Surface transport processes in charged porous media

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

Gabitto, Jorge; Tsouris, Costas

Surface transport processes are important in chemistry, colloidal sciences, engineering, biology, and geophysics. Natural or externally produced charges on surfaces create electrical double layers (EDLs) at the solid-liquid interface. The existence of the EDLs produces several complex processes including bulk and surface transport of ions. In this work, a model is presented to simulate bulk and transport processes in homogeneous porous media comprising big pores. It is based on a theory for capacitive charging by ideally polarizable porous electrodes without Faradaic reactions or specific adsorption of ions. A volume averaging technique is used to derive the averaged transport equations inmore » the limit of thin electrical double layers. Description of the EDL between the electrolyte solution and the charged wall is accomplished using the Gouy-Chapman-Stern (GCS) model. The surface transport terms enter into the average equations due to the use of boundary conditions for diffuse interfaces. Two extra surface transports terms appear in the closed average equations. One is a surface diffusion term equivalent to the transport process in non-charged porous media. The second surface transport term is a migration term unique to charged porous media. The effective bulk and transport parameters for isotropic porous media are calculated solving the corresponding closure problems.« less

High Interfacial Barriers at Narrow Carbon Nanotube-Water Interfaces.

PubMed

Varanasi, Srinivasa Rao; Subramanian, Yashonath; Bhatia, Suresh K

2018-06-26

Water displays anomalous fast diffusion in narrow carbon nanotubes (CNTs), a behavior that has been reproduced in both experimental and simulation studies. However, little is reported on the effect of bulk water-CNT interfaces, which is critical to exploiting the fast transport of water across narrow carbon nanotubes in actual applications. Using molecular dynamics simulations, we investigate here the effect of such interfaces on the transport of water across arm-chair CNTs of different diameters. Our results demonstrate that diffusion of water is significantly retarded in narrow CNTs due to bulk regions near the pore entrance. The slowdown of dynamics can be attributed to the presence of large energy barriers at bulk water-CNT interfaces. The presence of such intense barriers at the bulk-CNT interface arises due to the entropy contrast between the bulk and confined regions, with water molecules undergoing high translational and rotational entropy gain on entering from the bulk to the CNT interior. The intensity of such energy barriers decreases with increase in CNT diameter. These results are very important for emerging technological applications of CNTs and other nanoscale materials, such as in nanofluidics, water purification, nanofiltration, and desalination, as well as for biological transport processes.

First principles calculations of point defect diffusion in CdS buffer layers: Implications for Cu(In,Ga)(Se,S){sub 2} and Cu{sub 2}ZnSn(Se,S){sub 4}-based thin-film photovoltaics

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

Varley, J. B.; Lordi, V.; He, X.

2016-01-14

We investigate point defects in CdS buffer layers that may arise from intermixing with Cu(In,Ga)Se{sub 2} (CIGSe) or Cu{sub 2}ZnSn(S,Se){sub 4} (CZTSSe) absorber layers in thin-film photovoltaics (PV). Using hybrid functional calculations, we characterize the migration barriers of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities and assess the activation energies necessary for their diffusion into the bulk of the buffer. We find that Cu, In, and Ga are the most mobile defects in CIGS-derived impurities, with diffusion expected to proceed into the buffer via interstitial-hopping and cadmium vacancy-assisted mechanisms at temperatures ∼400 °C. Cu is predicted to stronglymore » favor migration paths within the basal plane of the wurtzite CdS lattice, which may facilitate defect clustering and ultimately the formation of Cu-rich interfacial phases as observed by energy dispersive x-ray spectroscopic elemental maps in real PV devices. Se, Zn, and Sn defects are found to exhibit much larger activation energies and are not expected to diffuse within the CdS bulk at temperatures compatible with typical PV processing temperatures. Lastly, we find that Na interstitials are expected to exhibit slightly lower activation energies than K interstitials despite having a larger migration barrier. Still, we find both alkali species are expected to diffuse via an interstitially mediated mechanism at slightly higher temperatures than enable In, Ga, and Cu diffusion in the bulk. Our results indicate that processing temperatures in excess of ∼400 °C will lead to more interfacial intermixing with CdS buffer layers in CIGSe devices, and less so for CZTSSe absorbers where only Cu is expected to significantly diffuse into the buffer.« less

Spreading of a liquid film on a substrate by the evaporation-adsorption process

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

Wayner, P.C. Jr.; Schonberg, J.

1992-09-01

The importance of evaporation followed by multilayer adsorption in comparison to liquid flow at the leading edge of a volatile spreading film is analyzed. Presuming that both flows are functions of the same chemical potential gradient, a dimensionless group (N) which delineates the relative importance of vapor diffusion flow to viscous flow on the surface is obtained: N = [rho][sub i]D[nu]x/([minus][bar A][pi]). The relative importance of vapor flow increases with the vapor-pressure dependent partial density, [rho][sub i], and diffusivity, D, of the diffusing vapor, the kinematic viscosity of the liquid, [nu], and the distance downstream from the bulk liquid region,more » x, and decreases with the Hamaker constant, 6[pi][bar A]. Using physical properties the modifiers volatile'' and nonvolatile'' can thereby be put in perspective. Changes in the interfacial force field are a function of [bar A]. The spreading velocity due to the vapor diffusion process is obtained and is found to decrease with a decrease in the interfacial force field and the bulk vapor pressure. The infinite stress at the contact line can be easily relieved by evaporation-adsorption in many systems.« less

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Hoffmann, C.; Kolesnikov, A. I.; Mamontov, E.; Podlesnyak, A. A.; Wang, X.; Kent, P. R. C.; Anovitz, L. M.

2018-05-01

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factor reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10-100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

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

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Fast Rotational Diffusion of Water Molecules in a 2D Hydrogen Bond Network at Cryogenic Temperatures

DOE PAGES

Prisk, Timothy; Hoffmann, Christina; Kolesnikov, Alexander I.; ...

2018-05-09

Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less

Comparison of GEOS-5 AGCM planetary boundary layer depths computed with various definitions

NASA Astrophysics Data System (ADS)

McGrath-Spangler, E. L.; Molod, A.

2014-07-01

Accurate models of planetary boundary layer (PBL) processes are important for forecasting weather and climate. The present study compares seven methods of calculating PBL depth in the GEOS-5 atmospheric general circulation model (AGCM) over land. These methods depend on the eddy diffusion coefficients, bulk and local Richardson numbers, and the turbulent kinetic energy. The computed PBL depths are aggregated to the Köppen-Geiger climate classes, and some limited comparisons are made using radiosonde profiles. Most methods produce similar midday PBL depths, although in the warm, moist climate classes the bulk Richardson number method gives midday results that are lower than those given by the eddy diffusion coefficient methods. Additional analysis revealed that methods sensitive to turbulence driven by radiative cooling produce greater PBL depths, this effect being most significant during the evening transition. Nocturnal PBLs based on Richardson number methods are generally shallower than eddy diffusion coefficient based estimates. The bulk Richardson number estimate is recommended as the PBL height to inform the choice of the turbulent length scale, based on the similarity to other methods during the day, and the improved nighttime behavior.

Comparison of GEOS-5 AGCM Planetary Boundary Layer Depths Computed with Various Definitions

NASA Technical Reports Server (NTRS)

Mcgrath-Spangler, E. L.; Molod, A.

2014-01-01

Accurate models of planetary boundary layer (PBL) processes are important for forecasting weather and climate. The present study compares seven methods of calculating PBL depth in the GEOS-5 atmospheric general circulation model (AGCM) over land. These methods depend on the eddy diffusion coefficients, bulk and local Richardson numbers, and the turbulent kinetic energy. The computed PBL depths are aggregated to the Koppen climate classes, and some limited comparisons are made using radiosonde profiles. Most methods produce similar midday PBL depths, although in the warm, moist climate classes, the bulk Richardson number method gives midday results that are lower than those given by the eddy diffusion coefficient methods. Additional analysis revealed that methods sensitive to turbulence driven by radiative cooling produce greater PBL depths, this effect being most significant during the evening transition. Nocturnal PBLs based on Richardson number are generally shallower than eddy diffusion coefficient based estimates. The bulk Richardson number estimate is recommended as the PBL height to inform the choice of the turbulent length scale, based on the similarity to other methods during the day, and the improved nighttime behavior.

Comparison of GEOS-5 AGCM planetary boundary layer depths computed with various definitions

NASA Astrophysics Data System (ADS)

McGrath-Spangler, E. L.; Molod, A.

2014-03-01

Accurate models of planetary boundary layer (PBL) processes are important for forecasting weather and climate. The present study compares seven methods of calculating PBL depth in the GEOS-5 atmospheric general circulation model (AGCM) over land. These methods depend on the eddy diffusion coefficients, bulk and local Richardson numbers, and the turbulent kinetic energy. The computed PBL depths are aggregated to the Köppen climate classes, and some limited comparisons are made using radiosonde profiles. Most methods produce similar midday PBL depths, although in the warm, moist climate classes, the bulk Richardson number method gives midday results that are lower than those given by the eddy diffusion coefficient methods. Additional analysis revealed that methods sensitive to turbulence driven by radiative cooling produce greater PBL depths, this effect being most significant during the evening transition. Nocturnal PBLs based on Richardson number are generally shallower than eddy diffusion coefficient based estimates. The bulk Richardson number estimate is recommended as the PBL height to inform the choice of the turbulent length scale, based on the similarity to other methods during the day, and the improved nighttime behavior.

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

Perriot, Romain; Dholabhai, Pratik P.; Uberuaga, Blas P.

In this paper, we use molecular dynamics simulations to investigate the role of grain boundaries (GBs) on ionic diffusion in pyrochlores, as a function of the GB type, chemistry of the compound, and level of cation disorder. We observe that the presence of GBs promotes oxygen transport in ordered and low-disordered systems, as the GBs are found to have a higher concentration of mobile carriers with higher mobilities than in the bulk. Thus, in ordered samples, the ionic diffusion is 2D, localized along the grain boundary. When cation disorder is introduced, bulk carriers begin to contribute to the overall diffusion,more » while the GB contribution is only slightly enhanced. In highly disordered samples, the diffusive behavior at the GBs is bulk-like, and the two contributions (bulk vs. GB) can no longer be distinguished. There is thus a transition from 2D/GB dominated oxygen diffusivity to 3D/bulk dominated diffusivity versus disorder in pyrochlores. Finally, these results provide new insights into the possibility of using internal interfaces to enhance ionic conductivity in nanostructured complex oxides.« less

Revisited reaction-diffusion model of thermal desorption spectroscopy experiments on hydrogen retention in material

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

Guterl, Jerome, E-mail: jguterl@ucsd.edu; Smirnov, R. D.; Krasheninnikov, S. I.

Desorption phase of thermal desorption spectroscopy (TDS) experiments performed on tungsten samples exposed to flux of hydrogen isotopes in fusion relevant conditions is analyzed using a reaction-diffusion model describing hydrogen retention in material bulk. Two regimes of hydrogen desorption are identified depending on whether hydrogen trapping rate is faster than hydrogen diffusion rate in material during TDS experiments. In both regimes, a majority of hydrogen released from material defects is immediately outgassed instead of diffusing deeply in material bulk when the evolution of hydrogen concentration in material is quasi-static, which is the case during TDS experiments performed with tungsten samplesmore » exposed to flux of hydrogen isotopes in fusion related conditions. In this context, analytical expressions of the hydrogen outgassing flux as a function of the material temperature are obtained with sufficient accuracy to describe main features of thermal desorption spectra (TDSP). These expressions are then used to highlight how characteristic temperatures of TDSP depend on hydrogen retention parameters, such as trap concentration or activation energy of detrapping processes. The use of Arrhenius plots to characterize retention processes is then revisited when hydrogen trapping takes place during TDS experiments. Retention processes are also characterized using the shape of desorption peaks in TDSP, and it is shown that diffusion of hydrogen in material during TDS experiment can induce long desorption tails visible aside desorption peaks at high temperature in TDSP. These desorption tails can be used to estimate activation energy of diffusion of hydrogen in material.« less

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

NASA Astrophysics Data System (ADS)

Shiraiwa, Manabu; Pfrang, Christian; Pöschl, Ulrich

2010-05-01

Aerosols are ubiquitous in the atmosphere and have strong effects on climate and public health. Gas-particle interactions can significantly change the physical and chemical properties of aerosols such as toxicity, reactivity, hygroscopicity and radiative properties. Chemical reactions and mass transport lead to continuous transformation and changes in the composition of atmospheric aerosols ("chemical aging"). Resistor model formulations are widely used to describe and investigate heterogeneous reactions and multiphase processes in laboratory, field and model studies of atmospheric chemistry. The traditional resistor models, however, are usually based on simplifying assumptions such as steady state conditions, homogeneous mixing, and limited numbers of non-interacting species and processes. In order to overcome these limitations, Pöschl, Rudich and Ammann have developed a kinetic model framework (PRA framework) with a double-layer surface concept and universally applicable rate equations and parameters for mass transport and chemical reactions at the gas-particle interface of aerosols and clouds [1]. Based on the PRA framework, we present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB) [2]. The model includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical life-times of multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (~10-10 cm2 s-1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models. References [1] Pöschl et al., Atmos. Chem. and Phys., 7, 5989-6023 (2007). [2] Shiraiwa et al., Atmos. Chem. Phys. Discuss., 10, 281-326 (2010).

Crystal surface integrity and diffusion measurements on Earth and planetary materials

NASA Astrophysics Data System (ADS)

Watson, E. B.; Cherniak, D. J.; Thomas, J. B.; Hanchar, J. M.; Wirth, R.

2016-09-01

Characterization of diffusion behavior in minerals is key to providing quantitative constraints on the ages and thermal histories of Earth and planetary materials. Laboratory experiments are a vital source of the needed diffusion measurements, but these can pose challenges because the length scales of diffusion achievable in a laboratory time are commonly less than 1 μm. An effective strategy for dealing with this challenge is to conduct experiments involving inward diffusion of the element of interest from a surface source, followed by quantification of the resulting diffusive-uptake profile using a high-resolution depth-profiling technique such as Rutherford backscattering spectroscopy (RBS), nuclear reaction analysis (NRA), or ion microprobe (SIMS). The value of data from such experiments is crucially dependent on the assumption that diffusion in the near-surface of the sample is representative of diffusion in the bulk material. Historical arguments suggest that the very process of preparing a polished surface for diffusion studies introduces defects-in the form of dislocations and cracks-in the outermost micrometer of the sample that make this region fundamentally different from the bulk crystal in terms of its diffusion properties. Extensive indirect evidence suggests that, in fact, the near-surface region of carefully prepared samples is no different from the bulk crystal in terms of its diffusion properties. A direct confirmation of this conclusion is nevertheless clearly important. Here we use transmission electron microscopy to confirm that the near-surface regions of olivine, quartz and feldspar crystals prepared using careful polishing protocols contain no features that could plausibly affect diffusion. This finding does not preclude damage to the mineral structure from other techniques used in diffusion studies (e.g., ion implantation), but even in this case the role of possible structural damage can be objectively assessed and controlled. While all evidence points to the reliability of diffusivities obtained from in-diffusion experiments, we do not recommend experiments of this type using a powder source as a means of obtaining diffusant solubility or partitioning information for the mineral of interest.

Multimodel analysis of anisotropic diffusive tracer-gas transport in a deep arid unsaturated zone

USGS Publications Warehouse

Green, Christopher T.; Walvoord, Michelle Ann; Andraski, Brian J.; Striegl, Robert G.; Stonestrom, David A.

2015-01-01

Gas transport in the unsaturated zone affects contaminant flux and remediation, interpretation of groundwater travel times from atmospheric tracers, and mass budgets of environmentally important gases. Although unsaturated zone transport of gases is commonly treated as dominated by diffusion, the characteristics of transport in deep layered sediments remain uncertain. In this study, we use a multimodel approach to analyze results of a gas-tracer (SF6) test to clarify characteristics of gas transport in deep unsaturated alluvium. Thirty-five separate models with distinct diffusivity structures were calibrated to the tracer-test data and were compared on the basis of Akaike Information Criteria estimates of posterior model probability. Models included analytical and numerical solutions. Analytical models provided estimates of bulk-scale apparent diffusivities at the scale of tens of meters. Numerical models provided information on local-scale diffusivities and feasible lithological features producing the observed tracer breakthrough curves. The combined approaches indicate significant anisotropy of bulk-scale diffusivity, likely associated with high-diffusivity layers. Both approaches indicated that diffusivities in some intervals were greater than expected from standard models relating porosity to diffusivity. High apparent diffusivities and anisotropic diffusivity structures were consistent with previous observations at the study site of rapid lateral transport and limited vertical spreading of gas-phase contaminants. Additional processes such as advective oscillations may be involved. These results indicate that gases in deep, layered unsaturated zone sediments can spread laterally more quickly, and produce higher peak concentrations, than predicted by homogeneous, isotropic diffusion models.

Anomalous Surface Diffusion of Protons on Lipid Membranes

PubMed Central

Wolf, Maarten G.; Grubmüller, Helmut; Groenhof, Gerrit

2014-01-01

The cellular energy machinery depends on the presence and properties of protons at or in the vicinity of lipid membranes. To asses the energetics and mobility of a proton near a membrane, we simulated an excess proton near a solvated DMPC bilayer at 323 K, using a recently developed method to include the Grotthuss proton shuttling mechanism in classical molecular dynamics simulations. We obtained a proton surface affinity of −13.0 ± 0.5 kJ mol−1. The proton interacted strongly with both lipid headgroup and linker carbonyl oxygens. Furthermore, the surface diffusion of the proton was anomalous, with a subdiffusive regime over the first few nanoseconds, followed by a superdiffusive regime. The time- and distance dependence of the proton surface diffusion coefficient within these regimes may also resolve discrepancies between previously reported diffusion coefficients. Our simulations show that the proton anomalous surface diffusion originates from restricted diffusion in two different surface-bound states, interrupted by the occasional bulk-mediated long-range surface diffusion. Although only a DMPC membrane was considered in this work, we speculate that the restrictive character of the on-surface diffusion is highly sensitive to the specific membrane conditions, which can alter the relative contributions of the surface and bulk pathways to the overall diffusion process. Finally, we discuss the implications of our findings for the energy machinery. PMID:24988343

Anomalous surface diffusion of protons on lipid membranes.

