum, J.; Kiefer, M.; Kluck, H.; Kraus, H.; Lanfranchi, J.-C.; Loebell, J.; Mancuso, M.; Münster, A.; Pagliarone, C.; Petricca, F.; Potzel, W.; Pröbst, F.; Puig, R.; Reindl, F.; Schäffner, K.; Schieck, J.; Schönert, S.; Seidel, W.; Stahlberg, M.; Stodolsky, L.; Strandhagen, C.; Strauss, R.; Tanzke, A.; Trinh Thi, H. H.; Türkoǧlu, C.; Uffinger, M.; Ulrich, A.; Usherov, I.; Wawoczny, S.; Willers, M.; Wüstrich, M.; Zöller, A.

2017-09-01

Understanding the nature and origin of dark matter is one of the most important challenges for modern particle physics. During the previous decade the sensitivities of direct dark matter searches have improved by several orders of magnitude. These experiments focus their work mainly on the search for dark-matter particles interacting with nuclei (e.g. Weakly Interacting Massive Particles, WIMPs). However, there exists a large variety of different candidates for dark-matter particles. One of these candidates, the so-called dark photon, is a long-lived vector boson with a kinetic mixing to the standard-model photon. In this work we present the preliminary results of our search for dark photons. Using data from the direct dark matter search CRESST-II Phase 2 we can improve the existing constraints for the kinetic mixing for dark-photon masses between 0.3 and 0.5 keV/c2. In addition, we also present projected sensitivities for the next phases of the CRESST-III experiment showing great potential to improve the sensitivity for dark-photon masses below 1 keV.

An Unusual Salt Effect in an Interfacial Nucleophilic Substitution Reaction.

PubMed

Li, Shuheng; Mrksich, Milan

2018-06-12

This paper reports a kinetic characterization of the interfacial reaction of N-methylpyrrolidine with a self-assembled monolayer presenting an iodoalkyl group. SAMDI (self-assembled monolayers for matrix-assisted laser desorption/ionization) mass spectrometry was used to determine the extent of reaction for monolayers that were treated with a range of concentrations of the nucleophile for a range of times. These data revealed a second-order rate constant for the reaction that was approximately 100-fold greater than that for the analogous solution-phase reaction. However, addition of sodium iodide to the reaction mixture resulted in a 7-fold decrease in the reaction rate. Addition of bromide and chloride salts also gave slower rate constants for the reaction, but only at 100- and 1000-fold higher concentrations than was observed with iodide, respectively. The corresponding solution-phase reactions, by contrast, had rate constants that were unaffected by the concentration of halide salts. This work provides a well-characterized example illustrating the extent to which the kinetics and properties of an interfacial reaction can depart substantially from their better-understood solution-phase counterparts.

Study of non-thermal photon production under different scenarios in solar flares. 1: Scenarios and formulations

NASA Technical Reports Server (NTRS)

Perez-Peraza, J.; Alvarez, M.; Gallegos, A.

1985-01-01

In order to study the overall phenomenology involved in solar flares, it is necessary to understand their individual manifestation before building a corresponding description of the global phenomenon. Here the concern is with the production of X and gamma rays in solar flares. Flares are initiated very often within the closed magnetic field configurations of active centers. According (2) when beta = kinetic energy density/magnetic energy density approximately 0.2, the magnetic trap configuration is destructed within the time scale of the impulsive phase of flares ( 100 s). A first particle acceleration stage occurs during this phase as indicated by impulsive microwave and hard X-rays bursts. In some flare events, when the field strength beta is very high, the broken field lines may close again, such that later, in the course of the flash and main phases more hot plasma of very high conductivity is created, and so, the field and frozen plasma expand outward, as the kinetic pressure inside the closed loops increases. The magnetically trapped particles excite strong Alfven wave turbulence of small transverse scale.

Phase Transitions in Model Active Systems

NASA Astrophysics Data System (ADS)

Redner, Gabriel S.

The amazing collective behaviors of active systems such as bird flocks, schools of fish, and colonies of microorganisms have long amazed scientists and laypeople alike. Understanding the physics of such systems is challenging due to their far-from-equilibrium dynamics, as well as the extreme diversity in their ingredients, relevant time- and length-scales, and emergent phenomenology. To make progress, one can categorize active systems by the symmetries of their constituent particles, as well as how activity is expressed. In this work, we examine two categories of active systems, and explore their phase behavior in detail. First, we study systems of self-propelled spherical particles moving in two dimensions. Despite the absence of an aligning interaction, this system displays complex emergent dynamics, including phase separation into a dense active solid and dilute gas. Using simulations and analytic modeling, we quantify the phase diagram and separation kinetics. We show that this nonequilibrium phase transition is analogous to an equilibrium vapor-liquid system, with binodal and spinodal curves and a critical point. We also characterize the dense active solid phase, a unique material which exhibits the structural signatures of a crystalline solid near the crystal-hexatic transition point, as well as anomalous dynamics including superdiffusive motion on intermediate timescales. We also explore the role of interparticle attraction in this system. We demonstrate that attraction drastically changes the phase diagram, which contains two distinct phase-separated regions and is reentrant as a function of propulsion speed. We interpret this complex situation with a simple kinetic model, which builds from the observed microdynamics of individual particles to a full description of the macroscopic phase behavior. We also study active nematics, liquid crystals driven out of equilibrium by energy-dissipating active stresses. The equilibrium nematic state is unstable in these materials, leading to beautiful and surprising behaviors including the spontaneous generation of topological defect pairs which stream through the system and later annihilate, yielding a complex, seemingly chaotic dynamical steady-state. Here, we describe the emergence of order from this chaos in the form of previously unknown broken-symmetry phases in which the topological defects themselves undergo orientational ordering. We have identified these defect-ordered phases in two realizations of an active nematic: first, a suspension of extensile bundles of microtubules and molecular motor proteins, and second, a computational model of extending hard rods. We will describe the defect-stabilized phases that manifest in these systems, our current understanding of their origins, and discuss whether such phases may be a general feature of extensile active nematics.

Nuclear Quantum Effects in Water at the Triple Point: Using Theory as a Link Between Experiments.

PubMed

Cheng, Bingqing; Behler, Jörg; Ceriotti, Michele

2016-06-16

One of the most prominent consequences of the quantum nature of light atomic nuclei is that their kinetic energy does not follow a Maxwell-Boltzmann distribution. Deep inelastic neutron scattering (DINS) experiments can measure this effect. Thus, the nuclear quantum kinetic energy can be probed directly in both ordered and disordered samples. However, the relation between the quantum kinetic energy and the atomic environment is a very indirect one, and cross-validation with theoretical modeling is therefore urgently needed. Here, we use state of the art path integral molecular dynamics techniques to compute the kinetic energy of hydrogen and oxygen nuclei in liquid, solid, and gas-phase water close to the triple point, comparing three different interatomic potentials and validating our results against equilibrium isotope fractionation measurements. We will then show how accurate simulations can draw a link between extremely precise fractionation experiments and DINS, therefore establishing a reliable benchmark for future measurements and providing key insights to increase further the accuracy of interatomic potentials for water.

The response of the HMX-based material PBXN-9 to thermal insults: thermal decomposition kinetics and morphological changes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glascoe, E A; Hsu, P C; Springer, H K

PBXN-9, an HMX-formulation, is thermally damaged and thermally decomposed in order to determine the morphological changes and decomposition kinetics that occur in the material after mild to moderate heating. The material and its constituents were decomposed using standard thermal analysis techniques (DSC and TGA) and the decomposition kinetics are reported using different kinetic models. Pressed parts and prill were thermally damaged, i.e. heated to temperatures that resulted in material changes but did not result in significant decomposition or explosion, and analyzed. In general, the thermally damaged samples showed a significant increase in porosity and decrease in density and a smallmore » amount of weight loss. These PBXN-9 samples appear to sustain more thermal damage than similar HMX-Viton A formulations and the most likely reasons are the decomposition/evaporation of a volatile plasticizer and a polymorphic transition of the HMX from {beta} to {delta} phase.« less

Kinetic Phase Diagrams of Ternary Al-Cu-Li System during Rapid Solidification: A Phase-Field Study

PubMed Central

Yang, Xiong; Zhang, Lijun; Sobolev, Sergey; Du, Yong

2018-01-01

Kinetic phase diagrams in technical alloys at different solidification velocities during rapid solidification are of great importance for guiding the novel alloy preparation, but are usually absent due to extreme difficulty in performing experimental measurements. In this paper, a phase-field model with finite interface dissipation was employed to construct kinetic phase diagrams in the ternary Al-Cu-Li system for the first time. The time-elimination relaxation scheme was utilized. The solute trapping phenomenon during rapid solidification could be nicely described by the phase-field simulation, and the results obtained from the experiment measurement and/or the theoretical model were also well reproduced. Based on the predicted kinetic phase diagrams, it was found that with the increase of interface moving velocity and/or temperature, the gap between the liquidus and solidus gradually reduces, which illustrates the effect of solute trapping and tendency of diffusionless solidification. PMID:29419753

Effect of Niobium on Phase Transformations, Mechanical Properties and Corrosion of Supermartensitic Stainless Steel

NASA Astrophysics Data System (ADS)

de Oliveira, Mariana Perez; Calderón-Hernández, José Wilmar; Magnabosco, Rodrigo; Hincapie-Ladino, Duberney; Alonso-Falleiros, Neusa

2017-04-01

The influence of niobium addition in a supermartensitic stainless steel with 13Cr-5Ni-2Mo has been studied. The steel with Nb tempered at 600 °C for 2 h showed improved mechanical resistance properties and lower degree of sensitization, without compromising elongation and pitting corrosion resistance, when compared to the reference steel. In order to understand the Nb effect in such steel, mainly regarding phase transformation, different tempering time intervals have been studied. The better performance of the SM2MoNb is attributed to the hindering effect that Nb has in the kinetics of the phase transformations during tempering, delaying the precipitation start and coarsening stages of the present phases.

Kinetics-based phase change approach for VOF method applied to boiling flow

NASA Astrophysics Data System (ADS)

Cifani, Paolo; Geurts, Bernard; Kuerten, Hans

2014-11-01

Direct numerical simulations of boiling flows are performed to better understand the interaction of boiling phenomena with turbulence. The multiphase flow is simulated by solving a single set of equations for the whole flow field according to the one-fluid formulation, using a VOF interface capturing method. Interface terms, related to surface tension, interphase mass transfer and latent heat, are added at the phase boundary. The mass transfer rate across the interface is derived from kinetic theory and subsequently coupled with the continuum representation of the flow field. The numerical model was implemented in OpenFOAM and validated against 3 cases: evaporation of a spherical uniformly heated droplet, growth of a spherical bubble in a superheated liquid and two dimensional film boiling. The computational model will be used to investigate the change in turbulence intensity in a fully developed channel flow due to interaction with boiling heat and mass transfer. In particular, we will focus on the influence of the vapor bubble volume fraction on enhancing heat and mass transfer. Furthermore, we will investigate kinetic energy spectra in order to identify the dynamics associated with the wakes of vapor bubbles. Department of Applied Mathematics, 7500 AE Enschede, NL.

Fourth-Order Conservative Vlasov-Maxwell Solver for Cartesian and Cylindrical Phase Space Coordinates

NASA Astrophysics Data System (ADS)

Vogman, Genia

Plasmas are made up of charged particles whose short-range and long-range interactions give rise to complex behavior that can be difficult to fully characterize experimentally. One of the most complete theoretical descriptions of a plasma is that of kinetic theory, which treats each particle species as a probability distribution function in a six-dimensional position-velocity phase space. Drawing on statistical mechanics, these distribution functions mathematically represent a system of interacting particles without tracking individual ions and electrons. The evolution of the distribution function(s) is governed by the Boltzmann equation coupled to Maxwell's equations, which together describe the dynamics of the plasma and the associated electromagnetic fields. When collisions can be neglected, the Boltzmann equation is reduced to the Vlasov equation. High-fidelity simulation of the rich physics in even a subset of the full six-dimensional phase space calls for low-noise high-accuracy numerical methods. To that end, this dissertation investigates a fourth-order finite-volume discretization of the Vlasov-Maxwell equation system, and addresses some of the fundamental challenges associated with applying these types of computationally intensive enhanced-accuracy numerical methods to phase space simulations. The governing equations of kinetic theory are described in detail, and their conservation-law weak form is derived for Cartesian and cylindrical phase space coordinates. This formulation is well known when it comes to Cartesian geometries, as it is used in finite-volume and finite-element discretizations to guarantee local conservation for numerical solutions. By contrast, the conservation-law weak form of the Vlasov equation in cylindrical phase space coordinates is largely unexplored, and to the author's knowledge has never previously been solved numerically. Thereby the methods described in this dissertation for simulating plasmas in cylindrical phase space coordinates present a new development in the field of computational plasma physics. A fourth-order finite-volume method for solving the Vlasov-Maxwell equation system is presented first for Cartesian and then for cylindrical phase space coordinates. Special attention is given to the treatment of the discrete primary variables and to the quadrature rule for evaluating the surface and line integrals that appear in the governing equations. The finite-volume treatment of conducting wall and axis boundaries is particularly nuanced when it comes to phase space coordinates, and is described in detail. In addition to the mechanics of each part of the finite-volume discretization in the two different coordinate systems, the complete algorithm is also presented. The Cartesian coordinate discretization is applied to several well-known test problems. Since even linear analysis of kinetic theory governing equations is complicated on account of velocity being an independent coordinate, few analytic or semi-analytic predictions exist. Benchmarks are particularly scarce for configurations that have magnetic fields and involve more than two phase space dimensions. Ensuring that simulations are true to the physics thus presents a difficulty in the development of robust numerical methods. The research described in this dissertation addresses this challenge through the development of more complete physics-based benchmarks based on the Dory-Guest-Harris instability. The instability is a special case of perpendicularly-propagating kinetic electrostatic waves in a warm uniformly magnetized plasma. A complete derivation of the closed-form linear theory dispersion relation for the instability is presented. The electric field growth rates and oscillation frequencies specified by the dispersion relation provide concrete measures against which simulation results can be quantitatively compared. Furthermore, a specialized form of perturbation is shown to strongly excite the fastest growing mode. The fourth-order finite-volume algorithm is benchmarked against the instability, and is demonstrated to have good convergence properties and close agreement with theoretical growth rate and oscillation frequency predictions. The Dory-Guest-Harris instability benchmark extends the scope of standard test problems by providing a substantive means of validating continuum kinetic simulations of warm magnetized plasmas in higher-dimensional 3D ( x,vx,vy) phase space. The linear theory analysis, initial conditions, algorithm description, and comparisons between theoretical predictions and simulation results are presented. The cylindrical coordinate finite-volume discretization is applied to model axisymmetric systems. Since mitigating the prohibitive computational cost of simulating six dimensions is another challenge in phase space simulations, the development of a robust means of exploiting symmetry is a major advance when it comes to numerically solving the Vlasov-Maxwell equation system. The discretization is applied to a uniform distribution function to assess the nature of the singularity at the axis, and is demonstrated to converge at fourth-order accuracy. The numerical method is then applied to simulate electrostatic ion confinement in an axisymmetric Z-pinch configuration. To the author's knowledge this presents the first instance of a conservative finite-volume discretization of the cylindrical coordinate Vlasov equation. The computational framework for the Vlasov-Maxwell solver is described, and an outlook for future research is presented.

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

A first approximation kinetic model to predict methane generation from an oil sands tailings settling basin.

PubMed

Siddique, Tariq; Gupta, Rajender; Fedorak, Phillip M; MacKinnon, Michael D; Foght, Julia M

2008-08-01

A small fraction of the naphtha diluent used for oil sands processing escapes with tailings and supports methane (CH(4)) biogenesis in large anaerobic settling basins such as Mildred Lake Settling Basin (MLSB) in northern Alberta, Canada. Based on the rate of naphtha metabolism in tailings incubated in laboratory microcosms, a kinetic model comprising lag phase, rate of hydrocarbon metabolism and conversion to CH(4) was developed to predict CH(4) biogenesis and flux from MLSB. Zero- and first-order kinetic models, respectively predicted generation of 5.4 and 5.1 mmol CH(4) in naphtha-amended microcosms compared to 5.3 (+/-0.2) mmol CH(4) measured in microcosms during 46 weeks of incubation. These kinetic models also predicted well the CH(4) produced by tailings amended with either naphtha-range n-alkanes or BTEX compounds at concentrations similar to those expected in MLSB. Considering 25% of MLSB's 200 million m(3) tailings volume to be methanogenic, the zero- and first-order kinetic models applied over a wide range of naphtha concentrations (0.01-1.0 wt%) predicted production of 8.9-400 million l CH(4) day(-1) from MLSB, which exceeds the estimated production of 3-43 million l CH(4) day(-1). This discrepancy may result from heterogeneity and density of the tailings, presence of nutrients in the microcosms, and/or overestimation of the readily biodegradable fraction of the naphtha in MLSB tailings.

Application of global kinetic models to HMX beta-delta transition and cookoff processes.

PubMed

Wemhoff, Aaron P; Burnham, Alan K; Nichols, Albert L

2007-03-08

The reduction of the number of reactions in kinetic models for both the HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia instrumented thermal ignition (SITI) and scaled thermal explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on one-dimensional time to explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as well with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multistep Arrhenius model and can contain up to 90% fewer chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from differential scanning calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multistep Arrhenius approach, and up to 11% using a Prout-Tompkins cookoff model.

A new hybrid-Lagrangian numerical scheme for gyrokinetic simulation of tokamak edge plasma

DOE PAGES

Ku, S.; Hager, R.; Chang, C. S.; ...

2016-04-01

In order to enable kinetic simulation of non-thermal edge plasmas at a reduced computational cost, a new hybrid-Lagrangian δf scheme has been developed that utilizes the phase space grid in addition to the usual marker particles, taking advantage of the computational strengths from both sides. The new scheme splits the particle distribution function of a kinetic equation into two parts. Marker particles contain the fast space-time varying, δf, part of the distribution function and the coarse-grained phase-space grid contains the slow space-time varying part. The coarse-grained phase-space grid reduces the memory-requirement and the computing cost, while the marker particles providemore » scalable computing ability for the fine-grained physics. Weights of the marker particles are determined by a direct weight evolution equation instead of the differential form weight evolution equations that the conventional delta-f schemes use. The particle weight can be slowly transferred to the phase space grid, thereby reducing the growth of the particle weights. The non-Lagrangian part of the kinetic equation – e.g., collision operation, ionization, charge exchange, heat-source, radiative cooling, and others – can be operated directly on the phase space grid. Deviation of the particle distribution function on the velocity grid from a Maxwellian distribution function – driven by ionization, charge exchange and wall loss – is allowed to be arbitrarily large. In conclusion, the numerical scheme is implemented in the gyrokinetic particle code XGC1, which specializes in simulating the tokamak edge plasma that crosses the magnetic separatrix and is in contact with the material wall.« less

Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

PubMed

Stloukal, Petr; Pekařová, Silvie; Kalendova, Alena; Mattausch, Hannelore; Laske, Stephan; Holzer, Clemens; Chitu, Livia; Bodner, Sabine; Maier, Guenther; Slouf, Miroslav; Koutny, Marek

2015-08-01

The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

A new hybrid-Lagrangian numerical scheme for gyrokinetic simulation of tokamak edge plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ku, S.; Hager, R.; Chang, C. S.

In order to enable kinetic simulation of non-thermal edge plasmas at a reduced computational cost, a new hybrid-Lagrangian δf scheme has been developed that utilizes the phase space grid in addition to the usual marker particles, taking advantage of the computational strengths from both sides. The new scheme splits the particle distribution function of a kinetic equation into two parts. Marker particles contain the fast space-time varying, δf, part of the distribution function and the coarse-grained phase-space grid contains the slow space-time varying part. The coarse-grained phase-space grid reduces the memory-requirement and the computing cost, while the marker particles providemore » scalable computing ability for the fine-grained physics. Weights of the marker particles are determined by a direct weight evolution equation instead of the differential form weight evolution equations that the conventional delta-f schemes use. The particle weight can be slowly transferred to the phase space grid, thereby reducing the growth of the particle weights. The non-Lagrangian part of the kinetic equation – e.g., collision operation, ionization, charge exchange, heat-source, radiative cooling, and others – can be operated directly on the phase space grid. Deviation of the particle distribution function on the velocity grid from a Maxwellian distribution function – driven by ionization, charge exchange and wall loss – is allowed to be arbitrarily large. In conclusion, the numerical scheme is implemented in the gyrokinetic particle code XGC1, which specializes in simulating the tokamak edge plasma that crosses the magnetic separatrix and is in contact with the material wall.« less

A new hybrid-Lagrangian numerical scheme for gyrokinetic simulation of tokamak edge plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ku, S., E-mail: sku@pppl.gov; Hager, R.; Chang, C.S.

In order to enable kinetic simulation of non-thermal edge plasmas at a reduced computational cost, a new hybrid-Lagrangian δf scheme has been developed that utilizes the phase space grid in addition to the usual marker particles, taking advantage of the computational strengths from both sides. The new scheme splits the particle distribution function of a kinetic equation into two parts. Marker particles contain the fast space-time varying, δf, part of the distribution function and the coarse-grained phase-space grid contains the slow space-time varying part. The coarse-grained phase-space grid reduces the memory-requirement and the computing cost, while the marker particles providemore » scalable computing ability for the fine-grained physics. Weights of the marker particles are determined by a direct weight evolution equation instead of the differential form weight evolution equations that the conventional delta-f schemes use. The particle weight can be slowly transferred to the phase space grid, thereby reducing the growth of the particle weights. The non-Lagrangian part of the kinetic equation – e.g., collision operation, ionization, charge exchange, heat-source, radiative cooling, and others – can be operated directly on the phase space grid. Deviation of the particle distribution function on the velocity grid from a Maxwellian distribution function – driven by ionization, charge exchange and wall loss – is allowed to be arbitrarily large. The numerical scheme is implemented in the gyrokinetic particle code XGC1, which specializes in simulating the tokamak edge plasma that crosses the magnetic separatrix and is in contact with the material wall.« less

A physics-based fractional order model and state of energy estimation for lithium ion batteries. Part I: Model development and observability analysis

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Fan, Guodong; Pan, Ke; Wei, Guo; Zhu, Chunbo; Rizzoni, Giorgio; Canova, Marcello

2017-11-01

The design of a lumped parameter battery model preserving physical meaning is especially desired by the automotive researchers and engineers due to the strong demand for battery system control, estimation, diagnosis and prognostics. In light of this, a novel simplified fractional order electrochemical model is developed for electric vehicle (EV) applications in this paper. In the model, a general fractional order transfer function is designed for the solid phase lithium ion diffusion approximation. The dynamic characteristics of the electrolyte concentration overpotential are approximated by a first-order resistance-capacitor transfer function in the electrolyte phase. The Ohmic resistances and electrochemical reaction kinetics resistance are simplified to a lumped Ohmic resistance parameter. Overall, the number of model parameters is reduced from 30 to 9, yet the accuracy of the model is still guaranteed. In order to address the dynamics of phase-change phenomenon in the active particle during charging and discharging, variable solid-state diffusivity is taken into consideration in the model. Also, the observability of the model is analyzed on two types of lithium ion batteries subsequently. Results show the fractional order model with variable solid-state diffusivity agrees very well with experimental data at various current input conditions and is suitable for electric vehicle applications.

Transformers: the changing phases of low-dimensional vanadium oxide bronzes.

PubMed

Marley, Peter M; Horrocks, Gregory A; Pelcher, Kate E; Banerjee, Sarbajit

2015-03-28

In this feature article, we explore the electronic and structural phase transformations of ternary vanadium oxides with the composition MxV2O5 where M is an intercalated cation. The periodic arrays of intercalated cations ordered along quasi-1D tunnels or layered between 2D sheets of the V2O5 framework induce partial reduction of the framework vanadium atoms giving rise to charge ordering patterns that are specific to the metal M and stoichiometry x. This periodic charge ordering makes these materials remarkably versatile platforms for studying electron correlation and underpins the manifestation of phenomena such as colossal metal-insulator transitions, quantized charge corrals, and superconductivity. We describe current mechanistic understanding of these emergent phenomena with a particular emphasis on the benefits derived from scaling these materials to nanostructured dimensions wherein precise ordering of cations can be obtained and phase relationships can be derived that are entirely inaccessible in the bulk. In particular, structural transformations induced by intercalation are dramatically accelerated due to the shorter diffusion path lengths at nanometer-sized dimensions, which cause a dramatic reduction of kinetic barriers to phase transformations and facilitate interconversion between the different frameworks. We conclude by summarizing numerous technological applications that have become feasible due to recent advances in controlling the structural chemistry and both electronic and structural phase transitions in these versatile frameworks.

Pulsed Electrodeposition of Amorphous and Composite Alloys.

DTIC Science & Technology

1983-09-01

lamellar- eutectic composites. A new phenomenon was dis- covered that deposits consisting of alternate layers of the same phase and essentially the...phenomenon will be discussed in connection with the Cu-Zn alloys. The recrystallization kinetics of the Ni-Mo alloys were investigated in order to find...transmission-electron-microscopic examination. The percent of the area which had recrystallized was determined on photographs using a planimeter. From a

Advanced Communication for Wireless Sensor Networks

DTIC Science & Technology

2016-08-22

characteristic peaks of the PZT crystallography and the presence of non-desired secondary phases. Regarding the spinel thin film, a new sol gel process...particles with the desired crystallography were obtained. As shown in Figure 21 (left), the particle morphology and size can be seen using TEM...film. The crystallography of the films was characterized at different annealing temperatures in order to determine the crystallization kinetics. It

Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases

NASA Astrophysics Data System (ADS)

Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.

2016-03-01

Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.

Experiments on Nucleation in Different Flow Regimes

NASA Technical Reports Server (NTRS)

Bayuzick, R. J.; Hofmeister, W. H.; Morton, C. M.; Robinson, M. B.

1999-01-01

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods. Dilatometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Kinetic Electric Field Signatures Associated with Magnetic Turbulence and Their Impact on Space Plasma Environments

NASA Astrophysics Data System (ADS)

Goodrich, K. A.

Magnetic turbulence is a universal phenomenon that occurs in space plasma physics, the small-scale processes of which is not well understood. This thesis presents on observational analysis of kinetic electric field signatures associated with magnetic turbulence, in an attempt to examine its underlying microphysics. Such kinetic signatures include small-scale magnetic holes, double layers, and phase-space holes. The first and second parts of this thesis presents observations of small-scale magnetic holes, observed depressions in total magnetic field strength with spatial widths on the order of or less than the ion Larmor radius, in the near-Earth plasmasheet. Here I demonstrate electric field signatures associated small-scale magnetic holes are consistent with the presence of electron Hall currents, currents oriented perpendicularly to the magnetic field. Further investigation of these fields indicates that the Hall electron current is primarily responsible for the depletion of | B| associated with small-scale magnetic holes. I then present evidence that suggests these currents can descend to smaller spatial scales, indicating they participate in a turbulent cascade to smaller scales, a link that has not been observable suggested until now. The last part of this thesis investigates the presence of double layers and phase-space holes in a magnetically turbulent region of the terrestrial bow shock. In this part, I present evidence that these same signatures can be generated via field-aligned currents generated by strong magnetic fluctuations. I also show that double layers and phase-space holes, embedded within localized nonlinear ion acoustic waves, correlate with localized electron heating and possible ion deceleration, indicating they play a role in turbulent dissipation of kinetic to thermal energy. This thesis clearly demonstrates that energy dissipation in turbulent plasma is closely linked to the small-scale electric field environment.

Course 12: Proteins: Structural, Thermodynamic and Kinetic Aspects

NASA Astrophysics Data System (ADS)

Finkelstein, A. V.

1 Introduction 2 Overview of protein architectures and discussion of physical background of their natural selection 2.1 Protein structures 2.2 Physical selection of protein structures 3 Thermodynamic aspects of protein folding 3.1 Reversible denaturation of protein structures 3.2 What do denatured proteins look like? 3.3 Why denaturation of a globular protein is the first-order phase transition 3.4 "Gap" in energy spectrum: The main characteristic that distinguishes protein chains from random polymers 4 Kinetic aspects of protein folding 4.1 Protein folding in vivo 4.2 Protein folding in vitro (in the test-tube) 4.3 Theory of protein folding rates and solution of the Levinthal paradox

The Dynamics of Disorder-Order Transition in Hard Sphere Colloidal Dispersions

NASA Technical Reports Server (NTRS)

Chaikin, Paul M.; Zhu, Jixiang; Cheng, Zhengdong; Phan, See-Eng; Russel, William B.; Lant, Christian T.; Doherty, Michael P.; Meyer, William V.; Rogers, Richard; Cannell, D. S.;

Liquid-phase separation of reactive dye by wood-rotting fungus: a biotechnological approach.

PubMed

Binupriya, Arthur R; Sathishkumar, Muthuswamy; Dhamodaran, Kavitha; Jayabalan, Rasu; Swaminathan, Krishnaswamy; Yun, Sei Eok

2007-08-01

The live and pretreated mycelial pellets/biomass of Trametes versicolor was used for the biosorption of a textile dye, reactive blue MR (RBMR) from aqueous solution. The parameters that affect the biosorption of RBMR, such as contact time, concentration of dye and pH, on the extent of RBMR adsorption were investigated. To develop an effective and accurate design model for removal of dye, adsorption kinetics and equilibrium data are essential basic requirements. Lagergren first-order, second-order and Bangham's model were used to fit the experimental data. Results of the kinetic studies showed that the second order kinetic model fitted well for the present experimental data. The Langmuir, Freundlich and Temkin adsorption models were used for the mathematical description of the biosorption equilibrium. The biosorption equilibrium data obeyed well for Langmuir isotherm and the maximum adsorption capacities were found to be 49.8, 51.6, 47.4 and 46.7 mg/g for live, autoclaved, acid- and alkali-pretreated biomass. The dye uptake capacity order of the fungal biomass was found as autoclaved > live > acid-treated > alkali-pretreated. The Freundlich and Temkin models were also able to describe the biosorption equilibrium on RBMR on live and pretreated fungal biomass. Acidic pH was favorable for the adsorption of dye. Studies on pH effect and desorption show that chemisorption seems to play a major role in the adsorption process. On comparison with fixed bed adsorption, batch mode adsorption was more efficient in adsorption of RBMR.

Biosorption of inorganic tin and methyltin compounds by estuarine macroalgae

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wright, P.J.; Weber, J.H.

1991-02-01

Biosorption kinetics of total recoverable inorganic tin (TRISn), MeSn{sup 3+}, Me{sub 2}Sn{sup 2+}, and Me{sub 3}Sn{sup +} compounds onto tissue from the macroalga Fucus vesiculosus and onto a mixed community of Enteromorpha spp. (a filamentous genus) showed that after 48-h accumulation of tin compounds followed the trend TRISn {approximately} MeSn{sup 3+} > Me{sub 2}Sn{sup 2+} > Me{sub 3}Sn{sup +}. Uptake of tin compounds onto F. vesiculosus consisted of three phases: rapid phase 1, intermediate phase 2 (modeled by first-order kinetics). Uptake of tin compounds by Enteromorpha spp. occurred in rapid phase 1 and intermediate, saturating phase 2, which was completemore » in 3 h for TRISn and MeSn{sup 3+} and in 18 h for Me{sub 2}Sn{sup 2+} and Me{sub 2}Sn{sup 2+} and Me{sub 3}Sn{sup +}. After 24 h, (TRISn) and (MeSn{sup 3+}) in dark-incubated plants, suggesting active uptake processes during phase 3. Enteromorpha spp. incubated in the dark for 1 h contained significantly less TRISn and MeSn{sup 3+}, but not less Me{sub 2}Sn{sup 2+} and Me{sub 3}Sn{sup +}, than light-incubated plants. Interactions with different compartments of the algal thallus account for differences in amounts of biosorbed tin compounds. Initial phase 1 biosorption by both algae was probably adsorption onto the thallus surface.« less

Reactions of chlorine nitrate with HCl and H2O. [ozone controlling chemistry in stratosphere

NASA Technical Reports Server (NTRS)

Hatakeyama, Shiro; Leu, Ming-Taun

1986-01-01

The kinetics of the reactions of chlorine nitrate with HCl and H2O are characterized using a static photolysis/Fourier transform infrared spectrophotometer apparatus. For the homogeneous gas-phase reaction with HCl, an upper limit for the rate constant of less than 8.4 x 10 to the -21st, and for the reaction with H2O, a limit of less than 3.4 x 10 to the -21st cu cm/molecule per s, were obtained at 296 + or - 2 K. The yield of HNO3 is almost unity in both cases, and no synergistic effect is noted between HCl and H2O. The kinetic behavior of the reaction with H2O is well described by simple first-order kinetics, while the behavior of the reaction with HCl is described in terms of the Langmuir adsorption isotherm.

Biophysical synaptic dynamics in an analog VLSI network of Hodgkin-Huxley neurons.

PubMed

Yu, Theodore; Cauwenberghs, Gert

2009-01-01

We study synaptic dynamics in a biophysical network of four coupled spiking neurons implemented in an analog VLSI silicon microchip. The four neurons implement a generalized Hodgkin-Huxley model with individually configurable rate-based kinetics of opening and closing of Na+ and K+ ion channels. The twelve synapses implement a rate-based first-order kinetic model of neurotransmitter and receptor dynamics, accounting for NMDA and non-NMDA type chemical synapses. The implemented models on the chip are fully configurable by 384 parameters accounting for conductances, reversal potentials, and pre/post-synaptic voltage-dependence of the channel kinetics. We describe the models and present experimental results from the chip characterizing single neuron dynamics, single synapse dynamics, and multi-neuron network dynamics showing phase-locking behavior as a function of synaptic coupling strength. The 3mm x 3mm microchip consumes 1.29 mW power making it promising for applications including neuromorphic modeling and neural prostheses.

Simulations of the thermodynamics and kinetics of NH3 at the RuO2 (110) surface

NASA Astrophysics Data System (ADS)

Erdtman, Edvin; Andersson, Mike; Lloyd Spetz, Anita; Ojamäe, Lars

2017-02-01

Ruthenium(IV)oxide (RuO2) is a material used for various purposes. It acts as a catalytic agent in several reactions, for example oxidation of carbon monoxide. Furthermore, it is used as gate material in gas sensors. In this work theoretical and computational studies were made on adsorbed molecules on RuO2 (110) surface, in order to follow the chemistry on the molecular level. Density functional theory calculations of the reactions on the surface have been performed. The calculated reaction and activation energies have been used as input for thermodynamic and kinetics calculations. A surface phase diagram was calculated, presenting the equilibrium composition of the surface at different temperature and gas compositions. The kinetics results are in line with the experimental studies of gas sensors, where water has been produced on the surface, and hydrogen is found at the surface which is responsible for the sensor response.

Ordering tendencies and electronic properties in quaternary Heusler derivatives

NASA Astrophysics Data System (ADS)

Neibecker, Pascal; Gruner, Markus E.; Xu, Xiao; Kainuma, Ryosuke; Petry, Winfried; Pentcheva, Rossitza; Leitner, Michael

2017-10-01

The phase stabilities and ordering tendencies in the quaternary full-Heusler alloys NiCoMnAl and NiCoMnGa have been investigated by in situ neutron diffraction, calorimetry, and magnetization measurements. NiCoMnGa was found to adopt the L 21 structure, with distinct Mn and Ga sublattices but a common Ni-Co sublattice. A second-order phase transition to the B 2 phase with disorder also between Mn and Ga was observed at 1160 K . In contrast, in NiCoMnAl slow cooling or low-temperature annealing treatments are required to induce incipient L 21 ordering, otherwise the system displays only B 2 order. Linked to L 21 ordering, a drastic increase in the magnetic transition temperature was observed in NiCoMnAl, while annealing affected the magnetic behavior of NiCoMnGa only weakly due to the low degree of quenched-in disorder. First principles calculations were employed to study the thermodynamics as well as order-dependent electronic properties of both compounds. It was found that a near half-metallic pseudogap emerges in the minority spin channel only for the completely ordered Y structure. However, this structure is energetically unstable compared to a tetragonal structure with alternating layers of Ni and Co, which is predicted to be the low-temperature ground state. The experimental inaccessibility of the totally ordered structures is explained by kinetic limitations due to the low ordering energies.

Diffuse polymer interfaces in lobed nanoemulsions preserved in aqueous media.

PubMed

Kim, Ginam; Sousa, Alioscka; Meyers, Deborah; Shope, Marilyn; Libera, Matthew

2006-05-24

Using valence electron energy loss spectroscopy (EELS) in the cryo-scanning transmission electron microscopy (STEM), we found that the polymer-polymer interface in two-phase nanocolloids of polydimethyl siloxane (PDMS) and copolymer (methyl acrylate (MA)-methyl methacrylate (MMA)-vinyl acetate (VA)) preserved in water was diffuse despite the fact that equilibrium thermodynamics indicates it should only be on the order of a few nanometers. The diffuse interface is a result of the kinetic trapping of the copolymer within the PDMS phase, and this finding suggests new nonequilibrium pathways to control interfaces during the synthesis of multicomponent polymeric nanostructures.

Drug Delivery and Transport into the Central Circulation: An Example of Zero-Order In vivo Absorption of Rotigotine from a Transdermal Patch Formulation.

PubMed

Cawello, Willi; Braun, Marina; Andreas, Jens-Otto

2018-01-13

Pharmacokinetic studies using deconvolution methods and non-compartmental analysis to model clinical absorption of drugs are not well represented in the literature. The purpose of this research was (1) to define the system of equations for description of rotigotine (a dopamine receptor agonist delivered via a transdermal patch) absorption based on a pharmacokinetic model and (2) to describe the kinetics of rotigotine disposition after single and multiple dosing. The kinetics of drug disposition was evaluated based on rotigotine plasma concentration data from three phase 1 trials. In two trials, rotigotine was administered via a single patch over 24 h in healthy subjects. In a third trial, rotigotine was administered once daily over 1 month in subjects with early-stage Parkinson's disease (PD). A pharmacokinetic model utilizing deconvolution methods was developed to describe the relationship between drug release from the patch and plasma concentrations. Plasma-concentration over time profiles were modeled based on a one-compartment model with a time lag, a zero-order input (describing a constant absorption via skin into central circulation) and first-order elimination. Corresponding mathematical models for single- and multiple-dose administration were developed. After single-dose administration of rotigotine patches (using 2, 4 or 8 mg/day) in healthy subjects, a constant in vivo absorption was present after a minor time lag (2-3 h). On days 27 and 30 of the multiple-dose study in patients with PD, absorption was constant during patch-on periods and resembled zero-order kinetics. Deconvolution based on rotigotine pharmacokinetic profiles after single- or multiple-dose administration of the once-daily patch demonstrated that in vivo absorption of rotigotine showed constant input through the skin into the central circulation (resembling zero-order kinetics). Continuous absorption through the skin is a basis for stable drug exposure.

Harmonic Chain with Velocity Flips: Thermalization and Kinetic Theory

NASA Astrophysics Data System (ADS)

Lukkarinen, Jani; Marcozzi, Matteo; Nota, Alessia

2016-12-01

We consider the detailed structure of correlations in harmonic chains with pinning and a bulk velocity flip noise during the heat relaxation phase which occurs on diffusive time scales, for t=O(L^2) where L is the chain length. It has been shown earlier that for non-degenerate harmonic interactions these systems thermalize, and the dominant part of the correlations is given by local thermal equilibrium determined by a temperature profile which satisfies a linear heat equation. Here we are concerned with two new aspects about the thermalization process: the first order corrections in 1 / L to the local equilibrium correlations and the applicability of kinetic theory to study the relaxation process. Employing previously derived explicit uniform estimates for the temperature profile, we first derive an explicit form for the first order corrections to the particle position-momentum correlations. By suitably revising the definition of the Wigner transform and the kinetic scaling limit we derive a phonon Boltzmann equation whose predictions agree with the explicit computation. Comparing the two results, the corrections can be understood as arising from two different sources: a current-related term and a correction to the position-position correlations related to spatial changes in the phonon eigenbasis.

Liquid Phase adsorption kinetics and equilibrium of toluene by novel modified-diatomite.

PubMed

Sheshdeh, Reza Khalighi; Abbasizadeh, Saeed; Nikou, Mohammad Reza Khosravi; Badii, Khashayar; Sharafi, Mohammad Sadegh

2014-01-01

The adsorption equilibria of toluene from aqueous solutions on natural and modified diatomite were examined at different operation parameters such as pH, contact time, initial toluene concentration was evaluated and optimum experimental conditions were identified. The surface area and morphology of the nanoparticles were characterized by SEM, BET, XRD, FTIR and EDX analysis. It was found that in order to obtain the highest possible removal of toluene, the experiments can be carried out at pH 6, temperature 25°C, an agitation speed of 200 rpm, an initial toluene concentration of 150 mg/L, a centrifugal rate of 4000 rpm, adsorbent dosage = 0.1 g and a process time of 90 min. The results of this work show that the maximum percentage removal of toluene from aqueous solution in the optimum conditions for NONMD was 96.91% (145.36 mg/g). Furthermore, under same conditions, the maximum adsorption of natural diatomite was 71.45% (107.18 mg/g). Both adsorption kinetic and isotherm experiments were carried out. The experimental data showed that the adsorption follows the Langmuir model and Freundlich model on natural and modified diatomite respectively. The kinetics results were found to conform well to pseudo-second order kinetics model with good correlation. Thus, this study demonstrated that the modified diatomite could be used as potential adsorbent for removal of toluene from aqueous solution.

Inactivation of Mycobacterium avium with free chlorine.

PubMed

Luh, Jeanne; Mariñas, Benito J

2007-07-15

The inactivation kinetics of Mycobacterium avium with free chlorine was characterized by two stages: an initial phase at a relatively fast rate followed by a slower second stage of pseudo first-order kinetics. The inactivation rate of each stage was approximately the same for all experiments performed at a certain condition of pH and temperature; however, variability was observed for the disinfectant exposure at which the transition between the two stages occurred. This variability was not a function of the initial disinfectant concentration, the initial bacterial density, or the bacterial stock. However, the transition to the second stage varied more significantly at high temperatures (30 degrees C), while lower variability was observed at lower temperatures (5 and 20 degrees C). Experiments conducted at pH values in the range of 6-9 revealed that the inactivation of M. avium was primarily due to hypochlorous acid, with little contribution from hypochlorite ion within this pH range. The inactivation kinetics was represented with a two-population model. The activation energies for the resulting pseudo first-order rate constants for the populations with fast and slow kinetics were 100.3 and 96.5 kJ/mol, respectively. The magnitude of these values suggested that for waters of relatively high pH and low temperatures, little inactivation of M. avium would be achieved within treatment plants, providing a seeding source for distribution systems.

Fractal kinetics of radiation-induced point-defect formation and decay in amorphous insulators: Application to color centers in silica-based optical fibers

NASA Astrophysics Data System (ADS)

Griscom, David L.

2001-11-01

Formalisms have been developed to express the time evolution of bimolecular processes taking place in fractal spaces. These ``stretched-second-order'' solutions are specifically applicable to radiation-induced electron-hole pairs and/or vacancy-interstitial pairs in insulating glasses. Like the analogous Kohlrausch-type (stretched-first-order) expressions, the present solutions are functions of (kt)β, where 0<β<1, k is an effective rate coefficient, and t is time. Both the new second-order formalism and the familiar Kohlrausch approach have been used to fit experimental data (induced optical absorptions in silica-based glasses monitored at selected wavelengths) that serve as proxies for the numbers of color centers created by γ irradiation and/or destroyed by processes involving thermal, optical, or γ-ray activation. Two material systems were investigated: (1) optical fibers with Ge-doped-silica cores and (2) fibers with low-OH/low-chloride pure-silica cores. Successful fits of the growth curves for the Ge-doped-silica-core fibers at four widely separated dose rates were accomplished using solutions for color-center concentrations, N[(kt)β], which approach steady-state values, Nsat, as t-->∞. The parametrization of these fits reveals some unexpected, and potentially useful, empirical rules regarding the dose-rate dependences of β, k, and Nsat in the fractal regime (0<β<1). Similar, though possibly not identical, rules evidently apply to color centers in the pure-silica-core fibers as well. In both material systems, there appear to be fractal<==> classical phase transitions at certain threshold values of dose rate, below which the dose-rate dependencies of k and Nsat revert to those specified by classical (β=1) first- or second-order kinetics. For kt<<1, both the first- and second-order fractal kinetic growth curves become identical, i.e., N((kt)β)~Atβ, where the coefficient A depends on dose rate but not kinetic order. It is found empirically that A depends on the 3β/2 power of dose rate in both first- and second-order kinetics, thus ``accidentally'' becoming linearly proportional to dose rate in cases where β~2/3 (characteristic of random fractals and many disordered materials). If interfering dose-rate-independent components are absent, it is possible to distinguish the order of the kinetics from the shapes of the growth and decay curves in both fractal and classical regimes. However, for reasons that are discussed, the parameters that successfully fit the experimental growth curves could not be used as bases for closed-form predictions of the shapes of the decay curves recorded when the irradiation is interrupted.

Microwave spectroscopic observation of distinct electron solid phases in wide quantum wells

NASA Astrophysics Data System (ADS)

Hatke, A. T.; Liu, Yang; Magill, B. A.; Moon, B. H.; Engel, L. W.; Shayegan, M.; Pfeiffer, L. N.; West, K. W.; Baldwin, K. W.

2014-06-01

In high magnetic fields, two-dimensional electron systems can form a number of phases in which interelectron repulsion plays the central role, since the kinetic energy is frozen out by Landau quantization. These phases include the well-known liquids of the fractional quantum Hall effect, as well as solid phases with broken spatial symmetry and crystalline order. Solids can occur at the low Landau-filling termination of the fractional quantum Hall effect series but also within integer quantum Hall effects. Here we present microwave spectroscopy studies of wide quantum wells that clearly reveal two distinct solid phases, hidden within what in d.c. transport would be the zero diagonal conductivity of an integer quantum-Hall-effect state. Explanation of these solids is not possible with the simple picture of a Wigner solid of ordinary (quasi) electrons or holes.