PubMed

Wolf, Maarten G; Grubmüller, Helmut; Groenhof, Gerrit

2014-07-01

The cellular energy machinery depends on the presence and properties of protons at or in the vicinity of lipid membranes. To asses the energetics and mobility of a proton near a membrane, we simulated an excess proton near a solvated DMPC bilayer at 323 K, using a recently developed method to include the Grotthuss proton shuttling mechanism in classical molecular dynamics simulations. We obtained a proton surface affinity of -13.0 ± 0.5 kJ mol(-1). The proton interacted strongly with both lipid headgroup and linker carbonyl oxygens. Furthermore, the surface diffusion of the proton was anomalous, with a subdiffusive regime over the first few nanoseconds, followed by a superdiffusive regime. The time- and distance dependence of the proton surface diffusion coefficient within these regimes may also resolve discrepancies between previously reported diffusion coefficients. Our simulations show that the proton anomalous surface diffusion originates from restricted diffusion in two different surface-bound states, interrupted by the occasional bulk-mediated long-range surface diffusion. Although only a DMPC membrane was considered in this work, we speculate that the restrictive character of the on-surface diffusion is highly sensitive to the specific membrane conditions, which can alter the relative contributions of the surface and bulk pathways to the overall diffusion process. Finally, we discuss the implications of our findings for the energy machinery. Copyright © 2014 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Facilitated Diffusion of Transcription Factor Proteins with Anomalous Bulk Diffusion.

PubMed

Liu, Lin; Cherstvy, Andrey G; Metzler, Ralf

2017-02-16

What are the physical laws of the diffusive search of proteins for their specific binding sites on DNA in the presence of the macromolecular crowding in cells? We performed extensive computer simulations to elucidate the protein target search on DNA. The novel feature is the viscoelastic non-Brownian protein bulk diffusion recently observed experimentally. We examine the influence of the protein-DNA binding affinity and the anomalous diffusion exponent on the target search time. In all cases an optimal search time is found. The relative contribution of intermittent three-dimensional bulk diffusion and one-dimensional sliding of proteins along the DNA is quantified. Our results are discussed in the light of recent single molecule tracking experiments, aiming at a better understanding of the influence of anomalous kinetics of proteins on the facilitated diffusion mechanism.

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

Lee, Min Ho; Rhyee, Jong-Soo, E-mail: jsrhyee@khu.ac.kr

We investigated the thermoelectric properties of PbTe/Ag{sub 2}Te bulk composites, synthesized by hand milling, mixing, and hot press sintering. From x-ray diffraction and energy dispersive x-ray spectroscopy measurements, we observed Ag{sub 2}Te phase separation in the PbTe matrix without Ag atom diffusion. In comparison with previously reported pseudo-binary (PbTe){sub 1−x}(Ag{sub 2}Te){sub x} composites, synthesized by high temperature phase separation, the PbTe/Ag{sub 2}Te bulk composites fabricated with a low temperature phase mixing process give rise to p-type conduction of carriers with significantly decreased electrical conductivity. This indicates that Ag atom diffusion in the PbTe matrix changes the sign of the Seebeckmore » coefficient to n-type and also increases the carrier concentration. Effective p-type doping with low temperature phase separation by mixing and hot press sintering can enhance the thermoelectric performance of PbTe/Ag{sub 2}Te bulk composites, which can be used as a p-type counterpart of n-type (PbTe){sub 1−x}(Ag{sub 2}Te){sub x} bulk composites.« less

A model for the compositions of non-stoichiometric intermediate phases formed by diffusion reactions, and its application to Nb 3Sn superconductors

DOE PAGES

Xu, X.; Sumption, M. D.

2016-01-12

In this work we explore the compositions of non-stoichiometric intermediate phases formed by diffusion reactions: a mathematical framework is developed and tested against the specific case of Nb 3Sn superconductors. In the first part, the governing equations for the bulk diffusion and interphase interface reactions during the growth of a compound are derived, numerical solutions to which give both the composition profile and growth rate of the compound layer. The analytic solutions are obtained with certain approximations made. In the second part, we explain an effect that the composition characteristics of compounds can be quite different depending on whether itmore » is the bulk diffusion or grain boundary diffusion that dominates in the compounds, and that “frozen” bulk diffusion leads to unique composition characteristics that the bulk composition of a compound layer remains unchanged after its initial formation instead of varying with the diffusion reaction system; here the model is modified for the case of grain boundary diffusion. Lastly, we apply this model to the Nb 3Sn superconductors and propose approaches to control their compositions.« less

Multiphase chemical kinetics of OH radical uptake by molecular organic markers of biomass burning aerosols: humidity and temperature dependence, surface reaction, and bulk diffusion.

PubMed

Arangio, Andrea M; Slade, Jonathan H; Berkemeier, Thomas; Pöschl, Ulrich; Knopf, Daniel A; Shiraiwa, Manabu

2015-05-14

Multiphase reactions of OH radicals are among the most important pathways of chemical aging of organic aerosols in the atmosphere. Reactive uptake of OH by organic compounds has been observed in a number of studies, but the kinetics of mass transport and chemical reaction are still not fully understood. Here we apply the kinetic multilayer model of gas-particle interactions (KM-GAP) to experimental data from OH exposure studies of levoglucosan and abietic acid, which serve as surrogates and molecular markers of biomass burning aerosol (BBA). The model accounts for gas-phase diffusion within a cylindrical coated-wall flow tube, reversible adsorption of OH, surface-bulk exchange, bulk diffusion, and chemical reactions at the surface and in the bulk of the condensed phase. The nonlinear dependence of OH uptake coefficients on reactant concentrations and time can be reproduced by KM-GAP. We find that the bulk diffusion coefficient of the organic molecules is approximately 10(-16) cm(2) s(-1), reflecting an amorphous semisolid state of the organic substrates. The OH uptake is governed by reaction at or near the surface and can be kinetically limited by surface-bulk exchange or bulk diffusion of the organic reactants. Estimates of the chemical half-life of levoglucosan in 200 nm particles in a biomass burning plume increase from 1 day at high relative humidity to 1 week under dry conditions. In BBA particles transported to the free troposphere, the chemical half-life of levoglucosan can exceed 1 month due to slow bulk diffusion in a glassy matrix at low temperature.

TIME-DOMAIN METHODS FOR DIFFUSIVE TRANSPORT IN SOFT MATTER

PubMed Central

Fricks, John; Yao, Lingxing; Elston, Timothy C.; Gregory Forest, And M.

2015-01-01

Passive microrheology [12] utilizes measurements of noisy, entropic fluctuations (i.e., diffusive properties) of micron-scale spheres in soft matter to infer bulk frequency-dependent loss and storage moduli. Here, we are concerned exclusively with diffusion of Brownian particles in viscoelastic media, for which the Mason-Weitz theoretical-experimental protocol is ideal, and the more challenging inference of bulk viscoelastic moduli is decoupled. The diffusive theory begins with a generalized Langevin equation (GLE) with a memory drag law specified by a kernel [7, 16, 22, 23]. We start with a discrete formulation of the GLE as an autoregressive stochastic process governing microbead paths measured by particle tracking. For the inverse problem (recovery of the memory kernel from experimental data) we apply time series analysis (maximum likelihood estimators via the Kalman filter) directly to bead position data, an alternative to formulas based on mean-squared displacement statistics in frequency space. For direct modeling, we present statistically exact GLE algorithms for individual particle paths as well as statistical correlations for displacement and velocity. Our time-domain methods rest upon a generalization of well-known results for a single-mode exponential kernel [1, 7, 22, 23] to an arbitrary M-mode exponential series, for which the GLE is transformed to a vector Ornstein-Uhlenbeck process. PMID:26412904

Modelling of discrete TDS-spectrum of hydrogen desorption

NASA Astrophysics Data System (ADS)

Rodchenkova, Natalia I.; Zaika, Yury V.

2015-12-01

High concentration of hydrogen in metal leads to hydrogen embrittlement. One of the methods to evaluate the hydrogen content is the method of thermal desorption spectroscopy (TDS). As the sample is heated under vacuumization, atomic hydrogen diffuses inside the bulk and is desorbed from the surface in the molecular form. The extraction curve (measured by a mass-spectrometric analyzer) is recorded. In experiments with monotonous external heating it is observed that background hydrogen fluxes from the extractor walls and fluxes from the sample cannot be reliably distinguished. Thus, the extraction curve is doubtful. Therefore, in this case experimenters use discrete TDS-spectrum: the sample is removed from the analytical part of the device for the specified time interval, and external temperature is then increased stepwise. The paper is devoted to the mathematical modelling and simulation of experimental studies. In the corresponding boundary-value problem with nonlinear dynamic boundary conditions physical- chemical processes in the bulk and on the surface are taken into account: heating of the sample, diffusion in the bulk, hydrogen capture by defects, penetration from the bulk to the surface and desorption. The model aimed to analyze the dynamics of hydrogen concentrations without preliminary artificial sample saturation. Numerical modelling allows to choose the point on the extraction curve that corresponds to the initial quantity of the surface hydrogen, to estimate the values of the activation energies of diffusion, desorption, parameters of reversible capture and hydride phase decomposition.

Kinetics of heterogeneous chemical reactions: a theoretical model for the accumulation of pesticides in soil.

PubMed

Lin, S H; Sahai, R; Eyring, H

1971-04-01

A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method.

Kinetics of Heterogeneous Chemical Reactions: A Theoretical Model for the Accumulation of Pesticides in Soil

PubMed Central

Lin, S. H.; Sahai, R.; Eyring, H.

1971-01-01

A theoretical model for the accumulation of pesticides in soil has been proposed and discussed from the viewpoint of heterogeneous reaction kinetics with a basic aim to understand the complex nature of soil processes relating to the environmental pollution. In the bulk of soil, the pesticide disappears by diffusion and a chemical reaction; the rate processes considered on the surface of soil are diffusion, chemical reaction, vaporization, and regular pesticide application. The differential equations involved have been solved analytically by the Laplace-transform method. PMID:5279519

Effect of short wavelength illumination on the characteristic bulk diffusion length in ribbon silicon solar cells

NASA Technical Reports Server (NTRS)

Ho, C. T.; Mathias, J. D.

1981-01-01

The influence of short wavelength light on the characteristic bulk minority carrier diffusion length of the ribbon silicon photovoltaic cell has been investigated. We have measured the intensity and wavelength dependence of the diffusion length in an EFG ribbon cell, and compared it with a standard Czochralski grown silicon cell. While the various short wavelength illuminations have shown no influence on the diffusion length in the CZ cell, the diffusion lengths in the ribbon cell exhibit a strong dependence on the volume generation rate as well as on the wavelength of the superimposed lights. We have concluded that the trap-filling phenomenon at various depths in the bulk neutral region of the cell is consistent with the experimental observation.

Molecular Dynamics Simulations of Grain Boundary and Bulk Diffusion in Metals.

NASA Astrophysics Data System (ADS)

Plimpton, Steven James

Diffusion is a microscopic mass transport mechanism that underlies many important macroscopic phenomena affecting the structural, electrical, and mechanical properties of metals. This thesis presents results from atomistic simulation studies of diffusion both in bulk and in the fast diffusion paths known as grain boundaries. Using the principles of molecular dynamics single boundaries are studied and their structure and dynamic properties characterized. In particular, tilt boundary bicrystal and bulk models of fcc Al and bcc alpha-Fe are simulated. Diffusion coefficients and activation energies for atomic motion are calculated for both models and compared to experimental data. The influence of the interatomic pair potential on the diffusion is studied in detail. A universal relation between the melting temperature that a pair potential induces in a simulated bulk model and the potential energy barrier height for atomic hopping is derived and used to correlate results for a wide variety of pair potentials. Using these techniques grain boundary and bulk diffusion coefficients for any fcc material can be estimated from simple static calculations without the need to perform more time-consuming dynamic simulations. The influences of two other factors on grain boundary diffusion are also studied because of the interest of the microelectronics industry in the diffusion related reliability problem known as electromigration. The first factor, known to affect the self diffusion rate of Al, is the presence of Cu impurity atoms in Al tilt boundaries. The bicrystal model for Al is seeded randomly with Cu atoms and a simple hybrid Morse potential used to model the Al-Cu interaction. While some effect due to the Cu is noted, it is concluded that pair potentials are likely an inadequate approximation for the alloy system. The second factor studied is the effect of the boundary orientation angle on the diffusion rate. Symmetric bcc Fe boundaries are relaxed to find optimal structures and their diffusion coefficients calculated. Good agreement is found with the dislocation pipe model for tilt boundary diffusion.

Dynamics behavior of lithium in graphite lattice: MD calculation approach

NASA Astrophysics Data System (ADS)

Shimizu, A.; Tachikawa, H.

2000-12-01

In order to investigate the diffusion process of Li atom in graphite, molecular dynamics simulation was achieved on the basis of molecular mechanics 2 (MM2) method using four layers cluster model one of which is composed of C150H30 with terminating hydrogen atoms. According to the simulations at 500 K, Li atom stabilizes initially around the center of mass, gets out of the graphite layers after 3.0 ps through diffusion, which is different from the movement of Li+ ion captured by the dangling bonds of the edge carbon atoms. The diffusion process of Li atom is found to be composed of following four steps in series: (1) vibration around the stabilization point; (2) bulk diffusion; (3) vibration under influence of the dangling bonds of edge carbon atoms; and (4) escape from the graphite layers. The diffusivity for step (3) is smaller than that for step (2).

Utilization of Tabula Rasa to Stabilize Bulk Lifetimes in n-Cz Silicon for High-Performance Solar Cell Processing

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

LaSalvia, Vincenzo; Jensen, Mallory Ann; Youssef, Amanda

2016-11-21

We investigate a high temperature, high cooling-rate anneal Tabula Rasa (TR) and report its implications on n-type Czochralski-grown silicon (n-Cz Si) for photovoltaic fabrication. Tabula Rasa aims at dissolving and homogenizing oxygen precipitate nuclei that can grow during the cell process steps and degrade the cell performance due to their high internal gettering and recombination activity. The Tabula Rasa thermal treatment is performed in a clean tube furnace with cooling rates >100 degrees C/s. We characterize the bulk lifetime by Sinton lifetime and photoluminescence mapping just after Tabula Rasa, and after the subsequent cell processing. After TR, the bulk lifetimemore » surprisingly degrades to <; 0.1ms, only to recover to values equal or higher than the initial non-treated wafer (several ms), after typical high temperature cell process steps. Those include boron diffusion and oxidation; phosphorus diffusion/oxidation; ambient annealing at 850 degrees C; and crystallization annealing of tunneling-passivating contacts (doped polycrystalline silicon on 1.5 nm thermal oxide). The drastic lifetime improvement during high temperature cell processing is attributed to improved external gettering of metal impurities and annealing of intrinsic point defects. Time and injection dependent lifetime spectroscopy further reveals the mechanisms of lifetime improvement after Tabula Rasa treatment. Additionally, we report the efficacy of Tabula Rasa on n-type Cz-Si wafers and its dependence on oxygen concentration, correlated to position within the ingot.« less

Effects of Small Polar Molecules (MA+ and H2O) on Degradation Processes of Perovskite Solar Cells.

PubMed

Ma, Chunqing; Shen, Dong; Qing, Jian; Thachoth Chandran, Hrisheekesh; Lo, Ming-Fai; Lee, Chun-Sing

2017-05-03

Degradation mechanisms of methylammonium lead halide perovskite solar cells (PSCs) have drawn much attention recently. Herein, the bulk and surface degradation processes of the perovskite were differentiated for the first time by employing combinational studies using electrochemical impedance spectroscopy (EIS), capacitance frequency (CF), and X-ray diffraction (XRD) studies with particular attention on the roles of small polar molecules (MA + and H 2 O). CF study shows that short-circuit current density of the PSCs is increased by H 2 O at the beginning of the degradation process coupled with an increased surface capacitance. On the basis of EIS and XRD analysis, we show that the bulk degradation of PSCs involves a lattice expansion process, which facilitates MA + ion diffusion by creating more efficient channels. These results provide a better understanding of the roles of small polar molecules on degradation processes in the bulk and on the surface of the perovskite film.

Molecular simulation of structure and diffusion at smectite-water interfaces: Using expanded clay interlayers as model nanopores

DOE PAGES

Greathouse, Jeffery A.; Hart, David; Bowers, Geoffrey M.; ...

2015-07-20

In geologic settings relevant to a number of extraction and potential sequestration processes, nanopores bounded by clay mineral surfaces play a critical role in the transport of aqueous species. Solution structure and dynamics at clay–water interfaces are quite different from their bulk values, and the spatial extent of this disruption remains a topic of current interest. We have used molecular dynamics simulations to investigate the structure and diffusion of aqueous solutions in clay nanopores approximately 6 nm thick, comparing the effect of clay composition with model Na-hectorite and Na-montmorillonite surfaces. In addition to structural properties at the interface, water andmore » ion diffusion coefficients were calculated within each aqueous layer at the interface, as well as in the central bulk-like region of the nanopore. The results show similar solution structure and diffusion properties at each surface, with subtle differences in sodium adsorption complexes and water structure in the first adsorbed layer due to different arrangements of layer hydroxyl groups in the two clay models. Interestingly, the extent of surface disruption on bulk-like solution structure and diffusion extends to only a few water layers. Additionally, a comparison of sodium ion residence times confirms similar behavior of inner-sphere and outer-sphere surface complexes at each clay surface, but ~1% of sodium ions adsorb in ditrigonal cavities on the hectorite surface. Thus, the presence of these anhydrous ions is consistent with highly immobile anhydrous ions seen in previous nuclear magnetic resonance spectroscopic measurements of hectorite pastes.« less

Carbon diffusion in bulk hcp zirconium: A multi-scale approach

NASA Astrophysics Data System (ADS)

Xu, Y.; Roques, J.; Domain, C.; Simoni, E.

2016-05-01

In the framework of the geological repository of the used fuel claddings of pressurized water reactor, carbon behavior in bulk zirconium is studied by periodic Density Functional Theory calculations. The C interstitial sites were investigated and it was found that there are two possible carbon interstitial sites: a distorted basal tetragonal site and an octahedral site. There are four types of possible atomic jumps between them. After calculating the migration energies, the attempt frequencies and the jump probabilities for each possible migration path, kinetic Monte Carlo (KMC) simulations were performed to simulate carbon diffusion at the macroscopic scale. The results show that carbon diffusion in pure Zr bulk is extremely limited at the storage temperature (50 °C). Since there are defects in Zr bulk, in a second step, the effect of atomic vacancy was studied and it was proved that vacancies cannot increase carbon diffusion.

Reactive Radial Diffusion Model for the Aging/Sequestration Process

NASA Astrophysics Data System (ADS)

Ginn, T. R.; Basagaoglu, H.; McCoy, B. J.; Scow, K. M.

2001-12-01

A radial diffusion model has been formulated to simulate age-dependent bioavailability of chemical compounds to micro-organisms residing outside (and/or inside) the porous soil particles. Experimental findings in the literature indicate that the sequestration and reduction in bioavailability of contaminants are controlled presumably by the diffusion-limited sorption kinetics and the time-variant desorption process. Here we combine radial-diffusion mass transfer modeling with the exposure-time concept to generate mass-balance equations for the intra- and extra-particle concentrations. The model accomodates reversible sorption kinetics involving sorption time-dependence of the rate coefficients, distinct intra- and extra-particle biodegradation rates; and a dynamic mass interaction between the intra- and extra-particle concentrations arising from the radial diffusion concept. The model explicitly treats multiple particle classes distributed in size and chemical properties in a bulk aquifer or soil volume, which allows the simulation of the sequestration and bioavailability of contaminants in different particle size classes that have distinct diffusion, reaction, and aging properties.

General Model of Hindered Diffusion.

PubMed

Eloul, Shaltiel; Compton, Richard G

2016-11-03

The diffusion of a particle from bulk solution is slowed as it moves close to an adsorbing surface. A general model is reported that is easily applied by theoreticians and experimentalists. Specifically, it is shown here that in general and regardless of the space size, the magnitude of the effect of hindered diffusion on the flux is a property of the diffusion layer thickness. We explain and approximate the effect. Predictions of concentration profiles show that a "hindered diffusion layer" is formed near the adsorbing surface within the diffusion layer, observed even when the particle radius is just a 0.1% of the diffusion layer thickness. In particular, we focus on modern electrochemistry processes involving with impact of particles with either ultrasmall electrodes or particles in convective systems. The concept of the "hindered diffusion layer" is generally important for example in recent biophysical models of particles diffusion to small targets.

Classical Molecular Dynamics with Mobile Protons.

PubMed

Lazaridis, Themis; Hummer, Gerhard

2017-11-27

An important limitation of standard classical molecular dynamics simulations is the inability to make or break chemical bonds. This restricts severely our ability to study processes that involve even the simplest of chemical reactions, the transfer of a proton. Existing approaches for allowing proton transfer in the context of classical mechanics are rather cumbersome and have not achieved widespread use and routine status. Here we reconsider the combination of molecular dynamics with periodic stochastic proton hops. To ensure computational efficiency, we propose a non-Boltzmann acceptance criterion that is heuristically adjusted to maintain the correct or desirable thermodynamic equilibria between different protonation states and proton transfer rates. Parameters are proposed for hydronium, Asp, Glu, and His. The algorithm is implemented in the program CHARMM and tested on proton diffusion in bulk water and carbon nanotubes and on proton conductance in the gramicidin A channel. Using hopping parameters determined from proton diffusion in bulk water, the model reproduces the enhanced proton diffusivity in carbon nanotubes and gives a reasonable estimate of the proton conductance in gramicidin A.

Site-specific hydration and dehydration of San Carlos olivine

NASA Astrophysics Data System (ADS)

Ferriss, E.; Plank, T. A.; Walker, D.

2016-12-01

Hydrogen incorporation and diffusion in olivine is critical to understanding fundamental Earth processes such as mantle rheology, plate tectonics, melt generation and magma ascent. Interpreting measured H profiles in olivine requires a more comprehensive understanding of H point defect reactions than currently exists because H diffusivity (D) ranges over 6 orders of magnitude, from slow diffusing H incorporated as (4H+)Si­ [1] to rapid `proton-polaron' bulk H diffusion [2]. Here we present the first experiments on H diffusing into and then out of Fe-bearing olivine using the whole-block method [3], which allows a finely-resolved time series of H profiles in 3 crystallographic directions using the same sample for all dehydration steps. A piece of nearly-dry, oriented San Carlos olivine was hydrated in a piston cylinder apparatus using H2O and solid buffers of Ni/NiO and San Carlos olivine and enstatite at 800 °C and 10 kbar for 17.5 hours, just long enough to saturate the `proton-polaron' mechanism. The sample was then dehydrated in a CO/CO2 gas-mixing furnace at 800°C and 10-14 bar fO2 for total heating times of 1, 3, 7, 13, 19, 43, and 68 hrs, at which point most, but not all, of the H had left the crystal. FTIR profiles at 1, 3, and 7 hours show bulk H profiles consistent with `proton-polaron' diffusion. Later the pace of dehydration slowed, and in several cases the bulk H profile shape differed from what would be expected during simple diffusive loss. The small peak at 3600 cm-1, (4H+)Si, remained essentially unchanged throughout all experiments. The peak at 3573 cm-1, (Ti4+)Mg(2H+)Mg, was initially present but tiny, grew to become the largest peak after hydration, and then during dehydration returned to its initial height. The apparent diffusivity of this peak during hydration and the initial stages of dehydration is 4 orders of magnitude faster than the same peak in synthetic forsterite [2]. Peaks at 3542, 3525, 3489, and 3480 cm-1 were not present initially, grew during hydration, and were removed completely during dehydration. No lower-wavenumber H peaks were observed. These results represent a major step toward reconciling the peak-specific understanding of H diffusion [1] with the 2-mechanism H bulk diffusion model [2]. [1] Padrón-Navarta et al. 2014 [2] Kohlstedt & Mackwell 1998 [3] Ferriss et al. 2015

Approximation of effective moisture-diffusion coefficient to characterize performance of a barrier coating

NASA Astrophysics Data System (ADS)

Nagai, Shingo

2013-11-01

We report estimation of the effective diffusion coefficient of moisture through a barrier coating to develop an encapsulation technology for the thin-film electronics industry. This investigation targeted a silicon oxide (SiOx) film that was deposited on a plastic substrate by a large-process-area web coater. Using the finite difference method based on diffusion theory, our estimation of the effective diffusion coefficient of a SiOx film corresponded to that of bulk glass that was previously reported. This result suggested that the low diffusivities of barrier films can be obtained on a mass-production level in the factory. In this investigation, experimental observations and mathematical confirmation revealed the limit of the water vapor transmission rate on the single barrier coating.

Lithium diffusion at Si-C interfaces in silicon-graphene composites

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

Odbadrakh, Khorgolkhuu; McNutt, N. W.; Nicholson, D. M.

2014-08-04

Models of intercalated Li and its diffusion in Si-Graphene interfaces are investigated using density functional theory. Results suggest that the presence of interfaces alters the energetics of Li binding and diffusion significantly compared to bare Si or Graphene surfaces. Our results show that cavities along reconstructed Si surface provide diffusion paths for Li. Diffusion barriers calculated along these cavities are significantly lower than penetration barriers to bulk Si. Interaction with Si surface results in graphene defects, creating Li diffusion paths that are confined along the cavities but have still lower barrier than in bulk Si.

Effects of Material Degradation on the Structural Integrity of Composite Materials: Experimental Investigation and Modeling of High Temperature Degradation Mechanisms

NASA Technical Reports Server (NTRS)

Cunningham, Ronan A.; McManus, Hugh L.

1996-01-01

It has previously been demonstrated that simple coupled reaction-diffusion models can approximate the aging behavior of PMR-15 resin subjected to different oxidative environments. Based on empirically observed phenomena, a model coupling chemical reactions, both thermal and oxidative, with diffusion of oxygen into the material bulk should allow simulation of the aging process. Through preliminary modeling techniques such as this it has become apparent that accurate analytical models cannot be created until the phenomena which cause the aging of these materials are quantified. An experimental program is currently underway to quantify all of the reaction/diffusion related mechanisms involved. The following contains a summary of the experimental data which has been collected through thermogravimetric analyses of neat PMR-15 resin, along with analytical predictions from models based on the empirical data. Thermogravimetric analyses were carried out in a number of different environments - nitrogen, air and oxygen. The nitrogen provides data for the purely thermal degradation mechanisms while those in air provide data for the coupled oxidative-thermal process. The intent here is to effectively subtract the nitrogen atmosphere data (assumed to represent only thermal reactions) from the air and oxygen atmosphere data to back-figure the purely oxidative reactions. Once purely oxidative (concentration dependent) reactions have been quantified it should then be possible to quantify the diffusion of oxygen into the material bulk.

UO(2) Oxidative Corrosion by Nonclassical Diffusion.

PubMed

Stubbs, Joanne E; Chaka, Anne M; Ilton, Eugene S; Biwer, Craig A; Engelhard, Mark H; Bargar, John R; Eng, Peter J

2015-06-19

Using x-ray scattering, spectroscopy, and density-functional theory, we determine the structure of the oxidation front when a UO(2) (111) surface is exposed to oxygen at ambient conditions. In contrast to classical diffusion and previously reported bulk UO(2+x) structures, we find oxygen interstitials order into a nanoscale superlattice with three-layer periodicity and uranium in three oxidation states: IV, V, and VI. This oscillatory diffusion profile is driven by the nature of the electron transfer process, and has implications for understanding the initial stages of oxidative corrosion in materials at the atomistic level.

NMR investigation of water diffusion in different biofilm structures.

PubMed

Herrling, Maria P; Weisbrodt, Jessica; Kirkland, Catherine M; Williamson, Nathan H; Lackner, Susanne; Codd, Sarah L; Seymour, Joseph D; Guthausen, Gisela; Horn, Harald

2017-12-01

Mass transfer in biofilms is determined by diffusion. Different mostly invasive approaches have been used to measure diffusion coefficients in biofilms, however, data on heterogeneous biomass under realistic conditions is still missing. To non-invasively elucidate fluid-structure interactions in complex multispecies biofilms pulsed field gradient-nuclear magnetic resonance (PFG-NMR) was applied to measure the water diffusion in five different types of biomass aggregates: one type of sludge flocs, two types of biofilm, and two types of granules. Data analysis is an important issue when measuring heterogeneous systems and is shown to significantly influence the interpretation and understanding of water diffusion. With respect to numerical reproducibility and physico-chemical interpretation, different data processing methods were explored: (bi)-exponential data analysis and the Γ distribution model. Furthermore, the diffusion coefficient distribution in relation to relaxation was studied by D-T 2 maps obtained by 2D inverse Laplace transform (2D ILT). The results show that the effective diffusion coefficients for all biofilm samples ranged from 0.36 to 0.96 relative to that of water. NMR diffusion was linked to biofilm structure (e.g., biomass density, organic and inorganic matter) as observed by magnetic resonance imaging and to traditional biofilm parameters: diffusion was most restricted in granules with compact structures, and fast diffusion was found in heterotrophic biofilms with fluffy structures. The effective diffusion coefficients in the biomass were found to be broadly distributed because of internal biomass heterogeneities, such as gas bubbles, precipitates, and locally changing biofilm densities. Thus, estimations based on biofilm bulk properties in multispecies systems can be overestimated and mean diffusion coefficients might not be sufficiently informative to describe mass transport in biofilms and the near bulk. © 2017 Wiley Periodicals, Inc.

Isotope effects on desorption kinetics of hydrogen isotopes implanted into stainless steel by glow discharge

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

Matsuyama, M.; Kondo, M.; Noda, N.

2015-03-15

In a fusion device the control of fuel particles implies to know the desorption rate of hydrogen isotopes by the plasma-facing materials. In this paper desorption kinetics of hydrogen isotopes implanted into type 316L stainless steel by glow discharge have been studied by experiment and numerical calculation. The temperature of a maximum desorption rate depends on glow discharge time and heating rate. Desorption spectra observed under various experimental conditions have been successfully reproduced by numerical simulations that are based on a diffusion-limited process. It is suggested, therefore, that desorption rate of a hydrogen isotope implanted into the stainless steel ismore » limited by a diffusion process of hydrogen isotope atoms in bulk. Furthermore, small isotope effects were observed for the diffusion process of hydrogen isotope atoms. (authors)« less

Geomorphic control of radionuclide diffusion in desert soils

USGS Publications Warehouse

Pelletier, J.D.; Harrington, C.D.; Whitney, J.W.; Cline, M.; DeLong, S.B.; Keating, G.; Ebert, T.K.

2005-01-01

Diffusion is a standard model for the vertical migration of radionuclides in soil profiles. Here we show that diffusivity values inferred from fallout 137CS profiles in soils on the Fortymile Wash alluvial fan, Nye County, Nevada, have a strong inverse correlation with the age of the geomorphic surface. This result suggests that radionuclide-bound particles are predominantly transported by infiltration rather than by bulk-mixing processes such as wetting/ drying, freeze/thaw, and bioturbation. Our results provide a preliminary basis for using soil-geomorphic mapping, point-based calibration data, and the diffusion model to predict radionuclide trans desert soils within a pedotransfer-function approach. Copyright 2005 by the American Geophysical Union.

Diffused junction p(+)-n solar cells in bulk GaAs. I Fabrication and cell performance

NASA Technical Reports Server (NTRS)

Bhat, I.; Bhat, K. N.; Mathur, G.; Borrego, J. M.; Ghandhi, S. K.

1984-01-01

This paper describes the fabrication of solar cells made by a simple open tube p(+)-diffusion into bulk n-GaAs. In addition, cell performance is provided as an indicator of the quality of bulk GaAs for this application. Initial results using this technique (12.2 percent efficiency at AM1 for 0.5 sq cm cells) are promising, and indicate directions for materials improvement. It is shown that the introduction of the diffusant (zinc) with point defects significantly affects the material properties and results in an increase in current capability.

Is the wall of a cellulose fiber saturated with liquid whether or not permeable with CO2 dissolved molecules? Application to bubble nucleation in champagne wines.

PubMed

Liger-Belair, Gérard; Topgaard, Daniel; Voisin, Cédric; Jeandet, Philippe

2004-05-11

In this paper, the transversal diffusion coefficient D perpendicular of CO2 dissolved molecules through the wall of a hydrated cellulose fiber was approached, from the liquid bulk diffusion coefficient of CO2 dissolved molecules modified by an obstruction factor. The porous network between the cellulose microfibrils of the fiber wall was assumed being saturated with liquid. We retrieved information from previous NMR experiments on the self-diffusion of water in cellulose fibers to reach an order of magnitude for the transversal diffusion coefficient of CO2 molecules through the fiber wall. A value of about D perpendicular approximately 0.2D0 was proposed, D0 being the diffusion coefficient of CO2 molecules in the liquid bulk. Because most of bubble nucleation sites in a glass poured with carbonated beverage are cellulose fibers cast off from paper or cloth which floated from the surrounding air, or remaining from the wiping process, this result directly applies to the kinetics of carbon dioxide bubble formation from champagne and sparkling wines. If the cellulose fiber wall was impermeable with regard to CO2 dissolved molecules, it was suggested that the kinetics of bubbling would be about three times less than it is.

Diffusive interaction of multiple surface nanobubbles: shrinkage, growth, and coarsening.

PubMed

Zhu, Xiaojue; Verzicco, Roberto; Zhang, Xuehua; Lohse, Detlef

2018-03-14

Surface nanobubbles are nanoscopic spherical-cap shaped gaseous domains on immersed substrates which are stable, even for days. After the stability of a single surface nanobubble has been theoretically explained, i.e. contact line pinning and gas oversaturation are required to stabilize it against diffusive dissolution [Lohse and Zhang, Phys. Rev. E, 2015, 91, 031003(R)], here we focus on the collective diffusive interaction of multiple nanobubbles. For that purpose we develop a finite difference scheme for the diffusion equation with the appropriate boundary conditions and with the immersed boundary method used to represent the growing or shrinking bubbles. After validation of the scheme against the exact results of Epstein and Plesset for a bulk bubble [J. Chem. Phys., 1950, 18, 1505] and of Lohse and Zhang for a surface bubble, the framework of these simulations is used to describe the coarsening process of competitively growing nanobubbles. The coarsening process for such diffusively interacting nanobubbles slows down with advancing time and increasing bubble distance. The present results for surface nanobubbles are also applicable for immersed surface nanodroplets, for which better controlled experimental results of the coarsening process exist.

Plasma kinetic effects on atomistic mix in one dimension and at structured interfaces (I)

NASA Astrophysics Data System (ADS)

Yin, L.; Albright, B. J.; Vold, E. L.; Taitano, W.; Chacon, L.; Simakov, A.

2017-10-01

Kinetic effects on interfacial mix are examined using VPIC simulations. In 1D, comparisons are made to the results of analytic theory in the small Knudsen number limit. While the bulk mixing properties of interfaces are in general agreement, differences arise near the low-concentration fronts during the early evolution of a sharp interface when the species' perpendicular scattering rate dominates over the slowing down rate. In kinetic simulations, the diffusion velocities can be larger or comparable to the ion thermal speeds, and the Knudsen number can be large. Super-diffusive growth in mix widths (Δx ta where a >=1/2) is seen before transition to the slow diffusive process predicted from theory (a =1/2). Mixing at interfaces leads to persistent, bulk, hydrodynamic features in the center of mass flow profiles as a result of diffusion and momentum conservation. These conclusions are drawn from VPIC results together with simulations from the RAGE hydrodynamics code with an implementation of diffusion and viscosity from theory and an implicit Vlasov-Fokker-Planck code iFP. In perturbed 2D and 3D interfaces, it is found that 1D ambipolarity is still valid and that initial perturbations flatten out on a-few-ps time scale, implying that finite diffusivity and viscosity can slow instability growth in ICF and HED settings. Work supported by the LANL ASC and Science programs.