Re-evaluation of the impact of ternary additions of Ni and Cu on the A1 to L1{sub 0} transformation in FePt films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, B.; Barmak, K.

2011-06-15

The impact of ternary additions of Ni (1.6-21.5 at. %) and Cu (1.3-17.3 at. %) on the A1 (face centered cubic, fcc) to L1{sub 0} phase transformation in FePt films has been re-evaluated based on compositions obtained using energy dispersive x-ray spectrometry (EDS). The data presented here serve as corrections to results reported in six previous studies [D. C. Berry and K. Barmak, J. Appl. Phys. 102, 024912 (2007); 101, 014905 (2007); 99, 08G901 (2006); D. C. Berry, J. Kim, K. Barmak, K. Wierman, E. B. Svedberg, and J. K. Howard, Scr. Mater. 53, 423 (2005); K. Barmak, J. Kim,more » D. C. Berry, W. N. Hanani, K. Wierman, E. B. Svedberg, and J. K. Howard, J. Appl. Phys. 97, 024902 (2005); K. Barmak, J. Kim, D. C. Berry, K. W. Wierman, E. B. Svedberg, and J. K. Howard, ibid. 95, 7486 (2004)]. The new EDS compositions do not change the following conclusions of these previous studies: (i) when ternary FeNiPt and FeCuPt alloys are compared with binary FePt alloys with the same Pt content, it is seen that additions of Ni slow the transformation kinetics, whereas additions of Cu have no measurable impact on the kinetics, (ii) the Curie temperature of the L1{sub 0} phase is lowered by additions of Ni or Cu, (iii) the Curie temperature of the A1 phase is increased by additions of Ni, but lowered by additions of Cu, and (iv) the transformation enthalpy is lowered by large additions of Ni, but is unaffected by additions of Cu. The ordering behavior of FeCuPt alloys as evidenced by the kinetic ordering temperature is compared with other reports in the literature based on magnetic measurements.« less

Highly repeatable nanoscale phase coexistence in vanadium dioxide films

NASA Astrophysics Data System (ADS)

Huffman, T. J.; Lahneman, D. J.; Wang, S. L.; Slusar, T.; Kim, Bong-Jun; Kim, Hyun-Tak; Qazilbash, M. M.

2018-02-01

It is generally believed that in first-order phase transitions in materials with imperfections, the formation of phase domains must be affected to some extent by stochastic (probabilistic) processes. The stochasticity would lead to unreliable performance in nanoscale devices that have the potential to exploit the transformation of physical properties in a phase transition. Here we show that stochasticity at nanometer length scales is completely suppressed in the thermally driven metal-insulator transition (MIT) in sputtered vanadium dioxide (V O2 ) films. The nucleation and growth of domain patterns of metallic and insulating phases occur in a strikingly reproducible way. The completely deterministic nature of domain formation and growth in films with imperfections is a fundamental and unexpected finding about the kinetics of this material. Moreover, it opens the door for realizing reliable nanoscale devices based on the MIT in V O2 and similar phase-change materials.

FAST TRACK COMMUNICATION: Field dependence of temperature induced irreversible transformations of magnetic phases in Pr0.5Ca0.5Mn0.975Al0.025O3 crystalline oxide

NASA Astrophysics Data System (ADS)

Lakhani, Archana; Kushwaha, Pallavi; Rawat, R.; Kumar, Kranti; Banerjee, A.; Chaddah, P.

2010-01-01

Glass-like arrest has recently been reported in various magnetic materials. As in structural glasses, the kinetics of a first order transformation is arrested while retaining the higher entropy phase as a non-ergodic state. We show visual mesoscopic evidence of the irreversible transformation of the arrested antiferromagnetic-insulating phase in Pr0.5Ca0.5Mn0.975Al0.025O3 to its equilibrium ferromagnetic-metallic phase with an isothermal increase of magnetic field, similar to its iso-field transformation on warming. The magnetic field dependence of the non-equilibrium to equilibrium transformation temperature is shown to be governed by Le Chatelier's principle.

The Interplanetary Transport Effects on the Fe/O Ratio of Large Solar Energetic Particle Events

NASA Astrophysics Data System (ADS)

Qin, G.; Wang, Y.

2016-12-01

Mason and coauthors in 2006 invested the intensities of O and Fe in large western solar energetic particle (SEP) events observed by ACE spacecraft. It was found that the Fe/O ratio decreases with time at the same kinetic energy per nucleon during the rising phase of time-intensity profile, and the Fe/O ratio gradually becomes a constant during the decay phase of intensity. However, if the O intensity is compared at a higher kinetic energy with the Fe intensity, the behaviors of intensity profiles of O and Fe are similar. So they concluded that for such kind of events the injection profiles of Fe and O are similar near the Sun, and that scattering effects dominates. With numerical simulations, we find that in order to get such kind of SEPs behavior, Fe and O have to have similar injection profiles near the Sun, and similar diffusion and adiabatic cooling processes in the interplanetary space.

One-step large scale gas phase synthesis of Mn2 + doped ZnS nanoparticles in reducing flames

NASA Astrophysics Data System (ADS)

Athanassiou, E. K.; Grass, R. N.; Stark, W. J.

2010-05-01

Metal sulfide nanoparticles have attracted considerable interest because of their unique semiconducting and electronic properties. In order to prepare these fascinating materials at an industrial scale, however, solvent-free, dry processes would be most advantageous. In the present work, we demonstrate how traditional oxide nanoparticle synthesis in flames can be extended to sulfides if we apply a careful control on flame gas composition and sulfur content. The ultra-fast (<1 ms) gas phase kinetics at elevated temperatures allow direct sulfidization of metals in flames (\\mathrm {MO}_{x} \\Rightarrow \\mathrm {MS}_{x} ). As a representative example, we prepared air-stable Mn2 + doped zinc sulfide nanoparticles. Post-sintering of the initially polycrystalline nanopowder resulted in a material of high crystallinity and improved photoluminescence. An analysis of the thermodynamics, gas composition, and kinetics in these reducing flames indicates that the here-presented extension of flame synthesis provides access to a broad range of metal sulfide nanoparticles and offers an alternative to non-oxide phosphor preparation.

Effect of Ni-Co Ternary Molten Salt Catalysts on Coal Catalytic Pyrolysis Process

NASA Astrophysics Data System (ADS)

Cui, Xin; Qi, Cong; Li, Liang; Li, Yimin; Li, Song

2017-08-01

In order to facilitate efficient and clean utilization of coal, a series of Ni-Co ternary molten salt crystals are explored and the catalytic pyrolysis mechanism of Datong coal is investigated. The reaction mechanisms of coal are achieved by thermal gravimetric analyzer (TGA), and a reactive kinetic model is constructed. The microcosmic structure and macerals are observed by scanning electron microscope (SEM). The catalytic effects of ternary molten salt crystals at different stages of pyrolysis are analyzed. The experimental results show that Ni-Co ternary molten salt catalysts have the capability to bring down activation energy required by pyrolytic reactions at its initial phase. Also, the catalysts exert a preferable catalytic action on macromolecular structure decomposition and free radical polycondensation reactions. Furthermore, the high-temperature condensation polymerization is driven to decompose further with a faster reaction rate by the additions of Ni-Co ternary molten salt crystal catalysts. According to pyrolysis kinetic research, the addition of catalysts can effectively decrease the activation energy needed in each phase of pyrolysis reaction.

Coarsening Kinetics and Morphological Evolution in a Two-Phase Titanium Alloy During Heat Treatment

NASA Astrophysics Data System (ADS)

Xu, Jianwei; Zeng, Weidong; Jia, Zhiqiang; Sun, Xin; Zhao, Yawei

2016-03-01

The effects of alpha/beta heat treatment on microstructure evolution of Ti-17 alloy with a lamellar colony structure are established. Heat treatment experiments are conducted at 1103 or 1063 K for times ranging from 10 min to 8 h. The main features of microstructure evolution during heat treatment comprise static globularization and coarsening of primary alpha phase. Such behaviors can be accelerated by higher heat treatment temperature. Furthermore, globularization and coarsening behaviors show a faster rate at higher prestrain. In order to better understand the microstructure evolution of Ti-17 alloy during alpha/beta heat treatment, static globularization and coarsening behaviors are modeled in the theoretical frame of the Johnson-Mehl-Avarmi-Kolmogorov (JMAK) and Lifshitz-Slyozov-Wagner (LSW) theories, respectively. The JMAK and LSW kinetics parameters are derived under different experimental conditions. Agreements between measurements and predictions are found, indicating that the JMAK and LSW theories can be used to predict and trace static globularization and coarsening processes of Ti-17 alloy during alpha/beta heat treatment.

Numerical natural rubber curing simulation, obtaining a controlled gradient of the state of cure in a thick-section part

NASA Astrophysics Data System (ADS)

El Labban, A.; Mousseau, P.; Bailleul, J. L.; Deterre, R.

2007-04-01

Although numerical simulation has proved to be a useful tool to predict the rubber vulcanization process, few applications in the process control have been reported. Because the end-use rubber properties depend on the state of cure distribution in the parts thickness, the prediction of the optimal distribution remains a challenge for the rubber industry. The analysis of the vulcanization process requires the determination of the thermal behavior of the material and the cure kinetics. A nonisothermal vulcanization model with nonisothermal induction time is used in this numerical study. Numerical results are obtained for natural rubber (NR) thick-section part curing. A controlled gradient of the state of cure in the part thickness is obtained by a curing process that consists not only in mold heating phase, but also a forced convection mold cooling phase in order to stop the vulcanization process and to control the vulcanization distribution. The mold design that allows this control is described. In the heating phase, the state of cure is mainly controlled by the chemical kinetics (the induction time), but in the cooling phase, it is the heat diffusion that controls the state of cure distribution. A comparison among different cooling conditions is shown and a good state of cure gradient control is obtained.

Identification of unwanted photoproducts of cosmetic preservatives in personal care products under ultraviolet-light using solid-phase microextraction and micro-matrix solid-phase dispersion.

PubMed

Alvarez-Rivera, Gerardo; Llompart, Maria; Garcia-Jares, Carmen; Lores, Marta

2015-04-17

The photochemical transformation of widely used cosmetic preservatives including benzoates, parabens, BHA, BHT and triclosan has been investigated in this work applying an innovative double-approach strategy: identification of transformation products in aqueous photodegradation experiments (UV-light, 254nm), followed by targeted screening analysis of such photoproducts in UV-irradiated cosmetic samples. Solid-phase microextraction (SPME) was applied, using different fiber coatings, in order to widen the range of detectable photoproducts in water, whereas UV-irradiated personal care products (PCPs) containing the target preservatives were extracted by micro-matrix solid-phase dispersion (micro-MSPD). Both SPME and micro-MSPD-based methodologies were successfully optimized and validated. Degradation kinetics of parent species, and photoformation of their transformation by-products were monitored by gas chromatography coupled to mass spectrometry (GC-MS). Thirty nine photoproducts were detected in aqueous photodegradation experiments, being tentatively identified based on their mass spectra. Transformation pathways between structurally related by-products, consistent with their kinetic behavior were postulated. The photoformation of unexpected photoproducts such as 2- and 4-hydroxybenzophenones, and 2,8-dichlorodibenzo-p-dioxin in PCPs are reported in this work for the first time. Copyright © 2015 Elsevier B.V. All rights reserved.

From atomistic interfaces to dendritic patterns

NASA Astrophysics Data System (ADS)

Galenko, P. K.; Alexandrov, D. V.

2018-01-01

Transport processes around phase interfaces, together with thermodynamic properties and kinetic phenomena, control the formation of dendritic patterns. Using the thermodynamic and kinetic data of phase interfaces obtained on the atomic scale, one can analyse the formation of a single dendrite and the growth of a dendritic ensemble. This is the result of recent progress in theoretical methods and computational algorithms calculated using powerful computer clusters. Great benefits can be attained from the development of micro-, meso- and macro-levels of analysis when investigating the dynamics of interfaces, interpreting experimental data and designing the macrostructure of samples. The review and research articles in this theme issue cover the spectrum of scales (from nano- to macro-length scales) in order to exhibit recently developing trends in the theoretical analysis and computational modelling of dendrite pattern formation. Atomistic modelling, the flow effect on interface dynamics, the transition from diffusion-limited to thermally controlled growth existing at a considerable driving force, two-phase (mushy) layer formation, the growth of eutectic dendrites, the formation of a secondary dendritic network due to coalescence, computational methods, including boundary integral and phase-field methods, and experimental tests for theoretical models-all these themes are highlighted in the present issue. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

The Dynamics of Solid Propellant Combustion.

DTIC Science & Technology

1980-12-31

review the theory and summarize most of the nume- rical and experimental findings by our research group . The complete literature so far published by this...deradiation reported by the Princeton group (Refs. 58-59). Ciepluch (Refs.20-22) conducted one of the first systematic experimental studies of depressurization...is the reaction order of the overall, one-step, irreversible kinetics controlling the gas phase heat release. Taking into account the quasi -steady

Design and testing of temperature tunable de Laval nozzles for applications in gas-phase reaction kinetics

NASA Astrophysics Data System (ADS)

Canosa, A.; Ocaña, A. J.; Antiñolo, M.; Ballesteros, B.; Jiménez, E.; Albaladejo, J.

2016-09-01

A series of three de Laval nozzles initially designed to generate uniform supersonic flows in helium at 23 and 36 K and in argon at 50 K have been used with either pure nitrogen or mixtures of nitrogen with helium or argon in order to make a sequence of pulsed supersonic flows working at different temperatures. For this, a computer homemade program has been used to design de Laval nozzles contours for gas mixtures in order to determine the theoretical pressure P and temperature T in these supersonic flows. Spatial evolution of T along the flow axis downstream of the nozzle exit has been characterized with a fast response Pitot tube instrument newly developed. Twenty-eight different gas mixture conditions have been tested, indicating a very good agreement with the corresponding calculated flow conditions. The length of uniformity Δ L of the supersonic flows have been found to be >30 cm in more than 80 % of the situations and >50 cm for more than 50 % of the tested conditions. Fine temperature tunability was achieved in the range 22-107 K with very small fluctuations of the mean temperature along Δ L. Advantages and limits of these new developments for studies of gas-phase reaction kinetics are discussed.

Precursor preparation for Ca-Al layered double hydroxide to remove hexavalent chromium coexisting with calcium and magnesium chlorides

NASA Astrophysics Data System (ADS)

Zhong, Lihua; He, Xiaoman; Qu, Jun; Li, Xuewei; Lei, Zhiwu; Zhang, Qiwu; Liu, Xinzhong

2017-01-01

Al(OH)3 and Ca(OH)2 powders are co-ground to prepare a precursor which hydrates into a layered double hydroxide (LDH) phase by agitation in aqueous solution with target hexavalent chromium (Cr(VI)) at room temperature, to achieve an obvious improvement in removal efficiency of Cr(VI) through an easy incorporation into the structure. Although the prepared precursor transforms into LDH phases also when agitated in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist. The adsorption isotherm and kinetic studies show that the phenomena occurring on the Al-Ca precursor fit a pseudo-second-order kinetics with a Langmuir adsorption capacity of 59.45 mg/g. Besides, characterizations of the prepared precursor and the samples after adsorption are also performed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Transmission electron microscope (TEM) to understand the reason of the preferential incorporation of Cr(VI) to the coexisting chloride salts during the LDH phase formation. Ca-Al precursor (C3A) was agitated in a hexavalent chromium (Cr(VI)) solution to form Al-Ca-CrO4 LDH product. Ca-Al-CrO4 LDH phase occurred preferentially to Ca-Al-MCl2 LDH phases in the solutions of calcium and magnesium chlorides, it incorporates Cr(VI) preferentially to the chloride salts when they coexist.

Gas uptake and chemical aging of semisolid organic aerosol particles

PubMed Central

Shiraiwa, Manabu; Ammann, Markus; Koop, Thomas; Pöschl, Ulrich

2011-01-01

Organic substances can adopt an amorphous solid or semisolid state, influencing the rate of heterogeneous reactions and multiphase processes in atmospheric aerosols. Here we demonstrate how molecular diffusion in the condensed phase affects the gas uptake and chemical transformation of semisolid organic particles. Flow tube experiments show that the ozone uptake and oxidative aging of amorphous protein is kinetically limited by bulk diffusion. The reactive gas uptake exhibits a pronounced increase with relative humidity, which can be explained by a decrease of viscosity and increase of diffusivity due to hygroscopic water uptake transforming the amorphous organic matrix from a glassy to a semisolid state (moisture-induced phase transition). The reaction rate depends on the condensed phase diffusion coefficients of both the oxidant and the organic reactant molecules, which can be described by a kinetic multilayer flux model but not by the traditional resistor model approach of multiphase chemistry. The chemical lifetime of reactive compounds in atmospheric particles can increase from seconds to days as the rate of diffusion in semisolid phases can decrease by multiple orders of magnitude in response to low temperature or low relative humidity. The findings demonstrate that the occurrence and properties of amorphous semisolid phases challenge traditional views and require advanced formalisms for the description of organic particle formation and transformation in atmospheric models of aerosol effects on air quality, public health, and climate. PMID:21690350

[Kinetics of alkylphenols degradation in aqueous phase with excilamp irradiation].

PubMed

Liu, Yu-Hai; Ye, Zhao-Lian; Wen, Ying-Pin; Bi, Cheng-Lu

2014-06-01

The 206 nm irradiation from excilamp was able to directly photo-degrade 4-nonylphenol (4-NP) and 4-octylphenol (4-OP), but it could not oxidize them completely into CO2. Under the same irradiation condition, the removal efficiency of 4-OP was higher than that of 4-NP. Pseudo-first order kinetic model and modified kinetic model were used to fit the kinetics of photo-degradation process, and the direct photolysis rate constants under 206 nm UV irradiation were obtained. The experimental results demonstrated that the photolysis rate constant was higher at lower initial concentration of alkylphenols. Two kinetic models were appropriate for the direct photolysis of alkylphenols at low concentration, but the modified model did not fit for high concentrations. Degradation rate can be obviously enhanced when adding H2O2 into the reaction, but the TOC removal was distinct only when the dosage of H2O2 was high. At last, we concluded that the direct photolysis rate constant k(d) was 0.032 8 min(-1) and the reaction rate constant k(pH) between 4-OP and H2O2 was 17.4520 L x (mol x min)(-1).

Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

NASA Astrophysics Data System (ADS)

Izacard, Olivier

2016-08-01

In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basis sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main results, it is shown that (i) the empirical formula for the secondary electron emission is not consistent with a MDF due to the presence of super-thermal particles, (ii) the super-thermal particles can replace a diffusion parameter in the Langmuir probe current formula, and (iii) the entropy can explicitly decrease in presence of sources only for the introduced INMDF without violating the second law of thermodynamics. Moreover, the first order entropy of an infinite number of super-thermal tails stays the same as the entropy of a MDF. The latter demystifies the Maxwell's demon by statistically describing non-isolated systems.

Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Izacard, Olivier, E-mail: izacard@llnl.gov

In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basismore » sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main results, it is shown that (i) the empirical formula for the secondary electron emission is not consistent with a MDF due to the presence of super-thermal particles, (ii) the super-thermal particles can replace a diffusion parameter in the Langmuir probe current formula, and (iii) the entropy can explicitly decrease in presence of sources only for the introduced INMDF without violating the second law of thermodynamics. Moreover, the first order entropy of an infinite number of super-thermal tails stays the same as the entropy of a MDF. The latter demystifies the Maxwell's demon by statistically describing non-isolated systems.« less

Identification of sigma and chi phases in duplex stainless steels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Llorca-Isern, Núria, E-mail: nullorca@ub.edu; López-Luque, Héctor, E-mail: hlopezlu7@alumnes.ub.edu; López-Jiménez, Isabel, E-mail: ilopezji9@alumnes.ub.edu

The aim of this work is to find out the most suitable method for detecting and analyzing accurately the formation conditions of secondary phases, particularly Sigma-phase (σ-phase) and Chi-phase (χ-phase) in duplex stainless steels (UNS S32205 and UNS S32750). The microstructure was characterized after a solution annealing at 1080 °C followed by an isothermal heating at 830 °C for different time ranges, ranging from 1 min to 9 h, in order to enlighten the controversial point concerning the mechanism of χ-phase nucleation in relation with the σ-phase. Etched samples were observed using optical microscopy (MO), and scanning electron microscopy (FESEM)more » with a backscattered electron detector (BSE) was used on unetched samples. Compositional microanalysis (EDS) was carried out for identifying the different phases present in the steels. Sigma phase was easily observed using different etching procedures, whereas χ-phase was only clearly detected with FESEM–BSE on unetched samples. The compositional analyses showed that the molybdenum content in χ-phase almost doubles the content of this element in σ-phase, and as a result the kinetics of nucleation and growth were also found to be remarkably faster when the alloy content in the steel is higher. In addition, chromium nitrides and carbides were also observed to precipitate as a result of the heat treatments and, in the case of the chromium nitrides, they act as a favorable site for the nucleation of σ-phase and χ-phase. - Highlights: • Microscopy was used on heat treated duplex steels for microstructure identification. • FESEM–BSE observation on unetched samples provided the best contrast between phases. • Analyses of carbides, nitrides, chi and sigma phases were possible by EDS and WDS. • Chromium nitrides act as favorable site for the nucleation of chi and sigma phases. • Secondary phases nucleation kinetics are faster in superduplex than in duplex steels.« less

A Simple "Boxed Molecular Kinetics" Approach To Accelerate Rare Events in the Stochastic Kinetic Master Equation.

PubMed

Shannon, Robin; Glowacki, David R

2018-02-15

The chemical master equation is a powerful theoretical tool for analyzing the kinetics of complex multiwell potential energy surfaces in a wide range of different domains of chemical kinetics spanning combustion, atmospheric chemistry, gas-surface chemistry, solution phase chemistry, and biochemistry. There are two well-established methodologies for solving the chemical master equation: a stochastic "kinetic Monte Carlo" approach and a matrix-based approach. In principle, the results yielded by both approaches are identical; the decision of which approach is better suited to a particular study depends on the details of the specific system under investigation. In this Article, we present a rigorous method for accelerating stochastic approaches by several orders of magnitude, along with a method for unbiasing the accelerated results to recover the "true" value. The approach we take in this paper is inspired by the so-called "boxed molecular dynamics" (BXD) method, which has previously only been applied to accelerate rare events in molecular dynamics simulations. Here we extend BXD to design a simple algorithmic strategy for accelerating rare events in stochastic kinetic simulations. Tests on a number of systems show that the results obtained using the BXD rare event strategy are in good agreement with unbiased results. To carry out these tests, we have implemented a kinetic Monte Carlo approach in MESMER, which is a cross-platform, open-source, and freely available master equation solver.

Application of Precipitate Free Zone Growth Kinetics to the β-Phase Depletion Behavior in a CoNiCrAlY Coating Alloy: An Analytical Approach

NASA Astrophysics Data System (ADS)

Chen, H.

2018-06-01

This paper concerns the β-phase depletion kinetics of a thermally sprayed free-standing CoNiCrAlY (Co-31.7 pct Ni-20.8 pct Cr-8.1 pct Al-0.5 pct Y, all in wt pct) coating alloy. An analytical β-phase depletion model based on the precipitate free zone growth kinetics was developed to calculate the β-phase depletion kinetics during isothermal oxidation. This approach, which accounts for the molar volume of the alloy, the interfacial energy of the γ/ β interface, and the Al concentration at γ/ γ + β boundary, requires the Al concentrations in the β-phase depletion zone as the input rather than the oxidation kinetics at the oxide/coating interface. The calculated β-phase depletion zones derived from the current model were compared with experimental results. It is shown that the calculated β-phase depletion zones using the current model are in reasonable agreement with those obtained experimentally. The constant compositional terms used in the model are likely to cause the discrepancies between the model predictions and experimental results. This analytical approach, which shows a reasonable correlation with experimental results, demonstrates a good reliability in the fast evaluation on lifetime prediction of MCrAlY coatings.

Application of Precipitate Free Zone Growth Kinetics to the β-Phase Depletion Behavior in a CoNiCrAlY Coating Alloy: An Analytical Approach

NASA Astrophysics Data System (ADS)

Chen, H.

2018-03-01

This paper concerns the β-phase depletion kinetics of a thermally sprayed free-standing CoNiCrAlY (Co-31.7 pct Ni-20.8 pct Cr-8.1 pct Al-0.5 pct Y, all in wt pct) coating alloy. An analytical β-phase depletion model based on the precipitate free zone growth kinetics was developed to calculate the β-phase depletion kinetics during isothermal oxidation. This approach, which accounts for the molar volume of the alloy, the interfacial energy of the γ/β interface, and the Al concentration at γ/γ + β boundary, requires the Al concentrations in the β-phase depletion zone as the input rather than the oxidation kinetics at the oxide/coating interface. The calculated β-phase depletion zones derived from the current model were compared with experimental results. It is shown that the calculated β-phase depletion zones using the current model are in reasonable agreement with those obtained experimentally. The constant compositional terms used in the model are likely to cause the discrepancies between the model predictions and experimental results. This analytical approach, which shows a reasonable correlation with experimental results, demonstrates a good reliability in the fast evaluation on lifetime prediction of MCrAlY coatings.

Evaporation Kinetics of Polyol Droplets: Determination of Evaporation Coefficients and Diffusion Constants

NASA Astrophysics Data System (ADS)

Su, Yong-Yang; Marsh, Aleksandra; Haddrell, Allen E.; Li, Zhi-Ming; Reid, Jonathan P.

2017-11-01

In order to quantify the kinetics of mass transfer between the gas and condensed phases in aerosol, physicochemical properties of the gas and condensed phases and kinetic parameters (mass/thermal accommodation coefficients) are crucial for estimating mass fluxes over a wide size range from the free molecule to continuum regimes. In this study, we report measurements of the evaporation kinetics of droplets of 1-butanol, ethylene glycol (EG), diethylene glycol (DEG), and glycerol under well-controlled conditions (gas flow rates and temperature) using the previously developed cylindrical electrode electrodynamic balance technique. Measurements are compared with a model that captures the heat and mass transfer occurring at the evaporating droplet surface. The aim of these measurements is to clarify the discrepancy in the reported values of mass accommodation coefficient (αM, equals to evaporation coefficient based on microscopic reversibility) for 1-butanol, EG, and DEG and improve the accuracy of the value of the diffusion coefficient for glycerol in gaseous nitrogen. The uncertainties in the thermophysical and experimental parameters are carefully assessed, the literature values of the vapor pressures of these components are evaluated, and the plausible ranges of the evaporation coefficients for 1-butanol, EG, and DEG as well as uncertainty in diffusion coefficient for glycerol are reported. Results show that αM should be greater than 0.4, 0.2, and 0.4 for EG, DEG, and 1-butanol, respectively. The refined values are helpful for accurate prediction of the evaporation/condensation rates.

Anomalous critical behavior in the polymer collapse transition of three-dimensional lattice trails.

PubMed

Bedini, Andrea; Owczarek, Aleksander L; Prellberg, Thomas

2012-07-01

Trails (bond-avoiding walks) provide an alternative lattice model of polymers to self-avoiding walks, and adding self-interaction at multiply visited sites gives a model of polymer collapse. Recently a two-dimensional model (triangular lattice) where doubly and triply visited sites are given different weights was shown to display a rich phase diagram with first- and second-order collapse separated by a multicritical point. A kinetic growth process of trails (KGTs) was conjectured to map precisely to this multicritical point. Two types of low-temperature phases, a globule phase and a maximally dense phase, were encountered. Here we investigate the collapse properties of a similar extended model of interacting lattice trails on the simple cubic lattice with separate weights for doubly and triply visited sites. Again we find first- and second-order collapse transitions dependent on the relative sizes of the doubly and triply visited energies. However, we find no evidence of a low-temperature maximally dense phase with only the globular phase in existence. Intriguingly, when the ratio of the energies is precisely that which separates the first-order from the second-order regions anomalous finite-size scaling appears. At the finite-size location of the rounded transition clear evidence exists for a first-order transition that persists in the thermodynamic limit. This location moves as the length increases, with its limit apparently at the point that maps to a KGT. However, if one fixes the temperature to sit at exactly this KGT point, then only a critical point can be deduced from the data. The resolution of this apparent contradiction lies in the breaking of crossover scaling and the difference in the shift and transition width (crossover) exponents.

Biogas production enhancement using semi-aerobic pre-aeration in a hybrid bioreactor landfill.

PubMed

Cossu, Raffaello; Morello, Luca; Raga, Roberto; Cerminara, Giulia

2016-09-01

Landfilling continues to be one of the main methods used in managing Municipal Solid Waste (MSW) worldwide, particularly in developing countries. Although in many countries national legislation aims to reduce this practice as much as possible, landfill is a necessary and unavoidable step in closing the material cycle. The need for innovative waste management techniques to improve landfill management and minimize the adverse environmental impact produced has resulted in an increasing interest in innovative systems capable of accelerating waste stabilization. Landfill bioreactors allow decomposition kinetics to be increased and post-operational phase to be shortened; in particular, hybrid bioreactors combine the benefits afforded by both aerobic and anaerobic processes. Six bioreactor simulators were used in the present study: four managed as hybrid, with an initial semi-aerobic phase and a second anaerobic phase, and two as anaerobic control bioreactors. The main goal of the first aerated phase is to reduce Volatile Fatty Acids (VFA) in order to increase pH and enhance methane production during the anaerobic phase; for this reason, air injection was stopped only when these parameters reached the optimum range for methanogenic bacteria. Biogas and leachate were constantly monitored throughout the entire methanogenic phase with the aim of calibrating a Gompertz Model and evaluating the effects of pre-aeration on subsequent methane production. The results showed that moderate and intermittent pre-aeration produces a positive effect both on methane potential and in the kinetics of reaction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Growth Kinetics of Intracellular RNA/Protein Droplets: Signature of a Liquid-Liquid Phase Transition?

NASA Astrophysics Data System (ADS)

Berry, Joel; Weber, Stephanie C.; Vaidya, Nilesh; Zhu, Lian; Haataja, Mikko; Brangwynne, Clifford P.

2015-03-01

Nonmembrane-bound organelles are functional, dynamic assemblies of RNA and/or protein that can self-assemble and disassemble within the cytoplasm or nucleoplasm. The possibility that underlying intracellular phase transitions may drive and mediate the morphological evolution of some membrane-less organelles has been supported by several recent studies. In this talk, results from a collaborative experimental-theoretical study of the growth and dissolution kinetics of nucleoli and extranucleolar droplets (ENDs) in C. elegans embryos will be presented. We have employed Flory-Huggins solution theory, reaction-diffusion kinetics, and quantitative statistical dynamic scaling analysis to characterize the specific growth mechanisms at work. Our findings indicate that both in vivo and in vitro droplet scaling and growth kinetics are consistent with those resulting from an equilibrium liquid-liquid phase transition mediated by passive nonequilibrium growth mechanisms - simultaneous Brownian coalescence and Ostwald ripening. This supports a view in which cells can employ phase transitions to drive structural organization, while utilizing active processes, such as local transcriptional activity, to fine tune the kinetics of these phase transitions in response to given conditions.

A Mechanism for Bulk Energization in the Impulsive Phase of Solar Flares: MHD Turbulent Cascade

NASA Technical Reports Server (NTRS)

LaRosa, T. N.; Moore, R. L.

1993-01-01

We propose that the large production rate (approximately 10(exp 36)/s) of energetic electrons (greater than or approximately equal to 25 keV) required to account for the impulsive-phase hard X-ray burst in large flares is achieved through MHD turbulent cascade of the bulk kinetic energy of the outflows from many separate reconnection events. Focusing on large two- ribbon eruptive flares as representative of most large flares, we envision the reconnection events to be the driven reconnection of oppositely directed elementary flux tubes pressing into the flare-length current-sheet interface that forms in the wake of the eruption of the sheared core of the preflare bipolar field configuration. We point out that, because the outflows from these driven reconnection events have speeds of order the Alfven speed and because the magnetic field reduces the shear viscosity of the plasma, it is reasonable that the outflows are unstable and turbulent, so that the kinetic energy of an outflow is rapidly dissipated through turbulent cascade. If the largest eddies in the turbulence have diameters of order the expected widths of the outflows (10(exp 7)-10(exp 8)cm), then the cascade dissipation of each of these eddies could produce approximately 10(exp 26) erg burst of energized electrons (approximately 3 x (10(exp 33) 25 keV electrons) in approximately 0.3 s, which agrees well with hard X-ray and radio sub-bursts commonly observed during the impulsive phase. Of order 10(exp 2) simultaneous reconnection events with turbulent outflow would produce the observed rate of impulsive-phase plasma energization in the most powerful flares (approximately 10(exp 36) 25 keV electrons/ s); this number of reconnection sites can easily fit within the estimated 3 x 10(exp 9) cm span of the overall current-sheet dissipation region formed in these large flares. We therefore conclude that MHD turbulent cascade is a promising mechanism for the plasma energization observed in the impulsive phase of solar flares.

Effect of stress nonhomogeneity on the shear melting of a thin boundary lubrication layer.

PubMed

Lyashenko, Iakov A; Filippov, Alexander E; Popov, Mikhail; Popov, Valentin L

2016-11-01

We consider the dynamical properties of boundary lubrication in contact between two atomically smooth solid surfaces separated by an ultrathin layer of lubricant. In contrast to previous works on this topic, we explicitly consider the heterogeneity of tangential stresses, which arises in a contact of elastic bodies that are moved tangentially relative to each other. To describe phase transitions between structural states of the lubricant we use an approach based on the field theory of phase transitions. It is assumed that the lubricant layer, when stressed, can undergo a shear-melting transition of first or second order. While solutions for the homogeneous system can be easily obtained analytically, the kinetics of the phase transitions in the spatially heterogeneous system can only be studied numerically. In our numerical experiments melting of the lubricant layer starts from the outer boundary of contact and propagates to its center. The melting wave is followed by a wave of solidification. This process repeats itself periodically, following the stick-slip pattern that is characteristic of such systems. Depending on the thermodynamic and kinetic parameters of the model, different modes of sliding with almost complete or only partial intermediate solidification are possible.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasileiadis, Thomas; Department of Materials Science, University of Patras, GR-26504 Rio-Patras; Yannopoulos, Spyros N., E-mail: sny@iceht.forth.gr

Controlled photo-induced oxidation and amorphization of elemental trigonal tellurium are achieved by laser irradiation at optical wavelengths. These processes are monitored in situ by time-resolved Raman scattering and ex situ by electron microscopies. Ultrathin TeO₂ films form on Te surfaces, as a result of irradiation, with an interface layer of amorphous Te intervening between them. It is shown that irradiation, apart from enabling the controllable transformation of bulk Te to one-dimensional nanostructures, such as Te nanotubes and hybrid core-Te/sheath-TeO₂ nanowires, causes also a series of light-driven (athermal) phase transitions involving the crystallization of the amorphous TeO₂ layers and its transformationmore » to a multiplicity of crystalline phases including the γ-, β-, and α-TeO₂ crystalline phases. The kinetics of the above photo-induced processes is investigated by Raman scattering at various laser fluences revealing exponential and non-exponential kinetics at low and high fluence, respectively. In addition, the formation of ultrathin (less than 10 nm) layers of amorphous TeO₂ offers the possibility to explore structural transitions in 2D glasses by observing changes in the short- and medium-range structural order induced by spatial confinement.« less

Twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+x studied by neutron powder diffraction and gas volumetry

NASA Astrophysics Data System (ADS)

Poulsen, H. F.; Andersen, N. H.; Lebech, B.

1991-02-01

We report experimental results of twin-domain size and bulk oxygen in-diffusion kinetics of YBa 2Cu 3O 6+ x, which supplement a previous and simultaneous study of the structural phase diagram and oxygen equilibrium partial pressure. Analysis of neutron powder diffraction peak broadening show features which are identified to result from temperature independent twin-domain formation in to different orthorhombic phases with domain sizes and 250 and 350Å, respectively. The oxygen in-diffusion flow shows simple relaxation type behaviour J=J 0 exp( {-t}/{τ}) despite a rather broad particle size distribution. At higher temperatures, τ is activated with activation energies 0.55 and 0.25 eV in the tetragonal and orthorhombic phases, respectively. Comparison between twin-domain sizes and bulk oxygen in-diffusion time constants indicates that the twin-domain boundaries may contribute to the effective bulk oxygen in-diffusion. All our results may be interpreted in terms of the 2D ASYNNNI model description of the oxygen basal plane ordering, and they suggest that recent first principles interaction parameters should be modified.

Multiscale Models for the Two-Stream Instability

NASA Astrophysics Data System (ADS)

Joseph, Ilon; Dimits, Andris; Banks, Jeffrey; Berger, Richard; Brunner, Stephan; Chapman, Thomas

2017-10-01

Interpenetrating streams of plasma found in many important scenarios in nature and in the laboratory can develop kinetic two-stream instabilities that exchange momentum and energy between the streams. A quasilinear model for the electrostatic two-stream instability is under development as a component of a multiscale model that couples fluid simulations to kinetic theory. Parameters of the model will be validated with comparison to full kinetic simulations using LOKI and efficient strategies for numerical solution of the quasilinear model and for coupling to the fluid model will be discussed. Extending the kinetic models into the collisional regime requires an efficient treatment of the collision operator. Useful reductions of the collision operator relative to the full multi-species Landau-Fokker-Plank operator are being explored. These are further motivated both by careful consideration of the parameter orderings relevant to two-stream scenarios and by the particular 2D+2V phase space used in the LOKI code. Prepared for US DOE by LLNL under Contract DE-AC52-07NA27344 and LDRD project 17- ERD-081.

Order, viscoelastic, and dielectric properties of symmetric and asymmetric alkyl[1]benzothieno[3,2-b][1]benzothiophenes.

PubMed

Grigoriadis, Christos; Niebel, Claude; Ruzié, Christian; Geerts, Yves H; Floudas, George

2014-02-06

The morphology, the viscoelastic, the dielectric properties and the dynamics of phase transformation are studied in symmetrically and asymmetrically substituted alkyl[1]benzothieno[3,2-b][1]benzothiophenes (C8-BTBT) by X-ray scattering, rheology, and dielectric spectroscopy. The interlayer spacing reflects the molecular and supramolecular ordering, respectively, in the symmetrically and asymmetrically substituted BTBTs. In the asymmetric BTBT, the core layer is double in size with a broader network of intermolecular interactions though the increased S-S contacts that is prerequisite for the development of high performance OFET devices. Two crystal states with elastic and viscoelastic responses were identified in the symmetric compound. In contrast, the SmA phase in the asymmetric compound is a viscoelastic solid. A path-dependent dielectric environment with a switchable dielectric permittivity was found in both compounds by cooling below 0 °C with possible implications to charge transport. The kinetics of phase transformation to the crystalline and SmA phases revealed a nucleation and growth mechanism with rates dominated by the low activation barriers.

Time-resolved rhodopsin activation currents in a unicellular expression system.

PubMed Central

Sullivan, J M; Shukla, P

1999-01-01

The early receptor current (ERC) is the charge redistribution occurring in plasma membrane rhodopsin during light activation of photoreceptors. Both the molecular mechanism of the ERC and its relationship to rhodopsin conformational activation are unknown. To investigate whether the ERC could be a time-resolved assay of rhodopsin structure-function relationships, the distinct sensitivity of modern electrophysiological tools was employed to test for flash-activated ERC signals in cells stably expressing normal human rod opsin after regeneration with 11-cis-retinal. ERCs are similar in waveform and kinetics to those found in photoreceptors. The action spectrum of the major R(2) charge motion is consistent with a rhodopsin photopigment. The R(1) phase is not kinetically resolvable and the R(2) phase, which overlaps metarhodopsin-II formation, has a rapid risetime and complex multiexponential decay. These experiments demonstrate, for the first time, kinetically resolved electrical state transitions during activation of expressed visual pigment in a unicellular environment (single or fused giant cells) containing only 6 x 10(6)-8 x 10(7) molecules of rhodopsin. This method improves measurement sensitivity 7 to 8 orders of magnitude compared to other time-resolved techniques applied to rhodopsin to study the role particular amino acids play in conformational activation and the forces that govern those transitions. PMID:10465746

Solubilization of lipids and lipid phases by the styrene-maleic acid copolymer.

PubMed

Dominguez Pardo, Juan J; Dörr, Jonas M; Iyer, Aditya; Cox, Ruud C; Scheidelaar, Stefan; Koorengevel, Martijn C; Subramaniam, Vinod; Killian, J Antoinette

2017-01-01

A promising tool in membrane research is the use of the styrene-maleic acid (SMA) copolymer to solubilize membranes in the form of nanodiscs. Since membranes are heterogeneous in composition, it is important to know whether SMA thereby has a preference for solubilization of either specific types of lipids or specific bilayer phases. Here, we investigated this by performing partial solubilization of model membranes and analyzing the lipid composition of the solubilized fraction. We found that SMA displays no significant lipid preference in homogeneous binary lipid mixtures in the fluid phase, even when using lipids that by themselves show very different solubilization kinetics. By contrast, in heterogeneous phase-separated bilayers, SMA was found to have a strong preference for solubilization of lipids in the fluid phase as compared to those in either a gel phase or a liquid-ordered phase. Together the results suggest that (1) SMA is a reliable tool to characterize native interactions between membrane constituents, (2) any solubilization preference of SMA is not due to properties of individual lipids but rather due to properties of the membrane or membrane domains in which these lipids reside and (3) exploiting SMA resistance rather than detergent resistance may be an attractive approach for the isolation of ordered domains from biological membranes.

Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods.

PubMed

Ho, Yuh-Shan

2006-01-01

A comparison was made of the linear least-squares method and a trial-and-error non-linear method of the widely used pseudo-second-order kinetic model for the sorption of cadmium onto ground-up tree fern. Four pseudo-second-order kinetic linear equations are discussed. Kinetic parameters obtained from the four kinetic linear equations using the linear method differed but they were the same when using the non-linear method. A type 1 pseudo-second-order linear kinetic model has the highest coefficient of determination. Results show that the non-linear method may be a better way to obtain the desired parameters.

Uncovering the intrinsic size dependence of hydriding phase transformations in nanocrystals.

PubMed

Bardhan, Rizia; Hedges, Lester O; Pint, Cary L; Javey, Ali; Whitelam, Stephen; Urban, Jeffrey J

2013-10-01

A quantitative understanding of nanocrystal phase transformations would enable more efficient energy conversion and catalysis, but has been hindered by difficulties in directly monitoring well-characterized nanoscale systems in reactive environments. We present a new in situ luminescence-based probe enabling direct quantification of nanocrystal phase transformations, applied here to the hydriding transformation of palladium nanocrystals. Our approach reveals the intrinsic kinetics and thermodynamics of nanocrystal phase transformations, eliminating complications of substrate strain, ligand effects and external signal transducers. Clear size-dependent trends emerge in nanocrystals long accepted to be bulk-like in behaviour. Statistical mechanical simulations show these trends to be a consequence of nanoconfinement of a thermally driven, first-order phase transition: near the phase boundary, critical nuclei of the new phase are comparable in size to the nanocrystal itself. Transformation rates are then unavoidably governed by nanocrystal dimensions. Our results provide a general framework for understanding how nanoconfinement fundamentally impacts broad classes of thermally driven solid-state phase transformations relevant to hydrogen storage, catalysis, batteries and fuel cells.

Control and measurement of the phase behavior of aqueous solutions using microfluidics

PubMed Central

Shim, Jung-uk; Cristobal, Galder; Link, Darren R.; Thorsen, Todd; Jia, Yanwei; Piattelli, Katie; Fraden, Seth

2008-01-01

A microfluidic device denoted the Phase Chip has been designed to measure and manipulate the phase diagram of multi-component fluid mixtures. The Phase Chip exploits the permeation of water through poly(dimethylsiloxane) (PDMS) in order to controllably vary the concentration of solutes in aqueous nanoliter volume microdrops stored in wells. The permeation of water in the Phase Chip is modeled using the diffusion equation and good agreement between experiment and theory is obtained. The Phase Chip operates by first creating drops of the water/solute mixture whose composition varies sequentially. Next, drops are transported down channels and guided into storage wells using surface tension forces. Finally, the solute concentration of each stored drop is simultaneously varied and measured. Two applications of the Phase Chip are presented. First, the phase diagram of a polymer/salt mixture is measured on-chip and validated off-chip and second, protein crystallization rates are enhanced through the manipulation of the kinetics of nucleation and growth. PMID:17580868

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

PubMed

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wemhoff, A P; Burnham, A K; Nichols III, A L

The reduction of the number of reactions in kinetic models for both the HMX beta-delta phase transition and thermal cookoff provides an attractive alternative to traditional multi-stage kinetic models due to reduced calibration effort requirements. In this study, we use the LLNL code ALE3D to provide calibrated kinetic parameters for a two-reaction bidirectional beta-delta HMX phase transition model based on Sandia Instrumented Thermal Ignition (SITI) and Scaled Thermal Explosion (STEX) temperature history curves, and a Prout-Tompkins cookoff model based on One-Dimensional Time to Explosion (ODTX) data. Results show that the two-reaction bidirectional beta-delta transition model presented here agrees as wellmore » with STEX and SITI temperature history curves as a reversible four-reaction Arrhenius model, yet requires an order of magnitude less computational effort. In addition, a single-reaction Prout-Tompkins model calibrated to ODTX data provides better agreement with ODTX data than a traditional multi-step Arrhenius model, and can contain up to 90% less chemistry-limited time steps for low-temperature ODTX simulations. Manual calibration methods for the Prout-Tompkins kinetics provide much better agreement with ODTX experimental data than parameters derived from Differential Scanning Calorimetry (DSC) measurements at atmospheric pressure. The predicted surface temperature at explosion for STEX cookoff simulations is a weak function of the cookoff model used, and a reduction of up to 15% of chemistry-limited time steps can be achieved by neglecting the beta-delta transition for this type of simulation. Finally, the inclusion of the beta-delta transition model in the overall kinetics model can affect the predicted time to explosion by 1% for the traditional multi-step Arrhenius approach, while up to 11% using a Prout-Tompkins cookoff model.« less

H T P21/ c- C2/ c phase transition and kinetics of Fe2+-Mg order-disorder of an Fe-poor pigeonite: implications for the cooling history of ureilites

NASA Astrophysics Data System (ADS)

Alvaro, Matteo; Cámara, Fernando; Domeneghetti, M. Chiara; Nestola, Fabrizio; Tazzoli, Vittorio

2011-09-01

A natural Ca-poor pigeonite (Wo6En76Fs18) from the ureilite meteorite sample PCA82506-3, free of exsolved augite, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P21/ c, was annealed up to 1,093°C to induce a phase transition from P21/ c to C2/ c symmetry. The variation with increasing temperature of the lattice parameters and of the intensity of the b-type reflections ( h + k = 2 n + 1, present only in the P21/ c phase) showed a displacive phase transition P21/ c to C2/ c at a transition temperature T Tr = 944°C, first order in character. The Fe-Mg exchange kinetics was studied by ex situ single-crystal X-ray diffraction in a range of temperatures between the closure temperature of the Fe-Mg exchange reaction and the transition temperature. Isothermal disordering annealing experiments, using the IW buffer, were performed on three crystals at 790, 840 and 865°C. Linear regression of ln k D versus 1/ T yielded the following equation: ln k_{{D}} = - 3717( ± 416)/T(K) + 1.290( ± 0.378);quad (R2 = 0.988) . The closure temperature ( T c) calculated using this equation was ˜740(±30)°C. Analysis of the kinetic data carried out taking into account the e.s.d.'s of the atomic fractions used to define the Fe-Mg degree of order, performed according to Mueller's model, allowed us to retrieve the disordering rate constants C 0 K {dis/+} for all three temperatures yielding the following Arrhenius relation: ln ( {C0 K_{{dis}}^{ + } } ) = ln K0 - Q/(RT) = 20.99( ± 3.74) - 26406( ± 4165)/T(K);quad (R2 = 0.988) . An activation energy of 52.5(±4) kcal/mol for the Fe-Mg exchange process was obtained. The above relation was used to calculate the following Arrhenius relation modified as a function of X Fe (in the range of X Fe = 0.20-0.50): ln ( {C0 K_{{dis}}^{ + } } ) = (21.185 - 1.47X_{{Fe}} ) - {{(27267 - 4170X_{{Fe}} )}/T(K)} . The cooling time constant, η = 6 × 10-1 K-1 year-1 calculated on the PCA82506-3 sample, provided a cooling rate of the order of 1°C/min consistent with the extremely fast late cooling history of the ureilite parent body after impact excavation.