The effect of catastrophic collisional fragmentation and diffuse medium accretion on a computational interstellar dust system

NASA Technical Reports Server (NTRS)

Liffman, Kurt

1990-01-01

The effects of catastrophic collisional fragmentation and diffuse medium accretion on a the interstellar dust system are computed using a Monte Carlo computer model. The Monte Carlo code has as its basis an analytic solution of the bulk chemical evolution of a two-phase interstellar medium, described by Liffman and Clayton (1989). The model is subjected to numerous different interstellar processes as it transfers from one interstellar phase to another. Collisional fragmentation was found to be the dominant physical process that shapes the size spectrum of interstellar dust. It was found that, in the diffuse cloud phase, 90 percent of the refractory material is locked up in the dust grains, primarily due to accretion in the molecular medium. This result is consistent with the observed depletions of silicon. Depletions were found to be affected only slightly by diffuse cloud accretion.

Modeling of acetone biofiltration process

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

Hsiu-Mu Tang; Shyh-Jye Hwang; Wen-Chuan Wang

1996-12-31

The objective of this research was to investigate the kinetic behavior of the biofiltration process for the removal of acetone 41 which was used as a model compound for highly water soluble gas pollutants. A mathematical model was developed by taking into account diffusion and biodegradation of acetone and oxygen in the biofilm, mass transfer resistance in the gas film, and flow pattern of the bulk gas phase. The simulated results obtained by the proposed model indicated that mass transfer resistance in the gas phase was negligible for this biofiltration process. Analysis of the relative importance of various rate stepsmore » indicated that the overall acetone removal process was primarily limited by the oxygen diffusion rate. 11 refs., 6 figs., 1 tab.« less

Antimony diffusion in CdTe

DOE PAGES

Colegrove, Eric; Harvey, Steven P.; Yang, Ji -Hui; ...

2017-02-08

Group V dopants may be used for next-generation high-voltage cadmium telluride (CdTe) solar photovoltaics, but fundamental defect energetics and kinetics need to be understood. Here, antimony (Sb) diffusion is studied in single-crystal and polycrystalline CdTe under Cd-rich conditions. Diffusion profiles are determined by dynamic secondary ion mass spectroscopy and analyzed with analytical bulk and grain-boundary diffusion models. Slow bulk and fast grain-boundary diffusion are found. Density functional theory is used to understand formation energy and mechanisms. Lastly, the theory and experimental results create new understanding of group V defect kinetics in CdTe.

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

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

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Temperature- and composition-dependent hydrogen diffusivity in palladium from statistically-averaged molecular dynamics

DOE PAGES

Zhou, Xiaowang; Heo, Tae Wook; Wood, Brandon C.; ...

2018-03-09

Solid-state hydrogen storage materials undergo complex phase transformations whose kinetics is often limited by hydrogen diffusion. Among metal hydrides, palladium hydride undergoes a diffusional phase transformation upon hydrogen uptake, during which the hydrogen diffusivity varies with hydrogen composition and temperature. Here we perform robust statistically-averaged molecular dynamics simulations to obtain a well-converged analytical expression for hydrogen diffusivity in bulk palladium that is valid throughout all stages of the reaction. Our studies confirm significant dependence of the diffusivity on composition and temperature that elucidate key trends in the available experimental measurements. Whereas at low hydrogen compositions, a single process dominates, atmore » high hydrogen compositions, diffusion is found to exhibit behavior consistent with multiple hopping barriers. Further analysis, supported by nudged elastic band computations, suggests that the multi-barrier diffusion can be interpreted as two distinct mechanisms corresponding to hydrogen-rich and hydrogen-poor local environments.« less

Electrochemical oxidation of ciprofloxacin in two different processes: the electron transfer process on the anode surface and the indirect oxidation process in bulk solutions.

PubMed

Shen, Bo; Wen, Xianghua; Korshin, Gregory V

2018-05-14

Herein, the rotating disk electrode technique was used for the first time to investigate the effects of mass-transfer limitations and pH on the electrochemical oxidation of CPX, to determine the kinetics of CPX oxidation and to explore intrinsic mechanisms during the electron transfer process. Firstly, cyclic voltammetry revealed that an obvious irreversible CPX oxidation peak was observed within the potential window from 0.70 to 1.30 V at all pHs. Based on the Levich equation, the electrochemical oxidation of CPX in the electron transfer process was found to be controlled by both diffusion and kinetic processes when pH = 2, 5, 7 and 9; the diffusion coefficient of CPX at pH = 2 was calculated to be 1.5 × 10-7 cm2 s-1. Kinetic analysis indicated that the reaction on the electrode surface was adsorption-controlled compared to a diffusion process; the surface concentration of electroactive species was estimated to be 1.15 × 10-9 mol cm-2, the standard rate constant of the surface reaction was calculated to be 1.37 s-1, and CPX oxidation was validated to be a two-electron transfer process. Finally, a possible CPX oxidation pathway during the electron transfer process was proposed. The electrochemical degradation of CPX on a Ti-based anode was also conducted subsequently to investigate the electrochemical oxidation of CPX in the indirect oxidation process in bulk solutions. The effects of pH and current density were determined and compared to related literature results. The oxidation of CPX at different pHs is believed to be the result of a counterbalance between favorable and unfavorable factors, namely electromigration and side reactions of oxygen evolution, respectively. The effects of current density indicated a diffusion- and reaction-controlled process at low currents followed by a reaction-controlled process at high currents. The results presented in this study provide better understanding of the electrochemical oxidation of CPX and would enable the development of new treatment methods based on electrochemistry.

Annealing of gallium nitride under high-N 2 pressure

NASA Astrophysics Data System (ADS)

Porowski, S.; Jun, J.; Krukowski, S.; Grzegory, I.; Leszczynski, M.; Suski, T.; Teisseyre, H.; Foxon, C. T.; Korakakis, D.

1999-04-01

GaN is the key material for blue and ultraviolet optoelectronics. It is a strongly bonded wurztite structure semiconductor with the direct energy gap 3.5 eV. Due to strong bonding, the diffusion processes require high temperatures, above 1300 K. However at this temperature range at ambient pressure, GaN becomes unstable and dissociates into Ga and N 2. Therefore high pressure of N 2 is required to study the diffusion and other annealing related processes. We studied annealing of bulk GaN nitride single crystals grown under high pressure and also annealing of homo- and heteroepitaxial GaN layers grown by MOCVD technique. Annealing at temperatures above 1300 K influences strongly the structural and optical properties of GaN crystals and layers. At this temperature diffusion of the Mg and Zn acceptors have been observed. In spite of very interesting experimental observations the understanding of microscopic mechanisms of these processes is limited.

Particle Demagnetization in Collisionless Magnetic Reconnection

NASA Technical Reports Server (NTRS)

Hesse, Michael

2006-01-01

The dissipation mechanism of magnetic reconnection remains a subject of intense scientific interest. On one hand, one set of recent studies have shown that particle inertia-based processes, which include thermal and bulk inertial effects, provide the reconnection electric field in the diffusion region. In this presentation, we present analytical theory results, as well as 2.5 and three-dimensional PIC simulations of guide field magnetic reconnection. We will show that diffusion region scale sizes in moderate and large guide field cases are determined by electron Larmor radii, and that analytical estimates of diffusion region dimensions need to include description of the heat flux tensor. The dominant electron dissipation process appears to be based on thermal electron inertia, expressed through nongyrotropic electron pressure tensors. We will argue that this process remains viable in three dimensions by means of a detailed comparison of high resolution particle-in-cell simulations.

Modeling and experimental evaluation of the diffusion bonding of the oxide dispersion strengthened steel PM2000

NASA Astrophysics Data System (ADS)

Sittel, Wiebke; Basuki, Widodo W.; Aktaa, Jarir

2015-10-01

A modeling based optimization process of the solid state diffusion bonding is presented for joining ferritic oxide dispersion strengthened steels PM2000. An optimization study employing varying bonding temperatures and pressures results in almost the same strength and toughness of the bonded compared to the as received material. TEM investigations of diffusion bonded samples show a homogeneous distribution of oxide particles at the bonding seam similar to that in the bulk. Hence, no loss in strength or creep resistance due to oxide particle agglomeration is found, as verified by the mechanical properties observed for the joint.

Characterization of oxygen and titanium diffusion at the anatase TiO2(001) surface

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

Herman, Gregory S.; Zehr, Robert T.; Henderson, Michael A.

2013-06-01

The diffusion of intrinsic defects in a single crystal anatase TiO2(001) film was explored by isotopic labeling and static secondary ion mass spectrometry. Using both 46Ti and 18O as isotopic labels, we show that the anatase surface responds to redox imbalances by diffusion of both Ti and O into the bulk under vacuum reduction and (at least) Ti from the bulk to the surface during oxidation. The diffusion of Ti between the bulk and surface in anatase TiO2(001) closely resembles what was observed in the literature for the rutile TiO2(110) surface, however the latter is not known to have oxygenmore » diffusion between the bulk and surface under typical ultrahigh vacuum conditions. We speculate that the open lattice of the anatase bulk structure may facilitate independent diffusion of both point defects (Ti interstitials and O vacancies) or concerted diffusion of "TiO" subunits. The authors gratefully acknowledge S.A. Chambers of Pacific Northwest National Laboratory (PNNL) for providing the anatase samples. This research was supported by the U.S. Department of Energy (DOE) Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, the Office of Naval Research Contract Number 200CAR262, and the Oregon Nanoscience and Microtechnologies Institute. PNNL is operated for the U.S. DOE by Battelle under Contract Number DE05-AC76RL0 1830. The research was performed in the William R. Wiley Environmental Molecular Sciences Laboratory, a national scientific user facility funded by the U.S. DOE Office of Biological and Environmental Research.« 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.

Active-Site Hydration and Water Diffusion in Cytochrome P450cam: A Highly Dynamic Process

PubMed Central

Miao, Yinglong; Baudry, Jerome

2011-01-01

Long-timescale molecular dynamics simulations (300 ns) are performed on both the apo- (i.e., camphor-free) and camphor-bound cytochrome P450cam (CYP101). Water diffusion into and out of the protein active site is observed without biased sampling methods. During the course of the molecular dynamics simulation, an average of 6.4 water molecules is observed in the camphor-binding site of the apo form, compared to zero water molecules in the binding site of the substrate-bound form, in agreement with the number of water molecules observed in crystal structures of the same species. However, as many as 12 water molecules can be present at a given time in the camphor-binding region of the active site in the case of apo-P450cam, revealing a highly dynamic process for hydration of the protein active site, with water molecules exchanging rapidly with the bulk solvent. Water molecules are also found to exchange locations frequently inside the active site, preferentially clustering in regions surrounding the water molecules observed in the crystal structure. Potential-of-mean-force calculations identify thermodynamically favored trans-protein pathways for the diffusion of water molecules between the protein active site and the bulk solvent. Binding of camphor in the active site modifies the free-energy landscape of P450cam channels toward favoring the diffusion of water molecules out of the protein active site. PMID:21943431

Unsteady Crystal Growth Due to Step-Bunch Cascading

NASA Technical Reports Server (NTRS)

Vekilov, Peter G.; Lin, Hong; Rosenberger, Franz

1997-01-01

Based on our experimental findings of growth rate fluctuations during the crystallization of the protein lysozym, we have developed a numerical model that combines diffusion in the bulk of a solution with diffusive transport to microscopic growth steps that propagate on a finite crystal facet. Nonlinearities in layer growth kinetics arising from step interaction by bulk and surface diffusion, and from step generation by surface nucleation, are taken into account. On evaluation of the model with properties characteristic for the solute transport, and the generation and propagation of steps in the lysozyme system, growth rate fluctuations of the same magnitude and characteristic time, as in the experiments, are obtained. The fluctuation time scale is large compared to that of step generation. Variations of the governing parameters of the model reveal that both the nonlinearity in step kinetics and mixed transport-kinetics control of the crystallization process are necessary conditions for the fluctuations. On a microscopic scale, the fluctuations are associated with a morphological instability of the vicinal face, in which a step bunch triggers a cascade of new step bunches through the microscopic interfacial supersaturation distribution.

Adsorption-desorption mechanism of phosphate by immobilized nano-sized magnetite layer: interface and bulk interactions.

PubMed

Zach-Maor, Adva; Semiat, Raphael; Shemer, Hilla

2011-11-15

Phosphate adsorption mechanism by a homogenous porous layer of nano-sized magnetite particles immobilized onto granular activated carbon (nFe-GAC) was studied for both interface and bulk structures. X-ray Photoelectron Spectroscopy (XPS) analysis revealed phosphate bonding to the nFe-GAC predominantly through bidentate surface complexes. It was established that phosphate was adsorbed to the magnetite surface mainly via ligand exchange mechanism. Initially, phosphate was adsorbed by the active sites on the magnetite surface, after which it diffused into the interior of the nano-magnetite layer, as indicated by intraparticle diffusion model. This diffusion process continues regardless of interface interactions, revealing some of the outer magnetite binding sites for further phosphate uptake. Desorption, using NaOH solution, was found to be predominantly a surface reaction, at which hydroxyl ions replace the adsorbed phosphate ions only at the surface outer biding sites. Five successive fix-bed adsorption/regeneration cycles were successfully applied, without significant reduction in the nFe-GAC adsorption capacity and at high regeneration efficiency. Copyright © 2011 Elsevier Inc. All rights reserved.

Mathematical modeling of degradation for bulk-erosive polymers: applications in tissue engineering scaffolds and drug delivery systems.

PubMed

Chen, Yuhang; Zhou, Shiwei; Li, Qing

2011-03-01

The degradation of polymeric biomaterials, which are widely exploited in tissue engineering and drug delivery systems, has drawn significant attention in recent years. This paper aims to develop a mathematical model that combines stochastic hydrolysis and mass transport to simulate the polymeric degradation and erosion process. The hydrolysis reaction is modeled in a discrete fashion by a fundamental stochastic process and an additional autocatalytic effect induced by the local carboxylic acid concentration in terms of the continuous diffusion equation. Illustrative examples of microparticles and tissue scaffolds demonstrate the applicability of the model. It is found that diffusive transport plays a critical role in determining the degradation pathway, whilst autocatalysis makes the degradation size dependent. The modeling results show good agreement with experimental data in the literature, in which the hydrolysis rate, polymer architecture and matrix size actually work together to determine the characteristics of the degradation and erosion processes of bulk-erosive polymer devices. The proposed degradation model exhibits great potential for the design optimization of drug carriers and tissue scaffolds. Copyright © 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

On the Maxwell-Stefan approach to diffusion: a general resolution in the transient regime for one-dimensional systems.

PubMed

Leonardi, Erminia; Angeli, Celestino

2010-01-14

The diffusion process in a multicomponent system can be formulated in a general form by the generalized Maxwell-Stefan equations. This formulation is able to describe the diffusion process in different systems, such as, for instance, bulk diffusion (in the gas, liquid, and solid phase) and diffusion in microporous materials (membranes, zeolites, nanotubes, etc.). The Maxwell-Stefan equations can be solved analytically (only in special cases) or by numerical approaches. Different numerical strategies have been previously presented, but the number of diffusing species is normally restricted, with only few exceptions, to three in bulk diffusion and to two in microporous systems, unless simplifications of the Maxwell-Stefan equations are considered. In the literature, a large effort has been devoted to the derivation of the analytic expression of the elements of the Fick-like diffusion matrix and therefore to the symbolic inversion of a square matrix with dimensions n x n (n being the number of independent components). This step, which can be easily performed for n = 2 and remains reasonable for n = 3, becomes rapidly very complex in problems with a large number of components. This paper addresses the problem of the numerical resolution of the Maxwell-Stefan equations in the transient regime for a one-dimensional system with a generic number of components, avoiding the definition of the analytic expression of the elements of the Fick-like diffusion matrix. To this aim, two approaches have been implemented in a computational code; the first is the simple finite difference second-order accurate in time Crank-Nicolson scheme for which the full mathematical derivation and the relevant final equations are reported. The second is based on the more accurate backward differentiation formulas, BDF, or Gear's method (Shampine, L. F. ; Gear, C. W. SIAM Rev. 1979, 21, 1.), as implemented in the Livermore solver for ordinary differential equations, LSODE (Hindmarsh, A. C. Serial Fortran Solvers for ODE Initial Value Problems, Technical Report; https://computation.llnl.gov/casc/odepack/odepack_ home.html (2006).). Both methods have been applied to a series of specific problems, such as bulk diffusion of acetone and methanol through stagnant air, uptake of two components on a microporous material in a model system, and permeation across a microporous membrane in model systems, both with the aim to validate the method and to add new information to the comprehension of the peculiar behavior of these systems. The approach is validated by comparison with different published results and with analytic expressions for the steady-state concentration profiles or fluxes in particular systems. The possibility to treat a generic number of components (the limitation being essentially the computational power) is also tested, and results are reported on the permeation of a five component mixture through a membrane in a model system. It is worth noticing that the algorithm here reported can be applied also to the Fick formulation of the diffusion problem with concentration-dependent diffusion coefficients.

Evaluating the multimedia fate of organic chemicals: A level III fugacity model

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

Mackay, D.; Paterson, S.