Kinetic Monte Carlo Study of Li Intercalation in LiFePO4.

PubMed

Xiao, Penghao; Henkelman, Graeme

2018-01-23

Even as a commercial cathode material, LiFePO 4 remains of tremendous research interest for understanding Li intercalation dynamics. The partially lithiated material spontaneously separates into Li-poor and Li-rich phases at equilibrium. Phase segregation is a surprising property of LiFePO 4 given its high measured rate capability. Previous theoretical studies, aiming to describe Li intercalation in LiFePO 4 , include both atomic-scale density functional theory (DFT) calculations of static Li distributions and entire-particle-scale phase field models, based upon empirical parameters, studying the dynamics of the phase separation. Little effort has been made to bridge the gap between these two scales. In this work, DFT calculations are used to fit a cluster expansion for the basis of kinetic Monte Carlo calculations, which enables long time scale simulations with accurate atomic interactions. This atomistic model shows how the phases evolve in Li x FePO 4 without parameters from experiments. Our simulations reveal that an ordered Li 0.5 FePO4 phase with alternating Li-rich and Li-poor planes along the ac direction forms between the LiFePO 4 and FePO 4 phases, which is consistent with recent X-ray diffraction experiments showing peaks associated with an intermediate-Li phase. The calculations also help to explain a recent puzzling experiment showing that LiFePO 4 particles with high aspect ratios that are narrower along the [100] direction, perpendicular to the [010] Li diffusion channels, actually have better rate capabilities. Our calculations show that lateral surfaces parallel to the Li diffusion channels, as well as other preexisting sites that bind Li weakly, are important for phase nucleation and rapid cycling performance.

Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents: a kinetic and mechanistic study.

PubMed

Venkata Mohan, S; Chandrasekhar Rao, N; Karthikeyan, J

2002-03-01

This communication presents the results pertaining to the investigation conducted on color removal of trisazo direct dye, C.I. Direct Brown 1:1 by adsorption onto coal based sorbents viz. charfines, lignite coal, bituminous coal and comparing results with activated carbon (Filtrasorb-400). The kinetic sorption data indicated the sorption capacity of the different coal based sorbents. The sorption interaction of direct dye on to coal based sorbents obeys first-order irreversible rate equation and activated carbon fits with the first-order reversible rate equation. Intraparticle diffusion studies revealed the dye sorption interaction was complex and intraparticle diffusion was not only the rate limiting step. Isothermal data fit well with the rearranged Langmuir adsorption model. R(L) factor revealed the favorable nature of the isotherm of the dye-coal system. Neutral solution pH yielded maximum dye color removal. Desorption and interruption studies further indicated that the coal based sorbents facilitated chemisorption in the process of dye sorption while, activated carbon resulted in physisorption interaction.

Perpendicular and Parallel Ion Stochastic Heating by Kinetic Alfvén Wave Turbulence in the Solar Wind

NASA Astrophysics Data System (ADS)

Hoppock, I. W.; Chandran, B. D. G.

2017-12-01

The dissipation of turbulence is a prime candidate to explain the heating of collisionless plasmas like the solar wind. We consider the heating of protons and alpha particles using test particle simulations with a broad spectrum of randomly phased kinetic Alfvén waves (KAWs). Previous research extensively simulated and analytically considered stochastic heating at low plasma beta for conditions similar to coronal holes and the near-sun solar wind. We verify the analytical models of proton and alpha particle heating rates, and extend these simulations to plasmas with beta of order unity like in the solar wind at 1 au. Furthermore, we consider cases with very large beta of order 100, relevant to other astrophysical plasmas. We explore the parameter dependency of the critical KAW amplitude that breaks the gyro-center approximation and leads to stochastic gyro-orbits of the particles. Our results suggest that stochastic heating by KAW turbulence is an efficient heating mechanisms for moderate to high beta plasmas.

Grain growth mechanism and magnetic properties in L10-FePt thin films

NASA Astrophysics Data System (ADS)

Li, W.; Chen, L.

2017-08-01

This paper focuses on the grain growth mechanisms and magnetic properties of FePt thin films during an annealing process. The grain size and grain orientation distribution have been quantitatively investigated by electron backscatter diffraction (EBSD), and the grain growth kinetics of thin films were described by the phenomenological kinetic grain growth model. The results show that the grain growth exponent and activation energy of the FePt thin films were 4.26 and 136 kJ/mol respectively, indicating that the grain growth mechanism is mainly controlled by the stochastic jumping of atoms crossing the grain boundaries. X-ray diffraction (XRD) results show that disorder-order transformation was concurrent with grain growth during the annealing process, slowing down the velocity of grain growth. The hysteresis loops reveal that the out-of-plane coercivity and squareness is enhanced with increasing annealing temperature and this can be attributed to the improvement of L10-ordered phase volume fraction and texture intensity.

A Chain of Modeling Tools For Gas and Aqueous Phase Chemstry

NASA Astrophysics Data System (ADS)

Audiffren, N.; Djouad, R.; Sportisse, B.

Atmospheric chemistry is characterized by the use of large set of chemical species and reactions. Handling with the set of data required for the definition of the model is a quite difficult task. We prsent in this short article a preprocessor for diphasic models (gas phase and aqueous phase in cloud droplets) named SPACK. The main interest of SPACK is the automatic generation of lumped species related to fast equilibria. We also developped a linear tangent model using the automatic differentiation tool named ODYSSEE in order to perform a sensitivity analysis of an atmospheric multi- phase mechanism based on RADM2 kinetic scheme.Local sensitivity coefficients are computed for two different scenarii. We focus in this study on the sensitivity of the ozone,NOx,HOx, system with respect to some aqueous phase reactions and we inves- tigate the influence of the reduction in the photolysis rates in the area below the cloud region.

Kinetics of phase transition in protein solutions on microscopic and mesoscopic length scales

NASA Astrophysics Data System (ADS)

Filobelo, Luis F.

2005-11-01

Phase transformations in solutions of macromolecules are fundamental for all living things, and of great importance in science and industry. For instance, insulin is biosynthesized in the beta cells of the pancreas and stored in crystalline form, which protects it form cleavage, until it is needed. Certain diseases such as Alzheimer, sickle cell anemia, and eye cataract are produced by the polymerization of protein molecules, which loose their functionality after the phase transition. Additionally, separation operations in manufacturing of pharmaceuticals can be eliminated if the crystals produced have a narrow size distribution. The nucleation and growth of crystals can be adequately controlled only if the mechanisms that govern these processes are well understood. Here we have investigated several facets of the kinetics controlling the behavior of phase transition in protein solutions. We performed experiments to determine the homogenous nucleation rate for lysozyme and insulin crystals and the contribution of heterogeneously nucleated crystals. In the first segment of this work we discuss the existence of a solution-to-crystal spinodal boundary derived from these determinations, and showed that the formation of crystalline nuclei from solution occur in two steps for lysozyme: the formation of quasi-droplets of a disordered intermediate, followed by the nucleation of ordered crystalline embryos within these droplets in which the rate of each step depends on a respective free energy barrier and on the growth rate of its near-critical clusters. We addressed experimentally the relative significance of the free-energy barriers and the kinetic factors for the nucleation of crystals from solution. Using dynamic and static light scattering along with differential refractometry, we also characterized the appearance of dense liquid droplets and the magnitude of the second osmotic virial coefficient B2 for insulin in both aqueous solution and in solution containing 15% (v/v) acetone and found that B2 was consistently lower for the acetone-containing insulin solutions, indicating stronger net attraction between insulin molecules. Since both conditions are inductive of crystallization, we conclude that the higher values of B 2 in acetone-free solutions reflect the presence of a repulsive maximum at intermediate separations in the intermolecular interaction potential, likely due to water structuring around the insulin molecules. We also found that the classic nucleation theory, in which fluctuations along one order parameters such as density are required for the phase transition to occur, applies to insulin. After establishing the rate-limiting role of kinetics in phase transitions, we characterized the temperature dependence of viscosity of protein solution in a wide range of concentrations. We found timescales dependence for lysozyme, suggesting that the probing beads move about local regions in short times, and through loosely bound networks in between local regions during longer times. We fitted our results to the Free Volume Theory and found that it does not apply at low protein concentrations. Finally, we found that hemoglobin undergoes aggregation in solution, which yields increased nucleation rates as the protein ages.

a Numerical Investigation of the Jamming Transition in Traffic Flow on Diluted Planar Networks

NASA Astrophysics Data System (ADS)

Achler, Gabriele; Barra, Adriano

In order to develop a toy model for car's traffic in cities, in this paper we analyze, by means of numerical simulations, the transition among fluid regimes and a congested jammed phase of the flow of kinetically constrained hard spheres in planar random networks similar to urban roads. In order to explore as timescales as possible, at a microscopic level we implement an event driven dynamics as the infinite time limit of a class of already existing model (Follow the Leader) on an Erdos-Renyi two-dimensional graph, the crossroads being accounted by standard Kirchoff density conservations. We define a dynamical order parameter as the ratio among the moving spheres versus the total number and by varying two control parameters (density of the spheres and coordination number of the network) we study the phase transition. At a mesoscopic level it respects an, again suitable, adapted version of the Lighthill-Whitham model, which belongs to the fluid-dynamical approach to the problem. At a macroscopic level, the model seems to display a continuous transition from a fluid phase to a jammed phase when varying the density of the spheres (the amount of cars in a city-like scenario) and a discontinuous jump when varying the connectivity of the underlying network.

Light nuclei production as a probe of the QCD phase diagram

NASA Astrophysics Data System (ADS)

Sun, Kai-Jia; Chen, Lie-Wen; Ko, Che Ming; Pu, Jie; Xu, Zhangbu

2018-06-01

It is generally believed that the quark-hadron transition at small values of baryon chemical potentials μB is a crossover but changes to a first-order phase transition with an associated critical endpoint (CEP) as μB increases. Such a μB-dependent quark-hadron transition is expected to result in a double-peak structure in the collision energy dependence of the baryon density fluctuation in heavy-ion collisions with one at lower energy due to the spinodal instability during the first-order phase transition and another at higher energy due to the critical fluctuations in the vicinity of the CEP. By analyzing the data on the p, d and 3H yields in central heavy-ion collisions within the coalescence model for light nuclei production, we find that the relative neutron density fluctuation Δρn = 〈(δρn) 2 〉 /〈ρn 〉 2 at kinetic freeze-out indeed displays a clear peak at √{sNN } = 8.8GeV and a possible strong re-enhancement at √{sNN } = 4.86GeV. Our findings thus provide a strong support for the existence of a first-order phase transition at large μB and its critical endpoint at a smaller μB in the temperature versus baryon chemical potential plane of the QCD phase diagram.

Authigenic carbonate precipitation in Lake Acigöl, a hypersaline lake in southwestern Turkey

NASA Astrophysics Data System (ADS)

Balci, Nurgul; Menekse, Meryem; Gül Karagüler, Nevin; Seref Sönmez, M.; Meister, Patrick

2014-05-01

Lake Acigöl (Bitter Lake) is a hypersaline lake in southwestern Turkey at an elevation of 836 m above sea level showing authigenic precipitation of several different carbonate mineral phases. It is a perennial lake and closed drainage basin where a semiarid continental climate dominates. Due to the extreme water chemistry (salinity 8-200 mg/l; SO4 112-15232 mg/l; Cl 290-35320 mg/l; Mg, 82-3425 mg/l; Ca 102-745 mg/l) unique microorganisms flourish in the lake. We studied microbial diversity from enrichment cultures and performed precipitation experiments using similar water chemistry and adding bacterial enrichment cultures from lake sediments in order to elucidate whether the mineral assemblages found in the lake can be reproduced. Experiments using moderately halophilic bacteria obtained from the lake sediments demonstrate the formation of various calcium-/magnesium-carbonates: hydromagnesite, dypingite, huntite, monohydrocalcite and aragonite. The relative amounts of different mineral phases, particularly monohydrocalcite, hydromagnesite and dypingite, could be controlled by varying the sulphate concentration in the media from 0 to 56 mM. The similar mineral assemblages identified in the sediments of Lake Acigöl and in the experiments point to similar thermodynamic conditions and kinetics of crystal growth. In particular, the similar spherical morphology points to a rapid crystal growth under strong kinetic inhibition, possibly by organic polymers that are commonly produced by microbial communities. Our results demonstrate that the authigenic carbonate paragenesis of hypersaline lakes as Lake Acigöl can be reproduced in halophilic bacterial cultures. The exact thermodynamic conditions and precipitation kinetics under seasonally changing water chemistry or in batch experiment, however, still have to be constrained in order to establish a microbial model for carbonate precipitation in such environments.

Iron dissolution kinetics of mineral dust at low pH during simulated atmospheric processing

NASA Astrophysics Data System (ADS)

Shi, Z.; Bonneville, S.; Krom, M. D.; Carslaw, K. S.; Jickells, T. D.; Baker, A. R.; Benning, L. G.

2010-11-01

We investigated the iron (Fe) dissolution kinetics of African (Tibesti) and Asian (Beijing) dust samples at acidic pH with the aim of reproducing the low pH conditions in atmospheric aerosols. The Beijing dust and three size fractions of the Tibesti dust (<20 μm: PM20; <10 μm: PM10; and <2.5 μm: PM2.5) were dissolved at pH 1, 2 and/or 3 for up to 1000 h. In the first 10 min, all dust samples underwent an extremely fast Fe solubilisation. Subsequently, the Fe dissolution proceeded at a much slower rate before reaching a stable dissolution plateau. The time-dependant Fe dissolution datasets were best described by a model comprising three acid-extractable Fe pools each dissolving according to first-order kinetics. The dissolution rate constant k of each pool was independent of the source (Saharan or Asian) and the size (PM20, PM10 or PM2.5) of the dust but highly dependent on pH. The "fast" Fe pool had a k (25 h-1 at pH=1) of a similar magnitude to "dry" ferrihydrite nanoparticles and/or poorly crystalline Fe(III) oxyhydroxide, while the "intermediate" and "slow" Fe pools had k values respectively 50-60 times and 3000-4000 times smaller than the "fast" pool. The "slow" Fe pool was likely to consist of both crystalline Fe oxide phases (i.e., goethite and/or hematite) and Fe contained in the clay minerals. The initial mass of the "fast", "intermediate" and "slow" Fe pools represented respectively about 0.5-2%, 1-3% and 15-40% of the total Fe in the dust samples. Furthermore, we showed that in systems with low dust/liquid ratios, Fe can be dissolved from all three phases, whereas at high dust/liquid ratios (e.g., in aerosols), sufficient Fe is solubilised from the "fast" phase to dominate the Fe dissolved and to suppress the dissolution of Fe from the other Fe pools. These data demonstrated that dust/liquid ratio and pH are fundamental parameters controlling Fe dissolution kinetics in the dust. In order to reduce errors in atmospheric and climate models, these fundamental controlling factors need to be included.

Modelling nifedipine photodegradation, photostability and actinometric properties.

PubMed

Maafi, Wassila; Maafi, Mounir

2013-11-01

The photodegradation of drugs obeying unimolecular mechanisms such as that of nifedipine (NIF) were usually characterised in the literature by zero-, first- and second-order kinetics. This approach has been met with varying success. This paper addresses this issue and proposes a novel approach for unimolecular photodegradation kinetics. The photodegradation of the cardiovascular drug nifedipine is investigated within this framework. Experimental kinetic data of nifedipine photodegradation were obtained by continuous monochromatic irradiation and DAD analysis. Fourth-order Runge-Kutta calculated kinetic data served for the validation of the new semi-empirical integrated rate-law model proposed in this study. A new model equation has been developed and proposed which faithfully describes the kinetic behaviour of NIF in solution for non-isosbestic irradiations at wavelengths where both NIF and its photoproduct absorb. NIF absolute quantum yield values were determined and found to increase with irradiation wavelength according to a defined sigmoid relationship. The effects of increasing NIF or excipients' concentrations on NIF kinetics were successfully modelled and found to improve NIF photostability. The potential of NIF for actinometry has been explored and evaluated. A new reaction order (the so-called Φ-order) has been identified and specifically proposed for unimolecular photodegradation reactions. The semi-empirical and integrated rate-law models facilitated reliable kinetic studies of NIF photodegradation as an example of AB(1Φ) unimolecular reactions. It allowed filling a gap in kinetic studies of drugs since, thus far, thermal first-order or a combination of first- and zero- order kinetic equations were generally applied for drug photoreactions in the literature. Also, a new reaction order, the "Φ-order", has been evidenced and proposed as a specific alternative for photodegradation kinetics. Copyright © 2013 Elsevier B.V. All rights reserved.

Persistent Step-Flow Growth of Strained Films on Vicinal Substrates

NASA Astrophysics Data System (ADS)

Hong, Wei; Lee, Ho Nyung; Yoon, Mina; Christen, Hans M.; Lowndes, Douglas H.; Suo, Zhigang; Zhang, Zhenyu

2005-08-01

We propose a model of persistent step flow, emphasizing dominant kinetic processes and strain effects. Within this model, we construct a morphological phase diagram, delineating a regime of step flow from regimes of step bunching and island formation. In particular, we predict the existence of concurrent step bunching and island formation, a new growth mode that competes with step flow for phase space, and show that the deposition flux and temperature must be chosen within a window in order to achieve persistent step flow. The model rationalizes the diverse growth modes observed in pulsed laser deposition of SrRuO3 on SrTiO3.

Restoring the Pauli principle in the random phase approximation ground state

NASA Astrophysics Data System (ADS)

Kosov, D. S.

2017-12-01

Random phase approximation ground state contains electronic configurations where two (and more) identical electrons can occupy the same molecular spin-orbital violating the Pauli exclusion principle. This overcounting of electronic configurations happens due to quasiboson approximation in the treatment of electron-hole pair operators. We describe the method to restore the Pauli principle in the RPA wavefunction. The proposed theory is illustrated by the calculations of molecular dipole moments and electronic kinetic energies. The Hartree-Fock based RPA, which is corrected for the Pauli principle, gives the results of comparable accuracy with Møller-Plesset second order perturbation theory and coupled-cluster singles and doubles method.

Mean field study of a propagation-turnover lattice model for the dynamics of histone marking

NASA Astrophysics Data System (ADS)

Yao, Fan; Li, FangTing; Li, TieJun

2017-02-01

We present a mean field study of a propagation-turnover lattice model, which was proposed by Hodges and Crabtree [Proc. Nat. Acad. Sci. 109, 13296 (2012)] for understanding how posttranslational histone marks modulate gene expression in mammalian cells. The kinetics of the lattice model consists of nucleation, propagation and turnover mechanisms, and exhibits second-order phase transition for the histone marking domain. We showed rigorously that the dynamics essentially depends on a non-dimensional parameter κ = k +/ k -, the ratio between the propagation and turnover rates, which has been observed in the simulations. We then studied the lowest order mean field approximation, and observed the phase transition with an analytically obtained critical parameter. The boundary layer analysis was utilized to investigate the structure of the decay profile of the mark density. We also studied the higher order mean field approximation to achieve sharper estimate of the critical transition parameter and more detailed features. The comparison between the simulation and theoretical results shows the validity of our theory.

Nonequilibrium phase transitions of sheared colloidal microphases: Results from dynamical density functional theory

NASA Astrophysics Data System (ADS)

Stopper, Daniel; Roth, Roland

2018-06-01

By means of classical density functional theory and its dynamical extension, we consider a colloidal fluid with spherically symmetric competing interactions, which are well known to exhibit a rich bulk phase behavior. This includes complex three-dimensional periodically ordered cluster phases such as lamellae, two-dimensional hexagonally packed cylinders, gyroid structures, or spherical micelles. While the bulk phase behavior has been studied extensively in earlier work, in this paper we focus on such structures confined between planar repulsive walls under shear flow. For sufficiently high shear rates, we observe that microphase separation can become fully suppressed. For lower shear rates, however, we find that, e.g., the gyroid structure undergoes a kinetic phase transition to a hexagonally packed cylindrical phase, which is found experimentally and theoretically in amphiphilic block copolymer systems. As such, besides the known similarities between the latter and colloidal systems regarding the equilibrium phase behavior, our work reveals further intriguing nonequilibrium relations between copolymer melts and colloidal fluids with competing interactions.

Associations between timing in the baseball pitch and shoulder kinetics, elbow kinetics, and ball speed.

PubMed

Urbin, M A; Fleisig, Glenn S; Abebe, Asheber; Andrews, James R

2013-02-01

A baseball pitcher's ability to maximize ball speed while avoiding shoulder and elbow injuries is an important determinant of a successful career. Pitching injuries are attributed to microtrauma brought about by the repetitive stress of high-magnitude shoulder and elbow kinetics. Over a number of pitches, variations in timing peak angular velocities of trunk segment rotations will be significantly associated with ball speed and upper extremity kinetic parameters. Descriptive laboratory study. Kinematic and kinetic data were derived from 9 to 15 fastball pitches performed by 16 active, healthy collegiate (n = 8) and professional (n = 8) pitchers via 3-dimensional motion capture (240 Hz). Each pitch was decomposed into 4 phases corresponding to the time between peak angular velocities of sequential body segment rotations. Four mixed models were used to evaluate which phases varied significantly in relation to ball speed, peak shoulder proximal force, peak shoulder internal rotation torque, and peak elbow varus torque. Mixed-model parameter coefficient estimates were used to quantify the influence of these variations in timing on ball speed and upper extremity kinetics. All 4 mixed models were significant (P < .05). The time from stride-foot contact to peak pelvis angular velocity varied significantly in relation to all upper extremity kinetic parameters and ball speed. Increased time in this phase correlated with decreases in all parameters. Decreased ball speed also correlated with increased time between peak upper torso and elbow extension angular velocities. Decreased shoulder proximal force also correlated with increased time between peak pelvis and upper torso angular velocities. There are specific phases that vary in relation to ball speed and upper extremity kinetic parameters, reinforcing the importance of effectively and consistently timing segmental interactions. For the specific interactions that varied significantly, increased phase times were associated with decreased kinetics and ball speed. Although increased time within specific phases correlates with decreases in the magnitude of upper extremity kinetics linked to overuse injuries, it also correlates with decreased ball speed. Based on these findings, it may appear that minimizing the risk of injury (ie, decreased kinetics) and maximizing performance quality (ie, increased ball speed) are incompatible with one another. However, there may be an optimal balance in timing that is effective for satisfying both outcomes.

Kinetics of microbial reduction of Solid phase U(VI).

PubMed

Liu, Chongxuan; Jeon, Byong-Hun; Zachara, John M; Wang, Zheming; Dohnalkova, Alice; Fredrickson, James K

2006-10-15

Sodium boltwoodite (NaUO2SiO3OH x 1.5 H2O) was used to assess the kinetics of microbial reduction of solid-phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads in a nongrowth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solid-phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid-phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intragrain uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated that microbial reduction of solid-phase U(VI) is controlled by coupled biological, chemical, and physical processes.

Thermodynamic and Kinetic Properties of Metal Hydrides from First-Principles Calculations

NASA Astrophysics Data System (ADS)

Michel, Kyle Jay

In an effort to minimize the worldwide dependence on fossil fuels, much research has focused on the development of hydrogen fuel cell vehicles. Among the many challenges currently facing the transition to such an alternative energy economy is the storage of hydrogen in an economical and practical way. One class of materials that has presented itself as a possible candidate is solid metal hydrides. These materials chemically bind hydrogen and on heating, release the gas which can then be used to generate power as needed for the vehicle. In order to meet guidelines that have been set for such a storage system, hydrogen must be released rapidly in a narrow temperature range of -40 to 80°C with all reactions being reversible. This sets both thermodynamic and kinetic requirements for the design of candidate metal hydrides. First-principles calculations are well-suited for the task of exploring reactions involving metal hydrides. Here, density-functional theory is used to calculate properties of these materials at the quantum mechanical level of accuracy. In particular, three systems have been investigated: 1. Li-Mg-N-H. Reactions between all known compounds in this system are systematically investigated in order to predict thermodynamically allowed reactions that release hydrogen. The properties of these reactions are compared to the requirements set for hydrogen storage systems. Additionally, ground-state structures are predicted for Li2Mg(NH)2 and Li 4Mg(NH)3. 2. Na-Al-H. The kinetics of mass transport during the (de)hydrogenation of the well-known metal hydride NaAlH4 are investigated. A model is developed to study the flux of native defects through phases involved in these reactions. Since it is also known that titanium is an effective catalyst for both dehydrogenation and rehydrogenation, the effect of Ti substitution in bulk lattices on the kinetics of mass transport is investigated. Results are compared to experiments in order to determine if mass transport represents the rate-limiting process during de- or rehydrogenation and what the effect of Ti may be. 3. Si-H. Properties of the recently synthesized compound SiH4(H 2)2 are investigated. Under high pressures, hydrogen binding to SiH4 exhibits characteristics of both physical and chemical bonds. A ground-state structure is predicted for this phase and the vibrational and bonding properties are investigated in order to determine the origin of the unusual binding between H2 and SiH4.

Phase segregation and spontaneous symmetry breaking in a bidirectional two-channel non-conserving model with narrow entrances

NASA Astrophysics Data System (ADS)

Sharma, Natasha; Gupta, A. K.

2017-04-01

Motivated by connections between the inputs and outputs of several transport mechanisms and multi-species functionalities, we studied an open system of a two-species totally asymmetric simple exclusion process with narrow entrances, which assimilate the synergy of the particles with the surrounding environment through Langmuir kinetics (LK). We analyzed the model within the framework of mean-field theory, and examined complex phenomena such as boundary-induced phase transitions and spontaneous symmetry breaking for variant conditions of attachment and detachment rates. Based on the theoretical investigations we obtained the phase boundaries for various symmetric and asymmetric phases. Our finding displays a prolific behavior, highlighting the significant effect of LK rates on symmetry breaking. It is found that for lower orders of LK rates, the number of symmetrical and asymmetrical phases increases notably, while for their higher orders symmetry breaking disappears, revealing that the presence of bulk non-conserving processes can resume/break the uniformity between two species. The critical value of LK rates beyond which the asymmetrical phases disappears is identified. The theoretical findings are explored by extensive Monte Carlo simulations. The effect of the system size and symmetry breaking incident on the Monte Carlo simulation results has also been examined based on particle density histograms.

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold

Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. Itmore » was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.« less

Theoretical Basis for Estimated Test Times and Conditions for Drop Tower and Space-Based Droplet Burning Experiments With Methanol and N-Heptane

NASA Technical Reports Server (NTRS)

Marchese, Anthony J.; Dryer, Fredrick L.; Choi, Mun Y.

1994-01-01

In order to develop an extensive envelope of test conditions for NASA's space-based Droplet Combustion Experiment (DCE) as well those droplet experiments which can be performed using a drop tower, the transient vaporization and combustion of methanol and n-heptane droplets were simulated using a recently developed fully time-dependent, spherically symmetric droplet combustion model. The transient vaporization of methanol and n-heptane was modeled to characterize the instantaneous gas phase composition surrounding the droplet prior to the introduction of an ignition source. The results for methanol/air showed that the entire gas phase surrounding a 2 mm methanol droplet deployed in zero-g .quickly falls outside the lean flammability limit. The gas phase surrounding an identically-sized n-heptane droplet, on the other hand, remains flammable. The combustion of methanol was then modeled considering a detailed gas phase chemical kinetic mechanism (168 steps, 26 species) and the effect of the dissolution of flame-generated water into the liquid droplet. These results were used to determine the critical ignition diameter required to achieve quasi-steady droplet combustion in a given oxidizing environment. For droplet diameters greater than the critical ignition diameter, the model predicted a finite diameter at which the flame would extinguish. These extinction diameters were found to vary significantly with initial droplet diameter. This phenomenon appears to be unique to the transient heat transfer, mass transfer and chemical kinetics of the system and thus has not been reported elsewhere to date. The extinction diameter was also shown to vary significantly with the liquid phase Lewis number since the amount of water present in the droplet at extinction is largely governed by the rate at which water is transported into the droplet via mass diffusion. Finally, the numerical results for n-heptane combustion were obtained using both 2 step and 96 step semi-emperical chemical kinetic mechanisms. Neither mechanism exhibited the variation of extinction diameter with initial diameter.

Curing behavior and reaction kinetics of binder resins for 3D-printing investigated by dielectric analysis (DEA)

NASA Astrophysics Data System (ADS)

Möginger, B.; Kehret, L.; Hausnerova, B.; Steinhaus, J.

2016-05-01

3D-Printing is an efficient method in the field of additive manufacturing. In order to optimize the properties of manufactured parts it is essential to adapt the curing behavior of the resin systems with respect to the requirements. Thus, effects of resin composition, e.g. due to different additives such as thickener and curing agents, on the curing behavior have to be known. As the resin transfers from a liquid to a solid glass the time dependent ion viscosity was measured using DEA with flat IDEX sensors. This allows for a sensitive measurement of resin changes as the ion viscosity changes two to four decades. The investigated resin systems are based on the monomers styrene and HEMA. To account for the effects of copolymerization in the calculation of the reaction kinetics it was assumed that the reaction can be considered as a homo-polymerization having a reaction order n≠1. Then the measured ion viscosity curves are fitted with the solution of the reactions kinetics - the time dependent degree of conversion (DC-function) - for times exceeding the initiation phase representing the primary curing. The measured ion viscosity curves can nicely be fitted with the DC-function and the determined fit parameters distinguish distinctly between the investigated resin compositions.

Insight into the kinetics and thermodynamics of the hydride transfer reactions between quinones and lumiflavin: a density functional theory study.

PubMed

Reinhardt, Clorice R; Jaglinski, Tanner C; Kastenschmidt, Ashly M; Song, Eun H; Gross, Adam K; Krause, Alyssa J; Gollmar, Jonathan M; Meise, Kristin J; Stenerson, Zachary S; Weibel, Tyler J; Dison, Andrew; Finnegan, Mackenzie R; Griesi, Daniel S; Heltne, Michael D; Hughes, Tom G; Hunt, Connor D; Jansen, Kayla A; Xiong, Adam H; Hati, Sanchita; Bhattacharyya, Sudeep

2016-09-01

The kinetics and equilibrium of the hydride transfer reaction between lumiflavin and a number of substituted quinones was studied using density functional theory. The impact of electron withdrawing/donating substituents on the redox potentials of quinones was studied. In addition, the role of these substituents on the kinetics of the hydride transfer reaction with lumiflavin was investigated in detail under the transition state (TS) theory assumption. The hydride transfer reactions were found to be more favorable for an electron-withdrawing substituent. The activation barrier exhibited a quadratic relationship with the driving force of these reactions as derived under the formalism of modified Marcus theory. The present study found a significant extent of electron delocalization in the TS that is stabilized by enhanced electrostatic, polarization, and exchange interactions. Analysis of geometry, bond-orders, and energetics revealed a predominant parallel (Leffler-Hammond) effect on the TS. Closer scrutiny reveals that electron-withdrawing substituents, although located on the acceptor ring, reduce the N-H bond order of the donor fragment in the precursor complex. Carried out in the gas-phase, this is the first ever report of a theoretical study of flavin's hydride transfer reactions with quinones, providing an unfiltered view of the electronic effect on the nuclear reorganization of donor-acceptor complexes.

A potential low cost adsorbent for the removal of cationic dyes from aqueous solutions

NASA Astrophysics Data System (ADS)

Uddin, Md. Tamez; Rahman, Md. Arifur; Rukanuzzaman, Md.; Islam, Md. Akhtarul

2017-10-01

This study was aimed at using mango leaf powder (MLP) as a potential adsorbent for the removal of methylene blue (MB) from aqueous solutions. Characterization of the adsorbent was carried out with scanning electron microscopy, Fourier transform infrared spectroscopy, and nitrogen adsorption-desorption analysis. The pH at the point of zero charge of the adsorbent was determined by titration method and was found a value to be 5.6 ± 0.2. Batch studies were performed to evaluate the influence of various experimental parameters like initial solution pH, contact time, initial concentration of dye and adsorbent dosage on the removal of MB. An adsorption-desorption study was carried out resulting the mechanism of adsorption was carried out by electrostatic force of attraction. The adsorption equilibrium time required for the adsorption of MB on MLP was almost 2 h and 85 ± 5% of the total amount of dye uptake was found to occur in the first rapid phase (30 min). The Langmuir and Freundlich isotherm models were used for modeling the adsorption equilibrium. The experimental equilibrium data could be well interpreted by Langmuir isotherm with maximum adsorption capacity of 156 mg/g. To state the sorption kinetics, the fits of pseudo-first-order and pseudo-second-order kinetic models were investigated. It was obtained that the adsorption process followed the pseudo-second-order rate kinetics. The above findings suggest that MLP can be effectively used for decontamination of dye containing wastewater.

MECHANISM AND KINETICS OF THE FORMATION OF NOX AND OTHER COMBUSTION POLLUTANTS. PHASE II. MODIFIED COMBUSTION

EPA Science Inventory

The report gives Phase II results of a combined experimental/theoretical study to define the mechanisms and kinetics of the formation of NOx and other combustion pollutants. Two experimental devices were used in Phase II. A special flat-flame burner with a controlled-temperature ...

Effect of electrolyte nature on kinetics of remazol yellow G removal by electrocoagulation

NASA Astrophysics Data System (ADS)

Rajabi, M.; Bagheri-Roochi, M.; Asghari, A.

2011-10-01

The present study describes an electrocoagulation process for the removal of remazol yellow G from dye solutions using Iron as the anode and Steel as the cathode. Pseudo-first-order, pseudo-second-order and intraparticle diffusion models were used to analyze the kinetic data obtained at different concentrations in different conditions. The adsorption kinetics was well described by the pseudo-second-order kinetic model.

Kinetics and dynamics of annealing during sub-gel phase formation in phospholipid bilayers

PubMed Central

Páli, Tibor; Bartucci, Rosa; Horváth, László I.; Marsh, Derek

1993-01-01

The saturation transfer electron spin resonance (STESR) spectra of spin-labeled phosphatidylcholine have been used to follow the kinetics of conversion from the gel phase to the sub-gel phase in aqueous bilayers of dipalmitoyl phosphatidylcholine. This is a simple, well-defined model system for lipid domain formation in membranes. The integrated intensity of the STESR spectrum from the chain-labeled lipid first increases and then decreases with time of incubation in the gel phase at 0°C. The first, more rapid phase of the kinetics is attributed to the conversion of germ nuclei to growth nuclei of the sub-gel phase. The increase in STESR intensity corresponds to the reduction in chain mobility of spin labels located in the gel phase at the boundaries of the growth nuclei and correlates with the increase in the diagnostic STESR line height ratios over this time range. The second, slower phase of the kinetics is attributed to growth of the domains of the sub-gel phase. The decrease in STESR intensity over this time regime corresponds to exclusion of the spin-labeled lipids from the tightly packed sub-gel phase and correlates quantitatively with calibrations of the spin label concentration dependence of the STESR intensity in the gel phase. The kinetics of formation of the sub-gel phase are consistent with the classical model for domain formation and growth. At 0°C, the half-time for conversion of germ nuclei to growth nuclei is ∼7.7 h and domain growth of the sub-gel phase is characterized by a rate constant of 0.025 h-1. The temperature dependence of the STESR spectra from samples annealed at 0°C suggests that the subtransition takes place via dissolution of sub-gel phase domains, possibly accompanied by domain fission. PMID:19431899

Kinetic description of rotating Tokamak plasmas with anisotropic temperatures in the collisionless regime

NASA Astrophysics Data System (ADS)

Cremaschini, Claudio; Tessarotto, Massimo

2011-11-01

A largely unsolved theoretical issue in controlled fusion research is the consistent kinetic treatment of slowly-time varying plasma states occurring in collisionless and magnetized axisymmetric plasmas. The phenomenology may include finite pressure anisotropies as well as strong toroidal and poloidal differential rotation, characteristic of Tokamak plasmas. Despite the fact that physical phenomena occurring in fusion plasmas depend fundamentally on the microscopic particle phase-space dynamics, their consistent kinetic treatment remains still essentially unchallenged to date. The goal of this paper is to address the problem within the framework of Vlasov-Maxwell description. The gyrokinetic treatment of charged particles dynamics is adopted for the construction of asymptotic solutions for the quasi-stationary species kinetic distribution functions. These are expressed in terms of the particle exact and adiabatic invariants. The theory relies on a perturbative approach, which permits to construct asymptotic analytical solutions of the Vlasov-Maxwell system. In this way, both diamagnetic and energy corrections are included consistently into the theory. In particular, by imposing suitable kinetic constraints, the existence of generalized bi-Maxwellian asymptotic kinetic equilibria is pointed out. The theory applies for toroidal rotation velocity of the order of the ion thermal speed. These solutions satisfy identically also the constraints imposed by the Maxwell equations, i.e., quasi-neutrality and Ampere's law. As a result, it is shown that, in the presence of nonuniform fluid and EM fields, these kinetic equilibria can sustain simultaneously toroidal differential rotation, quasi-stationary finite poloidal flows and temperature anisotropy.

Comparative analysis of human gait while wearing thong-style flip-flops versus sneakers.

PubMed

Shroyer, Justin F; Weimar, Wendi H

2010-01-01

Flip-flops are becoming a common footwear option. Casual observation has indicated that individuals wear flip-flops beyond their structural limit and have a different gait while wearing flip-flops versus shoes. This alteration in gait may cause the anecdotal foot and lower-limb discomfort associated with wearing flip-flops. To investigate the effect of sneakers versus thong-style flip-flops on gait kinematics and kinetics, 56 individuals (37 women and 19 men) were randomly assigned to a footwear order (flip-flops or sneakers first) and were asked to wear the assigned footwear on the day before and the day of testing. On each testing day, participants were videotaped as they walked at a self-selected pace across a force platform. A 2 (sex) x 2 (footwear) repeated-measures analysis of variance (P = .05) was used for statistical analysis. Significant interaction effects of footwear and sex were found for maximal anterior force, attack angle, and ankle angle during the swing phase. Footwear significantly affected stride length, ankle angle at the beginning of double support and during the swing phase, maximal braking impulse, and stance time. Flip-flops resulted in a shorter stride, a larger ankle angle at the beginning of double support and during the swing phase, a smaller braking impulse, and a shorter stance time compared with sneakers. The effects of footwear on gait kinetics and kinematics is extensive, but there is limited research on the effect of thong-style flip-flops on gait. These results suggest that flip-flops have an effect on several kinetic and kinematic variables compared with sneakers.

Kinetic modelling of ascorbic and dehydroascorbic acids concentrations in a model solution at different temperatures and oxygen contents.

PubMed

Gómez Ruiz, Braulio; Roux, Stéphanie; Courtois, Francis; Bonazzi, Catherine

2018-04-01

The degradation kinetics of vitamin C (ascorbic and dehydroascorbic acids, AA and DHA) were determined under controlled conditions of temperature (50-90 °C) and oxygen concentrations in the gas phase (10-30% mol/mol) using a specific reactor. The degradation of vitamin C in malate buffer (20 mM, pH 3.8), mimetic of an apple puree, was assessed by sampling at regular intervals and spectrophotometric quantification of AA and DHA levels at 243 nm. The results showed that AA degradation increased with temperature and oxygen concentration, while DHA exhibited the behaviour of an intermediate species, appearing then disappearing. A kinetic model was successfully developed to simulate the experimental data by two first order consecutive reactions. The first one represented AA degradation as a function of temperature and concentration in dissolved oxygen, and the second reflected DHA degradation as a function of temperature only, both adequately following Arrhenius' law. Copyright © 2018 Elsevier Ltd. All rights reserved.

Electrospray micromixer chip for on-line derivatization and kinetic studies.

PubMed

Abonnenc, Mélanie; Dayon, Loïc; Perruche, Brice; Lion, Niels; Girault, Hubert H

2008-05-01

An electrospray microchip for mass spectrometry comprising an integrated passive mixer to carry out on-chip chemical derivatizations is described. The microchip fabricated using UV-photoablation is composed of two microchannels linked together by a liquid junction. Downstream of this liquid junction, a mixing unit made of parallel oblique grooves is integrated to the microchannel in order to create flow perturbations. Several mixer designs are evaluated. The mixer efficiency is investigated both by fluorescence study and mass spectrometric monitoring of the tagging reaction of cysteinyl peptides with 1,4-benzoquinone. The comparisons with a microchip without a mixing unit and a kinetic model are used to assess the efficiency of the mixer showing tagging kinetics close to that of bulk reactions in an ideally mixed reactor. As an ultimate application, the electrospray micromixer is implemented in a LC-MS workflow. On-line derivatization of albumin tryptic peptides after a reversed-phase separation and counting of their cysteines drastically enhance the protein identification.

Lipid-protein interaction induced domains: Kinetics and conformational changes in multicomponent vesicles

NASA Astrophysics Data System (ADS)

Sreeja, K. K.; Sunil Kumar, P. B.

2018-04-01

The spatio-temporal organization of proteins and the associated morphological changes in membranes are of importance in cell signaling. Several mechanisms that promote the aggregation of proteins at low cell surface concentrations have been investigated in the past. We show, using Monte Carlo simulations, that the affinity of proteins for specific lipids can hasten their aggregation kinetics. The lipid membrane is modeled as a dynamically triangulated surface with the proteins defined as in-plane fields at the vertices. We show that, even at low protein concentrations, strong lipid-protein interactions can result in large protein clusters indicating a route to lipid mediated signal amplification. At high protein concentrations, the domains form buds similar to that seen in lipid-lipid interaction induced phase separation. Protein interaction induced domain budding is suppressed when proteins act as anisotropic inclusions and exhibit nematic orientational order. The kinetics of protein clustering and resulting conformational changes are shown to be significantly different for the isotropic and anisotropic curvature inducing proteins.

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

Strain control of oxygen kinetics in the Ruddlesden-Popper oxide La 1.85Sr 0.15CuO 4

DOE PAGES

Meyer, Tricia L.; Jacobs, Ryan; Lee, Dongkyu; ...

2018-01-08

Oxygen defect control has long been considered an important route to functionalizing complex oxide films. However, the nature of oxygen defects in thin films is often not investigated beyond basic redox chemistry. One of the model examples for oxygen-defect studies is the layered Ruddlesden–Popper phase La 2-xSr x CuO 4-δ (LSCO), in which the superconducting transition temperature is highly sensitive to epitaxial strain. However, previous observations of strain-superconductivity coupling in LSCO thin films were mainly understood in terms of elastic contributions to mechanical buckling, with minimal consideration of kinetic or thermodynamic factors. Here, we report that the oxygen nonstoichiometry commonlymore » reported for strained cuprates is mediated by the strain-modified surface exchange kinetics, rather than reduced thermodynamic oxygen formation energies. Remarkably, tensile-strained LSCO shows nearly an order of magnitude faster oxygen exchange rate than a compressively strained film, providing a strategy for developing high-performance energy materials.« less

Enzyme-Embedded, Microstructural Reactors for Industrial Biocatalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Baker, Sarah E.; Knipe, J. M.; Oakdale, J.

In this project we explored enzyme-catalyzed methane conversion to methanol. Industrial biological approaches to methane conversion using whole organisms are predicted to be more energy efficient than chemical approaches, but are limited by mass transfer of the gas phase reactants, methane and oxygen, to the organisms. We demonstrated that 3D printing the enzyme particulate Methane Mono Oxygenase (pMMO) embedded in a polymer can improve the kinetics of methane to methanol conversion. This improvement was likely due to the ability to increase the surface area of the catalytic material using 3D printing. We also demonstrated the first continuous use of pMMOmore » in a flow-through reactor. In order to understand the fundamental kinetic properties of pMMO, we conducted an in-depth study of pMMO kinetics using analytical tools developed in our lab. Finally, we developed a new copolymer system that allowed tuning of the gas permeability of the biocatalytic material.« less

Membrane crystallization of lysozyme: kinetic aspects

NASA Astrophysics Data System (ADS)

Profio, Gianluca Di; Curcio, Efrem; Cassetta, Alberto; Lamba, Doriano; Drioli, Enrico

2003-10-01

The relevant kinetic aspects related to an innovative method of biological macromolecules crystallization based on microporous hydrophobic membranes, used both as active surfaces to promote heterogeneous nucleation and as a mass-transfer apparatus to concentrate macromolecular solutions by solvent removal in vapour phase, have been evaluated. Polypropylene membranes, supplied in the form of hollow fibres, have been aligned in a versatile system, designed for an on-line spectrophotometric monitoring of hen egg white lysozyme crystallizing solutions (experimental conditions: 0.1 M NaAc/HAc Buffer pH 4.6, 0.5-5.8% wt/vol NaCl, 20°C). The turbidity measurements have been exploited in order to follow: (i) the induction time of crystallization, (ii) the early stage nucleation kinetics based on the Rayleigh scattering theory, and (iii) the crystal growth rate (coupled with data evaluated from image-analysis carried out by optical microscopy) under a model hypothesis of exponential growth of clusters. The crystals have been qualitatively assessed by an X-ray crystallographic analysis carried out at the synchrotron light laboratory ELETTRA.

The Kelvin-Helmholtz instability of boundary-layer plasmas in the kinetic regime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Steinbusch, Benedikt, E-mail: b.steinbusch@fz-juelich.de; Gibbon, Paul, E-mail: p.gibbon@fz-juelich.de; Department of Mathematics, Centre for Mathematical Plasma Astrophysics, Katholieke Universiteit Leuven

2016-05-15

The dynamics of the Kelvin-Helmholtz instability are investigated in the kinetic, high-frequency regime with a novel, two-dimensional, mesh-free tree code. In contrast to earlier studies which focused on specially prepared equilibrium configurations in order to compare with fluid theory, a more naturally occurring plasma-vacuum boundary layer is considered here with relevance to both space plasma and linear plasma devices. Quantitative comparisons of the linear phase are made between the fluid and kinetic models. After establishing the validity of this technique via comparison to linear theory and conventional particle-in-cell simulation for classical benchmark problems, a quantitative analysis of the more complexmore » magnetized plasma-vacuum layer is presented and discussed. It is found that in this scenario, the finite Larmor orbits of the ions result in significant departures from the effective shear velocity and width underlying the instability growth, leading to generally slower development and stronger nonlinear coupling between fast growing short-wavelength modes and longer wavelengths.« less

A facility for gas- and condensed-phase measurements behind shock waves

NASA Astrophysics Data System (ADS)

Petersen, Eric L.; Rickard, Matthew J. A.; Crofton, Mark W.; Abbey, Erin D.; Traum, Matthew J.; Kalitan, Danielle M.

2005-09-01

A shock-tube facility consisting of two, single-pulse shock tubes for the study of fundamental processes related to gas-phase chemical kinetics and the formation and reaction of solid and liquid aerosols at elevated temperatures is described. Recent upgrades and additions include a new high-vacuum system, a new gas-handling system, a new control system and electronics, an optimized velocity-detection scheme, a computer-based data acquisition system, several optical diagnostics, and new techniques and procedures for handling experiments involving gas/powder mixtures. Test times on the order of 3 ms are possible with reflected-shock pressures up to 100 atm and temperatures greater than 4000 K. Applications for the shock-tube facility include the study of ignition delay times of fuel/oxidizer mixtures, the measurement of chemical kinetic reaction rates, the study of fundamental particle formation from the gas phase, and solid-particle vaporization, among others. The diagnostic techniques include standard differential laser absorption, FM laser absorption spectroscopy, laser extinction for particle volume fraction and size, temporally and spectrally resolved emission from gas-phase species, and a scanning mobility particle sizer for particle size distributions. Details on the set-up and operation of the shock tube and diagnostics are given, the results of a detailed uncertainty analysis on the accuracy of the test temperature inferred from the incident-shock velocity are provided, and some recent results are presented.

Determination of the effect of lift characteristics on dynamic performance profiles during manual materials handling tasks.

PubMed

Khalaf, K A; Parnianpour, M; Sparto, P J; Barin, K

1999-01-01

In any quantitative gait or occupational biomechanics investigation, the quantification of the different kinematic, kinetic, and electromyographic parameters is essential towards assessment of functional capacity and development of a biomechanical profile of the task demands. In the current study, the authors presented a methodology for using inferential statistics to evaluate the effect of lift characteristics on phase-dependent and phase-independent variability in performance. Using a database of kinematic and kinetic profiles obtained from a manual lifting study, the phase-dependent effects of lift characteristics: box mass (load), mode (technique of lift), and speed (frequency of lift) were investigated through the use of analysis of variance (ANOVA) techniques, which recognize the vectorial constitution of the profiles. In addition, the Karhunen-Loeve Expansion (KLE) feature extraction method was used for representing the lifting patterns of measured joint angular position, velocity, acceleration, and net muscular torque profiles obtained from a 2-D biomechanical lifting model in order to study the phase-independent effects. In comparison to traditional descriptive statistical analyses currently used in various occupational biomechanics experimental investigations, this method allows the significant information content of the time varying signal to be captured, enhancing the sensitivity of subsequent hypothesis testing procedures. The application of this technique to MMH investigations allows identification of the lift characteristics that dominate the variability of task demands, hence aiding in the design and assessment of ergonomic solutions.

Pseudo-second order models for the adsorption of safranin onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth

2007-04-02

Kinetic experiments were carried out for the sorption of safranin onto activated carbon particles. The kinetic data were fitted to pseudo-second order model of Ho, Sobkowsk and Czerwinski, Blanchard et al. and Ritchie by linear and non-linear regression methods. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo-second order models were the same. Non-linear regression analysis showed that both Blanchard et al. and Ho have similar ideas on the pseudo-second order model but with different assumptions. The best fit of experimental data in Ho's pseudo-second order expression by linear and non-linear regression method showed that Ho pseudo-second order model was a better kinetic expression when compared to other pseudo-second order kinetic expressions.

Kinetics modelling of Cu(II) biosorption on to coconut shell and Moringa oleifera seeds from tropical regions.

PubMed

Acheampong, Mike A; Pereira, Joana P C; Meulepas, Roel J W; Lens, Piet N L

2012-01-01

Adsorption kinetic studies are of great significance in evaluating the performance of a given adsorbent and gaining insight into the underlying mechanism. This work investigated the sorption kinetics of Cu(II) on to coconut shell and Moringa oleifera seeds using batch techniques. To understand the mechanisms of the biosorption process and the potential rate-controlling steps, kinetic models were used to fit the experimental data. The results indicate that kinetic data were best described by the pseudo-second-order model with correlation coefficients (R2) of 0.9974 and 0.9958 for the coconut shell and Moringa oleifera seeds, respectively. The initial sorption rates obtained for coconut shell and Moringa oleifera seeds were 9.6395 x 10(-3) and 8.3292 x 10(-2) mg g(-1) min(-1), respectively. The values of the mass transfer coefficients obtained for coconut shell (1.2106 x 10(-3) cm s(-1)) and Moringa oleifera seeds (8.965 x 10(-4) cm s(-1)) indicate that the transport of Cu(II) from the bulk liquid to the solid phase was quite fast for both materials investigated. The results indicate that intraparticle diffusion controls the rate of sorption in this study; however, film diffusion cannot be neglected, especially at the initial stage of sorption.

Kinetics of hydrophobic organic contaminant extraction from sediment by granular activated carbon.

PubMed

Rakowska, M I; Kupryianchyk, D; Smit, M P J; Koelmans, A A; Grotenhuis, J T C; Rijnaarts, H H M

2014-03-15

Ex situ solid phase extraction with granular activated carbon (GAC) is a promising technique to remediate contaminated sediments. The methods' efficiency depends on the rate by which contaminants are transferred from the sediment to the surface of GAC. Here, we derive kinetic parameters for extraction of polycyclic aromatic hydrocarbons (PAH) from sediment by GAC, using a first-order multi-compartment kinetic model. The parameters were obtained by modeling sediment-GAC exchange kinetic data following a tiered model calibration approach. First, parameters for PAH desorption from sediment were calibrated using data from systems with 50% (by weight) GAC acting as an infinite sink. Second, the estimated parameters were used as fixed input to obtain GAC uptake kinetic parameters in sediment slurries with 4% GAC, representing the ex situ remediation scenario. PAH uptake rate constants (kGAC) by GAC ranged from 0.44 to 0.0005 d(-1), whereas GAC sorption coefficients (KGAC) ranged from 10(5.57) to 10(8.57) L kg(-1). These values are the first provided for GAC in the presence of sediment and show that ex situ extraction with GAC is sufficiently fast and effective to reduce the risks of the most available PAHs among those studied, such as fluorene, phenanthrene and anthracene. Copyright © 2013 Elsevier Ltd. All rights reserved.

Non-classical nuclei and growth kinetics of Cr precipitates in FeCr alloys during ageing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yulan; Hu, Shenyang Y.; Zhang, Lei

2014-01-10

In this manuscript, we quantitatively calculated the thermodynamic properties of critical nuclei of Cr precipitates in FeCr alloys. The concentration profiles of the critical nuclei and nucleation energy barriers were predicted by the constrained shrinking dimer dynamics (CSDD) method. It is found that Cr concentration distribution in the critical nuclei strongly depend on the overall Cr concentration as well as temperature. The critical nuclei are non-classical because the concentration in the nuclei is smaller than the thermodynamic equilibrium value. These results are in agreement with atomic probe observation. The growth kinetics of both classical and non-classical nuclei was investigated bymore » the phase field approach. The simulations of critical nucleus evolution showed a number of interesting phenomena: 1) a critical classical nucleus first shrinks toward its non-classical nucleus and then grows; 2) a non-classical nucleus has much slower growth kinetics at its earlier growth stage compared to the diffusion-controlled growth kinetics. 3) a critical classical nucleus grows faster at the earlier growth stage than the non-classical nucleus. All of these results demonstrate that it is critical to introduce the correct critical nuclei in order to correctly capture the kinetics of precipitation.« less

Experiments on Nucleation in Different Flow Regimes

NASA Technical Reports Server (NTRS)

Bayuzick, Robert J.

1999-01-01

The vast majority of metallic engineering materials are solidified from the liquid phase. Understanding the solidification process is essential to control microstructure, which in turn, determines the properties of materials. The genesis of solidification is nucleation, where the first stable solid forms from the liquid phase. Nucleation kinetics determine the degree of undercooling and phase selection. As such, it is important to understand nucleation phenomena in order to control solidification or glass formation in metals and alloys. Early experiments in nucleation kinetics were accomplished by droplet dispersion methods [1-6]. Dilitometry was used by Turnbull and others, and more recently differential thermal analysis and differential scanning calorimetry have been used for kinetic studies. These techniques have enjoyed success; however, there are difficulties with these experiments. Since materials are dispersed in a medium, the character of the emulsion/metal interface affects the nucleation behavior. Statistics are derived from the large number of particles observed in a single experiment, but dispersions have a finite size distribution which adds to the uncertainty of the kinetic determinations. Even though temperature can be controlled quite well before the onset of nucleation, the release of the latent heat of fusion during nucleation of particles complicates the assumption of isothermality during these experiments. Containerless processing has enabled another approach to the study of nucleation kinetics [7]. With levitation techniques it is possible to undercool one sample to nucleation repeatedly in a controlled manner, such that the statistics of the nucleation process can be derived from multiple experiments on a single sample. The authors have fully developed the analysis of nucleation experiments on single samples following the suggestions of Skripov [8]. The advantage of these experiments is that the samples are directly observable. The nucleation temperature can be measured by noncontact optical pyrometry, the mass of the sample is known, and post processing analysis can be conducted on the sample. The disadvantages are that temperature measurement must have exceptionally high precision, and it is not possible to isolate specific heterogeneous sites as in droplet dispersions.

Chemkin-II: A Fortran chemical kinetics package for the analysis of gas-phase chemical kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kee, R.J.; Rupley, F.M.; Miller, J.A.

1989-09-01

This document is the user's manual for the second-generation Chemkin package. Chemkin is a software package for whose purpose is to facilitate the formation, solution, and interpretation of problems involving elementary gas-phase chemical kinetics. It provides an especially flexible and powerful tool for incorporating complex chemical kinetics into simulations of fluid dynamics. The package consists of two major software components: an Interpreter and Gas-Phase Subroutine Library. The Interpreter is a program that reads a symbolic description of an elementary, user-specified chemical reaction mechanism. One output from the Interpreter is a data file that forms a link to the Gas-Phase Subroutinemore » Library. This library is a collection of about 100 highly modular Fortran subroutines that may be called to return information on equation of state, thermodynamic properties, and chemical production rates.« less

Kinetic modeling of sporulation and product formation in stationary phase by Bacillus coagulans RK-02 vis-à-vis other Bacilli.

PubMed

Das, Subhasish; Sen, Ramkrishna

2011-10-01

A logistic kinetic model was derived and validated to characterize the dynamics of a sporogenous bacterium in stationary phase with respect to sporulation and product formation. The kinetic constants as determined using this model are particularly important for describing intrinsic properties of a sporogenous bacterial culture in stationary phase. Non-linear curve fitting of the experimental data into the mathematical model showed very good correlation with the predicted values for sporulation and lipase production by Bacillus coagulans RK-02 culture in minimal media. Model fitting of literature data of sporulation and product (protease and amylase) formation in the stationary phase by some other Bacilli and comparison of the results of model fitting with those of Bacillus coagulans helped validate the significance and robustness of the developed kinetic model. Copyright © 2011 Elsevier Ltd. All rights reserved.

In Situ X-Ray Studies of Crystallization Kinetics and Ordering in Functional Organic and Hybrid Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Bin; Keum, Jong K.; Geohegan, David B.

In-Situ and time-resolved X-ray scattering and diffraction is dedicated to yielding the change of structural information as the materials are processed or grown in a controlled environment. In this chapter, we introduce the use of in situ and time-resolved X-ray techniques to understand molecular packing, crystal orientation, and phase transformation during the synthesis and processing of functional organic semiconductors, organic nanowires, and hybrid perovskite materials.

Formulation, characterization, and in vitro/ex vivo evaluation of quercetin-loaded microemulsion for topical application.

PubMed

Kajbafvala, Azar; Salabat, Alireza; Salimi, Anayatollah

2016-12-09

The aim of this study was to develop a new microemulsion formulation for topical application of poorly soluble drug named quercetin. In order to design suitable microemulsion system, the pseudo-ternary phase diagrams of microemulsion systems were constructed at different surfactant/co-surfactant ratios using tween 80 as surfactant, transcutol ® P as a co-surfactant and oleic acid as an oil phase. Some physicochemical properties such as droplet size, density, refractive index, electrical conductivity, pH, surface tension, and viscosity of the microemulsion systems were measured at 298.15 K. The average hydrodynamic droplet size of the optimized microemulsions was obtained by dynamic light scattering method. Morphology assessment of the optimized quercetin-loaded microemulsion by transmission electron microscopy analysis indicated that the particles have the size of about 25 nm and spherical with narrow size distribution. Equilibrium solubility, in vitro drug release at a 24 h time period, release kinetic evaluation as well as ex vivo permeation and retention of quercetin-loaded microemulsions through rat skin has been investigated. The obtained results showed a slow release behavior without any transdermal delivery. Most of the formulations fitted best with zero-order kinetic model with a non-Fickian mechanisms. This study illustrated that the proposed QU-microemulsion has a good potential for use in sunscreen formulations. [Formula: see text].

Phase transition kinetics in DIET of vanadium pentoxide. I. Experimental results

NASA Astrophysics Data System (ADS)

Ai, R.; Fan, H.-J.; Marks, L. D.

1993-01-01

Experimental results of the kinetics of phase transformation in vanadium pentoxide during surface loss of oxygen from electron irradiation are described. Phase transformations under three different regimes were examined: (a) low flux; (b) intermediate flux and (c) high flux. Different phase transformation routes were observed under different fluxes. In a companion paper, numerical calculations are presented demonstrating that these results are due to a mixed interface/diffusion controlled phase transition pumped by surface oxygen loss.

One step sintering of homogenized bauxite raw material and kinetic study

NASA Astrophysics Data System (ADS)

Gao, Chang-he; Jiang, Peng; Li, Yong; Sun, Jia-lin; Zhang, Jun-jie; Yang, Huan-ying

2016-10-01

A one-step sintering process of bauxite raw material from direct mining was completed, and the kinetics of this process was analyzed thoroughly. The results show that the sintering kinetics of bauxite raw material exhibits the liquid-phase sintering behavior. A small portion of impurities existed in the raw material act as a liquid phase. After X-ray diffraction analyses, scanning electron microscopy observations, and kinetics calculations, sintering temperature and heating duration were determined as the two major factors contributing to the sintering process and densification of bauxite ore. An elevated heating temperature and longer duration favor the densification process. The major obstacle for the densification of bauxite material is attributed to the formation of the enclosed blowhole during liquid-phase sintering.

Molecular-dynamics simulation of a model with incommensurate phases

NASA Astrophysics Data System (ADS)

Parlinski, Krzysztof

1987-06-01

Two-dimensional models of displacive and order-disorder behavior, in the form of crystallites with free boundary conditions and with one-dimensional incommensurate and/or commensurate phases, have been studied using the molecular-dynamics method. The incommensurate phase can be characterized with any wave vector by the appropriate choice of potential-energy parameters. The ground-state devil's staircases of the models are complete. By a series of cooling runs the phase diagram is established. The map of the particle configuration, a result of the cooling run, formed a nonideal incommensurate phase. In the diffraction pattern of that configuration the intensities of the satellites, especially those of higher order, are considerably lower. The displacive system shows a soft, underdamped phonon mode, which with lowering temperature condenses at the critical wave vector, producing the incommensurate phase, in which the phase and amplitude modes are observed. The phase-mode dispersion curve does not show a gap. Adding 2% point defects to the system does not influence the phase and amplitude modes. The kinetics of the variation of the wave-vector modulation of the incommensurate phase has also been studied. The relevant non- equilibrium devil's staircase exhibits quasisteps at irrational numbers which are attributed to the nucleation and growth of new incommensurate periods observed as a stripple. Examples of nucleation inside and at the edges of the crystallite are given. Point defects hinder the propagation of the deperiodization line which borders the stripple.

Relaxation of polar order in suspensions with Quincke effect.

PubMed

Belovs, M; Cēbers, A

2014-05-01

The Quincke effect--spontaneous rotation of dielectric particles in a liquid with low conductivity under the action of an electric field--is considered. The distribution functions for the orientation of particle rotation planes are introduced and a set of nonlinear kinetic equations is derived in the mean field approximation considering the dynamics of their orientation in the flow induced by rotating particles. As a result the nonequilibrium phase transition to the polar order, if the concentration of the particles is sufficiently high, is predicted and the condition of the synchronization of particle rotations is established. Two cases are considered: the layer of the Quincke suspension with one free boundary and the ensemble of the particles rolling on the solid wall under the action of a torque in an electric field. It is shown that in both cases the synchronization of particle rotations occurs due to the hydrodynamic interactions. In the limit of small spatial nonhomogeneity a set of nonlinear partial differential equations for the macroscopic variables--the concentration and the director of the polar order--is derived from the kinetic equation. Its properties are analyzed and compared with available recent experimental results.

Compensation effects and relation between the activation energy of spin transition and the hysteresis loop width for an iron(ii) complex.

PubMed

Bushuev, Mark B; Pishchur, Denis P; Nikolaenkova, Elena B; Krivopalov, Viktor P

2016-06-22

The enthalpy-entropy compensation was observed for the cooperative → spin transition (the phase is a mononuclear complex [FeL2](BF4)2, L is 4-(3,5-dimethyl-1H-pyrazol-1-yl)-2-(pyridin-2-yl)-6-methylpyrimidine). The physical origin of this effect is the fact that the → spin transition is the first order phase transition accompanied by noticeable variations in the Tonset↑, ΔH and ΔS values. Higher ΔH and ΔS values are correlated with higher Tonset↑ values. The higher the enthalpy and entropy of the spin transition, the wider the hysteresis loop. The kinetic compensation effect, i.e. a linear relationship between ln A and Ea, was observed for the → spin transition. Moreover, an isokinetic relationship was detected in this system: the Arrhenius lines (ln k vs. 1/T) obtained from magnetochemical data for different samples of the phase undergoing the → transition show a common point of intersection (Tiso = 490 ± 2 K, ln kiso = -6.0 ± 0.2). The validity of this conclusion was confirmed by the Exner-Linert statistical method. This means that the isokinetic relationship and the kinetic compensation effect (ln A vs. Ea) in this system are true ones. The existence of a true kinetic compensation effect is supported independently by the fact that the hysteresis loop width for the cooperative spin transition ↔ increases with increasing activation barrier height. Estimating the energy of excitations for the phase with Tiso ∼ 490 K yields wavenumbers of ca. 340 cm(-1) corresponding to the frequencies of the stretching vibrations of the Fe(LS)-N bonds, i.e. the bonds directly involved in the mechanism of the spin transition. This is the first observation of the kinetic compensation effect (ln A vs. Ea) and the isokinetic relationship for a cooperative spin crossover system showing thermal hysteresis. Our results provide the first experimental evidence that the higher the activation barrier for the spin transition, the wider the hysteresis loop for a series of related spin crossover systems.

Effect of solid-meal caloric content on gastric emptying kinetics of solids and liquids.

PubMed

Urbain, J L; Siegel, J A; Mortelmans, L; van Cutsem, E; van den Maegdenbergh, V; de Roo, M

1989-08-01

In this study, we have evaluated the effect of the caloric content of a physiological test meal on the gastric emptying kinetics of solids and liquids. 22 healthy male volunteers were studied in two groups matched for age. After an overnight fast, each volunteer underwent the same test procedure; in the first group (G I), 10 volunteers received a meal consisting of bread, 111In-DTPA water and 1 scrambled egg labeled with 99mTc-labelled sulphur colloid; in the second group (G II) 12 volunteers were given the same meal but with 2 labeled eggs in order to increase the caloric content of the solid phase meal. Simultaneous anterior and posterior images were recorded using a dual-headed gamma camera. Solid and liquid geometric mean data were analyzed to determine the lag phase, the emptying rate and the half-emptying time for both solids and liquids. Solid and liquid gastric half-emptying times were significantly prolonged in G II compared to G I volunteers. For the solid phased, the delay was accounted for by a longer lag phase and a decrease in the equilibrium emptying rate. The emptying rate of the liquid phase was significantly decreased in G II compared to G I. Within each group, no statistically significant difference was observed between solid and liquid emptying rates. We conclude that the caloric content of the solid portion of a meal not only alters the emptying of the solid phase but also affects the emptying of the liquid component of the meal.

Furfural production by 'acidic steam stripping' of lignocellulose.

PubMed

van Buijtenen, Jeroen; Lange, Jean-Paul; Espinosa Alonso, Leticia; Spiering, Wouter; Polmans, Rob F; Haan, Rene J

2013-11-01

Furfural and acetic acid are produced with approximately 60 and 90 mol % yield, respectively, upon stripping bagasse with a gaseous stream of HCl/steam and condensing the effluent to water/furfural/acetic acid. The reaction kinetics is 1(st)  order in furfural and 0.5(th)  order in HCl. A process concept with full recycling of the reaction effluents is proposed to reduce the energy demand to <10 tonsteam  tonfurfural (-1) and facilitate the product recovery through a simple liquid/liquid separation of the condensate into a water-rich and a furfural-rich phase. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymorphism and disorder in caffeine: Dielectric investigation of molecular mobilities

NASA Astrophysics Data System (ADS)

Descamps, M.; Decroix, A. A.

2014-12-01

Using dielectric relaxation data we have characterized the molecular mobilities of caffeine both in phase I (stable and metastable) and in phase II. In phase I effects of sublimation and phase transformation kinetics were carefully considered. In plane rotational motions were followed on a wide temperature range. A noticeable antiferroelectric short range order developing at the approach of the glass-like transition is characterized. Condition for occurrence of a critical-like behaviour is discussed. At high temperature the emergence of an additional ultra slow relaxation process is highlighted. Possible molecular mechanisms are proposed for both processes. In phase II the existence of a less intense relaxation process is confirmed. Close similarity with the main process developing in phase I hints at a common origin of the dipolar motions. Careful consideration of recent structure determinations leads to suggest that this process is associated to similar molecular in plane rotations but developing at the surface of crystalline samples. Lower cooperativity at the surface is reflected in the smaller activation entropy of the relaxation.

Effect of atomic order on the martensitic and magnetic transformations in Ni-Mn-Ga ferromagnetic shape memory alloys.

PubMed

Sánchez-Alarcos, V; Pérez-Landazábal, J I; Recarte, V; Rodríguez-Velamazán, J A; Chernenko, V A

2010-04-28

The influence of long-range L2(1) atomic order on the martensitic and magnetic transformations of Ni-Mn-Ga shape memory alloys has been investigated. In order to correlate the structural and magnetic transformation temperatures with the atomic order, calorimetric, magnetic and neutron diffraction measurements have been performed on polycrystalline and single-crystalline alloys subjected to different thermal treatments. It is found that both transformation temperatures increase with increasing atomic order, showing exactly the same linear dependence on the degree of L2(1) atomic order. A quantitative correlation between atomic order and transformation temperatures has been established, from which the effect of atomic order on the relative stability between the structural phases has been quantified. On the other hand, the kinetics of the post-quench ordering process taking place in these alloys has been studied. It is shown that the activation energy of the ordering process agrees quite well with the activation energy of the Mn self-diffusion process.

Investigation on Aging σ-Phase Precipitation Kinetics and Pitting Corrosion of 22 Pct Cr Economical Duplex Stainless Steel with Mn Addition

NASA Astrophysics Data System (ADS)

Yang, Yinhui; Qian, Hao

2018-05-01

The influence of Mn addition on σ-phase precipitation kinetics and pitting corrosion of Fe-22Cr-1.9Ni-2.3Mo-0.2N-xMn low nickel type duplex stainless steel was investigated by medium- and high-temperature aging treatments of 600 °C and 800 °C. The microstructure analysis showed that the fine rod-shaped and coarsening dendritelike σ-phase precipitates formed at 600 °C and 800 °C, respectively, and the precipitate growth with the higher temperature was accelerated due to the partition of Mn, but Mn is not a strong σ-phase forming element like Cr, Mo during aging treatment at these two temperatures. At an early aging time of 800 °C, more precipitated nuclei with more Mn addition promote refinement of σ precipitates in later aging time. The kinetic behavior at 600 °C and 800 °C is related to diffusion-controlled growth of σ phase, and the σ-phase nucleation and growth are enhanced with more Mn addition and higher aging temperature due to a faster Mn diffusion rate. The difference in precipitation morphology for two aging temperatures was attributed to the different nucleation modes caused by kinetics parameter n variation. Increasing the aging temperature from 600 °C to 800 °C increased the susceptibility to pitting with higher Mn addition due to faster σ-phase precipitation kinetics.

Effective field theory in the harmonic oscillator basis

DOE PAGES

Binder, S.; Ekström, Jan A.; Hagen, Gaute; ...

2016-04-25

In this paper, we develop interactions from chiral effective field theory (EFT) that are tailored to the harmonic oscillator basis. As a consequence, ultraviolet convergence with respect to the model space is implemented by construction and infrared convergence can be achieved by enlarging the model space for the kinetic energy. In oscillator EFT, matrix elements of EFTs formulated for continuous momenta are evaluated at the discrete momenta that stem from the diagonalization of the kinetic energy in the finite oscillator space. By fitting to realistic phase shifts and deuteron data we construct an effective interaction from chiral EFT at next-to-leadingmore » order. Finally, many-body coupled-cluster calculations of nuclei up to 132Sn converge fast for the ground-state energies and radii in feasible model spaces.« less

Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene

DOE PAGES

Lane, J. Matthew; Moore, Nathan W.

2018-02-01

Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less

Molecular and Kinetic Models for High-rate Thermal Degradation of Polyethylene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lane, J. Matthew; Moore, Nathan W.

Thermal degradation of polyethylene is studied under the extremely high rate temperature ramps expected in laser-driven and X-ray ablation experiments—from 10 10 to 10 14 K/s in isochoric, condensed phases. The molecular evolution and macroscopic state variables are extracted as a function of density from reactive molecular dynamics simulations using the ReaxFF potential. The enthalpy, dissociation onset temperature, bond evolution, and observed cross-linking are shown to be rate dependent. These results are used to parametrize a kinetic rate model for the decomposition and coalescence of hydrocarbons as a function of temperature, temperature ramp rate, and density. In conclusion, the resultsmore » are contrasted to first-order random-scission macrokinetic models often assumed for pyrolysis of linear polyethylene under ambient conditions.« less

Is the gas-phase OH+H2CO reaction a source of HCO in interstellar cold dark clouds? A kinetic, dynamic and modelling study

PubMed Central

Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.

2018-01-01

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme, which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients (k) of the gas-phase OH+H2CO reaction between 22 and 107 K. k values greatly increase from 2.1×10-11 cm3 s-1 at 107 K to 1.2×10-10 cm3 s-1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H2CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10K (2.6×10-10 cm3 s-1). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 105-106 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented. PMID:29880977

Is the Gas-phase OH+H2CO Reaction a Source of HCO in Interstellar Cold Dark Clouds? A Kinetic, Dynamic, and Modeling Study

NASA Astrophysics Data System (ADS)

Ocaña, A. J.; Jiménez, E.; Ballesteros, B.; Canosa, A.; Antiñolo, M.; Albaladejo, J.; Agúndez, M.; Cernicharo, J.; Zanchet, A.; del Mazo, P.; Roncero, O.; Aguado, A.

2017-11-01

The chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T ˜ 10-100 K). Scarce kinetic information is currently available for these kinds of reactions at T < 200 K. In this work, we use the Cinétique de Réaction en Ecoulement Supersonique Uniforme (CRESU; Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients (k) of the gas-phase OH+H2CO reaction between 22 and 107 K. The k values greatly increase from 2.1 × 10-11 cm3 s-1 at 107 K to 1.2 × 10-10 cm3 s-1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface that generates highly accurate potential and includes long-range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H2CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10 K (2.6 × 10-10 cm3 s-1). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 105-106 yr. The different sources of production of HCO are presented and the uncertainties in the chemical networks are discussed. The present reaction is shown to account for a few percent of the total HCO production rate. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. Extensions to photodissociation regions and diffuse cloud environments are also addressed.

Is the gas-phase OH+H2CO reaction a source of HCO in interstellar cold dark clouds? A kinetic, dynamic and modelling study.

PubMed

Ocaña, A J; Jiménez, E; Ballesteros, B; Canosa, A; Antiñolo, M; Albaladejo, J; Agúndez, M; Cernicharo, J; Zanchet, A; Del Mazo, P; Roncero, O; Aguado, A

2017-11-20

Chemical kinetics of neutral-neutral gas-phase reactions at ultralow temperatures is a fascinating research subject with important implications on the chemistry of complex organic molecules in the interstellar medium (T∼10-100K). Scarce kinetic information is currently available for this kind of reactions at T<200 K. In this work we use the CRESU ( Cinétique de Réaction en Ecoulement Supersonique Uniforme , which means Reaction Kinetics in a Uniform Supersonic Flow) technique to measure for the first time the rate coefficients ( k ) of the gas-phase OH+H 2 CO reaction between 22 and 107 K. k values greatly increase from 2.1×10 -11 cm 3 s -1 at 107 K to 1.2×10 -10 cm 3 s -1 at 22 K. This is also confirmed by quasi-classical trajectories (QCT) at collision energies down to 0.1 meV performed using a new full dimension and ab initio potential energy surface, recently developed which generates highly accurate potential and includes long range dipole-dipole interactions. QCT calculations indicate that at low temperatures HCO is the exclusive product for the OH+H 2 CO reaction. In order to revisit the chemistry of HCO in cold dense clouds, k is reasonably extrapolated from the experimental results at 10K (2.6×10 -10 cm 3 s -1 ). The modeled abundances of HCO are in agreement with the observations in cold dark clouds for an evolving time of 10 5 -10 6 yrs. The different sources of production of HCO are presented and the uncertainties in the chemical networks discussed. This reaction can be expected to be a competitive process in the chemistry of prestellar cores. The present reaction is shown to account for a few percent of the total HCO production rate. Extensions to photodissociation regions and diffuse clouds environments are also commented.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Das, Chandan K.; Singh, Jayant K., E-mail: jayantks@iitk.ac.in

The solid-liquid coexistence of a Lennard-Jones fluid confined in slit pores of variable pore size, H, is studied using molecular dynamics simulations. Three-stage pseudo-supercritical transformation path of Grochola [J. Chem. Phys. 120(5), 2122 (2004)] and multiple histogram reweighting are employed for the confined system, for various pore sizes ranging from 20 to 5 molecular diameters, to compute the solid-liquid coexistence. The Gibbs free energy difference is evaluated using thermodynamic integration method by connecting solid-liquid phases under confinement via one or more intermediate states without any first order phase transition among them. Thermodynamic melting temperature is found to oscillate with wallmore » separation, which is in agreement with the behavior seen for kinetic melting temperature evaluated in an earlier study. However, thermodynamic melting temperature for almost all wall separations is higher than the bulk case, which is contrary to the behavior seen for the kinetic melting temperature. The oscillation founds to decay at around H = 12, and beyond that pore size dependency of the shift in melting point is well represented by the Gibbs-Thompson equation.« less

Oil shale powders and their interactions with ciprofloxacin, ofloxacin, and oxytetracycline antibiotics.

PubMed

Gouza, Asmae; Saoiabi, Sanaa; El Karbane, Miloud; Masse, Sylvie; Laurent, Guillaume; Rami, Ahmed; Saoiabi, Ahmed; Laghzizil, Abdelaziz; Coradin, Thibaud

2017-11-01

The interaction of oil shale, as a widespread sedimentary rock, with common antibiotics ofloxacine, oxytetracycline, and ciprofloxacine was studied. The selected Moroccan deposit and its thermally treated forms were fully characterized from a chemical and structural point of view, indicating the prevalence of quartz as a mineral component together with aluminum- and iron-rich phase that are converted into Al-doped iron oxide phases upon heating. The presence of 4 wt% organics was also detected, which was removed at 550 °C without significant loss of specific surface area. The pseudo-second-order kinetic model and Langmuir equation were found the most adequate to reproduce the kinetics and isothermal sorption experiments. These analyses enlighten the contribution of the organic matter on antibiotic retention as well as the key role of hydrophobic interactions on the molecule-mineral surface interactions. Our results emphasize the possible contribution of raw oil shale in the accumulation of antibiotics in soils and suggest that thermally treated oil shell powders can constitute cheap mineral sorbents for environmental cleaning.

Thermochemical Kinetics of H2O and HNO3 on crystalline Nitric Acid Hydrates (alpha-, beta-NAT, NAD) in the range 175-200 K

NASA Astrophysics Data System (ADS)

Rossi, Michel J.; Iannarelli, Riccardo

2015-04-01

The growth of NAT (Nitric Acid Trihydrate, HNO3x3H2O) and NAD (Nitric Acid Dihydrate, HNO3x2H2O) on an ice substrate, the evaporative lifetime of NAT and NAD as well as the interconversion of alpha- and beta-NAT competing with evaporation and growth under UT/LS conditions depends on the interfacial kinetics of H2O and HNO3 vapor on the condensed phase. Despite the existence of some literature results we have embarked on a systematic investigation of the kinetics using a multidiagnostic experimental approach enabled by the simultaneous observation of both the gas (residual gas mass spectrometry) as well as the condensed phase (FTIR absorption in transmission). We report on thermochemically consistent mass accommodation coefficients alpha and absolute evaporation rates Rev/molecule s-1cm-3 as a function of temperature which yields the corresponding vapor pressures of both H2O and HNO3 in equilibrium with the crystalline phases, hence the term thermochemical kinetics. These results have been obtained using a stirred flow reactor (SFR) using a macroscopic pure ice film of 1 micron or so thickness as a starting substrate mimicking atmospheric ice particles and are reported in a phase diagram specifically addressing UT (Upper Troposphere)/LS (Lower Stratosphere) conditions as far as temperature and partial pressures are concerned. The experiments have been performed either at steady-state flow conditions or in transient supersaturation using a pulsed solenoid valve in order to generate gas pulses whose decay were subsequently monitored in real time. Special attention has been given to the effect of the stainless-steel vessel walls in that Langmuir adsorption isotherms for H2O and HNO3 have been used to correct for wall-adsorption of both probe gases. Typically, the accommodation coefficients of H2O and HNO3 are similar throughout the temperature range whereas the rates of evaporation Rev of H2O are significantly larger than for HNO3 thus leading to the difference in vapor pressure revealed in the phase diagram. A noteworthy effect seems to be that the accommodation coefficients obtained in pulsed gas admission experiments (transient supersaturation) lead to significantly lower values owing to surface saturation, especially in the case of the thermodynamically stable beta-NAT substrate.

Kinetic corrections from analytic non-Maxwellian distribution functions in magnetized plasmas

DOE PAGES

Izacard, Olivier

2016-08-02

In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basismore » sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main results, it is shown that (i) the empirical formula for the secondary electron emission is not consistent with a MDF due to the presence of super-thermal particles, (ii) the super-thermal particles can replace a diffusion parameter in the Langmuir probe current formula, and (iii) the entropy can explicitly decrease in presence of sources only for the introduced INMDF without violating the second law of thermodynamics. Moreover, the first order entropy of an infinite number of super-thermal tails stays the same as the entropy of a MDF. In conclusion, the latter demystifies the Maxwell's demon by statistically describing non-isolated systems.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Izacard, Olivier

In magnetized plasma physics, almost all developed analytic theories assume a Maxwellian distribution function (MDF) and in some cases small deviations are described using the perturbation theory. The deviations with respect to the Maxwellian equilibrium, called kinetic effects, are required to be taken into account especially for fusion reactor plasmas. Generally, because the perturbation theory is not consistent with observed steady-state non-Maxwellians, these kinetic effects are numerically evaluated by very central processing unit (CPU)-expensive codes, avoiding the analytic complexity of velocity phase space integrals. We develop here a new method based on analytic non-Maxwellian distribution functions constructed from non-orthogonal basismore » sets in order to (i) use as few parameters as possible, (ii) increase the efficiency to model numerical and experimental non-Maxwellians, (iii) help to understand unsolved problems such as diagnostics discrepancies from the physical interpretation of the parameters, and (iv) obtain analytic corrections due to kinetic effects given by a small number of terms and removing the numerical error of the evaluation of velocity phase space integrals. This work does not attempt to derive new physical effects even if it could be possible to discover one from the better understandings of some unsolved problems, but here we focus on the analytic prediction of kinetic corrections from analytic non-Maxwellians. As applications, examples of analytic kinetic corrections are shown for the secondary electron emission, the Langmuir probe characteristic curve, and the entropy. This is done by using three analytic representations of the distribution function: the Kappa distribution function, the bi-modal or a new interpreted non-Maxwellian distribution function (INMDF). The existence of INMDFs is proved by new understandings of the experimental discrepancy of the measured electron temperature between two diagnostics in JET. As main results, it is shown that (i) the empirical formula for the secondary electron emission is not consistent with a MDF due to the presence of super-thermal particles, (ii) the super-thermal particles can replace a diffusion parameter in the Langmuir probe current formula, and (iii) the entropy can explicitly decrease in presence of sources only for the introduced INMDF without violating the second law of thermodynamics. Moreover, the first order entropy of an infinite number of super-thermal tails stays the same as the entropy of a MDF. In conclusion, the latter demystifies the Maxwell's demon by statistically describing non-isolated systems.« less

Effects of Soot Structure on Soot Oxidation Kinetics

DTIC Science & Technology

2011-06-01

information from PSDs, temperature, gas -phase composition was used to develop an oxidation kinetic expression that accounts for the effects of...from PSDs, temperature, gas -phase composition was used to develop an oxidation kinetic expression that accounts for the effects of temperature, O2, and...systematic studies of these effects under the temperatures and times of interest to soot oxidation in gas turbine engines. Studies have shown that soot

The role of amorphous precursors in the crystallization of La and Nd carbonates

NASA Astrophysics Data System (ADS)

Vallina, Beatriz; Rodriguez-Blanco, Juan Diego; Brown, Andrew P.; Blanco, Jesus A.; Benning, Liane G.

2015-07-01

Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion.Crystalline La and Nd carbonates can be formed from poorly-ordered nanoparticulate precursors, termed amorphous lanthanum carbonate (ALC) and amorphous neodymium carbonate (ANC). When reacted in air or in aqueous solutions these precursors show highly variable lifetimes and crystallization pathways. We have characterized these precursors and the crystallization pathways and products with solid-state, spectroscopic and microscopic techniques to explain the differences in crystallization mechanisms between the La and Nd systems. ALC and ANC consist of highly hydrated, 10-20 nm spherical nanoparticles with a general formula of REE2(CO3)3.5H2O (REE = La, Nd). The stabilities differ by ~2 orders of magnitude, with ANC being far more stable than ALC. This difference is due to the Nd3+ ion having a far higher hydration energy compared to the La3+ ion. This, together with temperature and reaction times, leads to clear differences not only in the kinetics and mechanisms of crystallization of the amorphous precursor La- and Nd-carbonate phases but also in the resulting crystallite sizes and morphologies of the end products. All crystalline La and Nd carbonates developed spherulitic morphologies when crystallization occurred from hydrous phases in solution at temperatures above 60 °C (La system) and 95 °C (Nd system). We suggest that spherulitic growth occurs due to a rapid breakdown of the amorphous precursors and a concurrent rapid increase in supersaturation levels in the aqueous solution. The kinetic data show that the crystallization pathway for both La and Nd carbonate systems is dependent on the reaction temperature and the ionic potential of the REE3+ ion. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr01497b

Synthesis of molecularly imprinted polymers using acrylamide-β-cyclodextrin as a cofunctional monomer for the specific capture of tea saponins from the defatted cake extract of Camellia oleifera.

PubMed

Guo, Huiqin; Xiong, Jingjing; Ma, Wentian; Wu, Minghuo; Yan, Liushui; Li, Kexin; Liu, Yu

2016-11-01

Molecularly imprinted polymers were synthesized using mixed tea saponins as a template and acrylamide-β-cyclodextrin as a cofunctional monomer for the specific binding and purification of tea saponins from the defatted cake extract of Camellia oleifera. The adsorption properties of the prepared polymers were systematically evaluated including adsorption kinetics, adsorption isotherms, and selective recognition characteristics. It showed that the adsorption kinetics followed the pseudo first-order kinetic model (R 2 = 0.995) with an equilibrium time of 3 h, adsorption isotherm data fitted well with the Langmuir-Freundlich model (R 2 = 0.984) with an adsorption capacity of 14.23 mg/g. The relative selectivity coefficient (k´) in the presence of the analogues glycyrrhizic acid and glycyrrhetinic acid were 1.16 and 17.21, respectively. The performance of the molecularly imprinted polymers as solid-phase extraction materials was investigated and the results indicated that using acrylamide-β-cyclodextrin as a cofunctional monomer improved both the adsorption capacity and active sites stability of the imprinted polymers. The solid-phase extraction using the polymers as packing materials was subsequently applied for the separation of tea saponins in raw C. oleifera press extract, and targets were obtained with a purity reaching 89%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic freeze-out conditions for the production of resonances, hadronic molecules, and light nuclei

NASA Astrophysics Data System (ADS)

Cho, Sungtae; Song, Taesoo; Lee, Su Houng

2018-02-01

We investigate the freeze-out conditions of a particle in an expanding system of interacting particles in order to understand the productions of resonances, hadronic molecules, and light nuclei in heavy-ion collisions. Applying the kinetic freeze-out condition with explicit hydrodynamic calculations for the expanding hadronic phase to the daughter particles of K* mesons, we find that the larger suppression of the yield ratio of K*/K at the Large Hadron Collider (LHC) than at the Relativisitic Heavy Ion Collider (RHIC) compared to the expectations from the statistical hadronization model based on chemical freeze-out parameters reflects the lower kinetic freeze-out temperature at LHC than at RHIC. Furthermore, we point out that for the light nuclei or hadronic molecules that are bound, the freeze-out condition should be applied to the respective particle in the hadronic matter. It is then shown through the rate equation that when the nucleon and pion numbers are kept constant at the chemical freeze-out value during the hadronic phase, the deuteron number quickly approaches an asymptotic value that is close to the statistical model prediction at the chemical freeze-out point. We argue that the reduction seen in K* numbers is a typical result for a particle that has a large natural decay width decaying into daughter particles, while that for deuteron is typical for a stable hadronic bound state.

Effect of Ultrasonic Pretreatment on Biomethane Potential of Two-Phase Olive Mill Solid Waste: Kinetic Approach and Process Performance

PubMed Central

Rincón, B.; Bujalance, L.; Fermoso, F. G.; Martín, A.

2014-01-01

The effect of ultrasound (US) pretreatment on two-phase olive mil solid waste (OMSW) composition and subsequent anaerobic biodegradation was evaluated by chemical oxygen demand solubilization and biochemical methane potential (BMP) tests. OMSW was ultrasonically pretreated at a power of 200 W and frequency of 24 kHz for time periods of 20, 40, 60, 90, 120, and 180 minutes, corresponding to specific energies of 11367, 21121, 34072, 51284, 68557, and 106003 kJ/kg total solids, respectively. In order to evaluate the US pretreatment, a low, medium, and high exposure time, that is, 20, 90, and 180 min, were selected for BMP tests. Methane yields of 311 ± 15, 393 ± 14, and 370 ± 20 mL CH4/g VSadded (VS: volatile solids) were obtained for 20, 90, and 180 minutes, respectively, while the untreated OMSW gave 373 ± 4 mL CH4/g VSadded. From a kinetic point of view, the BMP tests showed a first exponential stage and a second sigmoidal stage. In the first stage, the kinetic constant obtained for US pretreated OMSW at 20 minutes was 46% higher than those achieved for the pretreated OMSW at 90 and 180 minutes and 48% higher than that for untreated OMSW. The maximum methane production rate achieved was 12% higher than that obtained for untreated OMSW. PMID:25197705

Roles of sulfuric acid in elemental mercury removal by activated carbon and sulfur-impregnated activated carbon.