A multimedia model is developed and applied to selected organic chemicals in evaluative and real regional environments. The model employs the fugacity concept and treats four bulk compartments: air, water, soil, and bottom sediment, which consist of subcompartments of varying proportions of air, water, and mineral and organic matter. Chemical equilibrium is assumed to apply within (but not between) each bulk compartment. Expressions are included for emissions, advective flows, degrading reactions, and interphase transport by diffusive and non-diffusive processes. Input to the model consists of a description of the environment, the physical-chemical and reaction properties of the chemical, and emissionmore » rates. For steady-state conditions the solution is a simple algebraic expression. The model is applied to six chemicals in the region of southern Ontario and the calculated fate and concentrations are compared with observations. The results suggest that the model may be used to determine the processes that control the environmental fate of chemicals in a region and provide approximate estimates of relative media concentrations.« less

Theoretical study of oxygen sorption and diffusion in the volume and on the surface of a γ-TiAl alloy

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

Bakulin, A. V., E-mail: bakulin@ispms.tsc.ru; Kulkova, S. E.; Hu, Q. M.

2015-02-15

The oxygen sorption on the low-index (001), (100), and (110) surfaces of a γ-TiAl alloy is studied by the pseudopotential method with the generalized gradient approximation for the exchange-correlation functional. The most preferred sites for oxygen sorption in the bulk and on the surface of the alloy are determined. The titanium-rich octahedral site is shown to be preferred for oxygen sorption in the bulk material. The effect of the oxygen concentration on the atomic and electronic structures of the stoichiometric TiAl(100) surface is studied. It is shown that, at the first stage of oxidation, oxygen prefers to form bonds withmore » titanium. The energy barriers for oxygen diffusion on the stoichiometric (100) surface and in the bulk of the material are calculated. The energy barriers are shown to depend substantially on the local environments of oxygen and to increase during diffusion from titanium-rich sites. The most possible mechanism of oxygen diffusion from the (100) surface to the bulk of the material is oxygen migration through tetrahedral sites.« less

Communication: Surface-to-bulk diffusion of isolated versus interacting C atoms in Ni(111) and Cu(111) substrates: A first principle investigation.

PubMed

Harpale, Abhilash; Panesi, Marco; Chew, Huck Beng

2015-02-14

Using first principle calculations, we study the surface-to-bulk diffusion of C atoms in Ni(111) and Cu(111) substrates, and compare the barrier energies associated with the diffusion of an isolated C atom versus multiple interacting C atoms. We find that the preferential Ni-C bonding over C-C bonding induces a repulsive interaction between C atoms located at diagonal octahedral voids in Ni substrates. This C-C interaction accelerates C atom diffusion in Ni with a reduced barrier energy of ∼1 eV, compared to ∼1.4-1.6 eV for the diffusion of isolated C atoms. The diffusion barrier energy of isolated C atoms in Cu is lower than in Ni. However, bulk diffusion of interacting C atoms in Cu is not possible due to the preferential C-C bonding over C-Cu bonding, which results in C-C dimer pair formation near the surface. The dramatically different C-C interaction effects within the different substrates explain the contrasting growth mechanisms of graphene on Ni(111) and Cu(111) during chemical vapor deposition.

Modeling gas displacement kinetics in coal with Maxwell-Stefan diffusion theory

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

Wei, X.R.; Wang, G.X.; Massarotto, P.

2007-12-15

The kinetics of binary gas counter-diffusion and Darcy flow in a large coal sample were modeled, and the results compared with data from experimental laboratory investigations. The study aimed for a better understanding of the CO{sub 2}-sequestration enhanced coalbed methane (ECBM) recovery process. The transport model used was based on the bidisperse diffusion mechanism and Maxwell-Stefan (MS) diffusion theory. This provides an alternative approach to simulate multicomponent gas diffusion and flow in bulk coals. A series of high-stress core flush tests were performed on a large coal sample sourced from a Bowen Basin coal mine in Queensland, Australia to investigatemore » the kinetics of one gas displacing another. These experimental results were used to derive gas diffusivities, and to examine the predictive capability of the diffusion model. The simulations show good agreements with the displacement experiments revealing that MS diffusion theory is superior for describing diffusion of mixed gases in coals compared with the constant Fick diffusivity model. The optimized effective micropore and macropore diffusivities are comparable with experimental measurements achieved by other researchers.« less

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

NASA Astrophysics Data System (ADS)

Steimer, S. S.; Lampimäki, M.; Coz, E.; Grzinic, G.; Ammann, M.

2014-03-01

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a Scanning Transmission X-ray Microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid-water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the time scale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

The influence of physical state on shikimic acid ozonolysis: a case for in situ microspectroscopy

NASA Astrophysics Data System (ADS)

Steimer, S. S.; Lampimäki, M.; Coz, E.; Grzinic, G.; Ammann, M.

2014-10-01

Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid-water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.

Reactions between palladium and gallium arsenide: Bulk versus thin-film studies

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

Lin, J.; Hsieh, K.; Schulz, K.J.

1988-01-01

Reactions between Pd and GaAs have been studied using bulk-diffusion couples of Pd (approx.0.6 mm thick)/GaAs and thin-film Pd (50 and 160 nm)/GaAs samples. The sequence of phase formation at 600 /sup 0/C between bulk Pd and GaAs was established. Initial formation of the solution phase ..mu.. and the ternary phase T does not represent the stable configuration. The stable configuration is GaAs chemically bondepsilonchemically bondlambdachemically bond..gamma..chemically bond..nu..chemically bondPd and is termed the diffusion path between GaAs and Pd. The sequence of phase formation for the bulk-diffusion couples is similar at 500 /sup 0/C. Phase formation for the thin-film Pd/GaAsmore » specimens was studied at 180, 220, 250, 300, 350, 400, 450, 600, and 1000 /sup 0/C for various annealing times. The sequence of phase formation obtained from the thin-film experiments is rationalized readily from the known ternary phase equilibria of Ga--Pd--As and the results from the bulk-diffusion couples of Pd/GaAs. The thin-film results reported in the literature are likewise rationalized. The diffusion path concept provides a useful guide in understanding the phase formation in Pd--GaAs interface or any other M--GaAs interface. This information is important in designing a uniform, stable contact for the metallization of GaAs.« less

Ion Exchange Method - Diffusion Barrier Investigations

NASA Astrophysics Data System (ADS)

Pielak, G.; Szustakowski, M.; Kiezun, A.

1990-01-01

Ion exchange method is used to GRIN-rod lenses manufacturing. In this process the ion exchange occurs between bulk glass (rod) and a molten salt. It was find that diffusion barrier exists on a border of glass surface and molten salt. The investigations of this barrier show that it value varies with ion exchange time and process temperature. It was find that in the case when thalium glass rod was treated in KNO3, bath, the minimum of the potential after 24 h was in temperature of 407°C, after 48 h in 422°C, after 72 h in 438°C and so on. So there are the possibility to keep the minimum of diffusion barrier by changing the temperature of the process and then the effectiveness of ion exchange process is the most effective. The time needed to obtain suitable refractive index distribution in a process when temperature was linearly changed from 400°C to 460°C was shorter of about 30% compare with the process in which temperature was constant and equal 450°C.

Transport coefficients and heat fluxes in non-equilibrium high-temperature flows with electronic excitation

NASA Astrophysics Data System (ADS)

Istomin, V. A.; Kustova, E. V.

2017-02-01

The influence of electronic excitation on transport processes in non-equilibrium high-temperature ionized mixture flows is studied. Two five-component mixtures, N 2 / N2 + / N / N + / e - and O 2 / O2 + / O / O + / e - , are considered taking into account the electronic degrees of freedom for atomic species as well as the rotational-vibrational-electronic degrees of freedom for molecular species, both neutral and ionized. Using the modified Chapman-Enskog method, the transport coefficients (thermal conductivity, shear viscosity and bulk viscosity, diffusion and thermal diffusion) are calculated in the temperature range 500-50 000 K. Thermal conductivity and bulk viscosity coefficients are strongly affected by electronic states, especially for neutral atomic species. Shear viscosity, diffusion, and thermal diffusion coefficients are not sensible to electronic excitation if the size of excited states is assumed to be constant. The limits of applicability for the Stokes relation are discussed; at high temperatures, this relation is violated not only for molecular species but also for electronically excited atomic gases. Two test cases of strongly non-equilibrium flows behind plane shock waves corresponding to the spacecraft re-entry (Hermes and Fire II) are simulated numerically. Fluid-dynamic variables and heat fluxes are evaluated in gases with electronic excitation. In inviscid flows without chemical-radiative coupling, the flow-field is weakly affected by electronic states; however, in viscous flows, their influence can be more important, in particular, on the convective heat flux. The contribution of different dissipative processes to the heat transfer is evaluated as well as the effect of reaction rate coefficients. The competition of diffusion and heat conduction processes reduces the overall effect of electronic excitation on the convective heating, especially for the Fire II test case. It is shown that reliable models of chemical reaction rates are of great importance for accurate predictions of the fluid dynamic variables and heat fluxes.

DIFFUSE: a FORTRAN program for design computation of tritium transport through thermonuclear reactor components by combined ordinary and thermal diffusion when the principal resistance to diffusion is the bulk metal

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

Pendergrass, J.H.

1977-10-01

Based on the theory developed in an earlier report, a FORTRAN computer program, DIFFUSE, was written. It computes, for design purposes, rates of transport of hydrogen isotopes by temperature-dependent quasi-unidirectional, and quasi-static combined ordinary and thermal diffusion through thin, hot thermonuclear reactor components that can be represented by composites of plane, cylindrical-shell, and spherical-shell elements when the dominant resistance to transfer is that of the bulk metal. The program is described, directions for its use are given, and a listing of the program, together with sample problem results, is presented.

A transmission-grating-modulated pump-probe absorption spectroscopy and demonstration of diffusion dynamics of photoexcited carriers in bulk intrinsic GaAs film.

PubMed

Chen, Ke; Wang, Wenfang; Chen, Jianming; Wen, Jinhui; Lai, Tianshu

2012-02-13

A transmission-grating-modulated time-resolved pump-probe absorption spectroscopy is developed and formularized. The spectroscopy combines normal time-resolved pump-probe absorption spectroscopy with a binary transmission grating, is sensitive to the spatiotemporal evolution of photoinjected carriers, and has extensive applicability in the study of diffusion transport dynamics of photoinjected carriers. This spectroscopy has many advantages over reported optical methods to measure diffusion dynamics, such as simple experimental setup and operation, and high detection sensitivity. The measurement of diffusion dynamics is demonstrated on bulk intrinsic GaAs films. A carrier density dependence of carrier diffusion coefficient is obtained and agrees well with reported results.

Low b-value diffusion-weighted cardiac magnetic resonance imaging: initial results in humans using an optimal time-window imaging approach.

PubMed

Rapacchi, Stanislas; Wen, Han; Viallon, Magalie; Grenier, Denis; Kellman, Peter; Croisille, Pierre; Pai, Vinay M

2011-12-01

Diffusion-weighted imaging (DWI) using low b-values permits imaging of intravoxel incoherent motion in tissues. However, low b-value DWI of the human heart has been considered too challenging because of additional signal loss due to physiological motion, which reduces both signal intensity and the signal-to-noise ratio (SNR). We address these signal loss concerns by analyzing cardiac motion during a heartbeat to determine the time-window during which cardiac bulk motion is minimal. Using this information to optimize the acquisition of DWI data and combining it with a dedicated image processing approach has enabled us to develop a novel low b-value diffusion-weighted cardiac magnetic resonance imaging approach, which significantly reduces intravoxel incoherent motion measurement bias introduced by motion. Simulations from displacement encoded motion data sets permitted the delineation of an optimal time-window with minimal cardiac motion. A number of single-shot repetitions of low b-value DWI cardiac magnetic resonance imaging data were acquired during this time-window under free-breathing conditions with bulk physiological motion corrected for by using nonrigid registration. Principal component analysis (PCA) was performed on the registered images to improve the SNR, and temporal maximum intensity projection (TMIP) was applied to recover signal intensity from time-fluctuant motion-induced signal loss. This PCATMIP method was validated with experimental data, and its benefits were evaluated in volunteers before being applied to patients. Optimal time-window cardiac DWI in combination with PCATMIP postprocessing yielded significant benefits for signal recovery, contrast-to-noise ratio, and SNR in the presence of bulk motion for both numerical simulations and human volunteer studies. Analysis of mean apparent diffusion coefficient (ADC) maps showed homogeneous values among volunteers and good reproducibility between free-breathing and breath-hold acquisitions. The PCATMIP DWI approach also indicated its potential utility by detecting ADC variations in acute myocardial infarction patients. Studying cardiac motion may provide an appropriate strategy for minimizing the impact of bulk motion on cardiac DWI. Applying PCATMIP image processing improves low b-value DWI and enables reliable analysis of ADC in the myocardium. The use of a limited number of repetitions in a free-breathing mode also enables easier application in clinical conditions.

Diffused junction p(+)-n solar cells in bulk GaAs. II - Device characterization and modelling

NASA Technical Reports Server (NTRS)

Keeney, R.; Sundaram, L. M. G.; Rode, H.; Bhat, I.; Ghandhi, S. K.; Borrego, J. M.

1984-01-01

The photovoltaic characteristics of p(+)-n junction solar cells fabricated on bulk GaAs by an open tube diffusion technique are presented in detail. Quantum efficiency measurements were analyzed and compared to computer simulations of the cell structure in order to determine material parameters such as diffusion length, surface recombination velocity and junction depth. From the results obtained it is projected that proper optimization of the cell parameters can increase the efficiency of the cells to close to 20 percent.

The Interaction of Polycrystalline Copper Films with Dilute Aqueous Solutions of Cupric Chloride

DTIC Science & Technology

1989-10-01

to interconnect semiconductor devices and other computer components Electronic circuits are mass / produced to obtain poduct uniformity and lowestx...so one needs to determine what if any pH change is produced by this extraneous oxide film growth. Thus, in order to determine any interference which...diffusion type; bulk diffusion rates would lie between 10 - 1 3 and 6x10-12mol.h- 1cm-2 mixed grain -13 boundary and bulk diffusion would lie between 6x10

Localization Counteracts Decoherence in Noisy Floquet Topological Chains

NASA Astrophysics Data System (ADS)

Rieder, M.-T.; Sieberer, L. M.; Fischer, M. H.; Fulga, I. C.

2018-05-01

The topological phases of periodically driven, or Floquet systems, rely on a perfectly periodic modulation of system parameters in time. Even the smallest deviation from periodicity leads to decoherence, causing the boundary (end) states to leak into the system's bulk. Here, we show that in one dimension this decay of topologically protected end states depends fundamentally on the nature of the bulk states: a dispersive bulk results in an exponential decay, while a localized bulk slows the decay down to a diffusive process. The localization can be due to disorder, which remarkably counteracts decoherence even when it breaks the symmetry responsible for the topological protection. We derive this result analytically, using a novel, discrete-time Floquet-Lindblad formalism and confirm our findings with the help of numerical simulations. Our results are particularly relevant for experiments, where disorder can be tailored to protect Floquet topological phases from decoherence.

Process for fabricating a charge coupled device

DOEpatents

Conder, Alan D.; Young, Bruce K. F.

2002-01-01

A monolithic three dimensional charged coupled device (3D-CCD) which utilizes the entire bulk of the semiconductor for charge generation, storage, and transfer. The 3D-CCD provides a vast improvement of current CCD architectures that use only the surface of the semiconductor substrate. The 3D-CCD is capable of developing a strong E-field throughout the depth of the semiconductor by using deep (buried) parallel (bulk) electrodes in the substrate material. Using backside illumination, the 3D-CCD architecture enables a single device to image photon energies from the visible, to the ultra-violet and soft x-ray, and out to higher energy x-rays of 30 keV and beyond. The buried or bulk electrodes are electrically connected to the surface electrodes, and an E-field parallel to the surface is established with the pixel in which the bulk electrodes are located. This E-field attracts charge to the bulk electrodes independent of depth and confines it within the pixel in which it is generated. Charge diffusion is greatly reduced because the E-field is strong due to the proximity of the bulk electrodes.

Material Science Experiments on Mir

NASA Technical Reports Server (NTRS)

Kroes, Roger L.

1999-01-01

This paper describes the microgravity materials experiments carried out on the Shuttle/Mir program. There were six experiments, all of which investigated some aspect of diffusivity in liquid melts. The Liquid Metal Diffusion (LMD) experiment investigated the diffusivity of molten Indium samples at 185 C using a radioactive tracer, In-114m. By monitoring two different gamma ray energies (190 keV and 24 keV) emitted by the samples it was possible to measure independently the diffusion rates in the bulk and at the surface of the samples. The Queens University Experiment in Liquid Diffusion (QUELD) was the furnace facility used to process 213 samples for the five other experiments. These experiments investigated the diffusion, ripening, crystal growth, and glass formation in metal, semiconductor, and glass samples. This facility had the capability to process samples in an isothermal or gradient configuration for varying periods of time at temperatures up to 900 C. Both the LMD and the QUELD furnaces were mounted on the Microgravity Isolation Mount (MIM) which provided isolation from g-jitter. All the microgravity experiments were supported by the Space Acceleration Measurement System (SAMS); a three head three axes acceleration monitoring system which measured and recorded the acceleration environment.

Unravelling Li-Ion Transport from Picoseconds to Seconds: Bulk versus Interfaces in an Argyrodite Li6PS5Cl-Li2S All-Solid-State Li-Ion Battery.

PubMed

Yu, Chuang; Ganapathy, Swapna; de Klerk, Niek J J; Roslon, Irek; van Eck, Ernst R H; Kentgens, Arno P M; Wagemaker, Marnix

2016-09-07

One of the main challenges of all-solid-state Li-ion batteries is the restricted power density due to the poor Li-ion transport between the electrodes via the electrolyte. However, to establish what diffusional process is the bottleneck for Li-ion transport requires the ability to distinguish the various processes. The present work investigates the Li-ion diffusion in argyrodite Li6PS5Cl, a promising electrolyte based on its high Li-ion conductivity, using a combination of (7)Li NMR experiments and DFT based molecular dynamics simulations. This allows us to distinguish the local Li-ion mobility from the long-range Li-ion motional process, quantifying both and giving a coherent and consistent picture of the bulk diffusion in Li6PS5Cl. NMR exchange experiments are used to unambiguously characterize Li-ion transport over the solid electrolyte-electrode interface for the electrolyte-electrode combination Li6PS5Cl-Li2S, giving unprecedented and direct quantitative insight into the impact of the interface on Li-ion charge transport in all-solid-state batteries. The limited Li-ion transport over the Li6PS5Cl-Li2S interface, orders of magnitude smaller compared with that in the bulk Li6PS5Cl, appears to be the bottleneck for the performance of the Li6PS5Cl-Li2S battery, quantifying one of the major challenges toward improved performance of all-solid-state batteries.