PubMed

Morris, Eric A; Kirk, Donald W; Jia, Charles Q; Morita, Kazuki

2012-07-17

This work addresses the discrepancy in the literature regarding the effects of sulfuric acid (H(2)SO(4)) on elemental Hg uptake by activated carbon (AC). H(2)SO(4) in AC substantially increased Hg uptake by absorption particularly in the presence of oxygen. Hg uptake increased with acid amount and temperature exceeding 500 mg-Hg/g-AC after 3 days at 200 °C with AC treated with 20% H(2)SO(4). In the absence of other strong oxidizers, oxygen was able to oxidize Hg. Upon oxidation, Hg was more readily soluble in the acid, greatly enhancing its uptake by acid-treated AC. Without O(2), S(VI) in H(2)SO(4) was able to oxidize Hg, thus making it soluble in H(2)SO(4). Consequently, the presence of a bulk H(2)SO(4) phase within AC pores resulted in an orders of magnitude increase in Hg uptake capacity. However, the bulk H(2)SO(4) phase lowered the AC pore volume and could block the access to the active surface sites and potentially hinder Hg uptake kinetics. AC treated with SO(2) at 700 °C exhibited a much faster rate of Hg uptake attributed to sulfur functional groups enhancing adsorption kinetics. SO(2)-treated carbon maintained its fast uptake kinetics even after impregnation by 20% H(2)SO(4).

Kinetics of the gas-phase reaction between ozone and three unsaturated oxygenated compounds: Ethyl 3,3-dimethyl acrylate, 2-methyl-2-pentenal and 6-methyl-5-hepten-2-one at atmospheric pressure

NASA Astrophysics Data System (ADS)

Gaona Colmán, Elizabeth; Blanco, María B.; Barnes, Ian; Teruel, Mariano A.

2015-05-01

Rate coefficients for the gas-phase reactions of O3 molecules with three unsaturated oxygenated compounds have been determined using the relative kinetic technique in an environmental chamber with FTIR detection of the reactants at (298 ± 2) K in 760 Torr total pressure of synthetic air. The following rate coefficients (in units of 10-17 cm3 molecule-1 s-1) were determined: ethyl 3,3-dimethyl acrylate (0.82 ± 0.19), 2-methyl-2-pentenal (0.71 ± 0.16) and 6-methyl-5-hepten-2-one (26 ± 7). The different reactivity of the unsaturated oxygenated compounds toward O3 is discussed in terms of their chemical structure. In addition, a correlation between the reactivity of structurally different unsaturated compounds (alkenes and unsaturated oxygenated VOCs, such as ethers, esters, aldehydes, ketones and alcohols) toward O3 molecules and the HOMO (Highest Occupied Molecular Orbital) of the compounds is presented. Using the kinetic parameters determined in this work, residence times of these unsaturated compounds in the atmosphere with respect to reaction with O3 have been calculated. In urban and rural areas the main sink of 6-methyl-5-hepten-2-one is reaction with O3 molecules with a residence time in the order of few minutes.

Joint experimental and DFT study of the gas-phase unimolecular elimination kinetic of methyl trifluoropyruvate.

PubMed

Tosta, María M; Mora, José R; Córdova, Tania; Chuchani, Gabriel

2010-08-05

The elimination kinetics of methyl trifluoropyruvate in the gas phase was determined in a static system, where the reaction vessel was always deactivated with allyl bromide, and in the presence of at least a 3-fold excess of the free-radical chain inhibitor toluene. The working temperature range was 388.5-430.1 degrees C, and the pressure range was 38.6-65.8 Torr. The reaction was found to be homogeneous and unimolecular and to obey a first-order rate law. The products of the reaction are methyl trifluoroacetate and CO gas. The Arrhenius equation of this elimination was found to be as follows: log k(1) (s(-1)) = (12.48 +/- 0.32) - (204.2 +/- 4.2) kJ mol(-1)(2.303RT)(-1) (r = 0.9994). The theoretical calculation of the kinetic and thermodynamic parameters and the mechanism of this reaction were carried out at the B3LYP/6-31G(d,p), B3LYP/6-31++G(d,p), MPW1PW91/6-31G(d,p), MPW1PW91/6-31++G(d,p), PBEPBE/6-31G(d,p), and PBEPBE/6-31G++(d,p) levels of theory. The theoretical study showed that the preferred reaction channel is a 1,2-migration of OCH(3) involving a three-membered cyclic transition state in the rate-determining step.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tan, Y.B.; Yang, L.H.; Duan, J.L.

The kinetics of the β → α phase transformation in the 47Zr–45Ti–5Al–3V (wt.%) alloy with different initial β grain sizes under isothermal conditions was investigated by X-ray diffraction. The results showed that the volume fraction of α phase first increased with increasing aging time, and then reached an equilibrium value. The equilibrium value of α phase decreased with increased aging temperature. At the same aging temperature and time, the volume fraction of α phase in the 47Zr–45Ti–5Al–3V alloy solution-treated at 850 °C was higher than at 1050 °C, and the size of α phase in the 47Zr–45Ti–5Al–3V alloy solution-treated atmore » 850 °C was larger than that at 1050 °C. The kinetics of the β → α phase transformation was modeled under isothermal conditions in the theoretical frame of the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory. The Avrami index (n) increased with increasing aging temperature, while the reaction rate constant (k) decreased. - Highlights: • The kinetics of the β → α phase transformation in the ZrTiAlV alloy was investigated. • The volume fraction of α phase first increased and then reached an equilibrium value. • The kinetics of the β → α phase transformation was modeled by the JMAK theory. • The n increased with increasing aging temperature, while the k decreased.« less

Volatile-bearing phases in carbonaceous chondrites: Compositions, modal abundance, and reaction kinetics

NASA Technical Reports Server (NTRS)

Ganguly, Jibamitra

1990-01-01

The spectral and density characteristics of Phobos and Deimos (the two small natural satellites of Mars) strongly suggest that a significant fraction of the near-earth asteroids are made of carbonaceous chondrites, which are rich in volatile components and, thus, could serve as potential resources for propellants and life supporting systems in future planetary missions. However, in order to develop energy efficient engineering designs for the extraction of volatiles, knowledge of the nature and modal abundance of the minerals in which the volatiles are structurally bound and appropriate kinetic data on the rates of the devolatilization reactions is required. Theoretical calculations to predict the modal abundances and compositions of the major volatile-bearing and other mineral phases that could develop in the bulk compositions of C1 and C2 classes (the most volatile rich classes among the carbonaceous chondrites) were performed as functions of pressure and temperature. The rates of dehydration of talc at 585, 600, 637, and 670 C at P(total) = 1 bar were determine for the reaction: Talc = 3 enstatite + quartz + water. A scanning electron microscopic study was conducted to see if the relative abundance of phases can be determined on the basis of the spectral identification and x ray mapping. The results of this study and the other studies within the project are discussed.

Numerical Simulation of Combustion and Extinction of a Solid Cylinder in Low-Speed Cross Flow

NASA Technical Reports Server (NTRS)

Tien, J. S.; Yang, Chin Tien

1998-01-01

The combustion and extinction behavior of a diffusion flame around a solid fuel cylinder (PMMA) in low-speed forced flow in zero gravity was studied numerically using a quasi-steady gas phase model. This model includes two-dimensional continuity, full Navier Stokes' momentum, energy, and species equations with a one-step overall chemical reaction and second-order finite-rate Arrhenius kinetics. Surface radiation and Arrhenius pyrolysis kinetics are included on the solid fuel surface description and a parameter Phi, representing the percentage of gas-phase conductive heat flux going into the solid, is introduced into the interfacial energy balance boundary condition to complete the description for the quasi-steady gas-phase system. The model was solved numerically using a body-fitted coordinate transformation and the SIMPLE algorithm. The effects of varying freestream velocity and Phi were studied. These parameters have a significant effect on the flame structure and extinction limits. Two flame modes were identified: envelope flame and wake flame. Two kinds of flammability limits were found: quenching at low-flow speeds due to radiative loss and blow-off at high flow speeds due to insufficient gas residence time. A flammability map was constructed showing the existence of maximum Phi above which the solid is not flammable at any freestream velocity.

The La{sub 2}S{sub 3}-LaS{sub 2} system: Thermodynamic and kinetic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasilyeva, I.G., E-mail: kamarz@niic.nsc.r; Nikolaev, R.E.

2010-08-15

A detailed thermodynamic study of the LaS{sub 2}-La{sub 2}S{sub 3} system in the temperature range 350-1000 {sup o}C was performed, starting from high quality crystals LaS{sub 2} as the highest polysulfide in the system, and using a sensitive static tensimetric method with a quartz Bourdon gauge and a membrane as a null-point instrument. The p{sub S}-T-x diagram obtained has shown that the phase region covering the composition between LaS{sub 2} and La{sub 2}S{sub 3}, which was previously described as a single grossly nonstoichiometric phase, consists of three discrete stoichiometric phases, LaS{sub 2.00}, LaS{sub 1.91}, and LaS{sub 1.76}, where compositions couldmore » be determined with an accuracy of {+-}0.01 f.u. The thermodynamic characteristics of evaporation of the polysulfides as well as standard heat of LaS{sub 2} formation were calculated. The role of kinetics in the formation of ordered superstructures of sulfur-poorer polysulfides with different formal concentration of vacancies is considered. - Graphical abstract: The p{sub S}-T stability fields for La-polysulfides in the concentration range between LaS{sub 2} and La{sub 2}S{sub 3}.« less

PVDF membranes containing hybrid nanoparticles for adsorbing cationic dyes: physical insights and mechanism

NASA Astrophysics Data System (ADS)

Sharma, Maya; Madras, Giridhar; Bose, Suryasarathi

2016-07-01

In this study, Fe (iron) and Ag (silver) based adsorbents were synthesized using solution combustion and in situ reduction techniques. The synthesized adsorbents were comprehensively characterized by different techniques including electron microscopy, BET, XRD, Zeta potential etc. Three chlorinated cationic dyes used were malachite green, methyl violet and pyronin Y. These dyes were adsorbed on various synthesized adsorbents [iron III oxide (Fe2O3)], iron III oxide decorated silver nanoparticles by combustion synthesis technique [Fe2O3-Ag(C)] and iron III oxide decorated silver nanoparticles using in situ reduction, [Fe2O3-Ag (S)]. The isotherm and the adsorption kinetics have been studied systematically. The kinetic data can be explained by the pseudo second order model and the adsorption equilibrium followed Langmuir isotherm. The equilibrium and kinetics results suggest that Fe2O3-Ag(S) nanoparticles showed the maximum adsorption among all the adsorbents. Hence, Polyvinylidene fluoride based membranes containing Fe2O3-Ag(S) nanoparticles were prepared via phase inversion (precipitation immersion using DMF/water) technique. The adsorption kinetics were studied in detail and it was observed that the composite membrane showed synergistic improvement in dye adsorption. Such membranes can be used for water purification.

Formation of aqueous-phase secondary organic aerosols from glycolaldehyde and ammonium sulfate/amines: A kinetic and mechanistic study

NASA Astrophysics Data System (ADS)

Yi, Yayi; Cao, Zhaoyu; Zhou, Xuehua; Xue, Likun; Wang, Wenxing

2018-05-01

Atmospheric particles are largely represented by secondary organic aerosols (SOAs) produced by either aqueous- or gas-phase reactions. Recently, the contribution of the former to SOA formation has been shown to substantially increase and even reach that of the latter, which necessitates in-depth mechanistic investigations. For a deeper understanding of aqueous-phase SOA generation, we herein studied the production of these aerosols in the dark from glycolaldehyde (GAld) and ammonium sulfate (AS)/amines (methylamine (MAm) and glycine (Gly)). UV-vis spectroscopy showed that reaction mixtures featured two main absorption bands (at 209-230 and 280-330 nm) that were attributed to the π-π* transitions of Schiff bases and the n-π* transitions of oligomers produced in the above reactions, respectively. Further studies revealed that irrespective of reactant concentration and pH, all the investigated reactions were well fitted by first-order kinetics and were accelerated by increasing AS/MAm concentrations and solution pH under acidic conditions. The reaction rate constants (determined from changes of absorption at 300 nm) followed the order of Gly (kI = 2.39 × 10-6 s-1) > MAm (kI = 1.19 × 10-6 s-1) > AS (kI = 8.33 × 10-7 s-1) at identical low AS/amine concentrations and were in the order of MAm (kI = 2.5 × 10-6 s-1) > AS (kI = 1.39 × 10-6 s-1) at high AS/MAm concentrations. The main reaction pathways corresponded to the aldol self-condensation of GAld and the nucleophilic attack of AS/amines on GAld followed by dehydration, which afforded imines as the major products. The stronger light absorption of (GAld + Gly) mixtures than that of (glyoxal/methylglyoxal + Gly) mixtures was ascribed to the increased amount of imine- and carbonyl group-containing products produced in the former case.

Kinetics of Methylmercury Production Revisited

DOE PAGES

Olsen, Todd A.; Muller, Katherine A.; Painter, Scott L.; ...

2018-01-27

Laboratory measurements of the biologically mediated methylation of mercury (Hg) to the neurotoxin monomethylmercury (MMHg) often exhibit kinetics that are inconsistent with first-order kinetic models. Using time-resolved measurements of filter passing Hg and MMHg during methylation/demethylation assays, a multisite kinetic sorption model, and reanalyses of previous assays, we show in this paper that competing kinetic sorption reactions can lead to time-varying availability and apparent non-first-order kinetics in Hg methylation and MMHg demethylation. The new model employing a multisite kinetic sorption model for Hg and MMHg can describe the range of behaviors for time-resolved methylation/demethylation data reported in the literature includingmore » those that exhibit non-first-order kinetics. Additionally, we show that neglecting competing sorption processes can confound analyses of methylation/demethylation assays, resulting in rate constant estimates that are systematically biased low. Finally, simulations of MMHg production and transport in a hypothetical periphyton biofilm bed illustrate the implications of our new model and demonstrate that methylmercury production may be significantly different than projected by single-rate first-order models.« less

Kinetics of Microbial Reduction of Solid Phase U(VI)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Chongxuan; Jeon, Byong Hun; Zachara, John M.

2006-10-01

Sodium boltwoodite (NaUO2SiO3OH ?1.5H2O) was used to assess the kinetics of microbial reduction of solid phase U(VI) by a dissimilatory metal-reducing bacterium (DMRB), Shewanella oneidensis strain MR-1. The bioreduction kinetics was studied with Na-boltwoodite in suspension or within alginate beads. Concentrations of U(VI)tot and cell number were varied to evaluate the coupling of U(VI) dissolution, diffusion, and microbial activity. Batch experiments were performed in a non-growth medium with lactate as electron donor at pH 6.8 buffered with PIPES. Microscopic and spectroscopic analyses with transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and laser-induced fluorescence spectroscopy (LIFS) collectively indicated that solidmore » phase U(VI) was first dissolved and diffused out of grain interiors before it was reduced on bacterial surfaces and/or within the periplasm. The kinetics of solid phase U(VI) bioreduction was well described by a coupled model of bicarbonate-promoted dissolution of Na-boltwoodite, intraparticle uranyl diffusion, and Monod type bioreduction kinetics with respect to dissolved U(VI) concentration. The results demonstrated the intimate coupling of biological, chemical, and physical processes in microbial reduction of solid phase U(VI).« less

Large-moment antiferromagnetic order in overdoped high-Tc superconductor 154SmFeAsO1-xDx

NASA Astrophysics Data System (ADS)

Iimura, Soshi; Okanishi, Hiroshi; Matsuishi, Satoru; Hiraka, Haruhiro; Honda, Takashi; Ikeda, Kazutaka; Hansen, Thomas C.; Otomo, Toshiya; Hosono, Hideo

2017-05-01

In iron-based superconductors, high critical temperature (Tc) superconductivity over 50 K has only been accomplished in electron-doped hREFeAsO (hRE is heavy rare earth (RE) element). Although hREFeAsO has the highest bulk Tc (58 K), progress in understanding its physical properties has been relatively slow due to difficulties in achieving high-concentration electron doping and carrying out neutron experiments. Here, we present a systematic neutron powder diffraction study of 154SmFeAsO1-xDx, and the discovery of a long-range antiferromagnetic ordering with x ≥ 0.56 (AFM2) accompanying a structural transition from tetragonal to orthorhombic. Surprisingly, the Fe magnetic moment in AFM2 reaches a magnitude of 2.73 μB/Fe, which is the largest in all nondoped iron pnictides and chalcogenides. Theoretical calculations suggest that the AFM2 phase originates in kinetic frustration of the Fe-3dxy orbital, in which the nearest-neighbor hopping parameter becomes zero. The unique phase diagram, i.e., highest-Tc superconducting phase adjacent to the strongly correlated phase in electron-overdoped regime, yields important clues to the unconventional origins of superconductivity.

Physiological-phased kinetic characteristics of microalgae Chlorella vulgaris growth and lipid synthesis considering synergistic effects of light, carbon and nutrients.

PubMed

Liao, Qiang; Chang, Hai-Xing; Fu, Qian; Huang, Yun; Xia, Ao; Zhu, Xun; Zhong, Nianbing

2018-02-01

To comprehensively understand kinetic characteristics of microalgae growth and lipid synthesis in different phases, a phase-feeding strategy was proposed to simultaneously regulate light, carbon and nutrients in adaption, growth and stationary phases of microalgae cultivation. Physiological-phased kinetic characteristics of microalgae Chlorella vulgaris growth and lipid synthesis under synergistic effects of light, carbon and nutrients were investigated, and supply-demand relationships of electrons and energy between light and dark reactions of photosynthesis process were discussed. Finally, the optimized cultivation strategy for microalgae in various phases were obtained, under which the lipid productivity was significantly improved from 130.11 mg/L/d to 163.42 mg/L/d. The study provided some important guidance for the large-scale production of biofuels from microalgae. Copyright © 2017 Elsevier Ltd. All rights reserved.

Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films.

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered (aggregated) phases is shown to exist when liquid vapor is confined in capillaries (condensation-liquefaction-evaporation and flux). This pheno-menon can be experimentally illustrated with suspended nano-sized particles (flocculation-coagulation-peptisation of colloidal sols) being confined in sample holders of varying size. The self-assembled aggregates represent critical self-similar equilibrium structures corres-ponding to rate determining complexes in kinetics. Overall, a self-consistent thermodynamic framework is established for the characterization of two- and three-dimensional phase separations in one-, two- and three-component systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Transient competitive complexation in biological kinetic isotope fractionation explains non-steady isotopic effects: Theory and application to denitrification in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maggi, F.M.; Riley, W.J.

2009-06-01

The theoretical formulation of biological kinetic reactions in isotopic applications often assume first-order or Michaelis-Menten-Monod kinetics under the quasi-steady-state assumption to simplify the system kinetics. However, isotopic e ects have the same order of magnitude as the potential error introduced by these simpli cations. Both formulations lead to a constant fractionation factor which may yield incorrect estimations of the isotopic effect and a misleading interpretation of the isotopic signature of a reaction. We have analyzed the isotopic signature of denitri cation in biogeochemical soil systems by Menyailo and Hungate [2006], where high {sup 15}N{sub 2}O enrichment during N{sub 2}O productionmore » and inverse isotope fractionation during N{sub 2}O consumption could not be explained with first-order kinetics and the Rayleigh equation, or with the quasi-steady-state Michaelis-Menten-Monod kinetics. When the quasi-steady-state assumption was relaxed, transient Michaelis-Menten-Monod kinetics accurately reproduced the observations and aided in interpretation of experimental isotopic signatures. These results may imply a substantial revision in using the Rayleigh equation for interpretation of isotopic signatures and in modeling biological kinetic isotope fractionation with first-order kinetics or quasi-steady-state Michaelis-Menten-Monod kinetics.« less

Microbial Degradation of Propylene Glycol - Modelling Approach of a Batch Experiment

NASA Astrophysics Data System (ADS)

Dathe, Annette; Fernandez, Perrine; Bakken, Lars; Bloem, Esther; French, Helen

2016-04-01

De-icing chemicals are applied in large amounts at airports during winter conditions to keep the runways and aircrafts ice-free. At Gardermoen airport, Norway, most of the applied chemicals can be captured, but about 10 to 20 % infiltrate into the soil along the runways and during take-off. While the commonly used propylene glycol (PG) is easily degradable by local microbial communities, its biological oxygen demand is high, anoxic zones can develop and soluble Fe+2 and Mn+2 ions eventually can reach the groundwater. The objectives of the presented study are to quantify the mechanisms, which control the order of reduction processes in an unsaturated sandy soil, and to test whether measured redox potentials can help to determine underlying biogeochemical reactions. To investigate the mechanisms of microbial degradation, the water phase of soil samples from Gardermoen Airport was replaced by deionized water with 10 mMol PG or 10 mMol glutamate and the samples were incubated at 10°C for about two weeks. The gas phase was sampled and analyzed automatically every three hours. Microbial degradation of the substrate (PG or glutamate) was modelled following a Monod kinetics using the FME (Flexible Modelling Environment) package of R (Project for Statistical Computing). The model was calibrated against measurements of O2 depletion and CO2 production. The initial concentrations of O2, CO2 and PG or glutamate are known and microbial yields and stoichiometric constants can be calculated from the measurements. Parameter values for the initial microbial population size, maximum microbial growth rate, the half saturation constant, and microbial degradation and respiration rates were fitted using the FME package. The model accounts for carbon from the substrate (PG or glutamate) incorporated into the biomass. Results are promising, but because of the large number of parameters needed to fit a Monod kinetics it is challenging to accurately model a whole redox sequence. The ultimate goal of implementing PG degrading processes into a soil water transport model is still a challenge, and simpler approaches like a first- and second order kinetic are investigated and compared to the behavior of the Monod kinetic.

Domain shape instabilities and dendrite domain growth in uniaxial ferroelectrics

NASA Astrophysics Data System (ADS)

Shur, Vladimir Ya.; Akhmatkhanov, Andrey R.

2018-01-01

The effects of domain wall shape instabilities and the formation of nanodomains in front of moving walls obtained in various uniaxial ferroelectrics are discussed. Special attention is paid to the formation of self-assembled nanoscale and dendrite domain structures under highly non-equilibrium switching conditions. All obtained results are considered in the framework of the unified kinetic approach to domain structure evolution based on the analogy with first-order phase transformation. This article is part of the theme issue `From atomistic interfaces to dendritic patterns'.

Support effects in catalysis studied by in-situ sum frequency generation vibrational spectroscopy and in-situ x-ray spectroscopies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kennedy, Griffin John

Here, kinetic measurements are paired with in-situ spectroscopic characterization tools to investigate colloidally based, supported Pt catalytic model systems in order to elucidate the mechanisms by which metal and support work in tandem to dictate activity and selectivity. The results demonstrate oxide support materials, while inactive in absence of Pt nanoparticles, possess unique active sites for the selective conversion of gas phase molecules when paired with an active metal catalyst.

Ultrasonic determination of recrystallization

NASA Technical Reports Server (NTRS)

Generazio, E. R.

1986-01-01

Ultrasonic attenuation was measured for cold worked Nickel 200 samples annealed at increasing temperatures. Localized dislocation density variations, crystalline order and colume percent of recrystallized phase were determined over the anneal temperature range using transmission electron microscopy, X-ray diffraction, and metallurgy. The exponent of the frequency dependence of the attenuation was found to be a key variable relating ultrasonic attenuation to the thermal kinetics of the recrystallization process. Identification of this key variable allows for the ultrasonic determination of onset, degree, and completion of recrystallization.

Transitions between homogeneous phases of polar active liquids

NASA Astrophysics Data System (ADS)

Dauchot, Olivier; Nguyen Thu Lam, Khanh Dang; Schindler, Michael; EC2M Team; PCT Team

2015-03-01

Polar active liquids, composed of aligning self-propelled particle exhibit large scale collective motion. Simulations of Vicsek-like models of constant-speed point particles, aligning with their neighbors in the presence of noise, have revealed the existence of a transition towards a true long range order polar-motion phase. Generically, the homogenous polar state is unstable; non-linear propagative structures develop; and the transition is discontinuous. The long range dynamics of these systems has been successfully captured using various scheme of kinetic theories. However the complexity of the dynamics close to the transition has somewhat hindered more basics questions. Is there a simple way to predict the existence and the order of a transition to collective motion for a given microscopic dynamics? What would be the physically meaningful and relevant quantity to answer this question? Here, we tackle these questions, restricting ourselves to the study of the homogeneous phases of polar active liquids in the low density limit and obtain a very intuitive understanding of the conditions which particle interaction must satisfy to induce a transition towards collective motion.

A Membrane-Free Ferrocene-Based High-Rate Semiliquid Battery.

PubMed

Ding, Yu; Zhao, Yu; Yu, Guihua

2015-06-10

We report here a ferrocene-based membrane-free, high-rate semiliquid battery that takes advantage of a highly soluble ferrocene/ferrocenium redox couple in nonaqueous phase. The designed battery exhibits stable capacity retention up to 94% of theoretical capacity of ferrocene (145 mAh g(-1)) at a broad current rate up to 60 C owing to rapid mass transport in a liquid phase and fast redox kinetics. The diffusion coefficient and the standard reaction constant are determined to be in the order of 10(-6) cm(2) s(-1) and 10(-1) cm s(-1), respectively, orders of magnitude greater than those in a solid-phase electrode and those in conventional redox flow batteries. Additionally, the battery demonstrates power density and energy density exceeding 1400 W L(-1) and 40 Wh L(-1), respectively, and stable cyclability with capacity retention of ∼80% for 500 cycles. Compared with state-of-the-art energy storage technologies such as Li-ion batteries or conventional redox flow batteries, the proposed liquid battery shows the potential to be an efficient energy storage system with exceptionally high power and reasonable energy density.

Reordering transitions during annealing of block copolymer cylinder phases

DOE PAGES

Majewski, Pawel W.; Yager, Kevin G.

2015-10-06

While equilibrium block-copolymer morphologies are dictated by energy-minimization effects, the semi-ordered states observed experimentally often depend on the details of ordering pathways and kinetics. In this study, we explore reordering transitions in thin films of block-copolymer cylinder-forming polystyrene- block-poly(methyl methacrylate). We observe several transient states as films order towards horizontally-aligned cylinders. In particular, there is an early-stage reorganization from randomly-packed cylinders into hexagonally-packed vertically-aligned cylinders; followed by a reorientation transition from vertical to horizontal cylinder states. These transitions are thermally activated. The growth of horizontal grains within an otherwise vertical morphology proceeds anisotropically, resulting in anisotropic grains in the finalmore » horizontal state. The size, shape, and anisotropy of grains are influenced by ordering history; for instance, faster heating rates reduce grain anisotropy. These results help elucidate aspects of pathway-dependent ordering in block-copolymer thin films.« less

Pseudo second order kinetics and pseudo isotherms for malachite green onto activated carbon: comparison of linear and non-linear regression methods.

PubMed

Kumar, K Vasanth; Sivanesan, S

2006-08-25

Pseudo second order kinetic expressions of Ho, Sobkowsk and Czerwinski, Blanachard et al. and Ritchie were fitted to the experimental kinetic data of malachite green onto activated carbon by non-linear and linear method. Non-linear method was found to be a better way of obtaining the parameters involved in the second order rate kinetic expressions. Both linear and non-linear regression showed that the Sobkowsk and Czerwinski and Ritchie's pseudo second order model were the same. Non-linear regression analysis showed that both Blanachard et al. and Ho have similar ideas on the pseudo second order model but with different assumptions. The best fit of experimental data in Ho's pseudo second order expression by linear and non-linear regression method showed that Ho pseudo second order model was a better kinetic expression when compared to other pseudo second order kinetic expressions. The amount of dye adsorbed at equilibrium, q(e), was predicted from Ho pseudo second order expression and were fitted to the Langmuir, Freundlich and Redlich Peterson expressions by both linear and non-linear method to obtain the pseudo isotherms. The best fitting pseudo isotherm was found to be the Langmuir and Redlich Peterson isotherm. Redlich Peterson is a special case of Langmuir when the constant g equals unity.

Formation of volatile compounds during heating of spice paprika (Capsicum annuum) powder.

PubMed

Cremer, D R; Eichner, K

2000-06-01

Spice paprika (red pepper; Capsicum annuum) is the most cultivated spice worldwide and is used mainly for its color and pungency. However, current research is also focusing on the flavor as an important parameter. This paper deals with the kinetics of the formation of those volatiles that indicate a decrease in spice paprika quality due to Maillard reaction, hydrolytic reactions, and oxidative degradation reactions of lipids such as fatty acids and carotenoids. Spice paprika volatiles were quantitatively analyzed by means of headspace gas chromatography (HS-GC) and solid-phase microextraction (SPME) followed by gas chromatography-mass spectrometry (GC-MS). The kinetics of their formation were investigated, and the respective activation energies determined. Strecker aldehyde, acetone, and methanol formation followed a pseudo-zero-order reaction kinetic, and formation of dimethyl sulfide (DMS) was characterized by a first-order kinetic. The activation energies determined were between 86.3 and 101.8 for the Strecker aldehydes acetaldehyde (AA), 2-methylpropanal (2-MP), 3-methylbutanal (3-MB), and 2-methylbutanal (2-MB), 130.7 for acetone, 114.2 for methanol, and 109.7 kJ/mol for DMS. The amounts of Strecker aldehydes formed were correlated to the concentrations of the corresponding free amino acids present in the samples. The formation of hexanal and 6-methyl-5-hepten-2-one in Capsicum annuum during processing was confirmed, and the formation of beta-ionone was probably described for the first time. During heating, the concentration of hexanal increased rapidly. The formation of 6-methyl-5-hepten-2-one confirms that Capsicum annuum fruits contain lycopene.

Computational modeling of fully-ionized, magnetized plasmas using the fluid approximation

NASA Astrophysics Data System (ADS)

Schnack, Dalton

2005-10-01

Strongly magnetized plasmas are rich in spatial and temporal scales, making a computational approach useful for studying these systems. The most accurate model of a magnetized plasma is based on a kinetic equation that describes the evolution of the distribution function for each species in six-dimensional phase space. However, the high dimensionality renders this approach impractical for computations for long time scales in relevant geometry. Fluid models, derived by taking velocity moments of the kinetic equation [1] and truncating (closing) the hierarchy at some level, are an approximation to the kinetic model. The reduced dimensionality allows a wider range of spatial and/or temporal scales to be explored. Several approximations have been used [2-5]. Successful computational modeling requires understanding the ordering and closure approximations, the fundamental waves supported by the equations, and the numerical properties of the discretization scheme. We review and discuss several ordering schemes, their normal modes, and several algorithms that can be applied to obtain a numerical solution. The implementation of kinetic parallel closures is also discussed [6].[1] S. Chapman and T.G. Cowling, ``The Mathematical Theory of Non-Uniform Gases'', Cambridge University Press, Cambridge, UK (1939).[2] R.D. Hazeltine and J.D. Meiss, ``Plasma Confinement'', Addison-Wesley Publishing Company, Redwood City, CA (1992).[3] L.E. Sugiyama and W. Park, Physics of Plasmas 7, 4644 (2000).[4] J.J. Ramos, Physics of Plasmas, 10, 3601 (2003).[5] P.J. Catto and A.N. Simakov, Physics of Plasmas, 11, 90 (2004).[6] E.D. Held et al., Phys. Plasmas 11, 2419 (2004)

Development and evaluation of intestinal targeted mucoadhesive microspheres of Bacillus coagulans.

PubMed

Alli, Sk Md Athar; Ali, Sk Md Ajhar; Samanta, Amalesh

2011-11-01

Intestinal targeted mucoadhesive microsphere of probiotics may provide numerous associated health benefits. To develop mucoadhesive microspheres that will deliver viable probiotic cells into gut protectively against harsh environmental conditions of stomach for extended period. Core mucoadhesive microspheres of Bacillus coagulans were prepared using hypromellose, following coacervation and phase separation technique and were then coated with hypromellose phthalate to achieve their site-specific release. Microspheres were evaluated for percent yield, entrapment efficiency, surface morphology, particle size and size distribution, flow property, swelling property, mucoadhesion property by the in vitro wash-off and the ex vivo mucoadhesive strength tests, in vitro release profile and release kinetic, in vivo probiotic activity, and stability. The values for kinetic constant and regression coefficient of model-dependent approaches and the difference factor, the similarity factor, and the Rescigno index of model-independent approaches were determined for accessing and comparing in vitro performance. Microsphere formulation batches have percent yield value between 56.26% and 69.13% and entrapment efficiency value between 66.95% and 77.89%. Microspheres were coarser with spherical shape having mean particle size from 28.03 to 48.31 μm. In vitro B. coagulans release profile follows zero-order kinetics and depends on the grade of hypromellose and the B. coagulans-to-hypromellose ratio. Experimental microspheres rendered adequate stability to B. coagulans at room temperature. Microspheres had delivered B. coagulans in simulated intestinal condition following zero-order kinetics, protectively in simulated gastric condition, exhibiting appreciable mucoadhesion in intestinal condition, which could be useful to achieve site-specific delivery for extended period.

Group-kinetic theory of turbulence

NASA Technical Reports Server (NTRS)

Tchen, C. M.

1986-01-01

The two phases are governed by two coupled systems of Navier-Stokes equations. The couplings are nonlinear. These equations describe the microdynamical state of turbulence, and are transformed into a master equation. By scaling, a kinetic hierarchy is generated in the form of groups, representing the spectral evolution, the diffusivity and the relaxation. The loss of memory in formulating the relaxation yields the closure. The network of sub-distributions that participates in the relaxation is simulated by a self-consistent porous medium, so that the average effect on the diffusivity is to make it approach equilibrium. The kinetic equation of turbulence is derived. The method of moments reverts it to the continuum. The equation of spectral evolution is obtained and the transport properties are calculated. In inertia turbulence, the Kolmogoroff law for weak coupling and the spectrum for the strong coupling are found. As the fluid analog, the nonlinear Schrodinger equation has a driving force in the form of emission of solitons by velocity fluctuations, and is used to describe the microdynamical state of turbulence. In order for the emission together with the modulation to participate in the transport processes, the non-homogeneous Schrodinger equation is transformed into a homogeneous master equation. By group-scaling, the master equation is decomposed into a system of transport equations, replacing the Bogoliubov system of equations of many-particle distributions. It is in the relaxation that the memory is lost when the ensemble of higher-order distributions is simulated by an effective porous medium. The closure is thus found. The kinetic equation is derived and transformed into the equation of spectral flow.

Organics removal from landfill leachate and activated sludge production in SBR reactors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klimiuk, Ewa; Kulikowska, Dorota

2006-07-01

This study is aimed at estimating organic compounds removal and sludge production in SBR during treatment of landfill leachate. Four series were performed. At each series, experiments were carried out at the hydraulic retention time (HRT) of 12, 6, 3 and 2 d. The series varied in SBR filling strategies, duration of the mixing and aeration phases, and the sludge age. In series 1 and 2 (a short filling period, mixing and aeration phases in the operating cycle), the relationship between organics concentration (COD) in the leachate treated and HRT was pseudo-first-order kinetics. In series 3 (with mixing and aerationmore » phases) and series 4 (only aeration phase) with leachate supplied by means of a peristaltic pump for 4 h of the cycle (filling during reaction period) - this relationship was zero-order kinetics. Activated sludge production expressed as the observed coefficient of biomass production (Y {sub obs}) decreased correspondingly with increasing HRT. The smallest differences between reactors were observed in series 3 in which Y {sub obs} was almost stable (0.55-0.6 mg VSS/mg COD). The elimination of the mixing phase in the cycle (series 4) caused the Y {sub obs} to decrease significantly from 0.32 mg VSS/mg COD at HRT 2 d to 0.04 mg VSS/mg COD at HRT 12 d. The theoretical yield coefficient Y accounted for 0.534 mg VSS/mg COD (series 1) and 0.583 mg VSS/mg COD (series 2). In series 3 and 4, it was almost stable (0.628 mg VSS/mg COD and 0.616 mg VSS/mg COD, respectively). After the elimination of the mixing phase in the operating cycle, the specific biomass decay rate increased from 0.006 d{sup -1} (series 3) to 0.032 d{sup -1} (series 4). The operating conditions employing mixing/aeration or only aeration phases enable regulation of the sludge production. The SBRs operated under aerobic conditions are more favourable at a short hydraulic retention time. At long hydraulic retention time, it can lead to a decrease in biomass concentration in the SBR as a result of cell decay. On the contrary, in the activated sludge at long HRT, a short filling period and operating cycle of the reactor with the mixing and aeration phases seem the most favourable.« less

Metastable Phase Evolution in Oxide Systems

NASA Astrophysics Data System (ADS)

Levi, Carlos G.

2005-03-01

Multi-component ceramics are often synthesized by routes that facilitate mixing at the molecular scale and subsequently generate a solid product at low homologous temperatures. Examples include chemical and physical vapor deposition, thermal spray, and pyrolytic decomposition of precursor solutions. In these processes the solid evolves rapidly from a highly energized state, typically in a temperature regime wherein long-range diffusion is largely constrained and the equilibrium configuration can be kinetically suppressed. The resulting product may exhibit various forms of metastability such as amorphization, nanocrystallinity, extended solid solubility and alternate crystalline forms. The approach allows access to novel combinations of structure and composition with unprecedented defect structures that, if reasonably durable, could have properties of potential technological interest. Understanding phase selection and evolution is facilitated by having a suitable reference framework depicting the thermodynamic hierarchy of the phases available to the system under the relevant processing conditions. When transformations are partitionless the phase menu and hierarchy can be readily derived from the relative position of the T0 curves/surfaces for the different pairs of phases. The result is a phase hierarchy map, which is an analog of the phase diagram for partitionless equilibrium. Such maps can then be used to assess the kinetic effects on the selection of metastable states and their subsequent evolution. This presentation will discuss the evolution of metastable phases in oxides, with emphasis on systems involving fluorite phases and their ordered or distorted derivatives. The concepts will be illustrated primarily with zirconia-based systems, notably those of interest in thermal barrier coatings, fuel cells and ferroelectrics (ZrO2-MO3/2, where M = Y, Sc, the lanthanides and combinations thereof, as well as ZrO2-YO3/2-TiO2, ZrO2-TiO2-PbO, etc.). Of particular interest are the durabilities of metastable phases in systems that operate at high temperature, their decomposition paths and the implications to their functionality.

Effect of composting and soil type on dissipation of veterinary antibiotics in land-applied manures.

PubMed

Chen, Chaoqi; Ray, Partha; Knowlton, Katharine F; Pruden, Amy; Xia, Kang

2018-04-01

The objective of this study was to determine the fate of commonly used veterinary antibiotics in their naturally excreted form when manure-based amendments are applied to soil. Beef cattle were administered sulfamethazine, tylosin, and chlortetracycline and dairy cows were treated with pirlimycin. The resulting manure was composted for 42 d under static or turned conditions and applied at agronomic N rates to sandy, silt, and silty clay loam soils and compared with amendment with corresponding raw manures in sacrificial microcosms over a 120-day period. Antibiotic dissipation in the raw manure-amended soils followed bi-phasic first order kinetics. The first phase half-lives for sulfamethazine, tylosin, chlortetracycline, and pirlimycin ranged from 6.0 to 18, 2.7 to 3.7, 23 to 25, and 5.5-8.2 d, respectively. During the second phase, dissipation of sulfamethazine was negligible, while the half-lives for tylosin, chlortetracycline, and pirlimycin ranged from 41 to 44, 75 to 144, and 87-142 d, respectively. By contrast, antibiotic dissipation in the compost-amended soils followed single-phase first order kinetics with negligible dissipation of sulfamethazine and half-lives of tylosin and chlortetracycline ranging from 15 to 16 and 49-104 d, respectively. Pirlimycin was below the detection limit in the compost-amended soils. After incubating 120 d, antibiotics in compost-amended soils (up to 3.1 μg kg -1 ) were significantly lower than in manure-amended soils (up to 19 μg kg -1 , p < .0001), with no major effect of soil type on the dissipation. Risk assessment suggested that composting can reduce antibiotic resistance selection potential in manure-amended soils. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coexistence of domains with distinct order and polarity in fluid bacterial membranes.

PubMed

Vanounou, Sharon; Pines, Dina; Pines, Ehud; Parola, Abraham H; Fishov, Itzhak

2002-07-01

In this study we sought the detection and characterization of bacterial membrane domains. Fluorescence generalized polarization (GP) spectra of laurdan-labeled Escherichia coli and temperature dependencies of both laurdan's GP and fluorescence anisotropy of 1,3-diphenyl-1,3,5-hexatriene (DPH) (rDPH) affirmed that at physiological temperatures, the E. coli membrane is in a liquid-crystalline phase. However, the strong excitation wavelength dependence of rlaurdan at 37 degrees C reflects membrane heterogeneity. Time-resolved fluorescence emission spectra, which display distinct biphasic redshift kinetics, verified the coexistence of two subpopulations of laurdan. In the initial phase, <50 ps, the redshift in the spectral mass center is much faster for laurdan excited at the blue edge (350 nm), whereas at longer time intervals, similar kinetics is observed upon excitation at either blue or red edge (400 nm). Excitation in the blue region selects laurdan molecules presumably located in a lipid domain in which fast intramolecular relaxation and low anisotropy characterize laurdan's emission. In the proteo-lipid domain, laurdan motion and conformation are restricted as exhibited by a slower relaxation rate, higher anisotropy and a lower GP value. Triple-Gaussian decomposition of laurdan emission spectra showed a sharp phase transition in the temperature dependence of individual components when excited in the blue but not in the red region. At least two kinds of domains of distinct polarity and order are suggested to coexist in the liquid-crystalline bacterial membrane: a lipid-enriched and a proteolipid domain. In bacteria with chloramphenicol (Cam)-inhibited protein synthesis, laurdan showed reduced polarity and restoration of an isoemissive point in the temperature-dependent spectra. These results suggest a decrease in membrane heterogeneity caused by Cam-induced domain dissipation.

Kinetics of steel slag leaching: Batch tests and modeling

DOE Office of Scientific and Technical Information (OSTI.GOV)

De Windt, Laurent, E-mail: laurent.dewindt@mines-paristech.fr; Chaurand, Perrine; Rose, Jerome

2011-02-15

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can bemore » used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.« less

Voltage gating by molecular subunits of Na+ and K+ ion channels: higher-dimensional cubic kinetics, rate constants, and temperature

PubMed Central

2015-01-01

The structural similarity between the primary molecules of voltage-gated Na and K channels (alpha subunits) and activation gating in the Hodgkin-Huxley model is brought into full agreement by increasing the model's sodium kinetics to fourth order (m3 → m4). Both structures then virtually imply activation gating by four independent subprocesses acting in parallel. The kinetics coalesce in four-dimensional (4D) cubic diagrams (16 states, 32 reversible transitions) that show the structure to be highly failure resistant against significant partial loss of gating function. Rate constants, as fitted in phase plot data of retinal ganglion cell excitation, reflect the molecular nature of the gating transitions. Additional dimensions (6D cubic diagrams) accommodate kinetically coupled sodium inactivation and gating processes associated with beta subunits. The gating transitions of coupled sodium inactivation appear to be thermodynamically irreversible; response to dielectric surface charges (capacitive displacement) provides a potential energy source for those transitions and yields highly energy-efficient excitation. A comparison of temperature responses of the squid giant axon (apparently Arrhenius) and mammalian channel gating yields kinetic Q10 = 2.2 for alpha unit gating, whose transitions are rate-limiting at mammalian temperatures; beta unit kinetic Q10 = 14 reproduces the observed non-Arrhenius deviation of mammalian gating at low temperatures; the Q10 of sodium inactivation gating matches the rate-limiting component of activation gating at all temperatures. The model kinetics reproduce the physiologically large frequency range for repetitive firing in ganglion cells and the physiologically observed strong temperature dependence of recovery from inactivation. PMID:25867741

Coupling Fluid and Kineitc Effects in Space Weather: an interdisciplinary task

NASA Astrophysics Data System (ADS)

Lapenta, Giovanni; González-Herrero, Diego; Boella, Elisabetta; Siddi, Lorenzo; Cazzola, Emanuele

2017-04-01

Two agents are key to space weather: electromagentic fields and energetic particles. Magnetic fields carried by plasmas in the solar wind interact with the Earth magnetosphere and solar energetic particles produced by solar events or in cosmic rays affect the space environment. Describing both is challenging. Magnetized plasmas are most effectively described by magneto-hydrodynamics, MHD, a fluid theory based on describing some fields defined in space: electromagnetic fields, density, velocity and temperature of the plasma. High energy particles, instead need a more detailed approach , kinetic theory, where statistical distributions of particles are governed by the Boltzmann equation. While fluid models are based on the ordinary space and time, kinetic models require a six dimensional space, called phase space, besides time. The two methods are not separated, the processes leading to the production of energetic particles are the same that involve space plasamas and fields. Arriving at a single self-consistent model has been the goal of the Swiff project funded by the EC in FP7 and it is now a key goal of the ongoing DEEP-ER project. We present a new approach developed with the goal of extending the reach of kinetic models to the fluid scales. Kinetic models are a higher order description and all fluid effects are included in them. However, the cost in terms of computing power is much higher and it has been so far prohibitively expensive to treat space weather events fully kinetically. We have now designed a new method capable of reducing that cost by several orders of magnitude making it possible for kinetic models to study space weather events [1,2]. We will report the new methodology and show its application to space weather mdeling. [1] Giovanni Lapenta,Exactly Energy Conserving Semi-Implicit Particle in Cell Formulation, to appear, JCP, arXiv:1602.06326 [2] Giovanni Lapenta, Diego Gonzalez-Herrero, Elisabetta Boella, Multiple scale kinetic simulations with the energy conserving semi implicit particle in cell (PIC) method, submitted JPP, arXiv:1612.08289

ICCK Conference Final Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, William H.

2013-05-28

The 7th International Conference on Chemical Kinetics (ICCK) was held July 10-14, 2011, at Massachusetts Institute of Technology (MIT), in Cambridge, MA, hosted by Prof. William H. Green of MIT's Chemical Engineering department. This cross-disciplinary meeting highlighted the importance of fundamental understanding of elementary reactions to the full range of chemical investigations. The specific conference focus was on elementary-step kinetics in both the gas phase and in condensed phase. The meeting provided a unique opportunity to discuss how the same reactive species and reaction motifs manifest under very different reaction conditions (e.g. atmospheric, aqueous, combustion, plasma, in nonaqueous solvents, onmore » surfaces.). The conference featured special sessions on new/improved experimental techniques, improved models and data analysis for interpreting complicated kinetics, computational kinetics (especially rate estimates for large kinetic models), and a panel discussion on how the community should document/archive kinetic data. In the past, this conference had been limited to homogeneous gas-phase and liquid-phase systems. This conference included studies of heterogeneous kinetics which provide rate constants for, or insight into, elementary reaction steps. This Grant from DOE BES covered about half of the subsidies we provided to students and postdocs who attended the conference, by charging them reduced-rate registration fees. The complete list of subsidies provided are listed in Table 1 below. This DOE funding was essential to making the conference affordable to graduate students, and indeed the attendance at this conference was higher than at previous conferences in this series. Donations made by companies provided additional subsidies, leveraging the DOE funding. The conference was very effective in educating graduate students and important in fostering scientific interactions, particularly between scientists studying gas phase and liquid phase kinetics, since those two communities do not meet very often (it had been 6 years since the last time this conference had been held). The conference at MIT was so successful that European scientists decided to organize a similar conference (it will be held in Seville, Spain in July 2013). Almost 200 scientists participated, with more than 100 oral presentations and many poster presentations. A complete list of the presentations and their abstracts are given in the attachment. The conference led to many peer-reviewed papers published in several Special Issues of the International Journal of Chemical Kinetics in early 2012.« less

NO—CO—O2 Reaction on a Metal Catalytic Surface using Eley—Rideal Mechanism

NASA Astrophysics Data System (ADS)

Waqar, Ahmad

2008-10-01

Interactions among the reacting species NO, CO and O2 on metal catalytic surfaces are studied by means of Monte Carlo simulation using the Eley-Rideal (ER) mechanism. The study of this three-component system is important for understanding of the reaction kinetics by varying the relative ratios of the reactants. It is found that contrary to the conventional Langmuir-Hinshelwood (LH) thermal mechanism in which two irreversible phase transitions are obtained between active states and poisoned states, a single phase transition is observed when the ER mechanism is combined with the LH mechanism. The phase diagrams of the surface coverage and the steady state production of CO2, N2 and N2 O are evaluated as a function of the partial pressures of the reactants in the gas phase. The continuous production of CO2 starts as soon as the CO pressure is switched on and the second order phase transition at the first critical point is eliminated, which is in agreement with the experimental findings.

Colossal Magnetoelectric Effect with Competing Multiferroic and Weak-Ferromagnetic Phases

NASA Astrophysics Data System (ADS)

Choi, Young Jai; Zhang, Chenglin; Lee, Nara; Cheong, Sang-Wook

2011-03-01

From our investigation of magnetoelectric properties of Eu 0.75 Y0.25 Mn O3 , where a multiferroic phase competes with a weak ferromagnetic phase in magnetic fields, we found intriguing hysteretic behaviors of physical properties with variation of temperature and magnetic field. These hysteretic behaviors arise from the kinetic arrest/de-arrest processes of the first order magnetic transition, resulting in freezing or melting of a magnetoelectric glass state with the coexistence of two competing phases. We note that most of large magnetoelectric coupling effects in multiferroics are associated with the large change of polarization with magnetic fields, but the control of ferromagnetic-type magnetization by applying electric fields is most relevant to technological applications, which is scarcely observed. This important issue of mutual controllability is achieved in Eu 0.75 Y0.25 Mn O3 utilizing dynamical modulations of the coexistence of two contraindicative phases, highly susceptible to the external perturbations such as electric and magnetic fields.

The leaching kinetics of cadmium from hazardous Cu-Cd zinc plant residues.

PubMed

Li, Meng; Zheng, Shili; Liu, Biao; Du, Hao; Dreisinger, David Bruce; Tafaghodi, Leili; Zhang, Yi

2017-07-01

A large amount of Cu-Cd zinc plant residues (CZPR) are produced from the hydrometallurgical zinc plant operations. Since these residues contain substantial amount of heavy metals including Cd, Zn and Cu, therefore, they are considered as hazardous wastes. In order to realize decontamination treatment and efficient extraction of the valuable metals from the CZPR, a comprehensive recovery process using sulfuric acid as the leaching reagent and air as the oxidizing reagent has been proposed. The effect of temperature, sulfuric acid concentration, particle size, solid/liquid ratio and stirring speed on the cadmium extraction efficiency was investigated. The leaching kinetics of cadmium was also studied. It was concluded that the cadmium leaching process was controlled by the solid film diffusion process. Moreover, the order of the reaction rate constant versus H 2 SO 4 concentration, particle size, solid/liquid ratio and stirring speed was calculated. The XRD and SEM-EDS analysis results showed that the main phases of the secondary sulfuric acid leaching residues were lead sulfate and calcium sulfate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetic study on the catalytic performance of Rh/TiO/sub 2/ reduced at different temperatures in the CO-H/sub 2/ reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujitsu, H.; Ikeyama, N.; Mochida, I.

1986-08-01

Catalytic CO-H/sub 2/ reaction on Rh/TiO/sub 2/ reduced at 200, 400, and 500/sup 0/C (Cat-200, -400, -500) for 2 h was kinetically studied at 250/sup 0/C using a circulating reactor and Fourier transform-infrared (FT-IR) spectroscopy to determine how Cat-400 exhibited the highest activity. The rate equation distinguished the best catalyst with zero and first orders in CO and H/sub 2/, respectively, from other catalysts with negative order in CO. The adsorption ability of the catalyst at 200/sup 0/C was comparable to that of Cat-200, and two to three times larger than that of Cat-500, although the ability of Cat-200 wasmore » much larger at room temperature. Carbon monoxide adsorbed on the catalysts reversibly as well as irreversibly. IR spectroscopy revealed that the major form of irreversibly adsorbed CO was linear on Cat-200, whereas similar amounts of linear and bridge forms were observed on Cat-400 and Cat-500. These latter forms were highly reactive against hydrogen molecules when no carbon monoxide was present in the gas phase. Based on these results, the highest activity of Cat-400 is ascribed to rhodium metal modified by properly reduced TiO/sub 2/ to show the appropriate adsorption ability of carbon monoxide which least retards the activation of hydrogen according to first-order kinetics. Typical strong metal-support interaction decreases the catalytic activity by decreasing the active sites and strengthening the CO adsorption too much.« less

ABTS as an Electron Shuttle to Enhance the Oxidation Kinetics of Substituted Phenols by Aqueous Permanganate.

PubMed

Song, Yang; Jiang, Jin; Ma, Jun; Pang, Su-Yan; Liu, Yong-Ze; Yang, Yi; Luo, Cong-Wei; Zhang, Jian-Qiao; Gu, Jia; Qin, Wen

2015-10-06

In this study, it was, interestingly, found that 2,2'-azino-bis(3-ethylbenzothiazoline)-6-sulfonate (ABTS), a widely used electron shuttle, could greatly accelerate the oxidation of substituted phenols by potassium permanganate (Mn(VII)) in aqueous solutions at pH 5-9. This was attributed to the fact that these substituted phenols could be readily oxidized by the stable radical cation (ABTS(•+)), which was quickly produced from the oxidation of ABTS by Mn(VII). The reaction of Mn(VII) with ABTS exhibited second-order kinetics, with stoichiometries of ∼5:1 at pH 5-6 and ∼3:1 at pH 7-9, and the rate constants varied negligibly from pH 5 to 9 (k = (9.44 ± 0.21) × 10(4) M(-1) s(-1)). Comparatively, the reaction of ABTS(•+) with phenol showed biphasic kinetics. The second-order rate constants for the reactions of ABTS(•+) with substituted phenols obtained in the initial phase were strongly affected by pH, and they were several orders of magnitude higher than those for the reactions of Mn(VII) with substituted phenols at each pH. Good Hammett-type correlations were found for the reactions of ABTS(•+) with undissociated (log(k) = 2.82-4.31σ) and dissociated phenols (log(k) = 7.29-5.90σ). The stoichiometries of (2.2 ± 0.06):1 (ABTS(•+) in excess) and (1.38 ± 0.18):1 (phenol in excess) were achieved in the reaction of ABTS(•+) with phenol, but they exhibited no pH dependency.

Influence of inocula with prior hydrocarbon exposure on biodegradation rates of diesel, synthetic diesel, and fish-biodiesel in soil.

PubMed

Horel, Agota; Schiewer, Silke

2014-08-01

To achieve effective bioremediation within short warm seasons of cold climates, microbial adaptation periods to the contaminant should be brief. The current study investigated growth phases for soil spiked with diesel, Syntroleum, or fish biodiesel, using microbial inocula adapted to the specific substrates. For modeling hydrocarbon degradation, multi-phase first order kinetics was assumed, comparing linear regression with nonlinear parameter optimization of rate constants and phase durations. Lag phase periods of 5 to >28d were followed by short and intense exponential growth phases with high rate constants (e.g. from kFish=0.0013±0.0002 to kSyntr=0.015±0.001d(-1)). Hydrocarbon mineralization was highest for Syntroleum contamination, where up to three times higher cumulative CO2 production was achieved than for diesel fuel, with fish biodiesel showing initially the slowest degradation. The amount of hydrocarbons recovered from the soil by GC-MS decreased in the order fish biodiesel>diesel>Syntroleum. During initial weeks, biodegradation was higher for microbial inocula adapted to a specific fuel type, whereby the main effect of the inoculum was to shorten the lag phase duration; however, the inoculum's importance diminished after daily respiration peaked. In conclusion, addition of an inoculum to increase biodegradation rates was not necessary. Copyright © 2014 Elsevier Ltd. All rights reserved.

Crystal Chemistry and Electrochemistry of Li xMn 1.5Ni 0.5O 4 Solid Solution Cathode Materials

DOE PAGES

Kan, Wang Hay; Kuppan, Saravanan; Cheng, Lei; ...

2017-07-19

For ordered high-voltage spinel LiMn 1.5Ni 0.5O 4 (LMNO) with the P4 32 1 symmetry, the two consecutive two-phase transformations at ~4.7 V (vs Li +/Li), involving three cubic phases of LMNO, Li 0.5Mn 1.5Ni 0.5O 4 (L 0.5MNO), and Mn 1.5Ni 0.5O 4 (MNO), have been well-established. Such a mechanism is traditionally associated with poor kinetics due to the slow movement of the phase boundaries and the large mechanical strain resulting from the volume changes among the phases, yet ordered LMNO has been shown to have excellent rate capability. In this paper, we show the ability of the phasesmore » to dissolve into each other and determine their solubility limit. We characterized the properties of the formed solid solutions and investigated the role of non-equilibrium single-phase redox processes during the charge and discharge of LMNO. Finally, by using an array of advanced analytical techniques, such as soft and hard X-ray spectroscopy, transmission X-ray microscopy, and neutron/X-ray diffraction, as well as bond valence sum analysis, the present study examines the metastable nature of solid-solution phases and provides new insights in enabling cathode materials that are thermodynamically unstable.« less

Method and turbine for extracting kinetic energy from a stream of two-phase fluid

NASA Technical Reports Server (NTRS)

Elliott, D. G. (Inventor)

1979-01-01

An axial flow separator turbine is described which includes a number of nozzles for delivering streams of a two-phase fluid along linear paths. A phase separator which responsively separates the vapor and liquid is characterized by concentrically related annuli supported for rotation within the paths. The separator has endless channels for confining the liquid under the influence of centrifugal forces. A vapor turbine fan extracts kinetic energy from the liquid. Angular momentum of both the liquid phase and the vapor phase of the fluid is converted to torque.

Effects of Different PER Translational Kinetics on the Dynamics of a Core Circadian Clock Model

PubMed Central

Nieto, Paula S.; Revelli, Jorge A.; Garbarino-Pico, Eduardo; Condat, Carlos A.; Guido, Mario E.; Tamarit, Francisco A.

2015-01-01

Living beings display self-sustained daily rhythms in multiple biological processes, which persist in the absence of external cues since they are generated by endogenous circadian clocks. The period (per) gene is a central player within the core molecular mechanism for keeping circadian time in most animals. Recently, the modulation PER translation has been reported, both in mammals and flies, suggesting that translational regulation of clock components is important for the proper clock gene expression and molecular clock performance. Because translational regulation ultimately implies changes in the kinetics of translation and, therefore, in the circadian clock dynamics, we sought to study how and to what extent the molecular clock dynamics is affected by the kinetics of PER translation. With this objective, we used a minimal mathematical model of the molecular circadian clock to qualitatively characterize the dynamical changes derived from kinetically different PER translational mechanisms. We found that the emergence of self-sustained oscillations with characteristic period, amplitude, and phase lag (time delays) between per mRNA and protein expression depends on the kinetic parameters related to PER translation. Interestingly, under certain conditions, a PER translation mechanism with saturable kinetics introduces longer time delays than a mechanism ruled by a first-order kinetics. In addition, the kinetic laws of PER translation significantly changed the sensitivity of our model to parameters related to the synthesis and degradation of per mRNA and PER degradation. Lastly, we found a set of parameters, with realistic values, for which our model reproduces some experimental results reported recently for Drosophila melanogaster and we present some predictions derived from our analysis. PMID:25607544

Effects of different per translational kinetics on the dynamics of a core circadian clock model.

PubMed

Nieto, Paula S; Revelli, Jorge A; Garbarino-Pico, Eduardo; Condat, Carlos A; Guido, Mario E; Tamarit, Francisco A

2015-01-01

Living beings display self-sustained daily rhythms in multiple biological processes, which persist in the absence of external cues since they are generated by endogenous circadian clocks. The period (per) gene is a central player within the core molecular mechanism for keeping circadian time in most animals. Recently, the modulation PER translation has been reported, both in mammals and flies, suggesting that translational regulation of clock components is important for the proper clock gene expression and molecular clock performance. Because translational regulation ultimately implies changes in the kinetics of translation and, therefore, in the circadian clock dynamics, we sought to study how and to what extent the molecular clock dynamics is affected by the kinetics of PER translation. With this objective, we used a minimal mathematical model of the molecular circadian clock to qualitatively characterize the dynamical changes derived from kinetically different PER translational mechanisms. We found that the emergence of self-sustained oscillations with characteristic period, amplitude, and phase lag (time delays) between per mRNA and protein expression depends on the kinetic parameters related to PER translation. Interestingly, under certain conditions, a PER translation mechanism with saturable kinetics introduces longer time delays than a mechanism ruled by a first-order kinetics. In addition, the kinetic laws of PER translation significantly changed the sensitivity of our model to parameters related to the synthesis and degradation of per mRNA and PER degradation. Lastly, we found a set of parameters, with realistic values, for which our model reproduces some experimental results reported recently for Drosophila melanogaster and we present some predictions derived from our analysis.

Thermodynamics and simulation of hard-sphere fluid and solid: Kinetic Monte Carlo method versus standard Metropolis scheme

NASA Astrophysics Data System (ADS)

Ustinov, E. A.

2017-01-01

The paper aims at a comparison of techniques based on the kinetic Monte Carlo (kMC) and the conventional Metropolis Monte Carlo (MC) methods as applied to the hard-sphere (HS) fluid and solid. In the case of the kMC, an alternative representation of the chemical potential is explored [E. A. Ustinov and D. D. Do, J. Colloid Interface Sci. 366, 216 (2012)], which does not require any external procedure like the Widom test particle insertion method. A direct evaluation of the chemical potential of the fluid and solid without thermodynamic integration is achieved by molecular simulation in an elongated box with an external potential imposed on the system in order to reduce the particle density in the vicinity of the box ends. The existence of rarefied zones allows one to determine the chemical potential of the crystalline phase and substantially increases its accuracy for the disordered dense phase in the central zone of the simulation box. This method is applicable to both the Metropolis MC and the kMC, but in the latter case, the chemical potential is determined with higher accuracy at the same conditions and the number of MC steps. Thermodynamic functions of the disordered fluid and crystalline face-centered cubic (FCC) phase for the hard-sphere system have been evaluated with the kinetic MC and the standard MC coupled with the Widom procedure over a wide range of density. The melting transition parameters have been determined by the point of intersection of the pressure-chemical potential curves for the disordered HS fluid and FCC crystal using the Gibbs-Duhem equation as a constraint. A detailed thermodynamic analysis of the hard-sphere fluid has provided a rigorous verification of the approach, which can be extended to more complex systems.

A photochemical kinetic model for solid dosage forms.

PubMed

Carvalho, Thiago C; La Cruz, Thomas E; Tábora, Jose E

2017-11-01

Photochemical kinetic models to describe the solution phase degradation of pharmaceutical compounds have been extensively reported, but formalisms applicable to the solid phase under polychromatic light have not received as much attention. The objective of this study was to develop a mathematical model to describe the solid state photodegradation of pharmaceutical powder materials under different area/volumetric scales and light exposure conditions. The model considered the previous formalism presented for photodegradation kinetics in solution phase with important elements applied to static powder material being irradiated with a polychromatic light source. The model also included the influence of optical phenomena (i.e. reflectance, scattering factors, etc.) by applying Beer-Lambert law to light attenuation, including effects of powder density. Drug substance and drug product intermediates (blends and tablet cores) were exposed to different light sources and intensities. The model reasonably predicted the photodegradation levels of powder beds of drug substance and drug product intermediates under white and yellow lights with intensities around 5-11kLux. Importantly, the model estimates demonstrated that the reciprocity law for photoreactions was held. Further model evaluation showed that, due to light attenuation, the powder bed is in virtual darkness at cake depths greater than 500μm. At 100μm, the photodegradation of the investigated compound is expected to be close to 100% in 10days under white fluorescent halophosphate light at 9.5kLux. For tablets, defining the volume over exposed surface area ratio is more challenging. Nevertheless, the model can consider a bracket between worst and best cases to provide a reasonable photodegradation estimate. This tool can be significantly leveraged to simulate different light exposure scenarios while assessing photostability risk in order to define appropriate control strategy in manufacturing. Copyright © 2017 Elsevier B.V. All rights reserved.

Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure

NASA Astrophysics Data System (ADS)

Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

2018-05-01

Tin niobate photocatalysts with the phase structures of froodite (SnNb2O6) and pyrochlore (Sn2Nb2O7) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb2O6 to Sn2Nb2O7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn4+ species in Sn2Nb2O7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb2O6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H2 evolution compared with the sample of Sn2Nb2O7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O2 -•, and OH• active species dominate the photodegradation of methyl orange.

Steering Charge Kinetics of Tin Niobate Photocatalysts: Key Roles of Phase Structure and Electronic Structure.

PubMed

Huang, Shushu; Wang, Chunyan; Sun, Hao; Wang, Xiaojing; Su, Yiguo

2018-05-23

Tin niobate photocatalysts with the phase structures of froodite (SnNb 2 O 6 ) and pyrochlore (Sn 2 Nb 2 O 7 ) were obtained by a facile solvothermal method in order to explore the impact of phase structure and electronic structure on the charge kinetics and photocatalytic performance. By employing tin niobate as a model compound, the effects of phase structure over electronic structure, photocatalytic activity toward methyl orange solution and hydrogen evolution were systematically investigated. It is found that the variation of phase structure from SnNb 2 O 6 to Sn 2 Nb 2 O 7 accompanied with modulation of particle size and band edge potentials that has great consequences on photocatalytic performance. In combination with the electrochemical impedance spectroscopy (EIS), transient photocurrent responses, transient absorption spectroscopy (TAS), and the analysis of the charge-carrier dynamics suggested that variation of electronic structure has great impacts on the charge separation and transfer rate of tin niobate photocatalysts and the subsequent photocatalytic performance. Moreover, the results of the X-ray photoelectron spectroscopy (XPS) indicated that the existent of Sn 4+ species in Sn 2 Nb 2 O 7 could result in a decrease in photocatalytic activity. Photocatalytic test demonstrated that the SnNb 2 O 6 (froodite) catalyst possesses a higher photocatalytic activity toward MO degradation and H 2 evolution compared with the sample of Sn 2 Nb 2 O 7 (pyrochlore). On the basis of spin resonance measurement and trapping experiment, it is expected that photogenerated holes, O 2 -• , and OH • active species dominate the photodegradation of methyl orange.

Confined Pattern-Directed Assembly of Polymer-Grafted Nanoparticles in a Phase Separating Blend with a Homopolymer Matrix.

PubMed

Zhang, Ren; Lee, Bongjoon; Bockstaller, Michael R; Douglas, Jack F; Stafford, Christopher M; Kumar, Sanat K; Raghavan, Dharmaraj; Karim, Alamgir

The controlled organization of nanoparticle (NP) constituents into superstructures of well-defined shape, composition and connectivity represents a continuing challenge in the development of novel hybrid materials for many technological applications. We show that the phase separation of polymer-tethered nanoparticles immersed in a chemically different polymer matrix provides an effective and scalable method for fabricating defined submicron-sized amorphous NP domains in melt polymer thin films. We investigate this phenomenon with a view towards understanding and controlling the phase separation process through directed nanoparticle assembly. In particular, we consider isothermally annealed thin films of polystyrene-grafted gold nanoparticles (AuPS) dispersed in a poly(methyl methacrylate) (PMMA) matrix. Classic binary polymer blend phase separation related morphology transitions, from discrete AuPS domains to bicontinuous to inverse domain structure with increasing nanoparticle composition is observed, yet the kinetics of the AuPS/PMMA polymer blends system exhibit unique features compared to the parent PS/PMMA homopolymer blend. We further illustrate how to pattern-align the phase-separated AuPS nanoparticle domain shape, size and location through the imposition of a simple and novel external symmetry-breaking perturbation via soft-lithography. Specifically, submicron-sized topographically patterned elastomer confinement is introduced to direct the nanoparticles into kinetically controlled long-range ordered domains, having a dense yet well-dispersed distribution of non-crystallizing nanoparticles. The simplicity, versatility and roll-to-roll adaptability of this novel method for controlled nanoparticle assembly should make it useful in creating desirable patterned nanoparticle domains for a variety of functional materials and applications.

Theoretical Assessment on the Phase Transformation Kinetic Pathways of Multi-component Ti Alloys: Application to Ti-6Al- 4V

DOE PAGES

Ji, Yanzhou; Heo, Tae Wook; Zhang, Fan; ...

2015-12-21

Here we present our theoretical assessment of the kinetic pathways during phase transformations of multi-component Ti alloys. Employing the graphical thermodynamic approach and an integrated free energy function based on the realistic thermodynamic database and assuming that a displacive structural transformation occurs much faster than long-range diffusional processes, we analyze the phase stabilities of Ti-6Al -4V (Ti-6wt.%Al -4wt.%V). Our systematic analyses predict a variety of possible kinetic pathways for β to (α + β) transformations leading to different types of microstructures under various heat treatment conditions. In addition, the possibility of unconventional kinetic pathways is discussed. Lastly, we also brieflymore » discuss the application of our approach to general multicomponent/multiphase alloy systems.« less

Aspects of reheating in first-order inflation

NASA Technical Reports Server (NTRS)

Watkins, Richard; Widrow, Lawrence M.

1991-01-01

Studied here is reheating in theories where inflation is completed by a first-order phase transition. In the scenarios, the Universe decays from its false vacuum state by bubble nucleation. In the first stage of reheating, vacuum energy is converted into kinetic energy for the bubble walls. To help understand this phase, researchers derive a simple expression for the equation of state of a universe filled with expanding bubbles. Eventually, the bubble walls collide. Researchers present numerical simulations of two-bubble collisions clarifying and extending previous work by Hawking, Moss, and Stewart. The researchers' results indicate that wall energy is efficiently converted into coherent scalar waves. Also discussed is particle production due to quantum effects. These effects lead to the decay of the coherent scalar waves. They also lead to direct particle production during bubble-wall collisions. Researchers calculate particle production for colliding walls in both sine-Gordon and theta (4) theories and show that it is far more efficient in the theta (4) case. The relevance of this work for recently proposed models of first order inflation is discussed.

Fragility of Liquids, Polyamorphism, Nucleation, and Folding Directions, in the Landscape Paradigm

NASA Astrophysics Data System (ADS)

Angell, C. A.

1998-03-01

Combination of the observations that cold glasses are rigid over eons, warm glasses (near their glass transitions) can densify, and most cooling liquids would, by extrapolation of observed entropy-temperature functions, achieve negative entropies well above OK if not salvaged by kinetics leads to the notion that substances which cannot find deep energy minima by 3 dimensional ordering of their particles must ``live" on a landscape of innumerable closely spaced and interconnected energy ``basins of probability" , the configuration space of amorphous substances. This energy hypersurface, which current studies suggest has a comparable multiplicity per heavy-atom particle regardless of how the particles are connected, provides the source of both excess liquid entropy and low temperature glass rigidity. If the energy distribution is narrow, the total entropy can be excited over a narrow temperature interval above T_g. The liquid then exhibits a high excess heat capacity and, directionally bonded cases aside, so called ``fragile" kinetic characteristics. A dynamic crossover to a liquid with different behavior occurs when the landscape entropy is almost fully excited. In extreme (highly cooperative) cases the crossover can occur via a first order transition in which much of the landscape entropy is excited isothermally. While this is rare in liquids, and in any case is difficult to observe because of promoted crystallization, it is quite common in mesoscopic systems which lack ordered packing possibilities but do have low energy amorphous configurations available. This is the case with proteins which often have ``all or nothing" transitions between folded and unfolded states, and behave like ``glassy" systems in their native (folded) states. Since phase transitions in many particle systems require nucleation, the identification of the nucleation step and its kinetic distinction from overall folding kinetics should be an important part of the understanding of the protein folding problem. The possibility exists that in certain cases an aberrant step in the nucleation event, facilitated by mutant nucleotide sequences or by third agents (heterogeneous nucleating agents), will trigger folding down an alternative and pathogenic route to a second stable state. This possibility should be evaluated, using nucleation kinetics analysis techniques, as an approach to understanding the initiation of ``mad cow" disease cerebral pathology.

Visual evaluation of kinetic characteristics of PET probe for neuroreceptors using a two-phase graphic plot analysis.

PubMed

Ito, Hiroshi; Ikoma, Yoko; Seki, Chie; Kimura, Yasuyuki; Kawaguchi, Hiroshi; Takuwa, Hiroyuki; Ichise, Masanori; Suhara, Tetsuya; Kanno, Iwao

2017-05-01

Objectives In PET studies for neuroreceptors, tracer kinetics are described by the two-tissue compartment model (2-TCM), and binding parameters, including the total distribution volume (V T ), non-displaceable distribution volume (V ND ), and binding potential (BP ND ), can be determined from model parameters estimated by kinetic analysis. The stability of binding parameter estimates depends on the kinetic characteristics of radioligands. To describe these kinetic characteristics, we previously developed a two-phase graphic plot analysis in which V ND and V T can be estimated from the x-intercept of regression lines for early and delayed phases, respectively. In this study, we applied this graphic plot analysis to visual evaluation of the kinetic characteristics of radioligands for neuroreceptors, and investigated a relationship between the shape of these graphic plots and the stability of binding parameters estimated by the kinetic analysis with 2-TCM in simulated brain tissue time-activity curves (TACs) with various binding parameters. Methods 90-min TACs were generated with the arterial input function and assumed kinetic parameters according to 2-TCM. Graphic plot analysis was applied to these simulated TACs, and the curvature of the plot for each TAC was evaluated visually. TACs with several noise levels were also generated with various kinetic parameters, and the bias and variation of binding parameters estimated by kinetic analysis were calculated in each TAC. These bias and variation were compared with the shape of graphic plots. Results The graphic plots showed larger curvature for TACs with higher specific binding and slower dissociation of specific binding. The quartile deviations of V ND and BP ND determined by kinetic analysis were smaller for radioligands with slow dissociation. Conclusions The larger curvature of graphic plots for radioligands with slow dissociation might indicate a stable determination of V ND and BP ND by kinetic analysis. For investigation of the kinetics of radioligands, such kinetic characteristics should be considered.

Methylene blue adsorption by algal biomass based materials: biosorbents characterization and process behaviour.

PubMed

Vilar, Vítor J P; Botelho, Cidália M S; Boaventura, Rui A R

2007-08-17

Dead algal biomass is a natural material that serves as a basis for developing a new family of sorbent materials potentially suitable for many industrial applications. In this work an algal industrial waste from agar extraction process, algae Gelidium and a composite material obtained by immobilization of the algal waste with polyacrylonitrile (PAN) were physical characterized and used as biosorbents for dyes removal using methylene blue as model. The apparent and real densities and the porosity of biosorbents particles were determined by mercury porosimetry and helium picnometry. The methylene blue adsorption in the liquid phase was the method chosen to calculate the specific surface area of biosorbent particles as it seems to reproduce better the surface area accessible to metal ions in the biosorption process than the N2 adsorption-desorption dry method. The porous texture of the biosorbents particles was also studied. Equilibrium isotherms are well described by the Langmuir equation, giving maximum uptake capacities of 171, 104 and 74 mg g(-1), respectively for algae, algal waste and composite material. Kinetic experiments at different initial methylene blue concentrations were performed to evaluate the equilibrium time and the importance of the driving force to overcome mass transfer resistances. The pseudo-first-order and pseudo-second-order kinetic models adequately describe the kinetic data. The biosorbents used in this work proved to be promising materials for removing methylene blue from aqueous solutions.

Kinetics of silicide formation over a wide range of heating rates spanning six orders of magnitude

DOE Office of Scientific and Technical Information (OSTI.GOV)

Molina-Ruiz, Manel; Lopeandía, Aitor F.; Gonzalez-Silveira, Marta

Kinetic processes involving intermediate phase formation are often assumed to follow an Arrhenius temperature dependence. This behavior is usually inferred from limited data over narrow temperature intervals, where the exponential dependence is generally fully satisfied. However, direct evidence over wide temperature intervals is experimentally challenging and data are scarce. Here, we report a study of silicide formation between a 12 nm film of palladium and 15 nm of amorphous silicon in a wide range of heating rates, spanning six orders of magnitude, from 0.1 to 10{sup 5 }K/s, or equivalently more than 300 K of variation in reaction temperature. The calorimetric traces exhibit severalmore » distinct exothermic events related to interdiffusion, nucleation of Pd{sub 2}Si, crystallization of amorphous silicon, and vertical growth of Pd{sub 2}Si. Interestingly, the thickness of the initial nucleation layer depends on the heating rate revealing enhanced mass diffusion at the fastest heating rates during the initial stages of the reaction. In spite of this, the formation of the silicide strictly follows an Arrhenius temperature dependence over the whole temperature interval explored. A kinetic model is used to fit the calorimetric data over the complete heating rate range. Calorimetry is complemented by structural analysis through transmission electron microscopy and both standard and in-situ synchrotron X-ray diffraction.« less

Role of valence electrons in phase transformation kinetics of thallium and its dilute alloys

NASA Technical Reports Server (NTRS)

Ahmed, R.; Ahmed, S.

1991-01-01

The kinetics of the phase transformation of thallium and its dilute alloys were investigated using XRD and calorimetry. Pure thallium exhibits a beta(bcc) to alpha(hcp) phase transformation on cooling at 508 K. With alloying additions, the crystal structure for each phase does not change, although the size of the unit cell increases. The enthalpy and the temperature of phase transformation of each alloy have been determined. The chemical free energy change associated with the phase transformation of each alloy was calculated. The valence electrons make an outstanding contribution to the chemical free energy change required for the phase change.

Tricritical points in a Vicsek model of self-propelled particles with bounded confidence

NASA Astrophysics Data System (ADS)

Romensky, Maksym; Lobaskin, Vladimir; Ihle, Thomas

2014-12-01

We study the orientational ordering in systems of self-propelled particles with selective interactions. To introduce the selectivity we augment the standard Vicsek model with a bounded-confidence collision rule: a given particle only aligns to neighbors who have directions quite similar to its own. Neighbors whose directions deviate more than a fixed restriction angle α are ignored. The collective dynamics of this system is studied by agent-based simulations and kinetic mean-field theory. We demonstrate that the reduction of the restriction angle leads to a critical noise amplitude decreasing monotonically with that angle, turning into a power law with exponent 3/2 for small angles. Moreover, for small system sizes we show that upon decreasing the restriction angle, the kind of the transition to polar collective motion changes from continuous to discontinuous. Thus, an apparent tricritical point with different scaling laws is identified and calculated analytically. We investigate the shifting and vanishing of this point due to the formation of density bands as the system size is increased. Agent-based simulations in small systems with large particle velocities show excellent agreement with the kinetic theory predictions. We also find that at very small interaction angles, the polar ordered phase becomes unstable with respect to the apolar phase. We derive analytical expressions for the dependence of the threshold noise on the restriction angle. We show that the mean-field kinetic theory also permits stationary nematic states below a restriction angle of 0.681 π . We calculate the critical noise, at which the disordered state bifurcates to a nematic state, and find that it is always smaller than the threshold noise for the transition from disorder to polar order. The disordered-nematic transition features two tricritical points: At low and high restriction angle, the transition is discontinuous but continuous at intermediate α . We generalize our results to systems that show fragmentation into more than two groups and obtain scaling laws for the transition lines and the corresponding tricritical points. A numerical method to evaluate the nonlinear Fredholm integral equation for the stationary distribution function is also presented. This method is shown to give excellent agreement with agent-based simulations, even in strongly ordered systems at noise values close to zero.

Topological superconductivity in the extended Kitaev-Heisenberg model

NASA Astrophysics Data System (ADS)

Schmidt, Johann; Scherer, Daniel D.; Black-Schaffer, Annica M.

2018-01-01

We study superconducting pairing in the doped Kitaev-Heisenberg model by taking into account the recently proposed symmetric off-diagonal exchange Γ . By performing a mean-field analysis, we classify all possible superconducting phases in terms of symmetry, explicitly taking into account effects of spin-orbit coupling. Solving the resulting gap equations self-consistently, we map out a phase diagram that involves several topologically nontrivial states. For Γ <0 , we find a competition between a time-reversal symmetry-breaking chiral phase with Chern number ±1 and a time-reversal symmetric nematic phase that breaks the rotational symmetry of the lattice. On the other hand, for Γ ≥0 we find a time-reversal symmetric phase that preserves all the lattice symmetries, thus yielding clearly distinguishable experimental signatures for all superconducting phases. Both of the time-reversal symmetric phases display a transition to a Z2 nontrivial phase at high doping levels. Finally, we also include a symmetry-allowed spin-orbit coupling kinetic energy and show that it destroys a tentative symmetry-protected topological order at lower doping levels. However, it can be used to tune the time-reversal symmetric phases into a Z2 nontrivial phase even at lower doping.

Core–shell PdPb@Pd aerogels with multiply-twinned intermetallic nanostructures: facile synthesis with accelerated gelation kinetics and their enhanced electrocatalytic properties

DOE PAGES

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang; ...

2018-04-04

Delicately engineering well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported a one-pot and facile method for synthesizing core–shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and an ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and the specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 h. As a result, owing to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performance towardsmore » ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.« less

Kinetics and Mechanism of Bioactivation via S-Oxygenation of Anti-Tubercular Agent Ethionamide by Peracetic Acid.

PubMed

Chipiso, Kudzanai; Logan, Isabelle E; Eskew, Matthew W; Omondi, Benard; Simoyi, Reuben H

2016-10-11

The kinetics and mechanism of the oxidation of the important antitubercular agent, ethionamide, ETA (2-ethylthioisonicotinamide), by peracetic acid (PAA) have been studied. It is effectively a biphasic reaction with an initial rapid first phase of the reaction which is over in about 5 s and a second slower phase of the reaction which can run up to an hour. The first phase involves the addition of a single oxygen atom to ethionamide to form the S-oxide. The second phase involves further oxidation of the S-oxide to desulfurization of ETA to give 2-ethylisonicotinamide. In contrast to the stability of most organosulfur compounds, the S-oxide of ETA is relatively stable and can be isolated. In conditions of excess ETA, the stoichiometry of the reaction was strictly 1:1: CH 3 CO 3 H + Et(C 5 H 4 )C(═S)NH 2 → CH 3 CO 2 H + Et(C 5 H 4 )C(═NH)SOH. In this oxidation, it was apparent that only the sulfur center was the reactive site. Though ETA was ultimately desulfurized, only the S-oxide was stable. Electrospray ionization (ESI) spectral analysis did not detect any substantial formation of the sulfinic and sulfonic acids. This suggests that cleavage of the carbon-sulfur bond occurs at the sulfenic acid stage, resulting in the formation of an unstable sulfur species that can react further to form more stable sulfur species. In this oxidation, no sulfate formation was observed. ESI spectral analysis data showed a final sulfur species in the form of a dimeric sulfur monoxide species, H 3 S 2 O 2 . We derived a bimolecular rate constant for the formation of the S-oxide of (3.08 ± 0.72) × 10 2 M -1 s -1 . Oxidation of the S-oxide further to give 2-ethylisonicotinamide gave zero order kinetics.

Hydration kinetics of cementitious materials composed of red mud and coal gangue

NASA Astrophysics Data System (ADS)

Zhang, Na; Li, Hong-xu; Liu, Xiao-ming

2016-10-01

To elucidate the intrinsic reaction mechanism of cementitious materials composed of red mud and coal gangue (RGC), the hydration kinetics of these cementitious materials at 20°C was investigated on the basis of the Krstulović-Dabić model. An isothermal calorimeter was used to characterize the hydration heat evolution. The results show that the hydration of RGC is controlled by the processes of nucleation and crystal growth (NG), interaction at phase boundaries (I), and diffusion (D) in order, and the pozzolanic reactions of slag and compound-activated red mud-coal gangue are mainly controlled by the I process. Slag accelerates the clinker hydration during NG process, whereas the compound-activated red mud-coal gangue retards the hydration of RGC and the time required for I process increases with increasing dosage of red mud-coal gangue in RGC.

Core–shell PdPb@Pd aerogels with multiply-twinned intermetallic nanostructures: facile synthesis with accelerated gelation kinetics and their enhanced electrocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang

Delicately engineering well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported a one-pot and facile method for synthesizing core–shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and an ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and the specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 h. As a result, owing to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performance towardsmore » ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.« less

Kinetics and Mechanism of in situ Simultaneous Formation of Metal Nanoparticles in Stabilizing Polymer Matrix

NASA Astrophysics Data System (ADS)

Pomogailo, Anatolii D.; Dzhardimalieva, Gulzhian I.; Rozenberg, Aleksander S.; Muraviev, Dmitri N.

2003-12-01

The kinetic peculiarities of the thermal transformations of unsaturated metal carboxylates (transition metal acrylates and maleates as well as their cocrystallites) and properties of metal-polymer nanocomposites formed have been studied. The composition and structure of metal-containing precursors and the products of the thermolysis were identified by X-ray analysis, optical and electron microscopy, magnetic measurements, EXAFS, IR and mass spectroscopy. The thermal transformations of metal-containing monomers studied are the complex process including dehydration, solid phase polymerization, and thermolysis process which proceed at varied temperature ranges. At 200-300°C the rate of thermal decay can be described by first-order equations. The products of decompositions are nanometer-sized particles of metal or its oxides with a narrow size distribution (the mean particle diameter of 5-10nm) stabilized by the polymer matrix.

Observation of glassy state relaxation during annealing of frozen sugar solutions by X-ray computed tomography.

PubMed

Nakagawa, Kyuya; Tamiya, Shinri; Do, Gabsoo; Kono, Shinji; Ochiai, Takaaki

2018-06-01

Glassy phase formation in a frozen product determines various properties of the freeze-dried products. When an aqueous solution is subjected to freezing, a glassy phase forms as a consequence of freeze-concentration. During post-freezing annealing, the relaxation of the glassy phase and the ripening of ice crystals (i.e. Ostwald ripening) spontaneously occur, where the kinetics are controlled by the annealing and glass transition temperatures. This study was motivated to observe the progress of glassy state relaxation separate from ice coarsening during annealing. X-ray computed tomography (CT) was used to observe a frozen and post-freezing annealed solutions by using monochromatized X-ray from the synchrotron radiation. CT images were successfully obtained, and the frozen matrix were analyzed based on the gray level values that were equivalent to the linear X-ray attenuation coefficients of the observed matters. The CT images obtained from rapidly frozen sucrose and dextrin solutions with different concentrations gave clear linear relationships between the linear X-ray attenuation coefficients values and the solute concentrations. It was confirmed that the glassy state relaxation progressed as increasing annealing time, and this trend was larger in the order of the glass transition temperature of the maximally freeze-concentrated phase. The sucrose-water system required nearly 20 h of annealing time at -5 °C for the completion of the glassy phase relaxation, whereas dextrin-water systems required much longer periods because of their higher glass transition temperatures. The trends of ice coarsening, however, did not perfectly correspond to the trends of the relaxation, suggesting that the glassy phase relaxation and Ostwald ripening would jointly control the ice crystal growth/ripening kinetics, and the dominant mechanism differed by the annealing stage. Copyright © 2018 Elsevier B.V. All rights reserved.

Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space.

PubMed

Clements, Aspen R; Berk, Brandon; Cooke, Ilsa R; Garrod, Robin T

2018-02-21

Dust grains in cold, dense interstellar clouds build up appreciable ice mantles through the accretion and subsequent surface chemistry of atoms and molecules from the gas. These mantles, of thicknesses on the order of 100 monolayers, are primarily composed of H 2 O, CO, and CO 2 . Laboratory experiments using interstellar ice analogues have shown that porosity could be present and can facilitate diffusion of molecules along the inner pore surfaces. However, the movement of molecules within and upon the ice is poorly described by current chemical kinetics models, making it difficult either to reproduce the formation of experimental porous ice structures or to extrapolate generalized laboratory results to interstellar conditions. Here we use the off-lattice Monte Carlo kinetics model MIMICK to investigate the effects that various deposition parameters have on laboratory ice structures. The model treats molecules as isotropic spheres of a uniform size, using a Lennard-Jones potential. We reproduce experimental trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature; ice density decreases when the incident angle or deposition rate is increased, while increasing temperature results in a more-compact water ice. The models indicate that the density behaviour at higher temperatures (≥80 K) is dependent on molecular rearrangement resulting from thermal diffusion. To reproduce trends at lower temperatures, it is necessary to take account of non-thermal diffusion by newly-adsorbed molecules, which bring kinetic energy both from the gas phase and from their acceleration into a surface binding site. Extrapolation of the model to conditions appropriate to protoplanetary disks, in which direct accretion of water from the gas-phase may be the dominant ice formation mechanism, indicate that these ices may be less porous than laboratory ices.

Kinematic and kinetic comparisons between American and Korean professional baseball pitchers.

PubMed

Escamilla, Rafael; Fleisig, Glen; Barrentine, Steven; Andrews, James; Moorman, Claude

2002-07-01

The purpose of this study was to quantify and compare kinematic, temporal, and kinetic characteristics of American and Korean professional pitchers in order to investigate differences in pitching mechanics, performance, and injury risks among two different cultures and populations of baseball pitchers. Eleven American and eight Korean healthy professional baseball pitchers threw multiple fastball pitches off an indoor throwing mound positioned at regulation distance from home plate. A Motion Analysis three-dimensional automatic digitizing system was used to collect 200 Hz video data from four electronically synchronized cameras. Twenty kinematic, six temporal, and 11 kinetic variables were analyzed at lead foot contact, during the arm cocking and arm acceleration phases, at ball release, and during the arm deceleration phase. A radar gun was used to quantify ball velocity. At lead foot contact, the American pitchers had significantly greater horizontal abduction of the throwing shoulder, while Korean pitchers exhibited significantly greater abduction and external rotation of the throwing shoulder. During arm cocking, the American pitchers displayed significantly greater maximum shoulder external rotation and maximum pelvis angular velocity. At the instant of ball release, the American pitchers had significantly greater forward trunk tilt and ball velocity and significantly less knee flexion, which help explain why the American pitchers had 10% greater ball velocity compared to the Korean pitchers. The American pitchers had significantly greater maximum shoulder internal rotation torque and maximum elbow varus torque during arm cocking, significantly greater elbow flexion torque during arm acceleration, and significantly greater shoulder and elbow proximal forces during arm deceleration. While greater shoulder and elbow forces and torques generated in the American pitchers helped generate greater ball velocity for the American group, these greater kinetics may predispose this group to a higher risk of shoulder and elbow injuries.

Self-Assembly through Noncovalent Preorganization of Reactants: Explaining the Formation of a Polyfluoroxometalate.

PubMed

Schreiber, Roy E; Avram, Liat; Neumann, Ronny

2018-01-09

High-order elementary reactions in homogeneous solutions involving more than two molecules are statistically improbable and very slow to proceed. They are not generally considered in classical transition-state or collision theories. Yet, rather selective, high-yield product formation is common in self-assembly processes that require many reaction steps. On the basis of recent observations of crystallization as well as reactions in dense phases, it is shown that self-assembly can occur by preorganization of reactants in a noncovalent supramolecular assembly, whereby directing forces can lead to an apparent one-step transformation of multiple reactants. A simple and general kinetic model for multiple reactant transformation in a dense phase that can account for many-bodied transformations was developed. Furthermore, the self-assembly of polyfluoroxometalate anion [H 2 F 6 NaW 18 O 56 ] 7- from simple tungstate Na 2 WO 2 F 4 was demonstrated by using 2D 19 F- 19 F NOESY, 2D 19 F- 19 F COSY NMR spectroscopy, a new 2D 19 F{ 183 W} NMR technique, as well as ESI-MS and diffusion NMR spectroscopy, and the crucial involvement of a supramolecular assembly was found. The deterministic kinetic reaction model explains the reaction in a dense phase and supports the suggested self-assembly mechanism. Reactions in dense phases may be of general importance in understanding other self-assembly reactions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Treatment of cyanide wastewater by bulk liquid membrane using tricaprylamine as a carrier.