Li diffusion in epitaxial (11 $bar 2$ 0) ZnO thin films

NASA Astrophysics Data System (ADS)

Wu, P.; Zhong, J.; Emanetoglu, N. W.; Chen, Y.; Muthukumar, S.; Lu, Y.

2004-06-01

Zinc oxide (ZnO) possesses many interesting properties, such as a wide energy bandgap, large photoconductivity, and high excitonic binding energy. Chemical-vapor-deposition-grown ZnO films generally show n-type conductivity. A compensation doping process is needed to achieve piezoelectric ZnO, which is needed for surface acoustic wave (SAW), bulk acoustic wave, and micro-electromechanical system devices. In this work, a gas-phase diffusion process is developed to achieve piezoelectric (11bar 20) ZnO films. Comparative x-ray diffraction (XRD) and scanning electron microscopy (SEM) measurements confirmed that high crystal quality and good surface morphology were preserved after diffusion. Photoluminescence (PL) measurements show a broad band emission with a peak wavelength at ˜580 nm, which is associated with Li doping. The SAW, including both Rayleigh-wave and Love-wave modes, is achieved along different directions in piezoelectric (11bar 20) ZnO films grown on an r-plane sapphire substrate.

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

A new approach to the problem of bulk-mediated surface diffusion.

PubMed

Berezhkovskii, Alexander M; Dagdug, Leonardo; Bezrukov, Sergey M

2015-08-28

This paper is devoted to bulk-mediated surface diffusion of a particle which can diffuse both on a flat surface and in the bulk layer above the surface. It is assumed that the particle is on the surface initially (at t = 0) and at time t, while in between it may escape from the surface and come back any number of times. We propose a new approach to the problem, which reduces its solution to that of a two-state problem of the particle transitions between the surface and the bulk layer, focusing on the cumulative residence times spent by the particle in the two states. These times are random variables, the sum of which is equal to the total observation time t. The advantage of the proposed approach is that it allows for a simple exact analytical solution for the double Laplace transform of the conditional probability density of the cumulative residence time spent on the surface by the particle observed for time t. This solution is used to find the Laplace transform of the particle mean square displacement and to analyze the peculiarities of its time behavior over the entire range of time. We also establish a relation between the double Laplace transform of the conditional probability density and the Fourier-Laplace transform of the particle propagator over the surface. The proposed approach treats the cases of both finite and infinite bulk layer thicknesses (where bulk-mediated surface diffusion is normal and anomalous at asymptotically long times, respectively) on equal footing.

Thermally activated diffusion of copper into amorphous carbon

DOE PAGES

Appy, David; Wallingford, Mark; Jing, Dapeng; ...

2017-07-11

Using x-ray photoelectron spectroscopy, the authors characterize the thermally activated changes that occur when Cu is deposited on amorphous carbon supported on Si at 300 K, then heated to 800 K. The authors compare data for Cu on the basal plane of graphite with pinning defects, where scanning tunneling microscopy reveals that coarsening is the main process in this temperature range. Coarsening begins at 500–600 K and causes moderate attenuation of the Cu photoelectron signal. For Cu on amorphous carbon, heating to 800 K causes Cu to diffuse into the bulk of the film, based on the strong attenuation ofmore » the Cu signal. Diffusion into the bulk of the amorphous carbon film is confirmed by changes in the shape of the Cu 2 p inelastic tail, and by comparison of attenuation between Cu 2 p and Cu 3 p lines. The magnitude of the photoelectron signal attenuation is compatible with Cu distributed homogeneously throughout the amorphous carbon film, and is not compatible with Cu at or below the C–Si interface under the conditions of our experiments. As a result, desorption is not significant at temperatures up to 800 K.« less

Annihilating vacancies via dynamic reflection and emission of interstitials in nano-crystal tungsten

NASA Astrophysics Data System (ADS)

Li, Xiangyan; Duan, Guohua; Xu, Yichun; Zhang, Yange; Liu, Wei; Liu, C. S.; Liang, Yunfeng; Chen, Jun-Ling; Luo, G.-N.

2017-11-01

Radiation damage not only seriously degrades the mechanical properties of tungsten (W) but also enhances hydrogen retention in the material. Introducing a large amount of defect sinks, e.g. grain boundaries (GBs) is an effective method for improving radiation-resistance of W. However, the mechanism by which the vacancies are dynamically annihilated at long timescale in nano-crystal W is still not clear. The dynamic picture for eliminating vacancies with single interstitials and small interstitial-clusters has been investigated by combining molecular dynamics, molecular statics and object Kinetic Monte Carlo methods. On one hand, the annihilation of bulk vacancies was enhanced due to the reflection of an interstitial-cluster of parallel ≤ft< 1 1 1 \\right> crowdions by the GB. The interstitial-cluster was observed to be reflected back into the grain interior when approaching a locally dense GB region. Near this region, the energy landscape for the interstitial was featured by a shoulder, different to the decreasing energy landscape of the interstitial near a locally loose region as indicative of the sink role of the GB. The bulk vacancy on the reflection path was annihilated. On the other hand, the dynamic interstitial emission efficiently anneals bulk vacancies. The single interstitial trapped at the GB firstly moved along the GB quickly and clustered to be the di-interstitial therein, reducing its mobility to a value comparable to that that for bulk vacancy diffusion. Then, the bulk vacancy was recombined via the coupled motion of the di-interstitial along the GB, the diffusion of the vacancy towards the GB and the accompanying interstitial emission. These results suggest that GBs play an efficient role in improving radiation-tolerance of nano-crystal W via reflecting highly-mobile interstitials and interstitial-clusters into the bulk and annihilating bulk vacancies, and via complex coupling of in-boundary interstitial diffusion, clustering of the interstitial and vacancy diffusion in the bulk.

Bulk and contact resistances of gas diffusion layers in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ye, Donghao; Gauthier, Eric; Benziger, Jay B.; Pan, Mu

2014-06-01

A multi-electrode probe is employed to distinguish the bulk and contact resistances of the catalyst layer (CL) and the gas diffusion layer (GDL) with the bipolar plate (BPP). Resistances are compared for Vulcan carbon catalyst layers (CL), carbon paper and carbon cloth GDL materials, and GDLs with microporous layers (MPL). The Vulcan carbon catalyst layer bulk resistance is 100 times greater than the bulk resistance of carbon paper GDL (Toray TG-H-120). Carbon cloth (CCWP) has bulk and contact resistances twice those of carbon paper. Compression of the GDL decreases the GDL contact resistance, but has little effect on the bulk resistance. Treatment of the GDL with polytetrafluoroethylene (PTFE) increases the contact resistance, but has little effect on the bulk resistance. A microporous layer (MPL) added to the GDL decreases the contact resistance, but has little effect on the bulk resistance. An equivalent circuit model shows that for channels less than 1 mm wide the contact resistance is the major source of electronic resistance and is about 10% of the total ohmic resistance associated with the membrane electrode assembly.

Measurements of True Leak Rates of MEMS Packages

PubMed Central

Han, Bongtae

2012-01-01

Gas transport mechanisms that characterize the hermetic behavior of MEMS packages are fundamentally different depending upon which sealing materials are used in the packages. In metallic seals, gas transport occurs through a few nanoscale leak channels (gas conduction) that are produced randomly during the solder reflow process, while gas transport in polymeric seals occurs through the bulk material (gas diffusion). In this review article, the techniques to measure true leak rates of MEMS packages with the two sealing materials are described and discussed: a Helium mass spectrometer based technique for metallic sealing and a gas diffusion based model for polymeric sealing. PMID:22736994

Solid-state diffusion-controlled growth of the phases in the Au-Sn system

NASA Astrophysics Data System (ADS)

Baheti, Varun A.; Kashyap, Sanjay; Kumar, Praveen; Chattopadhyay, Kamanio; Paul, Aloke

2018-01-01

The solid state diffusion-controlled growth of the phases is studied for the Au-Sn system in the range of room temperature to 200 °C using bulk and electroplated diffusion couples. The number of product phases in the interdiffusion zone decreases with the decrease in annealing temperature. These phases grow with significantly high rates even at the room temperature. The growth rate of the AuSn4 phase is observed to be higher in the case of electroplated diffusion couple because of the relatively small grains and hence high contribution of the grain boundary diffusion when compared to the bulk diffusion couple. The diffraction pattern analysis indicates the same equilibrium crystal structure of the phases in these two types of diffusion couples. The analysis in the AuSn4 phase relating the estimated tracer diffusion coefficients with grain size, crystal structure, the homologous temperature of experiments and the concept of the sublattice diffusion mechanism in the intermetallic compounds indicate that Au diffuses mainly via the grain boundaries, whereas Sn diffuses via both the grain boundaries and the lattice.

Sucrose diffusion in aqueous solution

PubMed Central

Murray, Benjamin J.

2016-01-01

The diffusion of sugar in aqueous solution is important both in nature and in technological applications, yet measurements of diffusion coefficients at low water content are scarce. We report directly measured sucrose diffusion coefficients in aqueous solution. Our technique utilises a Raman isotope tracer method to monitor the diffusion of non-deuterated and deuterated sucrose across a boundary between the two aqueous solutions. At a water activity of 0.4 (equivalent to 90 wt% sucrose) at room temperature, the diffusion coefficient of sucrose was determined to be approximately four orders of magnitude smaller than that of water in the same material. Using literature viscosity data, we show that, although inappropriate for the prediction of water diffusion, the Stokes–Einstein equation works well for predicting sucrose diffusion under the conditions studied. As well as providing information of importance to the fundamental understanding of diffusion in binary solutions, these data have technological, pharmaceutical and medical implications, for example in cryopreservation. Moreover, in the atmosphere, slow organic diffusion may have important implications for aerosol growth, chemistry and evaporation, where processes may be limited by the inability of a molecule to diffuse between the bulk and the surface of a particle. PMID:27364512

CO Diffusion and Desorption Kinetics in CO2 Ices

NASA Astrophysics Data System (ADS)

Cooke, Ilsa R.; Öberg, Karin I.; Fayolle, Edith C.; Peeler, Zoe; Bergner, Jennifer B.

2018-01-01

The diffusion of species in icy dust grain mantles is a fundamental process that shapes the chemistry of interstellar regions; yet, measurements of diffusion in interstellar ice analogs are scarce. Here we present measurements of CO diffusion into CO2 ice at low temperatures (T = 11–23 K) using CO2 longitudinal optical phonon modes to monitor the level of mixing of initially layered ices. We model the diffusion kinetics using Fick’s second law and find that the temperature-dependent diffusion coefficients are well fit by an Arrhenius equation, giving a diffusion barrier of 300 ± 40 K. The low barrier along with the diffusion kinetics through isotopically labeled layers suggest that CO diffuses through CO2 along pore surfaces rather than through bulk diffusion. In complementary experiments, we measure the desorption energy of CO from CO2 ices deposited at 11–50 K by temperature programmed desorption and find that the desorption barrier ranges from 1240 ± 90 K to 1410 ± 70 K depending on the CO2 deposition temperature and resultant ice porosity. The measured CO–CO2 desorption barriers demonstrate that CO binds equally well to CO2 and H2O ices when both are compact. The CO–CO2 diffusion–desorption barrier ratio ranges from 0.21 to 0.24 dependent on the binding environment during diffusion. The diffusion–desorption ratio is consistent with the above hypothesis that the observed diffusion is a surface process and adds to previous experimental evidence on diffusion in water ice that suggests surface diffusion is important to the mobility of molecules within interstellar ices.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

NASA Astrophysics Data System (ADS)

Pfrang, C.; Shiraiwa, M.; Pöschl, U.

2011-04-01

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles representative of atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant time scales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Chemical ageing and transformation of diffusivity in semi-solid multi-component organic aerosol particles

NASA Astrophysics Data System (ADS)

Pfrang, C.; Shiraiwa, M.; Pöschl, U.

2011-07-01

Recent experimental evidence underlines the importance of reduced diffusivity in amorphous semi-solid or glassy atmospheric aerosols. This paper investigates the impact of diffusivity on the ageing of multi-component reactive organic particles approximating atmospheric cooking aerosols. We apply and extend the recently developed KM-SUB model in a study of a 12-component mixture containing oleic and palmitoleic acids. We demonstrate that changes in the diffusivity may explain the evolution of chemical loss rates in ageing semi-solid particles, and we resolve surface and bulk processes under transient reaction conditions considering diffusivities altered by oligomerisation. This new model treatment allows prediction of the ageing of mixed organic multi-component aerosols over atmospherically relevant timescales and conditions. We illustrate the impact of changing diffusivity on the chemical half-life of reactive components in semi-solid particles, and we demonstrate how solidification and crust formation at the particle surface can affect the chemical transformation of organic aerosols.

Surface effects on exciton diffusion in non polar ZnO/ZnMgO heterostructures

NASA Astrophysics Data System (ADS)

Sakr, G.; Sartel, C.; Sallet, V.; Lusson, A.; Patriarche, G.; Galtier, P.; Barjon, J.

2017-12-01

The diffusion of excitons injected in ZnO/Zn0.92Mg0.08O quantum well heterostructures grown by metal-organic-vapor-phase-epitaxy on non-polar ZnO substrates is investigated at room temperature. Cathodoluminescence linescans in a field-emission-gun scanning-electron-microscope are performed across cleaved cross-sections. A 55 nm diffusion length is assessed for excitons in bulk ZnMgO. When prepared as small angle bevels using focused ion beam (FIB), the effective diffusion length of excitons is shown to decrease down to 8 nm in the thinner part of the slab. This effect is attributed to non-radiative surface recombinations, with a 7  ×  104 cm s-1 recombination velocity estimated at the FIB-machined ZnMgO surface. The strong reduction of the diffusion extent in such thin lamellae usually used for transmission electron microscopy could be use improve the spatial resolution of cathodoluminescence images, often limited by diffusion processes.

Redox-stratification controlled biofilm (ReSCoBi) for completely autotrophic nitrogen removal: the effect of co- versus counter-diffusion on reactor performance.

PubMed

Terada, Akihiko; Lackner, Susanne; Tsuneda, Satoshi; Smets, Barth F

2007-05-01

A multi-population biofilm model for completely autotrophic nitrogen removal was developed and implemented in the simulation program AQUASIM to corroborate the concept of a redox-stratification controlled biofilm (ReSCoBi). The model considers both counter- and co-diffusion biofilm geometries. In the counter-diffusion biofilm, oxygen is supplied through a gas-permeable membrane that supports the biofilm while ammonia (NH(4)(+)) is supplied from the bulk liquid. On the contrary, in the co-diffusion biofilm, both oxygen and NH(4)(+) are supplied from the bulk liquid. Results of the model revealed a clear stratification of microbial activities in both of the biofilms, the resulting chemical profiles, and the obvious effect of the relative surface loadings of oxygen and NH(4)(+) (J(O(2))/J(NH(4)(+))) on the reactor performances. Steady-state biofilm thickness had a significant but different effect on T-N removal for co- and counter-diffusion biofilms: the removal efficiency in the counter-diffusion biofilm geometry was superior to that in the co-diffusion counterpart, within the range of 450-1,400 microm; however, the efficiency deteriorated with a further increase in biofilm thickness, probably because of diffusion limitation of NH(4)(+). Under conditions of oxygen excess (J(O(2))/J(NH(4)(+)) > 3.98), almost all NH(4)(+) was consumed by aerobic ammonia oxidation in the co-diffusion biofilm, leading to poor performance, while in the counter-diffusion biofilm, T-N removal efficiency was maintained because of the physical location of anaerobic ammonium oxidizers near the bulk liquid. These results clearly reveal that counter-diffusion biofilms have a wider application range for autotrophic T-N removal than co-diffusion biofilms. (c) 2006 Wiley Periodicals, Inc.

Investigation of oxygen self-diffusion in PuO 2 by combining molecular dynamics with thermodynamic calculations

DOE PAGES

Saltas, V.; Chroneos, A.; Cooper, Michael William D.; ...

2016-01-01

In the present work, the defect properties of oxygen self-diffusion in PuO 2 are investigated over a wide temperature (300–1900 K) and pressure (0–10 GPa) range, by combining molecular dynamics simulations and thermodynamic calculations. Based on the well-established cBΩ thermodynamic model which connects the activation Gibbs free energy of diffusion with the bulk elastic and expansion properties, various point defect parameters such as activation enthalpy, activation entropy, and activation volume were calculated as a function of T and P. Molecular dynamics calculations provided the necessary bulk properties for the proper implementation of the thermodynamic model, in the lack of anymore » relevant experimental data. The estimated compressibility and the thermal expansion coefficient of activation volume are found to be more than one order of magnitude greater than the corresponding values of the bulk plutonia. As a result, the diffusion mechanism is discussed in the context of the temperature and pressure dependence of the activation volume.« less

Bulk Diffusion via a ``kick-out'' method for Lithium in the decomposition reaction LiAlH4/Li3AlH6

NASA Astrophysics Data System (ADS)

Rolih, Biljana; Ozolins, Vidvuds; Ozolins Team

2013-03-01

In the pursuit to find a practical system for hydrogen storage, complex metal hydrides have long been considered as viable candidates due to their high hydrogen content. However, some of the challenges faced with these types of systems are poor thermodynamics or kinetics. The underlying mechanisms, and their limiting processes, for the decomposition of these materials need to be understood. From experimental work on the decomposition of hydrogen storage materials, it has been suggested that bulk diffusion of metal species is the bottleneck for hydrogen release. In this work is the dehydrogenation we investigated the system LiAlH4  LiAlH6 with favorable hydrogen release (5.3 wt %), at moderate temperatures. Using first-principles density functional theory we found the defects facilitating mass transport by calculating individual formation energies, highest concentrations, and activation barriers for defect mobility. The mass transport of Lithium is found to be mediated by a ``kick-out'' mechanism. The results are used to further our understanding of the fundamental mechanism of mass transport and evaluate the possibility of kinetics as the limiting process in this reaction.