PubMed

Li, Guoping; Xue, Juanqin; Liu, Nina; Yu, Lihua

2016-01-01

The transport of cyanide from wastewater through a bulk liquid membrane (BLM) containing tricaprylamine (TOA) as a carrier was studied. The effect of cyanide concentration in the feed solution, TOA concentration in the organic phase, the stirring speed, NaOH concentration in the stripping solution and temperature on cyanide transport was determined through BLM. Mass transfer of cyanide through BLM was analyzed by following the kinetic laws of two consecutive irreversible first-order reactions, and the kinetic parameters (k(1), k(2), R(m)(max), t(max), J(a)(max), J(d)(max)) were also calculated. Apparently, increase in membrane entrance (k(1)) and exit rate (k(2)) constants was accompanied by a rise in temperature. The values of activation energies were obtained as 35.6 kJ/mol and 18.2 kJ/mol for removal and recovery, respectively. These values showed that both removal and recovery steps in cyanide transport is controlled by the rate of the chemical complexation reaction. The optimal reaction conditions were determined by BLM using trioctylamine as the carrier: feed phase: pH 4, carrier TOA possession ratio in organic phase: 2% (V/V), stripping phase concentration of NaOH: 1% (W/V), reaction time: 60 min, stirring speed: 250 r/min. Under the above conditions, the removal rate was up to 92.96%. The experiments demonstrated that TOA was a good carrier for cyanide transport through BLM in this study.

Self-assembly of amorphous biophotonic nanostructures by phase separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dufresne, Eric R.; Noh, Heeso; Saranathan, Vinodkumar

2009-04-23

Some of the most vivid colors in the animal kingdom are created not by pigments, but by wavelength-selective scattering of light from nanostructures. Here we investigate quasi-ordered nanostructures of avian feather barbs which produce vivid non-iridescent colors. These {beta}-keratin and air nanostructures are found in two basic morphologies: tortuous channels and amorphous packings of spheres. Each class of nanostructure is isotropic and has a pronounced characteristic length scale of variation in composition. These local structural correlations lead to strong backscattering over a narrow range of optical frequencies and little variation with angle of incidence. Such optical properties play important rolesmore » in social and sexual communication. To be effective, birds need to precisely control the development of these nanoscale structures, yet little is known about how they grow. We hypothesize that multiple lineages of birds have convergently evolved to exploit phase separation and kinetic arrest to self-assemble spongy color-producing nanostructures in feather barbs. Observed avian nanostructures are strikingly similar to those self-assembled during the phase separation of fluid mixtures; the channel and sphere morphologies are characteristic of phase separation by spinodal decomposition and nucleation and growth, respectively. These unstable structures are locked-in by the kinetic arrest of the {beta}-keratin matrix, likely through the entanglement or cross-linking of supermolecular {beta}-keratin fibers. Using the power of self-assembly, birds can robustly realize a diverse range of nanoscopic morphologies with relatively small physical and chemical changes during feather development.« less

On Localized Vapor Pressure Gradients Governing Condensation and Frost Phenomena.

PubMed

Nath, Saurabh; Boreyko, Jonathan B

2016-08-23

Interdroplet vapor pressure gradients are the driving mechanism for several phase-change phenomena such as condensation dry zones, interdroplet ice bridging, dry zones around ice, and frost halos. Despite the fundamental nature of the underlying pressure gradients, the majority of studies on these emerging phenomena have been primarily empirical. Using classical nucleation theory and Becker-Döring embryo formation kinetics, here we calculate the pressure field for all possible modes of condensation and desublimation in order to gain fundamental insight into how pressure gradients govern the behavior of dry zones, condensation frosting, and frost halos. Our findings reveal that in a variety of phase-change systems the thermodynamically favorable mode of nucleation can switch between condensation and desublimation depending upon the temperature and wettability of the surface. The calculated pressure field is used to model the length of a dry zone around liquid or ice droplets over a broad parameter space. The long-standing question of whether the vapor pressure at the interface of growing frost is saturated or supersaturated is resolved by considering the kinetics of interdroplet ice bridging. Finally, on the basis of theoretical calculations, we propose that there exists a new mode of frost halo that is yet to be experimentally observed; a bimodal phase map is developed, demonstrating its dependence on the temperature and wettability of the underlying substrate. We hope that the model and predictions contained herein will assist future efforts to exploit localized vapor pressure gradients for the design of spatially controlled or antifrosting phase-change systems.

Coherent and incoherent phase stabilities of thermoelectric rocksalt IV-VI semiconductor alloys

NASA Astrophysics Data System (ADS)

Doak, Jeff W.; Wolverton, C.

2012-10-01

Nanostructures formed by phase separation improve the thermoelectric figure of merit in lead chalcogenide semiconductor alloys, with coherent nanostructures giving larger improvements than incoherent nanostructures. However, large coherency strains in these alloys drastically alter the thermodynamics of phase stability. Incoherent phase stability can be easily inferred from an equilibrium phase diagram, but coherent phase stability is more difficult to assess experimentally. Therefore, we use density functional theory calculations to investigate the coherent and incoherent phase stability of the IV-VI rocksalt semiconductor alloy systems Pb(S,Te), Pb(Te,Se), Pb(Se,S), (Pb,Sn)Te, (Sn,Ge)Te, and (Ge,Pb)Te. Here we use the term coherent to indicate that there is a common and unbroken lattice between the phases under consideration, and we use the term incoherent to indicate that the lattices of coexisting phases are unconstrained and allowed to take on equilibrium volumes. We find that the thermodynamic ground state of all of the IV-VI pseudobinary systems studied is incoherent phase separation. We also find that the coherency strain energy, previously neglected in studies of these IV-VI alloys, is lowest along [111] (in contrast to most fcc metals) and is a large fraction of the thermodynamic driving force for incoherent phase separation in all systems. The driving force for coherent phase separation is significantly reduced, and we find that coherent nanostructures can only form at low temperatures where kinetics may prohibit their precipitation. Furthermore, by calculating the energies of ordered structures for these systems we find that the coherent phase stability of most IV-VI systems favors ordering over spinodal decomposition. Our results suggest that experimental reports of spinodal decomposition in the IV-VI rocksalt alloys should be re-examined.

Revisiting the ground state of CoAl 2 O 4 : Comparison to the conventional antiferromagnet MnAl 2 O 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

MacDougall, Gregory J.; Aczel, Adam A.; Su, Yixi

The A-site spinel material CoAl 2O 4 is a physical realization of the frustrated diamond-lattice antiferromagnet, a model in which unique incommensurate or “spin-spiral-liquid” ground states are predicted. Our previous single-crystal neutron scattering study instead classified it as a “kinetically inhibited” antiferromagnet, where the long-ranged correlations of a collinear Néel ground state are blocked by the freezing of domain-wall motion below a first-order phase transition at T*=6.5 K. This study provides new data sets from a number of experiments, which support and expand this work in several important ways. We show that the phenomenology leading to the kinetically inhibited ordermore » is unaffected by sample measured and instrument resolution, while new low-temperature measurements reveal spin correlations are unchanging between T=2 K and 250 mK, consistent with a frozen state. Polarized diffuse neutron measurements show several interesting magnetic features, which can be entirely explained by the existence of short-ranged Néel order. Finally, and crucially, this paper presents some neutron scattering studies of single crystalline MnAl 2O 4, which acts as an unfrustrated analog to CoAl 2O 4 and shows all the hallmarks of a classical antiferromagnet with a continuous phase transition to Néel order at T N=39 K. Direct comparison between the two compounds indicates that CoAl 2O 4 is unique, not in the nature of high-temperature diffuse correlations, but rather in the nature of the frozen state below T*. Finally, the higher level of cation inversion in the MnAl 2O 4 sample indicates that this behavior is primarily an effect of greater next-nearest-neighbor exchange.« less

Revisiting the ground state of CoAl 2 O 4 : Comparison to the conventional antiferromagnet MnAl 2 O 4

DOE PAGES

MacDougall, Gregory J.; Aczel, Adam A.; Su, Yixi; ...

2016-11-17

The A-site spinel material CoAl 2O 4 is a physical realization of the frustrated diamond-lattice antiferromagnet, a model in which unique incommensurate or “spin-spiral-liquid” ground states are predicted. Our previous single-crystal neutron scattering study instead classified it as a “kinetically inhibited” antiferromagnet, where the long-ranged correlations of a collinear Néel ground state are blocked by the freezing of domain-wall motion below a first-order phase transition at T*=6.5 K. This study provides new data sets from a number of experiments, which support and expand this work in several important ways. We show that the phenomenology leading to the kinetically inhibited ordermore » is unaffected by sample measured and instrument resolution, while new low-temperature measurements reveal spin correlations are unchanging between T=2 K and 250 mK, consistent with a frozen state. Polarized diffuse neutron measurements show several interesting magnetic features, which can be entirely explained by the existence of short-ranged Néel order. Finally, and crucially, this paper presents some neutron scattering studies of single crystalline MnAl 2O 4, which acts as an unfrustrated analog to CoAl 2O 4 and shows all the hallmarks of a classical antiferromagnet with a continuous phase transition to Néel order at T N=39 K. Direct comparison between the two compounds indicates that CoAl 2O 4 is unique, not in the nature of high-temperature diffuse correlations, but rather in the nature of the frozen state below T*. Finally, the higher level of cation inversion in the MnAl 2O 4 sample indicates that this behavior is primarily an effect of greater next-nearest-neighbor exchange.« less

On Riemann solvers and kinetic relations for isothermal two-phase flows with surface tension

NASA Astrophysics Data System (ADS)

Rohde, Christian; Zeiler, Christoph

2018-06-01

We consider a sharp interface approach for the inviscid isothermal dynamics of compressible two-phase flow that accounts for phase transition and surface tension effects. Kinetic relations are frequently used to fix the mass exchange and entropy dissipation rate across the interface. The complete unidirectional dynamics can then be understood by solving generalized two-phase Riemann problems. We present new well-posedness theorems for the Riemann problem and corresponding computable Riemann solvers that cover quite general equations of state, metastable input data and curvature effects. The new Riemann solver is used to validate different kinetic relations on physically relevant problems including a comparison with experimental data. Riemann solvers are building blocks for many numerical schemes that are used to track interfaces in two-phase flow. It is shown that the new Riemann solver enables reliable and efficient computations for physical situations that could not be treated before.

Kinetics of mineralization of organic compounds at low concentrations in soil.

PubMed Central

Scow, K M; Simkins, S; Alexander, M

1986-01-01

The kinetics of mineralization of 14C-labeled phenol and aniline were measured at initial concentrations ranging from 0.32 to 5,000 ng and 0.30 ng to 500 micrograms/g of soil, respectively. Mineralization of phenol at concentrations less than or equal to 32 ng/g of soil and of aniline at all concentrations began immediately, and the curves for the evolution of labeled CO2 were biphasic. The patterns of mineralization of 4.0 ng of 2,4-dichlorophenol per g of soil and 20 ng of nitrilotriacetic acid per g of soil were similar to the patterns for phenol and aniline. The patterns of mineralization of 1.0 to 100 ng of p-nitrophenol and 6.0 ng of benzylamine per g of soil were also biphasic but after a short apparent lag period. The curves of CO2 evolution from higher concentrations of phenol and p-nitrophenol had increasing apparent lag phases and were S-shaped or linear. Cumulative plots of the percentage of substrate converted to CO2 were fit by nonlinear regression to first-order, integrated Monod, logistic, logarithmic, zero-order, three-half-order, and two-compartment models. None of the models of the Monod family provided the curve of best fit to any of the patterns of mineralization. The linear growth form of the three-half-order model provided the best fit for the mineralization of p-nitrophenol, with the exception of the lowest concentrations, and of benzylamine. The two-compartment model provided the best fit for the mineralization of concentrations of phenol below 100 ng/g, of several concentrations of aniline, and of nitrilotriacetic acid. It is concluded that models derived from the Monod equation, including the first-order model, do not adequately describe the kinetics of mineralization of low concentrations of chemicals added to soil. PMID:3729388

In vitro dissolution kinetic study of theophylline from hydrophilic and hydrophobic matrices.

PubMed

Maswadeh, Hamzah M; Semreen, Mohammad H; Abdulhalim, Abdulatif A

2006-01-01

Oral dosage forms containing 300 mg theophylline in matrix type tablets, were prepared by direct compression method using two kinds of matrices, glycerylbehenate (hydrophobic), and (hydroxypropyl)methyl cellulose (hydrophilic). The in vitro release kinetics of these formulations were studied at pH 6.8 using the USP dissolution apparatus with the paddle assemble. The kinetics of the dissolution process were studied by analyzing the dissolution data using four kinetic equations, the zero-order equation, the first-order equation, the Higuchi square root equation and the Hixson-Crowell cube root law. The analysis of the dissolution kinetic data for the theophylline preparations in this study shows that it follows the first order kinetics and the release process involves erosion / diffusion and an alteration in the surface area and diameter of the matrix system, as well as in the diffusion path length from the matrix drug load during the dissolution process. This relation is best described by the use of both the first-order equation and the Hixson-Crowell cube root law.

Study on kinetics of adsorption of humic acid modified by ferric chloride on U(VI)

NASA Astrophysics Data System (ADS)

Zhang, Y. Y.; Lv, J. W.; Song, Y.; Dong, X. J.; Fang, Q.

2017-11-01

In order to reveal the adsorption mechanism of the ferric chloride modified humic acid on uranium, the influence of pH value and contact time of adsorption on uranium was studied through a series of batch experiments. Meanwhile, the adsorption kinetics was analyzed with pseudo-first order kinetic model and pseudo-second order kinetic model. The results show that adsorption is affected by the pH value of the solution and by contract time, and the best condition for adsorption on uranium is at pH=5 and the adsorption equilibrium time is about 80 min. Kinetics of HA-Fe adsorption on uranium accords with pseudo-second order kinetic model. The adsorption is mainly chemical adsorption, and complexes were produced by the reaction between uranium ions and the functional groups on the surface of HA-Fe, which can provide reference for further study of humic acid effecting on the migration of U(VI) in soil.

Formation kinetics of gemfibrozil chlorination reaction products: analysis and application.

PubMed

Krkosek, Wendy H; Peldszus, Sigrid; Huck, Peter M; Gagnon, Graham A

2014-07-01

Aqueous chlorination kinetics of the lipid regulator gemfibrozil and the formation of reaction products were investigated in deionized water over the pH range 3 to 9, and in two wastewater matrices. Chlorine oxidation of gemfibrozil was found to be highly dependent on pH. No statistically significant degradation of gemfibrozil was observed at pH values greater than 7. Gemfibrozil oxidation between pH 4 and 7 was best represented by first order kinetics. At pH 3, formation of three reaction products was observed. 4'-C1Gem was the only reaction product formed from pH 4-7 and was modeled with zero order kinetics. Chlorine oxidation of gemfibrozil in two wastewater matrices followed second order kinetics. 4'-C1Gem was only formed in wastewater with pH below 7. Deionized water rate kinetic models were applied to two wastewater effluents with gemfibrozil concentrations reported in literature in order to calculate potential mass loading rates of 4'C1Gem to the receiving water.

Structural Changes in PEO-PPO-PEO Gels Induced by Methylparaben and Dexamethasone Observed Using Time-Resolved SAXS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Meznarich, Norman A.K.; Juggernauth, K Anne; Batzli, Kiersten M

2011-11-17

Aqueous solutions of polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO) triblock copolymers (commercially available as Pluronic surfactants) micellize and structurally arrange into cubic quasicrystalline lattices as their temperature is raised. This structural evolution is seen macroscopically as a gelation, and the presence of these ordered phases can be controlled through both polymer concentration and temperature. The presence of added solutes within the dispersions can also affect the onset and kinetics of structure formation. Here we investigate the structures formed in Pluronic F127 solutions ranging from 20 to 30% with two pharmaceutical additives [methylparaben (MP) and dexamethasone (DX)] using small-angle X-ray scattering (SAXS). We observe bothmore » the progressive evolution and breakdown of these structures as the temperature is increased from 0 to 80 °C. Additionally, we conducted time-resolved SAXS measurements to elucidate the kinetics of the structural evolution. On the basis of the evolution of scattering peaks as the samples were being heated, we suggest that added MP changes the nucleation behavior of fcc phases within the sample from a heterogeneous process to a more homogeneous distribution of nucleated species. MP and DX also stabilize the micelle lattices, allowing them to persevere at higher temperatures. We observed the unusual result that the presence of DX caused the primary peaks of the structure factor to be suppressed, while preserving the higher order peaks. The primary peaks reappeared at the highest temperatures tested.« less

The crystallization and crystalline properties of LARC-TPI

NASA Technical Reports Server (NTRS)

Theil, Michael H.; Gangal, Pravin D.

1992-01-01

LARC-TPI, a thermoplastic polyimide, has been studied in order to develop an understanding of its crystalline phase transition. Our experiments suggest that samples synthesized in different laboratories apparently had different degrees of imidization and their thermal behaviors differed accordingly. When the most crystalline of these polyimides was studied in some detail, we found that it melted irreversibly in that once a sample was completely melted it would not recrystallize. A polymer that did not recrystallize displayed a glass transition, which increased in temperature upon subsequent cooling and reheating. Solubility experiments indicated that heating above the crystalline melting temperature led to network formation in the polymer, a conclusion that is consistent with other behavior just mentioned. Differential calorimetric studies revealed that annealing at slow heating rates or under isothermal conditions resulted in dual melting transitions. These studies, supported by X-ray diffraction results, strongly indicate that the annealing process involves a solid-liquid-solid transformation. From an existing phenomenological model for the kinetics of phase transitions, kinetic parameters for these crystallizations have been evaluated. The Avrami exponents n increased with the annealing temperature in the protocol used in this study. Their values were about 2 or lower, thus indicating that crystallization may have followed a mechanism that included heterogeneous nucleation of a low dimensional order in which all the embryonic crystallites formed at the beginning of the process. A positive temperature coefficient for these crystallizations indicated that diffusion may have had a rate controlling influence and affected the values of n.

Comparative evaluation of adsorption kinetics of diclofenac and isoproturon by activated carbon.

PubMed

Torrellas, Silvia A; Rodriguez, Araceli R; Escudero, Gabriel O; Martín, José María G; Rodriguez, Juan G

2015-01-01

Adsorption mechanism of diclofenac and isoproturon onto activated carbon has been proposed using Langmuir and Freundlich isotherms. Adsorption capacity and optimum adsorption isotherms were predicted by nonlinear regression method. Different kinetic equations, pseudo-first-order, pseudo-second-order, intraparticle diffusion model and Bangham kinetic model, were applied to study the adsorption kinetics of emerging contaminants on activated carbon in two aqueous matrices.

Metastable phase in binary and ternary 12-carat gold alloys at low temperature

NASA Astrophysics Data System (ADS)

Lamiri, Imene; Abdelbaky, Mohammed S. M.; Hamana, Djamel; García-Granda, Santiago

2018-04-01

Low temperature phase transitions in 12-carat gold alloys have been investigated for binary Au-Cu and ternary Au-Cu-Ag compositions. The thermal analyses investigations using differential scanning calorimetry (DSC) and the dilatometry were performed in the 50–300 °C temperature range in order to detect the structural transformations. The thermal analyses were carried out on annealed samples at 700 °C for two hour followed by water quenching. They reveal an important new reaction for both used compositions and both thermal techniques confirm each other. This reaction has been assessed as pre-ordering reaction. SEM and STM imaging were performed on annealed samples at 700 °C for two hours and water quenched followed by a heating from room temperature up to the temperature of the new peaks obtained in the thermal study. The imaging reveals the relationship between the pre-ordering reaction and the surface aspect presented in the fact of dendrite precipitates. A series of SEM observation have been performed in order to follow the kinetic of the observed precipitates by the way of several series of heating up, from 140 to 220 °C for the binary composition and from 100 to 180 °C for the ternary composition. Furthermore, this study shows that the silver accelerates the ordering reaction.

Application Of Empirical Phase Diagrams For Multidimensional Data Visualization Of High Throughput Microbatch Crystallization Experiments.

PubMed

Klijn, Marieke E; Hubbuch, Jürgen

2018-04-27

Protein phase diagrams are a tool to investigate cause and consequence of solution conditions on protein phase behavior. The effects are scored according to aggregation morphologies such as crystals or amorphous precipitates. Solution conditions affect morphological features, such as crystal size, as well as kinetic features, such as crystal growth time. Common used data visualization techniques include individual line graphs or symbols-based phase diagrams. These techniques have limitations in terms of handling large datasets, comprehensiveness or completeness. To eliminate these limitations, morphological and kinetic features obtained from crystallization images generated with high throughput microbatch experiments have been visualized with radar charts in combination with the empirical phase diagram (EPD) method. Morphological features (crystal size, shape, and number, as well as precipitate size) and kinetic features (crystal and precipitate onset and growth time) are extracted for 768 solutions with varying chicken egg white lysozyme concentration, salt type, ionic strength and pH. Image-based aggregation morphology and kinetic features were compiled into a single and easily interpretable figure, thereby showing that the EPD method can support high throughput crystallization experiments in its data amount as well as its data complexity. Copyright © 2018. Published by Elsevier Inc.

Size effects in martensitic microstructures: Finite-strain phase field model versus sharp-interface approach

NASA Astrophysics Data System (ADS)

Tůma, K.; Stupkiewicz, S.; Petryk, H.

2016-10-01

A finite-strain phase field model for martensitic phase transformation and twinning in shape memory alloys is developed and confronted with the corresponding sharp-interface approach extended to interfacial energy effects. The model is set in the energy framework so that the kinetic equations and conditions of mechanical equilibrium are fully defined by specifying the free energy and dissipation potentials. The free energy density involves the bulk and interfacial energy contributions, the latter describing the energy of diffuse interfaces in a manner typical for phase-field approaches. To ensure volume preservation during martensite reorientation at finite deformation within a diffuse interface, it is proposed to apply linear mixing of the logarithmic transformation strains. The physically different nature of phase interfaces and twin boundaries in the martensitic phase is reflected by introducing two order-parameters in a hierarchical manner, one as the reference volume fraction of austenite, and thus of the whole martensite, and the second as the volume fraction of one variant of martensite in the martensitic phase only. The microstructure evolution problem is given a variational formulation in terms of incremental fields of displacement and order parameters, with unilateral constraints on volume fractions explicitly enforced by applying the augmented Lagrangian method. As an application, size-dependent microstructures with diffuse interfaces are calculated for the cubic-to-orthorhombic transformation in a CuAlNi shape memory alloy and compared with the sharp-interface microstructures with interfacial energy effects.

Adsorption and desorption properties of macroporous resins for anthocyanins from the calyx extract of roselle (Hibiscus sabdariffa L.).

PubMed

Chang, Xiu-Lian; Wang, Dong; Chen, Bi-Yun; Feng, Yong-Mei; Wen, Shao-Hong; Zhan, Peng-Yuan

2012-03-07

Adsorption of roselle anthocynins, a natural pigment, onto various macroporous resins was optimized to develop a simple and efficient process for industrial separation and purification of roselle anthocyanins. Nine different macroporous resins (AB-8, X-5, HPD-100, SP-207, XAD-4, LS-305A, DM-21, LS-610B, and LS-305) were evaluated for the adsorption properties of the anthocyanins extracted from the calyx extract of Hibiscus sabdariffa L. The influences of phase contact time, solution pH, initial anthocyanin concentration, and ethanol concentration with different citric acid amounts were studied by the static adsorption/desorption method. The adsorption isotherm data were fitted well to the Langmuir isotherm, and according to this model, LS-610B and LS-305 exhibited the highest monolayer sorption capacities of 31.95 and 38.16 mg/g, respectively. The kinetic data were modeled using pseudo-first-order, pseudo-second-order, and intraparticle diffusion equations. The experimental data were well described by the pseudo-second-order kinetic model. Continuous column adsorption-regeneration cycles indicated negligible capacity loss of LS-305 during operation. The overall yield of pigment product was 49.6 mg/g dried calyces. The content of roselle anthocynins in the pigment product was 4.85%.

Development of a new adsorbent from agro-industrial waste and its potential use in endocrine disruptor compound removal.

PubMed

Rovani, Suzimara; Censi, Monique T; Pedrotti, Sidnei L; Lima, Eder C; Cataluña, Renato; Fernandes, Andreia N

2014-04-30

A new activated carbon (AC) material was prepared by pyrolysis of a mixture of coffee grounds, eucalyptus sawdust, calcium hydroxide and soybean oil at 800°C. This material was used as adsorbent for the removal of the endocrine disruptor compounds 17β-estradiol (E2) and 17α-ethinylestradiol (EE2) from aqueous solutions. The carbon material was characterized by scanning electron microscopy (SEM), infrared spectroscopy (FTIR), N2 adsorption/desorption curves and point of zero charge (pHPZC). Variables including the initial pH of the adsorbate solutions, adsorbent masses and contact time were optimized. The optimum range of initial pH for removal of endocrine disruptor compounds (EDC) was 2.0-11.0. The kinetics of adsorption were investigated using general order, pseudo first-order and pseudo-second order kinetic models. The Sips isotherm model gave the best fits of the equilibrium data (298K). The maximum amounts of E2 and EE2 removed at 298K were 7.584 (E2) and 7.883mgg(-1) (EE2) using the AC as adsorbent. The carbon adsorbent was employed in SPE (solid phase extraction) of E2 and EE2 from aqueous solutions. Copyright © 2014 Elsevier B.V. All rights reserved.

Size-dependent physicochemical and mechanical interactions in battery paste anodes of Si-microwires revealed by Fast-Fourier-Transform Impedance Spectroscopy

NASA Astrophysics Data System (ADS)

Hansen, Sandra; Quiroga-González, Enrique; Carstensen, Jürgen; Adelung, Rainer; Föll, Helmut

2017-05-01

Perfectly aligned silicon microwire arrays show exceptionally high cycling stability with record setting (high) areal capacities of 4.25 mAh cm-2. Those wires have a special, modified length and thickness in order to perform this good. Geometry and sizes are the most important parameters of an anode to obtain batteries with high cycling stability without irreversible losses. The wires are prepared with a unique etching fabrication method, which allows to fabricate wires of very precise sizes. In order to investigate how good randomly oriented silicon wires perform in contrast to the perfect order of the array, the wires are embedded in a paste. This study reveals the fundamental correlation between geometry, mechanics and charge transfer kinetics of silicon electrodes. Using a suitable RC equivalent circuit allows to evaluate data from cyclic voltammetry and simultaneous FFT-Impedance Spectroscopy (FFT-IS), yielding in time-resolved resistances, time constants, and their direct correlation to the phase transformations. The change of the resistances during lithiation and delithiation correlates to kinetics and charge transfer mechanisms. This study demonstrates how the mechanical and physiochemical interactions at the silicon/paste interface inside the paste electrodes lead to void formation around silicon and with it to material loss and capacity fading.

Study on the kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin using the fluorescence probe thioflavin T.

PubMed

Yan, Mingyan; Wang, Xinping

2018-05-27

The kinetic self-assembly of type I collagen from tilapia (Oreochromis niloticus) skin was characterized by the fluorescence method based on thioflavin T (ThT). The fluorescence probe could bind to the active monomeric collagen with a higher ordered degree of molecule, which displayed the pH and ionic strength dependence, the binding constant higher at neutral pH and proportional to the NaCl concentration. Compared to the turbidity method, ThT was more suitable to characterize the nucleation phase of collagen self-assembly. The nucleus size was determined through the ThT fluorescence and linear-polymerization model. At various pH and ionic strength, the nucleus size was nearly identical, either one or two monomers, demonstrating that one or two active monomeric collagen formed into the nucleus and different pH and ionic strength didn't alter the self-assembly mechanism of collagen. This approach was beneficial to advance the understanding of the kinetic self-assembly of the fish-sourced collagen in vitro. Copyright © 2018 Elsevier B.V. All rights reserved.

Prediction of Proper Temperatures for the Hot Stamping Process Based on the Kinetics Models

NASA Astrophysics Data System (ADS)

Samadian, P.; Parsa, M. H.; Mirzadeh, H.

2015-02-01

Nowadays, the application of kinetics models for predicting microstructures of steels subjected to thermo-mechanical treatments has increased to minimize direct experimentation, which is costly and time consuming. In the current work, the final microstructures of AISI 4140 steel sheets after the hot stamping process were predicted using the Kirkaldy and Li kinetics models combined with new thermodynamically based models in order for the determination of the appropriate process temperatures. In this way, the effect of deformation during hot stamping on the Ae3, Acm, and Ae1 temperatures was considered, and then the equilibrium volume fractions of phases at different temperatures were calculated. Moreover, the ferrite transformation rate equations of the Kirkaldy and Li models were modified by a term proposed by Åkerström to consider the influence of plastic deformation. Results showed that the modified Kirkaldy model is satisfactory for the determination of appropriate austenitization temperatures for the hot stamping process of AISI 4140 steel sheets because of agreeable microstructure predictions in comparison with the experimental observations.

Sequential and coordinated action of phytochromes A and B during Arabidopsis stem growth revealed by kinetic analysis

NASA Technical Reports Server (NTRS)

Parks, B. M.; Spalding, E. P.; Evans, M. L. (Principal Investigator)

1999-01-01

Photoreceptor proteins of the phytochrome family mediate light-induced inhibition of stem (hypocotyl) elongation during the development of photoautotrophy in seedlings. Analyses of overt mutant phenotypes have established the importance of phytochromes A and B (phyA and phyB) in this developmental process, but kinetic information that would augment emerging molecular models of phytochrome signal transduction is absent. We have addressed this deficiency by genetically dissecting phytochrome-response kinetics, after having solved the technical issues that previously limited growth studies of small Arabidopsis seedlings. We show here, with resolution on the order of minutes, that phyA initiated hypocotyl growth inhibition upon the onset of continuous red light. This primary contribution of phyA began to decrease after 3 hr of irradiation, the same time at which immunochemically detectable phyA disappeared and an exclusively phyB-dependent phase of inhibition began. The sequential and coordinated actions of phyA and phyB in red light were not observed in far-red light, which inhibited growth persistently through an exclusively phyA-mediated pathway.

Study on Kinetic Mechanism of Bastnaesite Concentrates Decomposition Using Calcium Hydroxide

NASA Astrophysics Data System (ADS)

Cen, Peng; Wu, Wenyuan; Bian, Xue

2018-06-01

The thermal decomposition of bastnaesite concentrates using calcium hydroxide was studied. Calcium hydroxide can effectively inhibit the emission of fluorine during roasting by transforming it to calcium fluoride. The decomposition rate increased with increasing reaction temperature and amount of calcium hydroxide. The decomposition kinetics were investigated. The decomposition reaction was determined to be a heterogeneous gas-solid reaction, and it followed an unreacted shrinking core model. By means of the integrated rate equation method, the reaction was proven to be kinetically first order. Different reaction models were fit to the experimental data to determine the reaction control process. The chemical reaction at the phase interface controlled the reaction rate in the temperatures ranging from 673 K to 773 K (400 °C to 500 °C) with an apparent activation energy of 82.044 kJ·mol-1. From 773 K to 973 K (500 °C to 700 °C), diffusion through the solid product's layer became the determining step, with a lower activation energy of 15.841 kJ·mol-1.

A comparison of zero-order, first-order, and monod biotransformation models

USGS Publications Warehouse

Bekins, B.A.; Warren, E.; Godsy, E.M.

1998-01-01

Under some conditions, a first-order kinetic model is a poor representation of biodegradation in contaminated aquifers. Although it is well known that the assumption of first-order kinetics is valid only when substrate concentration, S, is much less than the half-saturation constant, K(s), this assumption is often made without verification of this condition. We present a formal error analysis showing that the relative error in the first-order approximation is S/K(S) and in the zero-order approximation the error is K(s)/S. We then examine the problems that arise when the first-order approximation is used outside the range for which it is valid. A series of numerical simulations comparing results of first- and zero-order rate approximations to Monod kinetics for a real data set illustrates that if concentrations observed in the field are higher than K(s), it may better to model degradation using a zero-order rate expression. Compared with Monod kinetics, extrapolation of a first-order rate to lower concentrations under-predicts the biotransformation potential, while extrapolation to higher concentrations may grossly over-predict the transformation rate. A summary of solubilities and Monod parameters for aerobic benzene, toluene, and xylene (BTX) degradation shows that the a priori assumption of first-order degradation kinetics at sites contaminated with these compounds is not valid. In particular, out of six published values of KS for toluene, only one is greater than 2 mg/L, indicating that when toluene is present in concentrations greater than about a part per million, the assumption of first-order kinetics may be invalid. Finally, we apply an existing analytical solution for steady-state one-dimensional advective transport with Monod degradation kinetics to a field data set.A formal error analysis is presented showing that the relative error in the first-order approximation is S/KS and in the zero-order approximation the error is KS/S where S is the substrate concentration and KS is the half-saturation constant. The problems that arise when the first-order approximation is used outside the range for which it is valid are examined. A series of numerical simulations comparing results of first- and zero-order rate approximations to Monod kinetics for a real data set illustrates that if concentrations observed in the field are higher than KS, it may be better to model degradation using a zero-order rate expression.

Diffusive molecular dynamics simulations of lithiation of silicon nanopillars

NASA Astrophysics Data System (ADS)

Mendez, J. P.; Ponga, M.; Ortiz, M.

2018-06-01

We report diffusive molecular dynamics simulations concerned with the lithiation of Si nano-pillars, i.e., nano-sized Si rods held at both ends by rigid supports. The duration of the lithiation process is of the order of milliseconds, well outside the range of molecular dynamics but readily accessible to diffusive molecular dynamics. The simulations predict an alloy Li15Si4 at the fully lithiated phase, exceedingly large and transient volume increments up to 300% due to the weakening of Sisbnd Si iterations, a crystalline-to-amorphous-to-lithiation phase transition governed by interface kinetics, high misfit strains and residual stresses resulting in surface cracks and severe structural degradation in the form of extensive porosity, among other effects.

[Preparation of Coated CMC-Fe0 Using Rheological Phase Reaction Method and Research on Degradation of TCE in Water].

PubMed

Fan, Wen-jing; Cheng, Yue; Yu, Shu-zhen; Fan, Xiao-feng

2015-06-01

The coated nanoscale zero-valent iron (coated CMC-Fe0) was synthesized with cheap and environment friendly CMC as the coating agent using rheological phase reaction. The sample was characterized by means of XRD, SEM, TEM and N2 adsorption-stripping and used to study reductive dechlorination of TCE. The experimental results indicated that the removal rate of TCE was about 100% when the CMC-Fe0 dosage was 6 g x L(-1), the initial TCE concentration was 5 mg x L(-1) and the reaction time was 40 h. The TCE degradation reaction of coated CMC-Fe0 followed a pseudo-first-order kinetic model. Finally, the product could be simply recovered.

Fouling Resistant CA/PVA/TiO2 Imprinted Membranes for Selective Recognition and Separation Salicylic Acid from Waste Water

PubMed Central

Yu, Xiaopeng; Mi, Xueyang; He, Zhihui; Meng, Minjia; Li, Hongji; Yan, Yongsheng

2017-01-01

Highly selective cellulose acetate (CA)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO2) imprinted membranes were synthesized by phase inversion and dip coating technique. The CA blend imprinted membrane was synthesized by phase inversion technique with CA as membrane matrix, polyethyleneimine (PEI) as the functional polymer, and the salicylic acid (SA) as the template molecule. The CA/PVA/TiO2 imprinted membranes were synthesized by dip coating of CA blend imprinted membrane in PVA and different concentration (0.05, 0.1, 0.2, 0.4 wt %) of TiO2 nanoparticles aqueous solution. The SEM analysis showed that the surface morphology of membrane was strongly influenced by the concentration of TiO2 nanoparticles. Compared with CA/PVA-TiO2(0.05, 0.1, 0.2%)-MIM, the CA/PVA-TiO2(0.4%)-MIM possessed higher membrane flux, kinetic equilibrium adsorption amount, binding capacity and better selectivity for SA. It was found that the pseudo-second-order kinetic model was studied to describe the kinetic of CA/PVA-TiO2(0.2%)-MIM judging by multiple regression analysis. Adsorption isotherm analysis indicated that the maximum adsorption capacity for SA were 24.43 mg g−1. Moreover, the selectivity coefficients of CA/PVA-TiO2 (0.2%)-MIM for SA relative to p-hydroxybenzoic acid (p-HB) and methyl salicylate (MS) were 3.87 and 3.55, respectively. PMID:28184369

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

NASA Astrophysics Data System (ADS)

Wang, Gang; Wu, Nanhua; Chen, Jionghua; Wang, Jinjian; Shao, Jingling; Zhu, Xiaolei; Lu, Xiaohua; Guo, Lucun

2016-11-01

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold-gold interactions while a Lennard-Jones (L-J) potential is used to describe the gold-GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold-gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the εAu-C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order-disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.

Phase-plane analysis of the totally asymmetric simple exclusion process with binding kinetics and switching between antiparallel lanes

PubMed Central

Kuan, Hui-Shun; Betterton, Meredith D.

2016-01-01

Motor protein motion on biopolymers can be described by models related to the totally asymmetric simple exclusion process (TASEP). Inspired by experiments on the motion of kinesin-4 motors on antiparallel microtubule overlaps, we analyze a model incorporating the TASEP on two antiparallel lanes with binding kinetics and lane switching. We determine the steady-state motor density profiles using phase-plane analysis of the steady-state mean field equations and kinetic Monte Carlo simulations. We focus on the density-density phase plane, where we find an analytic solution to the mean field model. By studying the phase-space flows, we determine the model’s fixed points and their changes with parameters. Phases previously identified for the single-lane model occur for low switching rate between lanes. We predict a multiple coexistence phase due to additional fixed points that appear as the switching rate increases: switching moves motors from the higher-density to the lower-density lane, causing local jamming and creating multiple domain walls. We determine the phase diagram of the model for both symmetric and general boundary conditions. PMID:27627345

Demixing kinetics of phase separated polymer solutions in microgravity. [cell separation

NASA Technical Reports Server (NTRS)

Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.; Snyder, R. S.

1987-01-01

In preparation for performing cell partitioning in space the demixing behavior of aqueous two phase systems containing dextran and poly(ethylene glycol) in microgravity was modeled with an isopycnic system and studied on aircraft flights and on STS 51-D. In all types of experiments demixing occurs, eventually producing one phase localized around the wall of the container with the other internalized within it. The demixing kinetics were analyzed in each case.

Semi-local machine-learned kinetic energy density functional with third-order gradients of electron density

NASA Astrophysics Data System (ADS)

Seino, Junji; Kageyama, Ryo; Fujinami, Mikito; Ikabata, Yasuhiro; Nakai, Hiromi

2018-06-01

A semi-local kinetic energy density functional (KEDF) was constructed based on machine learning (ML). The present scheme adopts electron densities and their gradients up to third-order as the explanatory variables for ML and the Kohn-Sham (KS) kinetic energy density as the response variable in atoms and molecules. Numerical assessments of the present scheme were performed in atomic and molecular systems, including first- and second-period elements. The results of 37 conventional KEDFs with explicit formulae were also compared with those of the ML KEDF with an implicit formula. The inclusion of the higher order gradients reduces the deviation of the total kinetic energies from the KS calculations in a stepwise manner. Furthermore, our scheme with the third-order gradient resulted in the closest kinetic energies to the KS calculations out of the presented functionals.

Hydraulic separation of plastic wastes: Analysis of liquid-solid interaction.

PubMed

Moroni, Monica; Lupo, Emanuela; La Marca, Floriana

2017-08-01

The separation of plastic wastes in mechanical recycling plants is the process that ensures high-quality secondary raw materials. An innovative device employing a wet technology for particle separation is presented in this work. Due to the combination of the characteristic flow pattern developing within the apparatus and density, shape and size differences among two or more polymers, it allows their separation into two products, one collected within the instrument and the other one expelled through its outlet ducts. The kinematic investigation of the fluid flowing within the apparatus seeded with a passive tracer was conducted via image analysis for different hydraulic configurations. The two-dimensional turbulent kinetic energy results strictly connected to the apparatus separation efficacy. Image analysis was also employed to study the behaviour of mixtures of passive tracer and plastic particles with different physical characteristics in order to understand the coupling regime between fluid and solid phases. The two-dimensional turbulent kinetic energy analysis turned out to be fundamental to this aim. For the tested operating conditions, two-way coupling takes place, i.e., the fluid exerts an influence on the plastic particle and the opposite occurs too. Image analysis confirms the outcomes from the investigation of the two-phase flow via non-dimensional numbers (particle Reynolds number, Stokes number and solid phase volume fraction). Copyright © 2017 Elsevier Ltd. All rights reserved.

Graphene-a promising material for removal of perchlorate (ClO4-) from water.

PubMed

Lakshmi, Jothinathan; Vasudevan, Subramanyan

2013-08-01

A batch adsorption process was applied to investigate the removal of perchlorate (ClO4 (-)) from water by graphene. In doing so, the thermodynamic adsorption isotherm and kinetic studies were also carried out. Graphene was prepared by a facile liquid-phase exfoliation. Graphene was characterized by Raman spectroscopy, Fourier-transform infrared spectroscopy, powder X-ray diffraction, scanning electron microscope, and zeta potential measurements. A systematic study of the adsorption process was performed by varying pH, ionic strength, and temperature. The adsorption efficiency of graphene was 99.2 %, suggesting that graphene is an excellent adsorbent for ClO4 (-) removal from water. The rate constants for all these kinetic models were calculated, and the results indicate that second-order kinetics model was well suitable to model the kinetic adsorption of ClO4 (-). Equilibrium data were well described by the typical Langmuir adsorption isotherm. The experimental results showed that graphene is an excellent perchlorate adsorbent with an adsorbent capacity of up to 0.024 mg/g at initial perchlorate concentration of 2 mg/L and temperature of 298 K. Thermodynamic studies revealed that the adsorption reaction was a spontaneous and endothermic process. Graphene removed the perchlorate present in the water and reduced it to a permissible level making it drinkable.

Evaporation Kinetics of Laboratory Generated Secondary Organic Aerosols at Elevated Relative Humidity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, Jacqueline M.; Imre, D.; Beranek, Josef

2015-01-06

Secondary organic aerosols (SOA) dominate atmospheric organic aerosols that affect climate, air quality, and health. Recent studies indicate that, contrary to previously held assumptions, at low relative humidity (RH) these particles are semi-solid and evaporate orders of magnitude slower than expected. Elevated relative humidity has the potential to affect significantly formation, properties, and atmospheric evolution of SOA particles. Here we present a study of the effect of RH on the room-temperature evaporation kinetics of SOA particles formed by ozonolysis of α-pinene and limonene. Experiments were carried out on SOA particles generated, evaporated, and aged at 0%, 50% and 90% RH.more » We find that in all cases evaporation begins with a relatively fast phase, during which 30% to 70% of the particle mass evaporates in 2 hours, followed by a much slower evaporation rate. Evaporation kinetics at 0% and 50% RH are nearly the same, while at 90% RH a slightly larger fraction evaporates. In all cases, aging the particles prior to inducing evaporation reduces the evaporative losses, with aging at elevated RH leading to more significant effect. In all cases, SOA evaporation is nearly size-independent, providing direct evidence that oligomers play a crucial role in determining the evaporation kinetics.« less

In Situ Tracking Kinetic Pathways of Li+/Na+ Substitution during Ion-Exchange Synthesis of LixNa1.5-xVOPO4F0.5.

PubMed

Park, Young-Uk; Bai, Jianming; Wang, Liping; Yoon, Gabin; Zhang, Wei; Kim, Hyungsub; Lee, Seongsu; Kim, Sung-Wook; Looney, J Patrick; Kang, Kisuk; Wang, Feng

2017-09-13

Ion exchange is a ubiquitous phenomenon central to wide industrial applications, ranging from traditional (bio)chemical separation to the emerging chimie douce synthesis of materials with metastable structure for batteries and other energy applications. The exchange process is complex, involving substitution and transport of different ions under non-equilibrium conditions, and thus difficult to probe, leaving a gap in mechanistic understanding of kinetic exchange pathways toward final products. Herein, we report in situ tracking kinetic pathways of Li + /Na + substitution during solvothermal ion-exchange synthesis of Li x Na 1.5-x VOPO 4 F 0.5 (0 ≤ x ≤ 1.5), a promising multi-Li polyanionic cathode for batteries. The real-time observation, corroborated by first-principles calculations, reveals a selective replacement of Na + by Li + , leading to peculiar Na + /Li + /vacancy orderings in the intermediates. Contradicting the traditional belief of facile topotactic substitution via solid solution reaction, an abrupt two-phase transformation occurs and predominantly governs the kinetics of ion exchange and transport in the 1D polyanionic framework, consequently leading to significant difference of Li stoichiometry and electrochemical properties in the exchanged products. The findings may help to pave the way for rational design of ion exchange synthesis for making new materials.

Liquid phase adsorptions of Rhodamine B dye onto raw and chitosan supported mesoporous adsorbents: isotherms and kinetics studies

NASA Astrophysics Data System (ADS)

Inyinbor, A. A.; Adekola, F. A.; Olatunji, G. A.

2017-09-01

Irvingia gabonensis endocarp waste was charred (DNc) and subsequently coated with chitosan (CCDNc). Physicochemical characteristics of the two adsorbents were established, while Fourier transform infrared (FTIR), Scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) surface area methods were further employed for characterization. Efficiencies of the prepared adsorbents in the uptake of Rhodamine B (RhB) from aqueous effluent were investigated and adsorption data were tested using four isotherms and four kinetics models. The BET surface areas of the prepared adsorbent were 0.0092 and 4.99 m2/g for DNc and CCDNc, respectively, and maximum adsorption was recorded at pH between 3 and 4, respectively. While monolayer adsorption dominates the uptake of RhB onto DNc, uptake of RhB onto CCDNc was onto heterogeneous surface. The maximum monolayer adsorption capacities ( q max) obtained from the Langmuir equation are 52.90 and 217.39 mg/g for DNc and CCDNc, respectively. Pseudo second order and Elovich kinetic models well described the kinetics of the two adsorption processes. The mean sorption energy ( E) calculated from the D-R model and desorption efficiencies suggests that while the uptake of RhB onto DNc was physical in nature, for RhB-CCDNc system chemisorption dominates.

Subdiffusion kinetics of nanoprecipitate growth and destruction in solid solutions

NASA Astrophysics Data System (ADS)

Sibatov, R. T.; Svetukhin, V. V.

2015-06-01

Based on fractional differential generalizations of the Ham and Aaron-Kotler precipitation models, we study the kinetics of subdiffusion-limited growth and dissolution of new-phase precipitates. We obtain the time dependence of the number of impurities and dimensions of new-phase precipitates. The solutions agree with the Monte Carlo simulation results.

Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

PubMed

Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

2016-09-01

It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

Irreversible opinion spreading on scale-free networks

NASA Astrophysics Data System (ADS)

Candia, Julián

2007-02-01

We study the dynamical and critical behavior of a model for irreversible opinion spreading on Barabási-Albert (BA) scale-free networks by performing extensive Monte Carlo simulations. The opinion spreading within an inhomogeneous society is investigated by means of the magnetic Eden model, a nonequilibrium kinetic model for the growth of binary mixtures in contact with a thermal bath. The deposition dynamics, which is studied as a function of the degree of the occupied sites, shows evidence for the leading role played by hubs in the growth process. Systems of finite size grow either ordered or disordered, depending on the temperature. By means of standard finite-size scaling procedures, the effective order-disorder phase transitions are found to persist in the thermodynamic limit. This critical behavior, however, is absent in related equilibrium spin systems such as the Ising model on BA scale-free networks, which in the thermodynamic limit only displays a ferromagnetic phase. The dependence of these results on the degree exponent is also discussed for the case of uncorrelated scale-free networks.

Hydrogen and Ethene Plasma Assisted Ignition by NS discharge at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Starikovskiy, Andrey

2015-09-01

The kinetics of ignition in lean H2:O2:Ar and C2H4:O2:Ar mixtures has been studied experimentally and numerically after a high-voltage nanosecond discharge. The ignition delay time behind a reflected shock wave was measured with and without the discharge. It was shown that the initiation of the discharge with a specific deposited energy of 10 - 30 mJ/cm3 leads to an order of magnitude decrease in the ignition delay time. Discharge processes and following chain chemical reactions with energy release were simulated. The generation of atoms, radicals and excited and charged particles was numerically simulated using the measured time - resolved discharge current and electric field in the discharge phase. The calculated densities of the active particles were used as input data to simulate plasma-assisted ignition. Good agreement was obtained between the calculated ignition delay times and the experimental data. It follows from the analysis of the calculated results that the main mechanism of the effect of gas discharge on the ignition of hydrocarbons is the electron impact dissociation of O2 molecules in the discharge phase. Detailed kinetic mechanism for plasma assisted ignition of hydrogen and ethene is elaborated and verified.

Modelling the removal of p-TSA (para-toluenesulfonamide) during rapid sand filtration used for drinking water treatment.

PubMed

Meffe, Raffaella; Kohfahl, Claus; Holzbecher, Ekkehard; Massmann, Gudrun; Richter, Doreen; Dünnbier, Uwe; Pekdeger, Asaf

2010-01-01

A finite element model was set-up to determine degradation rate constants for p-TSA during rapid sand filtration (RSF). Data used for the model originated from a column experiment carried out in the filter hall of a drinking water treatment plant in Berlin (Germany). Aerated abstracted groundwater was passed through a 1.6m long column-shaped experimental sand filter applying infiltration rates from 2 to 6mh(-1). Model results were fitted to measured profiles and breakthrough curves of p-TSA for different infiltration rates using both first-order reaction kinetics and Michaelis-Menten kinetics. Both approaches showed that degradation rates varied both in space and time. Higher degradation rates were observed in the upper part of the column, probably related to higher microbial activity in this zone. Measured and simulated breakthrough curves revealed an adaption phase with lower degradation rates after infiltration rates were changed, followed by an adapted phase with more elevated degradation rates. Irrespective of the mathematical approach and the infiltration rate, degradation rates were very high, probably owing to the fact that filter sands have been in operation for decades, receiving high p-TSA concentrations with the raw water.

Large-moment antiferromagnetic order in overdoped high-Tc superconductor 154SmFeAsO1-x D x .

PubMed

Iimura, Soshi; Okanishi, Hiroshi; Matsuishi, Satoru; Hiraka, Haruhiro; Honda, Takashi; Ikeda, Kazutaka; Hansen, Thomas C; Otomo, Toshiya; Hosono, Hideo

2017-05-30

In iron-based superconductors, high critical temperature ( T c ) superconductivity over 50 K has only been accomplished in electron-doped hRE FeAsO ( hRE is heavy rare earth ( RE ) element). Although hRE FeAsO has the highest bulk T c (58 K), progress in understanding its physical properties has been relatively slow due to difficulties in achieving high-concentration electron doping and carrying out neutron experiments. Here, we present a systematic neutron powder diffraction study of 154 SmFeAsO 1- x D x , and the discovery of a long-range antiferromagnetic ordering with x ≥ 0.56 (AFM2) accompanying a structural transition from tetragonal to orthorhombic. Surprisingly, the Fe magnetic moment in AFM2 reaches a magnitude of 2.73 μ B /Fe, which is the largest in all nondoped iron pnictides and chalcogenides. Theoretical calculations suggest that the AFM2 phase originates in kinetic frustration of the Fe-3 d xy orbital, in which the nearest-neighbor hopping parameter becomes zero. The unique phase diagram, i.e., highest- T c superconducting phase adjacent to the strongly correlated phase in electron-overdoped regime, yields important clues to the unconventional origins of superconductivity.

Suppression of phase mixing in drift-kinetic plasma turbulence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, J. T., E-mail: joseph.parker@stfc.ac.uk; OCIAM, Mathematical Institute, University of Oxford, Andrew Wiles Building, Radcliffe Observatory Quarter, Woodstock Road, Oxford OX2 6GG; Brasenose College, Radcliffe Square, Oxford OX1 4AJ

2016-07-15

Transfer of free energy from large to small velocity-space scales by phase mixing leads to Landau damping in a linear plasma. In a turbulent drift-kinetic plasma, this transfer is statistically nearly canceled by an inverse transfer from small to large velocity-space scales due to “anti-phase-mixing” modes excited by a stochastic form of plasma echo. Fluid moments (density, velocity, and temperature) are thus approximately energetically isolated from the higher moments of the distribution function, so phase mixing is ineffective as a dissipation mechanism when the plasma collisionality is small.

The Dissipation Range of Interstellar Turbulence

NASA Astrophysics Data System (ADS)

Spangler, Steven R.; Buffo, J. J.

2013-06-01

Turbulence may play an important role in a number of interstellar processes. One of these is heating of the interstellar gas, as the turbulent energy is dissipated and changed into thermal energy of the gas, or at least other forms of energy. There have been very promising recent results on the mechanism for dissipation of turbulence in the Solar Wind (Howes et al, Phys. Plasm. 18, 102305, 2011). In the Solar Wind, the dissipation arises because small-scale irregularities develop properties of kinetic Alfven waves, and apparently damp like kinetic Alfven waves. A property of kinetic Alfven waves is that they become significantly compressive on size scales of order the ion Larmor radius. Much is known about the plasma properties of ionized components of interstellar medium such as HII regions and the Diffuse Ionized Gas (DIG) phase, including information on the turbulence in these media. The technique of radio wave scintillations can yield properties of HII region and DIG turbulence on scales of order the ion Larmor radius, which we refer to as the dissipation scale. In this paper, we collect results from a number of published radio scattering measurements of interstellar turbulence on the dissipation scale. These studies show evidence for a spectral break on the dissipation scale, but no evidence for enhanced compressibility of the fluctuations. The simplest explanation of our result is that turbulence in the ionized interstellar medium does not possess properties of kinetic Alfven waves. This could point to an important difference with Solar Wind turbulence. New observations, particularly with the Very Long Baseline Array (VLBA) could yield much better measurements of the power spectrum of interstellar turbulence in the dissipation range. This research was supported at the University of Iowa by grants AST09-07911 and ATM09-56901 from the National Science Foundation.

Nanoscale oxidation and complex oxide growth on single crystal iron surfaces and external electric field effects.

PubMed

Jeon, Byoungseon; Van Overmeere, Quentin; van Duin, Adri C T; Ramanathan, Shriram

2013-02-14

Oxidation of iron surfaces and oxide growth mechanisms have been studied using reactive molecular dynamics. Oxide growth kinetics on Fe(100), (110), and (111) surface orientations has been investigated at various temperatures and/or an external electric field. The oxide growth kinetics decreases in the order of (110), (111), and (100) surfaces at 300 K over 1 ns timescale while higher temperature increases the oxidation rate. The oxidation rate shows a transition after an initial high rate, implying that the oxide formation mechanism evolves, with iron cation re-ordering. In early stages of surface oxide growth, oxygen transport through iron interstitial sites is dominant, yielding non-stoichiometric wüstite characteristics. The dominant oxygen inward transport decreases as the oxide thickens, evolving into more stoichiometric oxide phases such as wüstite or hematite. This also suggests that cation outward transport increases correspondingly. In addition to oxidation kinetics simulations, formed oxide layers have been relaxed in the range of 600-1500 K to investigate diffusion characteristics, fitting these results into an Arrhenius relation. The activation energy of oxygen diffusion in oxide layers formed on Fe(100), (110), and (111) surfaces was estimated to be 0.32, 0.26, and 0.28 eV, respectively. Comparison between our modeling results and literature data is then discussed. An external electric field (10 MV cm(-1)) facilitates initial oxidation kinetics by promoting oxygen transport through iron lattice interstitial sites, but reaches self-limiting thickness, showing that similar oxide formation stages are maintained when cation transport increases. The effect of the external electric field on iron oxide structure, composition, and oxide activation energy is found to be minimal, whereas cation outward migration is slightly promoted.

Voltage gating by molecular subunits of Na+ and K+ ion channels: higher-dimensional cubic kinetics, rate constants, and temperature.

PubMed

Fohlmeister, Jürgen F

2015-06-01

The structural similarity between the primary molecules of voltage-gated Na and K channels (alpha subunits) and activation gating in the Hodgkin-Huxley model is brought into full agreement by increasing the model's sodium kinetics to fourth order (m(3) → m(4)). Both structures then virtually imply activation gating by four independent subprocesses acting in parallel. The kinetics coalesce in four-dimensional (4D) cubic diagrams (16 states, 32 reversible transitions) that show the structure to be highly failure resistant against significant partial loss of gating function. Rate constants, as fitted in phase plot data of retinal ganglion cell excitation, reflect the molecular nature of the gating transitions. Additional dimensions (6D cubic diagrams) accommodate kinetically coupled sodium inactivation and gating processes associated with beta subunits. The gating transitions of coupled sodium inactivation appear to be thermodynamically irreversible; response to dielectric surface charges (capacitive displacement) provides a potential energy source for those transitions and yields highly energy-efficient excitation. A comparison of temperature responses of the squid giant axon (apparently Arrhenius) and mammalian channel gating yields kinetic Q10 = 2.2 for alpha unit gating, whose transitions are rate-limiting at mammalian temperatures; beta unit kinetic Q10 = 14 reproduces the observed non-Arrhenius deviation of mammalian gating at low temperatures; the Q10 of sodium inactivation gating matches the rate-limiting component of activation gating at all temperatures. The model kinetics reproduce the physiologically large frequency range for repetitive firing in ganglion cells and the physiologically observed strong temperature dependence of recovery from inactivation. Copyright © 2015 the American Physiological Society.

Calorimetric investigation of precipitation kinetics in Al-Mg-Si-X(Cr,Be) alloys

NASA Astrophysics Data System (ADS)

Woo, K. D.; Lee, J. S.; Kim, S. W.

1999-07-01

This study has been carried out by differential scanning calorimetry (DSC) to study the kinetics of precipitation and the dissolution of metastable and stable phases in Al-Mg-Si-(Cr,Be) alloys which were heat treated by T6, two-step aging and RRA (retrogression and reaging) treatment. The heat flow variations by phase transformation in the as-quenched specimen were calculated from DSC thermograms obtained from heating rates of 5, 10, 15 and 20°C/min. Four exothermic peaks may be attributed to the precipitation of G.P.I zone, G.P.II zone(β″), β' and β (Mg2Si) phases, and three endothermic peaks may be attributed to the dissolution of G.P.I zone, β″ and the β' phases, respectively. The kinetic equation (dY/dt)=f(Y)koexp(-Q*/RT) can be used to study the precipitation kinetics of Ai-Mg-Si-(Cr, Be) alloys, where Q*, ko, and f(Y)are the activation energy, frequency factors and the function of Y, respectively. The kinetic parameters measured from DSC curves can be used to interpret the transformation kinetics.The formation rate of β″ phase in the Al-Mg-Si alloy increased by the small addition of Be. This is because Be increases the nucleating rate of the β″ phase due to the decrease of the matrix/β″ interface energy. By the addition of Be or Cr and Be in Al-Mg-Si alloy, G.P. zone was easily decomposed during retrogression treatment at 225°C for 3 min. Therefore, maximum hardness can be obtained by RRA (150°C/20 min→225°C/3 min→ 180°C/3O min) in Al-0.8%Mg-1.0%Si-0.05% Be and Al-0.8% Mg-l.0% Si-0.l% Cr-0.05% Be alloys owing to the high density of β″ and β' precipitates.

Kinetic field theory: exact free evolution of Gaussian phase-space correlations

NASA Astrophysics Data System (ADS)

Fabis, Felix; Kozlikin, Elena; Lilow, Robert; Bartelmann, Matthias

2018-04-01

In recent work we developed a description of cosmic large-scale structure formation in terms of non-equilibrium ensembles of classical particles, with time evolution obtained in the framework of a statistical field theory. In these works, the initial correlations between particles sampled from random Gaussian density and velocity fields have so far been treated perturbatively or restricted to pure momentum correlations. Here we treat the correlations between all phase-space coordinates exactly by adopting a diagrammatic language for the different forms of correlations, directly inspired by the Mayer cluster expansion. We will demonstrate that explicit expressions for phase-space density cumulants of arbitrary n-point order, which fully capture the non-linear coupling of free streaming kinematics due to initial correlations, can be obtained from a simple set of Feynman rules. These cumulants will be the foundation for future investigations of perturbation theory in particle interactions.

Symmetry breaking by heating in a continuous opinion model

NASA Astrophysics Data System (ADS)

Anteneodo, Celia; Crokidakis, Nuno

2017-04-01

We study the critical behavior of a continuous opinion model, driven by kinetic exchanges in a fully connected population. Opinions range in the real interval [-1 ,1 ] , representing the different shades of opinions against and for an issue under debate. Individuals' opinions evolve through pairwise interactions, with couplings that are typically positive, but a fraction p of negative ones is allowed. Moreover, a social temperature parameter T controls the tendency of the individual responses toward neutrality. Depending on p and T , different collective states emerge: symmetry broken (one side wins), symmetric (tie of opposite sides), and absorbing neutral (indecision wins). We find the critical points and exponents that characterize the phase transitions between them. The symmetry breaking transition belongs to the usual Ising mean-field universality class, but the absorbing-phase transitions, with β =0.5 , are out of the paradigmatic directed percolation class. Moreover, ordered phases can emerge by increasing social temperature.

Differential scanning calorimetry study and computer modeling of β ⇒ α phase transformation in a Ti-6Al-4V alloy

NASA Astrophysics Data System (ADS)

Malinov, S.; Guo, Z.; Sha, W.; Wilson, A.

2001-04-01

The relationship between heat-treatment parameters and microstructure in titanium alloys has so far been mainly studied empirically, using characterization techniques such as microscopy. Calculation and modeling of the kinetics of phase transformation have not yet been widely used for these alloys. Differential scanning calorimetry (DSC) has been widely used for the study of a variety of phase transformations. There has been much work done on the calculation and modeling of the kinetics of phase transformations for different systems based on the results from DSC study. In the present work, the kinetics of the β ⇒ α transformation in a Ti-6Al-4V titanium alloy were studied using DSC, at continuous cooling conditions with constant cooling rates of 5 °C, 10 °C, 20 °C, 30 °C, 40 °C, and 50 °C/min. The results from calorimetry were then used to trace and model the transformation kinetics in continuous cooling conditions. Based on suitably interpreted DSC results, continuous cooling-transformation (CCT) diagrams were calculated with lines of isotransformed fraction. The kinetics of transformation were modeled using the Johnson-Mehl-Avrami (JMA) theory and by applying the “concept of additivity.” The JMA kinetic parameters were derived. Good agreement between the calculated and experimental transformed fractions is demonstrated. Using the derived kinetic parameters, the β ⇒ α transformation in a Ti-6Al-4V alloy can be described for any cooling path and condition. An interpretation of the results from the point of view of activation energy for nucleation is also presented.

The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

PubMed

Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn

2017-02-01

The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

Geometric heterogeneity of the lattice and its effect on the kinetics phase transitions of surface reactions

NASA Astrophysics Data System (ADS)

Cortés, Joaquín.; Valencia, Eliana

1999-04-01

Two novel phenomena are discussed in this paper. The first one refers to the effect of the catalyst's surface heterogeneity on the smoothing of the first-order transition observed in the ( A+ B2) reaction (ZGB model). The second effect corresponds to obtaining information on the surface heterogeneity from the shape of the transition curve. Two types of heterogeneity were considered: the structure obtained by the random blocking of reactive sites, and the existence of a distribution in independent strips or terraces on the catalyst's surface.

Processing and Properties of Fire Resistant EPDM Rubber-Based Ceramifiable Composites

NASA Astrophysics Data System (ADS)

Anyszka, Rafał; Bieliński, Dariusz M.; Pędzich, Zbigniew; Zarzecka-Napierała, Magdalena; Imiela, Mateusz; Rybiński, Przemysław

2017-10-01

Low softening point temperature glassy frit, reinforcing silica, wollastonite and dicumyl peroxide were incorporated into ethylene-propylene-diene (EPDM) rubber matrix in different amounts in order to obtain ceramifiable composites. Kinetics of vulcanization of the mixes was measured. Mechanical properties, micromorphology, thermal properties and combustibility of the vulcanizates were studied as well as compression strength of the ceramic residue obtained after heat treatment. Studies show that optimal amount of glassy frit from the point of view of ceramification effectiveness in dispersed mineral phase is 40 % wt.

CC, CS, and IOS generalized phenomenological cross sections for atom--diatom mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fitz, D.E.; Kouri, D.J.; Evans, D.

1981-05-01

Close coupled expressions for phenomenological cross sections which describe transport properties of atom--diatom mixtures are obtained in the total-J coupling scheme and are related to the bracket integrals of kinetic theory. Coupled states and infinite order sudden expressions for the generalized phenomenological cross sections using initial, final, and average l-labeling are also given. Particular care is taken to use a phase convention for the CS and IOS approximations which is consistent with the Arthurs--Dalgarno formalism and which gives the correct behavior of degeneracy averaged differential cross sections.

Continuous theory of active matter systems with metric-free interactions.

PubMed

Peshkov, Anton; Ngo, Sandrine; Bertin, Eric; Chaté, Hugues; Ginelli, Francesco

2012-08-31

We derive a hydrodynamic description of metric-free active matter: starting from self-propelled particles aligning with neighbors defined by "topological" rules, not metric zones-a situation advocated recently to be relevant for bird flocks, fish schools, and crowds-we use a kinetic approach to obtain well-controlled nonlinear field equations. We show that the density-independent collision rate per particle characteristic of topological interactions suppresses the linear instability of the homogeneous ordered phase and the nonlinear density segregation generically present near threshold in metric models, in agreement with microscopic simulations.

Ultrasonic attenuation measurements determine onset, degree, and completion of recrystallization

NASA Technical Reports Server (NTRS)

Generazio, E. R.

1988-01-01

Ultrasonic attenuation was measured for cold worked Nickel 200 samples annealed at increasing temperatures. Localized dislocation density variations, crystalline order and volume percent of recrystallized phase were determined over the anneal temperature range using transmission electron microscopy, X-ray diffraction, and metallurgy. The exponent of the frequency dependence of the attenuation was found to be a key variable relating ultrasonic attenuation to the thermal kinetics of the recrystallization process. Identification of this key variable allows for the ultrasonic determination of onset, degree, and completion of recrystallization.

Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li XFePO 4 electrode particles

DOE PAGES

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

2015-04-08

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li XFePO 4 electrode particle for Li-ion batteries as a modelmore » system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.« less

Separation of non-racemic mixtures of enantiomers: an essential part of optical resolution.

PubMed

Faigl, Ferenc; Fogassy, Elemér; Nógrádi, Mihály; Pálovics, Emese; Schindler, József

2010-03-07

Non-racemic enantiomeric mixtures form homochiral and heterochiral aggregates in melt or suspension, during adsorption or recrystallization, and these diastereomeric associations determine the distribution of the enantiomers between the solid and other (liquid or vapour) phases. That distribution depends on the stability order of the homo- and heterochiral aggregates (conglomerate or racemate formation). Therefore, there is a correlation between the binary melting point phase diagrams and the experimental ee(I)vs. ee(0) curves (ee(I) refers to the crystallized enantiomeric mixtures, ee(0) is the composition of the starting ones). Accordingly, distribution of the enantiomeric mixtures between two phases is characteristic and usually significant enrichment can be achieved. There are two exceptions: no enrichment could be observed under thermodynamically controlled conditions when the starting enantiomer composition corresponded to the eutectic composition, or when the method used was unsuitable for separation. In several cases, when kinetic control governed the crystallization, the character of the ee(0)-ee(I) curve did not correlate with the melting point binary phase diagram.

The Power of Materials Science Tools for Gaining Insights into Organic Semiconductors

NASA Astrophysics Data System (ADS)

Treat, Neil D.; Westacott, Paul; Stingelin, Natalie

2015-07-01

The structure of organic semiconductors can be complex because features from the molecular level (such as molecular conformation) to the micrometer scale (such as the volume fraction and composition of phases, phase distribution, and domain size) contribute to the definition of the optoelectronic landscape of the final architectures and, hence, to device performance. As a consequence, a detailed understanding of how to manipulate molecular ordering, e.g., through knowledge of relevant phase transitions, of the solidification process, of relevant solidification mechanisms, and of kinetic factors, is required to induce the desired optoelectronic response. In this review, we discuss relevant structural features of single-component and multicomponent systems; provide a case study of the multifaceted structure that polymer:fullerene systems can adopt; and highlight relevant solidification mechanisms such as nucleation and growth, liquid-liquid phase separation, and spinodal decomposition. In addition, cocrystal formation, solid solutions, and eutectic systems are treated and their relevance within the optoelectronic area emphasized.

[Study of the phase transformation of TiO2 with in-situ XRD in different gas].

PubMed

Ma, Li-Jing; Guo, Lie-Jin

2011-04-01

TiO2 sample was prepared by sol-gel method from chloride titanium. The phase transformation of the prepared TiO2 sample was studied by in-situ XRD and normal XRD in different gas. The experimental results showed that the phase transformation temperatures of TiO2 were different under in-situ or normal XRD in different kinds of gas. The transformation of amorphous TiO2 to anatase was controlled by kinetics before 500 degrees C. In-situ XRD showed that the growth of anatase was inhibited, but the transformation of anatase to rutile was accelerated under inactive nitrogen in contrast to air. Also better crystal was obtained under hydrogen than in argon. These all showed that external oxygen might accelerate the growth of TiO2, but reduced gas might partly counteract the negative influence of lack of external oxygen. The mechanism of phase transformation of TiO2 was studied by in-situ XRD in order to control the structure in situ.

A solvable model of Vlasov-kinetic plasma turbulence in Fourier-Hermite phase space

NASA Astrophysics Data System (ADS)

Adkins, T.; Schekochihin, A. A.

2018-02-01

A class of simple kinetic systems is considered, described by the one-dimensional Vlasov-Landau equation with Poisson or Boltzmann electrostatic response and an energy source. Assuming a stochastic electric field, a solvable model is constructed for the phase-space turbulence of the particle distribution. The model is a kinetic analogue of the Kraichnan-Batchelor model of chaotic advection. The solution of the model is found in Fourier-Hermite space and shows that the free-energy flux from low to high Hermite moments is suppressed, with phase mixing cancelled on average by anti-phase-mixing (stochastic plasma echo). This implies that Landau damping is an ineffective route to dissipation (i.e. to thermalisation of electric energy via velocity space). The full Fourier-Hermite spectrum is derived. Its asymptotics are -3/2$ at low wavenumbers and high Hermite moments ( ) and -1/2k-2$ at low Hermite moments and high wavenumbers ( ). These conclusions hold at wavenumbers below a certain cutoff (analogue of Kolmogorov scale), which increases with the amplitude of the stochastic electric field and scales as inverse square of the collision rate. The energy distribution and flows in phase space are a simple and, therefore, useful example of competition between phase mixing and nonlinear dynamics in kinetic turbulence, reminiscent of more realistic but more complicated multi-dimensional systems that have not so far been amenable to complete analytical solution.

Core-Shell PdPb@Pd Aerogels with Multiply-Twinned Intermetallic Nanostructures: Facile Synthesis with Accelerated Gelation Kinetics and Their Enhanced Electrocatalytic Properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Chengzhou; Shi, Qiurong; Fu, Shaofang

2018-04-04

Delicately engineering the well-defined noble metal aerogels with favorable structural and compositional features is of vital importance for wide applications. Here, we reported one-pot and facile method for synthesizing core-shell PdPb@Pd hydrogels/aerogels with multiply-twinned grains and ordered intermetallic phase using sodium hypophosphite as a multifunctional reducing agent. Due to the accelerated gelation kinetics induced by increased reaction temperature and specific function of sodium hypophosphite, the formation of hydrogels can be completed within 4 hrs, far faster than the previous reports. Owe to their unique porous structure and favorable geometric and electronic effects, the optimized PdPb@Pd aerogels exhibit enhanced electrochemical performancemore » towards ethylene glycol oxidation with a mass activity of 5.8 times higher than Pd black.« less

Hydrolysis reaction of 2,4-dichlorophenoxyacetic acid. A kinetic and computational study

NASA Astrophysics Data System (ADS)

Romero, Jorge Marcelo; Jorge, Nelly Lidia; Grand, André; Hernández-Laguna, Alfonso

2015-10-01

The degradation of the 2,4-dichlorophenoxyacetic acid in aqueous solution is an hydrolysis reaction. Two products are identified: 2,4-dichlorophenol and glycolic acid. Reaction is investigated as a function of pH and temperature, and it is first-order kinetics and pH-dependent. Reaction is modeled in gas phase, where a proton catalyses the reaction. Critical points of PES are calculated at B3LYP/6-311++G(3df,2p), and aug-cc-pvqz//6-311++G(3df,2p) levels plus ZPE at 6-311++G(3df,2p) level. The activation barrier is 21.2 kcal/mol. Theoretical results agree with the experimental results. A second mechanism related with a Cl2Phsbnd Osbnd CH2sbnd COOH⋯H2O complex is found, but with a rate limiting step of 38.4 kcal/mol.

Kinetic theory of oxygen isotopic exchange between minerals and water

USGS Publications Warehouse

Criss, R.E.; Gregory, R.T.; Taylor, H.P.

1987-01-01

Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

Cesium and Strontium Retentions Governed by Aluminosilicate Gel in Alkali-Activated Cements

PubMed Central

Jang, Jeong Gook; Park, Sol Moi; Lee, Haeng Ki

2017-01-01

The present study investigates the retention mechanisms of cesium and strontium for alkali-activated cements. Retention mechanisms such as adsorption and precipitation were examined in light of chemical interactions. Batch adsorption experiments and multi-technical characterizations by using X-ray diffraction, zeta potential measurements, and the N2 gas adsorption/desorption methods were conducted for this purpose. Strontium was found to crystalize in alkali-activated cements, while no cesium-bearing crystalline phases were detected. The adsorption kinetics of alkali-activated cements having relatively high adsorption capacities were compatible with pseudo-second-order kinetic model, thereby suggesting that it is governed by complex multistep adsorption. The results provide new insight, demonstrating that characteristics of aluminosilicate gel with a highly negatively charged surface and high micropore surface area facilitated more effective immobilization of cesium and strontium in comparison with calcium silicate hydrates. PMID:28772803

Kinetics of gas phase formic acid decomposition on platinum single crystal and polycrystalline surfaces

NASA Astrophysics Data System (ADS)

Detwiler, Michael D.; Milligan, Cory A.; Zemlyanov, Dmitry Y.; Delgass, W. Nicholas; Ribeiro, Fabio H.

2016-06-01

Formic acid dehydrogenation turnover rates (TORs) were measured on Pt(111), Pt(100), and polycrystalline Pt foil surfaces at a total pressure of 800 Torr between 413 and 513 K in a batch reactor connected to an ultra-high vacuum (UHV) system. The TORs, apparent activation energies, and reaction orders are not sensitive to the structure of the Pt surface, within the precision of the measurements. CO introduced into the batch reactor depressed the formic acid dehydrogenation TOR and increased the reaction's apparent activation energies on Pt(111) and Pt(100), consistent with behavior predicted by the Temkin equation. Two reaction mechanisms were explored which explain the formic acid decomposition mechanism on Pt, both of which include dissociative adsorption of formic acid, rate limiting formate decomposition, and quasi-equilibrated hydrogen recombination and CO adsorption. No evidence was found that catalytic supports used in previous studies altered the reaction kinetics or mechanism.

Application of Synthetic Layered Sodium Silicate Magadiite Nanosheets for Environmental Remediation of Methylene Blue Dye in Water

PubMed Central

2017-01-01

The removal of methylene blue (MB) dye from water was investigated using synthetic nano-clay magadiite (SNCM). SNCM was synthesized by a hydrothermal treatment under autogenous pressure. A rosette-shaped single mesoporous magadiite phase with 16.63 nm average crystallite size and 33 m2∙g−1 Braunauer-Emmet-Teller (BET)-surface area was recorded. The adsorption results indicated the pronounced affinity of the SNCM to the MB dye molecules, which reached an adsorption uptake of 20.0 mg MB dye/g of SNCM. The elimination of MB dye by the SNCM was kinetically and thermodynamically considered; a pseudo-second-order kinetic model was attained, and its spontaneous, chemical, and endothermic nature was verified. SNCM was shown to be robust without a detectable reduction in the adsorption capacity after up to four times re-use. PMID:28773120

Degradation of high energetic and insensitive munitions compounds by Fe/Cu bimetal reduction.

PubMed

Koutsospyros, Agamemnon; Pavlov, Julius; Fawcett, Jacqueline; Strickland, David; Smolinski, Benjamin; Braida, Washington

2012-06-15

A reductive technology based on a completely mixed two-phase reactor (bimetallic particles and aqueous stream) was developed for the treatment of aqueous effluents contaminated with nitramines and nitro-substituted energetic materials. Experimental degradation studies were performed using solutions of three high energetics (RDX, HMX, TNT) and three insensitive-munitions components (NTO, NQ, DNAN). The study shows that, on laboratory scale, these energetic compounds are easily degraded in solution by suspensions of bimetallic particles (Fe/Ni and Fe/Cu) prepared by electro-less deposition. The type of bimetal pair (Fe/Cu or Fe/Ni) does not appear to affect the degradation kinetics of RDX, HMX, and TNT. The degradation of all components followed apparent first-order kinetics. The half-lives of all compounds except NTO were under 10 min. Additional parameters affecting the degradation processes were solids loading and initial pH. Copyright © 2012 Elsevier B.V. All rights reserved.

Saturation mechanisms of backward stimulated Raman scattering in a one-dimensional geometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Friou, A.; Bénisti, D.; Gremillet, L.

2013-10-15

In this paper, we investigate the saturation mechanisms of backward stimulated Raman scattering (BSRS) induced by nonlinear kinetic effects. In particular, we stress the importance of accounting for both the nonlinear frequency shift of the electron plasma wave and the growth of sidebands, in order to understand what stops the coherent growth of Raman scattering. Using a Bernstein-Greene-Kruskal approach, we provide an estimate for the maximum amplitude reached by a BSRS-driven plasma wave after the phase of monotonic growth. This estimate is in very good agreement with the results from kinetic simulations of stimulated Raman scattering using both a Vlasovmore » and a Particle in Cell code. Our analysis, which may be generalized to a multidimensional geometry, should provide a means to estimate the limits of backward Raman amplification or the effectiveness of strategies that aim at strongly reducing Raman reflectivity in a fusion plasma.« less

Fibril growth kinetics link buffer conditions and topology of 3D collagen I networks.

PubMed

Kalbitzer, Liv; Pompe, Tilo

2018-02-01

Three-dimensional fibrillar networks reconstituted from collagen I are widely used as biomimetic scaffolds for in vitro and in vivo cell studies. Various physicochemical parameters of buffer conditions for in vitro fibril formation are well known, including pH-value, ion concentrations and temperature. However, there is a lack of a detailed understanding of reconstituting well-defined 3D network topologies, which is required to mimic specific properties of the native extracellular matrix. We screened a wide range of relevant physicochemical buffer conditions and characterized the topology of the reconstituted 3D networks in terms of mean pore size and fibril diameter. A congruent analysis of fibril formation kinetics by turbidimetry revealed the adjustment of the lateral growth phase of fibrils by buffer conditions to be key in the determination of pore size and fibril diameter of the networks. Although the kinetics of nucleation and linear growth phase were affected by buffer conditions as well, network topology was independent of those two growth phases. Overall, the results of our study provide necessary insights into how to engineer 3D collagen matrices with an independent control over topology parameters, in order to mimic in vivo tissues in in vitro experiments and tissue engineering applications. The study reports a comprehensive analysis of physicochemical conditions of buffer solutions to reconstitute defined 3D collagen I matrices. By a combined analysis of network topology, i.e., pore size and fibril diameter, and the kinetics of fibril formation we can reveal the dependence of 3D network topology on buffer conditions, such as pH-value, phosphate concentration and sodium chloride content. With those results we are now able to provide engineering strategies to independently tune the topology parameters of widely used 3D collagen scaffolds based on the buffer conditions. By that, we enable the straightforward mimicking of extracellular matrices of in vivo tissues for in vitro cell culture experiments and tissue engineering applications. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Equilibrium, kinetic, and reactive transport models for plutonium

NASA Astrophysics Data System (ADS)

Schwantes, Jon Michael

Equilibrium, kinetic, and reactive transport models for plutonium (Pu) have been developed to help meet environmental concerns posed by past war-related and present and future peacetime nuclear technologies. A thorough review of the literature identified several hurdles that needed to be overcome in order to develop capable predictive tools for Pu. These hurdles include: (1) missing or ill-defined chemical equilibrium and kinetic constants for environmentally important Pu species; (2) no adequate conceptual model describing the formation of Pu oxy/hydroxide colloids and solids; and (3) an inability of two-phase reactive transport models to adequately simulate Pu behavior in the presence of colloids. A computer program called INVRS K was developed that integrates the geochemical modeling software of PHREEQC with a nonlinear regression routine. This program provides a tool for estimating equilibrium and kinetic constants from experimental data. INVRS K was used to regress on binding constants for Pu sorbing onto various mineral and humic surfaces. These constants enhance the thermodynamic database for Pu and improve the capability of current predictive tools. Time and temperature studies of the Pu intrinsic colloid were also conducted and results of these studies were presented here. Formation constants for the fresh and aged Pu intrinsic colloid were regressed upon using INVRS K. From these results, it was possible to develop a cohesive diagenetic model that describes the formation of Pu oxy/hydroxide colloids and solids. This model provides for the first time a means of deciphering historically unexplained observations with respect to the Pu intrinsic colloid, as well as a basis for simulating the behavior within systems containing these solids. Discussion of the development and application of reactive transport models is also presented and includes: (1) the general application of a 1-D in flow, three-phase (i.e., dissolved, solid, and colloidal), reactive transport model; (2) a simulation of the effects of dissolution of PuO2 solid and radiolysis on the behavior of Pu diffusing out of a confined pore space; and (3) application of a steady-state three phase reactive transport model to groundwater at the Nevada Test Site.

Persistence of glyphosate and aminomethylphosphonic acid in loess soil under different combinations of temperature, soil moisture and light/darkness.

PubMed

Bento, Célia P M; Yang, Xiaomei; Gort, Gerrit; Xue, Sha; van Dam, Ruud; Zomer, Paul; Mol, Hans G J; Ritsema, Coen J; Geissen, Violette

2016-12-01

The dissipation kinetics of glyphosate and its metabolite aminomethylphosphonic acid (AMPA) were studied in loess soil, under biotic and abiotic conditions, as affected by temperature, soil moisture (SM) and light/darkness. Nonsterile and sterile soil samples were spiked with 16mgkg -1 of glyphosate, subjected to three SM contents (20% WHC, 60% WHC, saturation), and incubated for 30days at 5°C and 30°C, under dark and light regimes. Glyphosate and AMPA dissipation kinetics were fit to single-first-order (SFO) or first-order-multicompartment (FOMC) models, per treatment combination. AMPA kinetic model included both the formation and decline phases. Glyphosate dissipation kinetics followed SFO at 5°C, but FOMC at 30°C. AMPA followed SFO dissipation kinetics for all treatments. Glyphosate and AMPA dissipation occurred mostly by microbial activity. Abiotic processes played a negligible role for both compounds. Under biotic conditions, glyphosate dissipation and AMPA formation/dissipation were primarily affected by temperature, but also by SM. Light regimes didn't play a significant role. Glyphosate DT50 varied between 1.5 and 53.5days, while its DT90 varied between 8.0 and 280days, depending on the treatment. AMPA persisted longer in soil than glyphosate, with its DT50 at 30°C ranging between 26.4 and 44.5days, and its DT90 between 87.8 and 148days. The shortest DT50/DT90 values for both compounds occurred at 30°C and under optimal/saturated moisture conditions, while the largest occurred at 5°C and reaching drought stress conditions. Based on these results, we conclude that glyphosate and AMPA dissipate rapidly under warm and rainy climate conditions. However, repeated glyphosate applications in fallows or winter crops in countries where cold and dry winters normally occur could lead to on-site soil pollution, with consequent potential risks to the environment and human health. To our knowledge, this study is the first evaluating the combined effect of temperature, soil moisture and light/dark conditions on AMPA formation/dissipation kinetics and behaviour. Copyright © 2016 Elsevier B.V. All rights reserved.

Modeling non‐linear kinetics of hyperpolarized [1‐13C] pyruvate in the crystalloid‐perfused rat heart

PubMed Central

Mariotti, E.; Orton, M. R.; Eerbeek, O.; Ashruf, J. F.; Zuurbier, C. J.; Southworth, R.

2016-01-01

Hyperpolarized 13C MR measurements have the potential to display non‐linear kinetics. We have developed an approach to describe possible non‐first‐order kinetics of hyperpolarized [1‐13C] pyruvate employing a system of differential equations that agrees with the principle of conservation of mass of the hyperpolarized signal. Simultaneous fitting to a second‐order model for conversion of [1‐13C] pyruvate to bicarbonate, lactate and alanine was well described in the isolated rat heart perfused with Krebs buffer containing glucose as sole energy substrate, or glucose supplemented with pyruvate. Second‐order modeling yielded significantly improved fits of pyruvate–bicarbonate kinetics compared with the more traditionally used first‐order model and suggested time‐dependent decreases in pyruvate–bicarbonate flux. Second‐order modeling gave time‐dependent changes in forward and reverse reaction kinetics of pyruvate–lactate exchange and pyruvate–alanine exchange in both groups of hearts during the infusion of pyruvate; however, the fits were not significantly improved with respect to a traditional first‐order model. The mechanism giving rise to second‐order pyruvate dehydrogenase (PDH) kinetics was explored experimentally using surface fluorescence measurements of nicotinamide adenine dinucleotide reduced form (NADH) performed under the same conditions, demonstrating a significant increase of NADH during pyruvate infusion. This suggests a simultaneous depletion of available mitochondrial NAD+ (the cofactor for PDH), consistent with the non‐linear nature of the kinetics. NADH levels returned to baseline following cessation of the pyruvate infusion, suggesting this to be a transient effect. © 2016 The Authors. NMR in Biomedicine published by John Wiley & Sons Ltd. PMID:26777799

Development of an automated method to detect sitting pivot transfer phases using biomechanical variables: toward a standardized method

PubMed Central

2012-01-01

Background Sitting pivot transfer (SPT) is one of the most important, but at the same time strenuous at the upper extremity, functional task for spinal cord injured individuals. In order to better teach this task to those individuals and to improve performance, a better biomechanical understanding during the different SPT phases is a prerequisite. However, no consensus has yet been reached on how to depict the different phases of the SPT. The definition of the phases of the SPT, along with the events characterizing these phases, will facilitate the interpretation of biomechanical outcome measures related to the performance of SPTs as well as strengthen the evidence generated across studies. Methods Thirty-five individuals with a spinal cord injury performed two SPTs between seats of similar height using their usual SPT technique. Kinematics and kinetics were recorded using an instrumented transfer assessment system. Based on kinetic and kinematic measurements, a relative threshold-based algorithm was developed to identify four distinct phases: pre-lift, upper arm loading, lift-pivot and post-lift phases. To determine the stability of the algorithm between the two SPTs, Student t-tests for dependent samples were performed on the absolute duration of each phase. Results The mean total duration of the SPT was 2.00 ± 0.49 s. The mean duration of the pre-lift, upper arm loading, lift-pivot and post-lift phases were 0.74 ± 0.29 s, 0.28 ± 0.13 s, 0.72 ± 0.24 s, 0.27 ± 0.14 s whereas their relative contributions represented approximately 35%, 15%, 35% and 15% of the overall SPT cycle, respectively. No significant differences were found between the trials (p = 0.480-0.891). Conclusion The relative threshold-based algorithm used to automatically detect the four distinct phases of the SPT, is rapid, accurate and repeatable. A quantitative and thorough description of the precise phases of the SPT is prerequisite to better interpret biomechanical findings and measure task performance. The algorithm could also become clinically useful to refine the assessment and training of SPTs. PMID:22305052

Three-dimensional theory of the magneto-optical trap

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prudnikov, O. N., E-mail: llf@laser.nsc.ru; Taichenachev, A. V.; Yudin, V. I.

2015-04-15

The kinetics of atoms in a three-dimensional magneto-optical trap (MOT) is considered. A three-dimensional MOT model has been constructed for an atom with the optical transition J{sub g} = 0 → J{sub e} = 1 (J{sub g,} {sub e} is the total angular momentum in the ground and excited states) in the semiclassical approximation by taking into account the influence of the relative phases of light fields on the kinetics of atoms. We show that the influence of the relative phases can be neglected only in the limit of low light field intensities. Generally, the choice of relative phases canmore » have a strong influence on the kinetics of atoms in a MOT.« less

Collective translational and rotational Monte Carlo cluster move for general pairwise interaction

NASA Astrophysics Data System (ADS)

Růžička, Štěpán; Allen, Michael P.

2014-09-01

Virtual move Monte Carlo is a cluster algorithm which was originally developed for strongly attractive colloidal, molecular, or atomistic systems in order to both approximate the collective dynamics and avoid sampling of unphysical kinetic traps. In this paper, we present the algorithm in the form, which selects the moving cluster through a wider class of virtual states and which is applicable to general pairwise interactions, including hard-core repulsion. The newly proposed way of selecting the cluster increases the acceptance probability by up to several orders of magnitude, especially for rotational moves. The results have their applications in simulations of systems interacting via anisotropic potentials both to enhance the sampling of the phase space and to approximate the dynamics.

Synchrotron Study on Crystallization Kinetics of Milk Fat under Shear Flow

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazzanti, G.; Marangoni, A; Idziak, S

A detailed synchrotron X-ray diffraction study on the kinetics of crystallization of anhydrous milk fat (AMF) and milk fat triacylglycerols (MFT) was done in a Couette cell at 17 C, 17.5 C and 20 C under shear rates between 0 and 2880 s-1. We observed shear-induced acceleration of the transition from phase ? to ?? and the presence of crystalline orientation, but no effect of shear on the onset time of phase ? was observed. A two stage regime was observed for the growth of phase ??. The first stage follows a series-parallel system of differential equations describing the conversionmore » between liquid and crystalline phases. The second stage follows a diffusion-controlled regime. These mechanisms are consistent with the crystalline orientation, the growth of the crystalline domains and the observed displacement of the diffraction peak positions. The absence of the polar lipids explains the faster kinetics of MFT.« less

Early stages of carbonate mineralization revealed from molecular simulations: Implications for biomineral formation

NASA Astrophysics Data System (ADS)

Wallace, A. F.; DeYoreo, J.; Banfield, J. F.

2011-12-01

The carbonate mineral constituents of many biomineralized products, formed both in and ex vivo, grow by a multi-stage crystallization process that involves the nucleation and structural reorganization of transient amorphous phases. The existence of transient phases and cluster species has significant implications for carbonate nucleation and growth in natural and engineered environments, both modern and ancient. The structure of these intermediate phases remains elusive, as does the nature of the disorder to order transition, however, these process details may strongly influence the interpretation of elemental and isotopic climate proxy data obtained from authigenic and biogenic carbonates. While molecular simulations have been applied to certain aspects of crystal growth, studies of metal carbonate nucleation are strongly inhibited by the presence of kinetic traps that prevent adequate sampling of the potential landscape upon which the growing clusters reside within timescales accessible by simulation. This research addresses this challenge by marrying the recent Kawska-Zahn (KZ) approach to simulation of crystal nucleation and growth from solution with replica-exchange molecular dynamics (REMD) techniques. REMD has been used previously to enhance sampling of protein conformations that occupy energy wells that are separated by sizable thermodynamic and kinetic barriers, and is used here to probe the initial formation and onset of order within hydrated calcium and iron carbonate cluster species during nucleation. Results to date suggest that growing clusters initiate as short linear ion chains that evolve into two- and three-dimensional structures with continued growth. The planar structures exhibit an obvious 2d lattice, while establishment of a 3d lattice is hindered by incomplete ion desolvation. The formation of a dehydrated core consisting of a single carbonate ion is observed when the clusters are ~0.75 nm. At the same size a distorted, but discernible calcite-type lattice is also apparent. Continued growth results in expansion of the dehydrated core, however, complete desolvation and incorporation of cations into the growing carbonate phase is not achieved until the cluster grows to ~1.2 nm. Exploration of the system free energy along the crystallization path reveals "special" cluster sizes that correlate with ion desolvation milestones. The formation of these species comprise critical bottlenecks on the energy landscape and for the establishment of order within the growing clusters.