Mapping the nanoscale energetic landscape in conductive polymer films with spatially super-resolved exciton dynamics

NASA Astrophysics Data System (ADS)

Ginsberg, Naomi

2015-03-01

The migration of Frenkel excitons, tightly-bound electron-hole pairs, in polymeric organic semiconducting films is critical to the efficiency of bulk heterojunction solar cells. While these materials exhibit a high degree of structural heterogeneity on the nanoscale, traditional measurements of exciton diffusion lengths are performed on bulk samples. Since both the characteristic length scales of structural heterogeneity and the reported bulk diffusion lengths are smaller than the optical diffraction limit, we adapt far-field super-resolution fluorescence imaging to uncover the correlations between the structural and energetic landscapes that the excitons explore.

Formation of VP-Zn complexes in bulk InP(Zn) by migration of P vacancies from the (110) surface

NASA Astrophysics Data System (ADS)

Slotte, J.; Saarinen, K.; Ebert, Ph.

2006-05-01

We apply a combination of positron annihilation spectroscopy and scanning tunneling microscopy to show that thermally generated P vacancies diffuse from the InP surface toward the bulk. The defect observed in the bulk can be identified as a complex consisting of a P vacancy and a Zn impurity. We infer that this pair is formed when the diffusing positive P vacancy is trapped at the Zn dopant. A rough estimate for the migration energy of the P vacancy results in a value of 1.3eV .

Thermally ruggedized ITO transparent electrode films for high power optoelectronics.

PubMed

Yoo, Jae-Hyuck; Matthews, Manyalibo; Ramsey, Phil; Barrios, Antonio Correa; Carter, Austin; Lange, Andrew; Bude, Jeff; Elhadj, Selim

2017-10-16

We present two strategies to minimize laser damage in transparent conductive films. The first consists of improving heat dissipation by selection of substrates with high thermal diffusivity or by addition of capping layer heatsinks. The second is reduction of bulk energy absorption by lowering free carrier density and increasing mobility, while maintaining film conductance with thicker films. Multi-pulse laser damage tests were performed on tin-doped indium oxide (ITO) films configured to improve optical lifetime damage performance. Conditions where improvements were not observed are also described. When bulk heating is not the dominant damage process, discrete defect-induced damage limits damage behavior.

SIMS study of oxygen diffusion in monoclinic HfO2

NASA Astrophysics Data System (ADS)

Mueller, Michael P.; De Souza, Roger A.

2018-01-01

The diffusion of oxygen in dense ceramics of monoclinic HfO2 was studied by means of (18O/16O) isotope exchange annealing and subsequent determination of isotope depth profiles by Secondary Ion Mass Spectrometry. Anneals were performed in the temperature range of 573 ≤T /K ≤ 973 at an oxygen partial pressure of p O2=200 mbar . All measured isotope profiles exhibited two features: the first feature, closer to the surface, was attributed mainly to slow oxygen diffusion in an impurity silicate phase; the second feature, deeper in the sample, was attributed to oxygen diffusion in bulk monoclinic HfO2 . The activation enthalpy of oxygen tracer diffusion in bulk HfO2 was found to be ΔHD∗≈0.5 eV .

Nanoscopic diffusion studies on III-V compound semiconductor structures: Experiment and theory

NASA Astrophysics Data System (ADS)

Gonzalez Debs, Mariam

The electronic structure of multilayer semiconductor heterostructures is affected by the detailed compositional profiles throughout the structure and at critical interfaces. The extent of interdiffusion across these interfaces places limits on both the processing time and temperatures for many applications based on the resultant compositional profile and associated electronic structure. Atomic and phenomenological methods were used in this work through the combination of experiment and theory to understand the nanoscopic mechanisms in complex heterostructures. Two principal studies were conducted. Tin diffusion in GaAs was studied by fitting complex experimental diffusion profiles to a phenomenological model which involved the diffusion of substitutional and interstitial dopant atoms. A methodology was developed combining both the atomistic model and the use of key features within these experimentally-obtained diffusion profiles to determine meaningful values of the transport and defect reaction rate parameters. Interdiffusion across AlSb/GaSb multi-quantum well interfaces was also studied. The chemical diffusion coefficient characterizing the AlSb/GaSb diffusion couple was quantitatively determined by fitting the observed photoluminescence (PL) peak shifts to the solution of the Schrodinger equation using a potential derived from the solution of the diffusion equation to quantify the interband transition energy shifts. First-principles calculations implementing Density Functional Theory were performed to study the thermochemistry of point defects as a function of local environment, allowing a direct comparison of interfacial and bulk diffusion phenomena within these nanoscopic structures. Significant differences were observed in the Ga and Al vacancy formation energies at the AlSb/GaSb interface when compared to bulk AlSb and GaSb with the largest change found for Al vacancies. The AlSb/GaSb structures were further studied using positron annihilation spectroscopy (PAS) to investigate the role of vacancies in the interdiffusion of Al and Ga in the superlattices. The PL and PAS experimental techniques together with the phenomenological and atomistic modeling allowed for the determination of the underlying mass transport mechanisms at the nanoscale.

Effects of sub-bandgap illumination on electrical properties and detector performances of CdZnTe:In

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

Xu, Lingyan; Jie, Wanqi, E-mail: jwq@nwpu.edu.cn; Zha, Gangqiang, E-mail: zha-gq@hotmail.com

2014-06-09

The effects of sub-bandgap illumination on electrical properties of CdZnTe:In crystals and spectroscopic performances of the fabricated detectors were discussed. The excitation process of charge carriers through thermal and optical transitions at the deep trap could be described by the modified Shockley-Read-Hall model. The ionization probability of the deep donor shows an increase under illumination, which should be responsible for the variation of electrical properties within CdZnTe bulk materials with infrared (IR) irradiation. By applying Ohm's law, diffusion model and interfacial layer-thermionic-diffusion theory, we obtain the decrease of bulk resistivity and the increase of space charge density in the illuminatedmore » crystals. Moreover, the illumination induced ionization will further contribute to improving carrier transport property and charge collection efficiency. Consequently, the application of IR irradiation in the standard working environment is of great significance to improve the spectroscopic characteristics of CdZnTe radiation detectors.« less

Towards a bulk approach to local interactions of hydrometeors

NASA Astrophysics Data System (ADS)

Baumgartner, Manuel; Spichtinger, Peter

2018-02-01

The growth of small cloud droplets and ice crystals is dominated by the diffusion of water vapor. Usually, Maxwell's approach to growth for isolated particles is used in describing this process. However, recent investigations show that local interactions between particles can change diffusion properties of cloud particles. In this study we develop an approach for including these local interactions into a bulk model approach. For this purpose, a simplified framework of local interaction is proposed and governing equations are derived from this setup. The new model is tested against direct simulations and incorporated into a parcel model framework. Using the parcel model, possible implications of the new model approach for clouds are investigated. The results indicate that for specific scenarios the lifetime of cloud droplets in subsaturated air may be longer (e.g., for an initially water supersaturated air parcel within a downdraft). These effects might have an impact on mixed-phase clouds, for example in terms of riming efficiencies.

Far-field analysis of coupled bulk and boundary layer diffusion toward an ion channel entrance.

PubMed Central

Schumaker, M F; Kentler, C J

1998-01-01

We present a far-field analysis of ion diffusion toward a channel embedded in a membrane with a fixed charge density. The Smoluchowski equation, which represents the 3D problem, is approximated by a system of coupled three- and two-dimensional diffusions. The 2D diffusion models the quasi-two-dimensional diffusion of ions in a boundary layer in which the electrical potential interaction with the membrane surface charge is important. The 3D diffusion models ion transport in the bulk region outside the boundary layer. Analytical expressions for concentration and flux are developed that are accurate far from the channel entrance. These provide boundary conditions for a numerical solution of the problem. Our results are used to calculate far-field ion flows corresponding to experiments of Bell and Miller (Biophys. J. 45:279, 1984). PMID:9591651

Diffusion of aqueous solutions of ionic, zwitterionic, and polar solutes

NASA Astrophysics Data System (ADS)

Teng, Xiaojing; Huang, Qi; Dharmawardhana, Chamila Chathuranga; Ichiye, Toshiko

2018-06-01

The properties of aqueous solutions of ionic, zwitterionic, and polar solutes are of interest to many fields. For instance, one of the many anomalous properties of aqueous solutions is the behavior of water diffusion in different monovalent salt solutions. In addition, solutes can affect the stabilities of macromolecules such as proteins in aqueous solution. Here, the diffusivities of aqueous solutions of sodium chloride, potassium chloride, tri-methylamine oxide (TMAO), urea, and TMAO-urea are examined in molecular dynamics simulations. The decrease in the diffusivity of water with the concentration of simple ions and urea can be described by a simple model in which the water molecules hydrogen bonded to the solutes are considered to diffuse at the same rate as the solutes, while the remainder of the water molecules are considered to be bulk and diffuse at almost the same rate as pure water. On the other hand, the decrease in the diffusivity of water with the concentration of TMAO is apparently affected by a decrease in the diffusion rate of the bulk water molecules in addition to the decrease due to the water molecules hydrogen bonded to TMAO. In other words, TMAO enhances the viscosity of water, while urea barely affects it. Overall, this separation of water molecules into those that are hydrogen bonded to solute and those that are bulk can provide a useful means of understanding the short- and long-range effects of solutes on water.

Physicochemical Study of Viral Nanoparticles at the Air/Water Interface.

PubMed

Torres-Salgado, Jose F; Comas-Garcia, Mauricio; Villagrana-Escareño, Maria V; Durán-Meza, Ana L; Ruiz-García, Jaime; Cadena-Nava, Ruben D

2016-07-07

The assembly of most single-stranded RNA (ssRNA) viruses into icosahedral nucleocapsids is a spontaneous process driven by protein-protein and RNA-protein interactions. The precise nature of these interactions results in the assembly of extremely monodisperse and structurally indistinguishable nucleocapsids. In this work, by using a ssRNA plant virus (cowpea chlorotic mottle virus [CCMV]) as a charged nanoparticle we show that the diffusion of these nanoparticles from the bulk solution to the air/water interface is an irreversible adsorption process. By using the Langmuir technique, we measured the diffusion and adsorption of viral nucleocapsids at the air/water interface at different pH conditions. The pH changes, and therefore in the net surface charge of the virions, have a great influence in the diffusion rate from the bulk solution to the air/water interface. Moreover, assembly of mesoscopic and microscopic viral aggregates at this interface depends on the net surface charge of the virions and the surface pressure. By using Brewster's angle microscopy we characterized these structures at the interface. Most common structures observed were clusters of virions and soap-frothlike micron-size structures. Furthermore, the CCMV films were compressed to form monolayers and multilayers from moderate to high surface pressures, respectively. After transferring the films from the air/water interface onto mica by using the Langmuir-Blodgett technique, their morphology was characterized by atomic force microscopy. These viral monolayers showed closed-packing nano- and microscopic arrangements.

Study of water diffusion on single-supported bilayer lipid membranes by quasielastic neutron scattering

NASA Astrophysics Data System (ADS)

Bai, M.; Miskowiec, A.; Hansen, F. Y.; Taub, H.; Jenkins, T.; Tyagi, M.; Diallo, S. O.; Mamontov, E.; Herwig, K. W.; Wang, S.-K.

2012-05-01

High-energy-resolution quasielastic neutron scattering has been used to elucidate the diffusion of water molecules in proximity to single bilayer lipid membranes supported on a silicon substrate. By varying sample temperature, level of hydration, and deuteration, we identify three different types of diffusive water motion: bulk-like, confined, and bound. The motion of bulk-like and confined water molecules is fast compared to those bound to the lipid head groups (7-10 H2O molecules per lipid), which move on the same nanosecond time scale as H atoms within the lipid molecules.

Connecting the molecular scale to the continuum scale for diffusion processes in smectite-rich porous media.

PubMed

Bourg, Ian C; Sposito, Garrison

2010-03-15

In this paper, we address the manner in which the continuum-scale diffusive properties of smectite-rich porous media arise from their molecular- and pore-scale features. Our starting point is a successful model of the continuum-scale apparent diffusion coefficient for water tracers and cations, which decomposes it as a sum of pore-scale terms describing diffusion in macropore and interlayer "compartments." We then apply molecular dynamics (MD) simulations to determine molecular-scale diffusion coefficients D(interlayer) of water tracers and representative cations (Na(+), Cs(+), Sr(2+)) in Na-smectite interlayers. We find that a remarkably simple expression relates D(interlayer) to the pore-scale parameter δ(nanopore) ≤ 1, a constrictivity factor that accounts for the lower mobility in interlayers as compared to macropores: δ(nanopore) = D(interlayer)/D(0), where D(0) is the diffusion coefficient in bulk liquid water. Using this scaling expression, we can accurately predict the apparent diffusion coefficients of tracers H(2)0, Na(+), Sr(2+), and Cs(+) in compacted Na-smectite-rich materials.

Tritium migration to the surfaces of Type 316 stainless steel; aluminum 6061; and oxygen-free, high-conductivity copper

DOE PAGES

Sharpe, M.; Shmayda, W. T.; Schroder, W. U.

2016-05-25

The migration of tritium to the surfaces of aluminum 6061, oxygen-free, high-conductivity copper (OFHC), and stainless-steel 316 from the bulk metal was studied using low-pressure Tonks–Langmuir argon plasma. The plasma is shown to be effective at removing tritium from metal surfaces in a controlled manner. Tritium is removed in decreasing quantities with successive plasma exposures, which suggests a depletion of the surface and near-surface tritium inventories. A diffusion model was developed to predict tritium migration from the bulk and its accumulation in the water layers present on the metal surface. The model reproduces the rate of tritium re-growth on themore » surface for all three metals and can be used to calculate the triton solubility in the water layers present on metal surfaces. The ratio of surface-to-bulk solubilities at the water-layer/bulk-metal interface uniquely determines the concentration ratio between these two media. Removing the tritium-rich water layers induces tritium to migrate from the bulk to the surface. Furthermore, this process is driven by a concentration gradient that develops in the bulk because of the perturbation on the surface.« less

Surface conservation laws at microscopically diffuse interfaces.

PubMed

Chu, Kevin T; Bazant, Martin Z

2007-11-01

In studies of interfaces with dynamic chemical composition, bulk and interfacial quantities are often coupled via surface conservation laws of excess surface quantities. While this approach is easily justified for microscopically sharp interfaces, its applicability in the context of microscopically diffuse interfaces is less theoretically well-established. Furthermore, surface conservation laws (and interfacial models in general) are often derived phenomenologically rather than systematically. In this article, we first provide a mathematically rigorous justification for surface conservation laws at diffuse interfaces based on an asymptotic analysis of transport processes in the boundary layer and derive general formulae for the surface and normal fluxes that appear in surface conservation laws. Next, we use nonequilibrium thermodynamics to formulate surface conservation laws in terms of chemical potentials and provide a method for systematically deriving the structure of the interfacial layer. Finally, we derive surface conservation laws for a few examples from diffusive and electrochemical transport.

Numerical study of the effects of physical parameters on the dynamic fuel retention in tungsten materials

NASA Astrophysics Data System (ADS)

Sang, Chaofeng; Sun, Jizhong; Bonnin, Xavier; Dai, Shuyu; Hu, Wanpeng; Wang, Dezhen

2014-12-01

Effects of different possible values of physical parameters on the fuel retention in tungsten (W) materials are studied in this work since W is considered as the primary plasma-facing surface material and fuel retention is a critical issue for next-step fusion devices. The upgraded Hydrogen Isotope Inventory Processes Code is used to conduct the study. First, the inventories of hydrogen isotopes (HI) inside W with different possible values of diffusivities and recombination rate coefficients are studied; then the influences of uncertainties in diffusivity, trap concentration, and recombination rate on the effective diffusion are also analyzed. Finally, an illustration of effective diffusion on the permeation and inventory is given. The enhancements of HI permeation flux and inventory in bulk W due to the presence of a carbide WxC layer on the PFS are explained.

Nanowire membrane-based nanothermite: towards processable and tunable interfacial diffusion for solid state reactions.

PubMed

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

NASA Astrophysics Data System (ADS)

Yang, Yong; Wang, Peng-Peng; Zhang, Zhi-Cheng; Liu, Hui-Ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-04-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants.

Multiscale diffusion in the mitotic Drosophila melanogaster syncytial blastoderm

PubMed Central

Daniels, Brian R.; Rikhy, Richa; Renz, Malte; Dobrowsky, Terrence M.; Lippincott-Schwartz, Jennifer

2012-01-01

Despite the fundamental importance of diffusion for embryonic morphogen gradient formation in the early Drosophila melanogaster embryo, there remains controversy regarding both the extent and the rate of diffusion of well-characterized morphogens. Furthermore, the recent observation of diffusional “compartmentalization” has suggested that diffusion may in fact be nonideal and mediated by an as-yet-unidentified mechanism. Here, we characterize the effects of the geometry of the early syncytial Drosophila embryo on the effective diffusivity of cytoplasmic proteins. Our results demonstrate that the presence of transient mitotic membrane furrows results in a multiscale diffusion effect that has a significant impact on effective diffusion rates across the embryo. Using a combination of live-cell experiments and computational modeling, we characterize these effects and relate effective bulk diffusion rates to instantaneous diffusion coefficients throughout the syncytial blastoderm nuclear cycle phase of the early embryo. This multiscale effect may be related to the effect of interphase nuclei on effective diffusion, and thus we propose that an as-yet-unidentified role of syncytial membrane furrows is to temporally regulate bulk embryonic diffusion rates to balance the multiscale effect of interphase nuclei, which ultimately stabilizes the shapes of various morphogen gradients. PMID:22592793

Effect of sample thickness on the extracted near-infrared bulk optical properties of Bacillus subtilis in liquid culture.

PubMed

Dzhongova, Elitsa; Harwood, Colin R; Thennadil, Suresh N

2011-11-01

In order to determine the bulk optical properties of a Bacillus subtilis culture during growth phase we investigated the effect of sample thickness on measurements taken with different measurement configurations, namely total diffuse reflectance and total diffuse transmittance. The bulk optical properties were extracted by inverting the measurements using the radiative transfer theory. While the relationship between reflectance and biomass changes with sample thickness and the intensity (absorbance) levels vary significantly for both reflectance and transmittance measurements, the extracted optical properties show consistent behavior in terms of both the relationship with biomass and magnitude. This observation indicates the potential of bulk optical properties for building models that could be more easily transferable compared to those built using raw measurements.

Comparison and analysis of theoretical models for diffusion-controlled dissolution.

PubMed

Wang, Yanxing; Abrahamsson, Bertil; Lindfors, Lennart; Brasseur, James G

2012-05-07

Dissolution models require, at their core, an accurate diffusion model. The accuracy of the model for diffusion-dominated dissolution is particularly important with the trend toward micro- and nanoscale drug particles. Often such models are based on the concept of a "diffusion layer." Here a framework is developed for diffusion-dominated dissolution models, and we discuss the inadequacy of classical models that are based on an unphysical constant diffusion layer thickness assumption, or do not correctly modify dissolution rate due to "confinement effects": (1) the increase in bulk concentration from confinement of the dissolution process, (2) the modification of the flux model (the Sherwood number) by confinement. We derive the exact mathematical solution for a spherical particle in a confined fluid with impermeable boundaries. Using this solution, we analyze the accuracy of a time-dependent "infinite domain model" (IDM) and "quasi steady-state model" (QSM), both formally derived for infinite domains but which can be applied in approximate fashion to confined dissolution with proper adjustment of a concentration parameter. We show that dissolution rate is sensitive to the degree of confinement or, equivalently, to the total concentration C(tot). The most practical model, the QSM, is shown to be very accurate for most applications and, consequently, can be used with confidence in design-level dissolution models so long as confinement is accurately treated. The QSM predicts the ratio of diffusion layer thickness to particle radius (the Sherwood number) as a constant plus a correction that depends on the degree of confinement. The QSM also predicts that the time required for complete saturation or dissolution in diffusion-controlled dissolution experiments is singular (i.e., infinite) when total concentration equals the solubility. Using the QSM, we show that measured differences in dissolution rate in a diffusion-controlled dissolution experiment are a result of differences in the degree of confinement on the increase in bulk concentration independent of container geometry and polydisperse vs single particle dissolution. We conclude that the constant diffusion-layer thickness assumption is incorrect in principle and should be replaced by the QSM with accurate treatment of confinement in models of diffusion-controlled dissolution.

In Situ Neutron Diffraction of Rare-Earth Phosphate Proton Conductors Sr/Ca-doped LaPO4 at Elevated Temperatures

NASA Astrophysics Data System (ADS)

Al-Wahish, Amal; Al-Binni, Usama; Bridges, C. A.; Huq, A.; Bi, Z.; Paranthaman, M. P.; Tang, S.; Kaiser, H.; Mandrus, D.

Acceptor-doped lanthanum orthophosphates are potential candidate electrolytes for proton ceramic fuel cells. We combined neutron powder diffraction (NPD) at elevated temperatures up to 800° C , X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) to investigate the crystal structure, defect structure, thermal stability and surface topography. NPD shows an average bond length distortion in the hydrated samples. We employed Quasi-Elastic Neutron Scattering (QENS) and electrochemical impedance spectroscopy (EIS) to study the proton dynamics of the rare-earth phosphate proton conductors 4.2% Sr/Ca-doped LaPO4. We determined the bulk diffusion and the self-diffusion coefficients. Our results show that QENS and EIS are probing fundamentally different proton diffusion processes. Supported by the U.S. Department of Energy.

The formation of diffuse discharge by short-front nanosecond voltage pulses and the modification of dielectrics in this discharge

NASA Astrophysics Data System (ADS)

Orlovskii, V. M.; Panarin, V. A.; Shulepov, M. A.

2014-07-01

The dynamics of diffuse discharge formation under the action of nanosecond voltage pulses with short fronts (below 1 ns) in the absence of a source of additional preionization and the influence of a dielectric film on this process have been studied. It is established that the diffuse discharge is induced by the avalanche multiplication of charge initiated by high-energy electrons and then maintained due to secondary breakdowns propagating via ionized gas channels. If a dielectric film (polyethylene, Lavsan, etc.) is placed on the anode, then multiply repeated discharge will lead to surface and bulk modification of the film material. Discharge-treated polyethylene film exhibits a change in the optical absorption spectrum in the near-IR range.

Spatial distribution of dialysate in patients and its implications to intradialysate diffusion.

PubMed

Hills, Brian A; Birch, Seamus; Burke, John R; LaMont, Anthony C

2002-01-01

To visualize and quantify the spatial distribution of dialysate in patients on continuous ambulatory peritoneal dialysis (CAPD) and, hence, estimate diffusion times for fluid "pockets" wherever intradialysate concentration gradients may not be dissipated by convective currents. Contrast medium was added to the dialysate of three supine CAPD patients before an exchange prior to computed tomographic (CT) scanning. Spatial information in the CT scanner was then downloaded to other computers and processed to produce impressive three-dimensional models of dialysate distribution using "wire frame technology." Models differed between patients but all demonstrated pooling of dialysate in the paracolic gutters, subphrenic space, and, especially, in the pelvic cavity. Some pockets of fluid were almost isolated. Quantitatively, the models can account for over 80% of the volume of the exchange (2.5 L), displaying an effective area of contact of 913-450 cm2 between parietal peritoneum and dialysate. This amounts to only 11% -21% of the anatomic area, again emphasizing the uneven distribution of dialysate. Ignoring very thin (< 0.1 mm) films of dialysate, the bulk (80%) had mean thicknesses ranging from 1.6 to 1.9 cm. Transcendental equations for bulk diffusion were then applied to these findings to determine a theoretical time for urea of about 2-3 hours to half-saturation, or 5-7 hours to 80% saturation, in the absence of convective currents. The distribution of dialysate within the peritoneal cavity is very uneven, resulting in long diffusion times in fluid pockets wherever convective currents may be minimal. Hence, intradialysate diffusion should not be ignored when modeling peritoneal dialysis.

Photovoltaic characteristics of diffused P/+N bulk GaAs solar cells

NASA Technical Reports Server (NTRS)

Borrego, J. M.; Keeney, R. P.; Bhat, I. B.; Bhat, K. N.; Sundaram, L. G.; Ghandhi, S. K.

1982-01-01

The photovoltaic characteristics of P(+)N junction solar cells fabricated on bulk GaAs by an open tube diffusion technique are described in this paper.Spectral response measurements were analyzed in detail and compared to a computer simulation in order to determine important material parameters. It is projected that proper optimization of the cell parameters can increase the efficiency of the cells from 12.2 percent to close to 20 percent.

Glymphatic solute transport does not require bulk flow

PubMed Central

Asgari, Mahdi; de Zélicourt, Diane; Kurtcuoglu, Vartan

2016-01-01

Observations of fast transport of fluorescent tracers in mouse brains have led to the hypothesis of bulk water flow directed from arterial to venous paravascular spaces (PVS) through the cortical interstitium. At the same time, there is evidence for interstitial solute transport by diffusion rather than by directed bulk fluid motion. It has been shown that the two views may be consolidated by intracellular water flow through astrocyte networks combined with mainly diffusive extracellular transport of solutes. This requires the presence of a driving force that has not been determined to date, but for which arterial pulsation has been suggested as the origin. Here we show that arterial pulsation caused by pulse wave propagation is an unlikely origin of this hypothetical driving force. However, we further show that such pulsation may still lead to fast para-arterial solute transport through dispersion, that is, through the combined effect of local mixing and diffusion in the para-arterial space. PMID:27929105

Mechanisms limiting the performance of large grain polycrystalline silicon solar cells

NASA Technical Reports Server (NTRS)

Culik, J. S.; Alexander, P.; Dumas, K. A.; Wohlgemuth, J. W.

1984-01-01

The open-circuit voltage and short-circuit current of large-grain (1 to 10 mm grain diameter) polycrystalline silicon solar cells is determined by the minority-carrier diffusion length within the bulk of the grains. This was demonstrated by irradiating polycrystalline and single-crystal (Czochralski) silicon solar cells with 1 MeV electrons to reduce their bulk lifetime. The variation of short-circuit current with minority-carrier diffusion length for the polycrystalline solar cells is identical to that of the single-crystal solar cells. The open-circuit voltage versus short-circuit current characteristic of the polycrystalline solar cells for reduced diffusion lengths is also identical to that of the single-crystal solar cells. The open-circuit voltage of the polycrystalline solar cells is a strong function of quasi-neutral (bulk) recombination, and is reduced only slightly, if at all, by grain-boundary recombination.

Investigation of impact of post-metallization annealing on reliability of 65 nm NOR floating-gate flash memories

NASA Astrophysics Data System (ADS)

Chiu, Shengfen; Xu, Yue; Ji, Xiaoli; Yan, Feng

2016-12-01

This paper investigates the impact of post-metallization annealing (PMA) in pure nitrogen ambient on the reliability of 65 nm NOR-type floating-gate flash memory devices. The experimental results show that, with PMA process, the cycling performance of flash cells, especially for the erasing speed is obviously degraded compared to that without PMA. It is found that the bulk oxide traps and tunnel oxide/Si interface traps are significantly increased with PMA treatment. The water/moisture residues left in the interlayer dielectric layers diffuse to tunnel oxide during PMA process is considered to be responsible for these traps generation, which further enhances the degradation of erase performance. Skipping PMA treatment is proposed to suppress the water diffusion effect on erase performance degradation of flash cells.

Creating unstable velocity-space distributions with barium injections

NASA Technical Reports Server (NTRS)

Pongratz, M. B.

1983-01-01

Ion velocity-space distributions resulting from barium injections from orbiting spacecraft and shaped charges are discussed. Active experiments confirm that anomalous ionization processes may operate, but photoionization accounts for the production of the bulk of the barium ions. Pitch-angle diffusion and/or velocity-space diffusion may occur, but observations of barium ions moving upwards against gravity suggests that the ions retain a significant enough fraction of their initial perpendicular velocity to provide a mirror force. The barium ion plasmas should have a range of Alfven Mach numbers and plasma betas. Because the initial conditions can be predicted these active experiments should permit testing plasma instability hypotheses.

Interstitial solute transport in 3D reconstructed neuropil occurs by diffusion rather than bulk flow.

PubMed

Holter, Karl Erik; Kehlet, Benjamin; Devor, Anna; Sejnowski, Terrence J; Dale, Anders M; Omholt, Stig W; Ottersen, Ole Petter; Nagelhus, Erlend Arnulf; Mardal, Kent-André; Pettersen, Klas H

2017-09-12

The brain lacks lymph vessels and must rely on other mechanisms for clearance of waste products, including amyloid [Formula: see text] that may form pathological aggregates if not effectively cleared. It has been proposed that flow of interstitial fluid through the brain's interstitial space provides a mechanism for waste clearance. Here we compute the permeability and simulate pressure-mediated bulk flow through 3D electron microscope (EM) reconstructions of interstitial space. The space was divided into sheets (i.e., space between two parallel membranes) and tunnels (where three or more membranes meet). Simulation results indicate that even for larger extracellular volume fractions than what is reported for sleep and for geometries with a high tunnel volume fraction, the permeability was too low to allow for any substantial bulk flow at physiological hydrostatic pressure gradients. For two different geometries with the same extracellular volume fraction the geometry with the most tunnel volume had [Formula: see text] higher permeability, but the bulk flow was still insignificant. These simulation results suggest that even large molecule solutes would be more easily cleared from the brain interstitium by diffusion than by bulk flow. Thus, diffusion within the interstitial space combined with advection along vessels is likely to substitute for the lymphatic drainage system in other organs.

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

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

Han, Binghong; Key, Baris; Lapidus, Saul H.

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

DOE PAGES

Han, Binghong; Key, Baris; Lapidus, Saul H.; ...

2017-11-01

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

Interplay between translational diffusion and large-amplitude angular jumps of water molecules

NASA Astrophysics Data System (ADS)

Liu, Chao; Zhang, Yangyang; Zhang, Jian; Wang, Jun; Li, Wenfei; Wang, Wei

2018-05-01

Understanding the microscopic mechanism of water molecular translational diffusion is a challenging topic in both physics and chemistry. Here, we report an investigation on the interplay between the translational diffusion and the large-amplitude angular jumps of water molecules in bulk water using molecular dynamics simulations. We found that large-amplitude angular jumps are tightly coupled to the translational diffusions. Particularly, we revealed that concurrent rotational jumps of spatially neighboring water molecules induce inter-basin translational jumps, which contributes to the fast component of the water translational diffusion. Consequently, the translational diffusion shows positional heterogeneity; i.e., the neighbors of the water molecules with inter-basin translational jumps have larger probability to diffuse by inter-basin translational jumps. Our control simulations showed that a model water molecule with moderate hydrogen bond strength can diffuse much faster than a simple Lennard-Jones particle in bulk water due to the capability of disturbing the hydrogen bond network of the surrounding water molecules. Our results added to the understanding of the microscopic picture of the water translational diffusion and demonstrated the unique features of water diffusion arising from their hydrogen bond network structure compared with those of the simple liquids.

Calibration of mass spectrometric measurements of gas phase reactions on steel surfaces

NASA Astrophysics Data System (ADS)

Falk, H.; Falk, M.; Wuttke, T.

2015-03-01

The sampling of the surface-near gas composition using a mass spectrometer (MS-Probe) is a valuable tool within a hot dip process simulator. Since reference samples with well characterized surface coverage are usually not available, steel samples can deliver quantifiable amounts of the process relevant species H2O, CO and H2 using the decarburization reaction with water vapor. Such "artificial calibration samples" (ACS) can be used for the calibration of the MS-Probe measurements. The carbon release rate, which is governed by the diffusion law, was determined by GDOES, since the diffusion coefficients of carbon in steel samples are usually not known. The measured carbon concentration profiles in the ACS after the thermal treatment confirmed the validity of the diffusion model described in this paper. The carbon bulk concentration > 100 ppm is sufficient for the use of a steel material as ACS. The experimental results reported in this paper reveal, that with the MS-Probe the LOQ of less than one monolayer of iron oxide can be achieved.

Joining engineering ceramics

NASA Astrophysics Data System (ADS)

Loehman, Ronald E.

Methods for joining ceramics are outlined with attention given to their fundamental properties, and some examples of ceramic bonding in engineering ceramic systems are presented. Ceramic-ceramic bonds using no filler material include diffusion and electric-field bonding and ceramic welding, and bonds with filler materials can be provided by Mo-Mn brazing, microwave joining, and reactive nonmetallic liquid bonding. Ceramic-metal joints can be effected with filler material by means of the same ceramic-ceramic processes and without filler material by means of use of molten glass or diffusion bonding. Key properties of the bonding processes include: bonds with discontinuous material properties, energies that are positive relative to the bulk material, and unique chemical and mechanical properties. The processes and properties are outlined for ceramic-metal joints and for joining silicon nitride, and the factors that control wetting, adhesion, and reaction on the atomic scale are critical for establishing successful joints.

Excimer laser annealing: A gold process for CZ silicon junction formation

NASA Technical Reports Server (NTRS)

Wong, David C.; Bottenberg, William R.; Byron, Stanley; Alexander, Paul

1987-01-01

A cold process using an excimer laser for junction formation in silicon has been evaluated as a way to avoid problems associated with thermal diffusion. Conventional thermal diffusion can cause bulk precipitation of SiOx and SiC or fail to completely activate the dopant, leaving a degenerate layer at the surface. Experiments were conducted to determine the feasibility of fabricating high quality p-n junctions using a pulsed excimer laser for junction formation at remelt temperature with ion-implanted surfaces. Solar-cell efficiency exceeding 16 percent was obtained using Czochralski single-crystal silicon without benefit of back surface field or surface passivation. Characterization shows that the formation of uniform, shallow junctions (approximately 0.25 micron) by excimer laser scanning preserves the minority carrier lifetime that leads to high current collection. However, the process is sensitive to initial surface conditions and handling parameters that drive the cost up.

Thermally ruggedized ITO transparent electrode films for high power optoelectronics

DOE PAGES

Yoo, Jae-Hyuck; Matthews, Manyalibo; Ramsey, Phil; ...

2017-10-06

Here, we present two strategies to minimize laser damage in transparent conductive films. The first consists of improving heat dissipation by selection of substrates with high thermal diffusivity or by addition of capping layer heatsinks. The second is reduction of bulk energy absorption by lowering free carrier density and increasing mobility, while maintaining film conductance with thicker films. Multi-pulse laser damage tests were performed on tin-doped indium oxide (ITO) films configured to improve optical lifetime damage performance. Conditions where improvements were not observed are also described. Finally, when bulk heating is not the dominant damage process, discrete defect-induced damage limitsmore » damage behavior.« less

Transient Mass and Thermal Transport during Methane Adsorption into the Metal-Organic Framework HKUST-1.

PubMed

Babaei, Hasan; McGaughey, Alan J H; Wilmer, Christopher E

2018-01-24

Methane adsorption into the metal-organic framework (MOF) HKUST-1 and the resulting heat generation and dissipation are investigated using molecular dynamics simulations. Transient simulations reveal that thermal transport in the MOF occurs two orders of magnitude faster than gas diffusion. A large thermal resistance at the MOF-gas interface (equivalent to 127 nm of bulk HKUST-1), however, prevents fast release of the generated heat. The mass transport resistance at the MOF-gas interface is equivalent to 1 nm of bulk HKUST-1 and does not present a bottleneck in the adsorption process. These results provide important insights into the application of MOFs for gas storage applications.

The surface diffusion coefficient for an arbitrarily curved fluid-fluid interface. (I). General expression

NASA Astrophysics Data System (ADS)

M. C. Sagis, Leonard

2001-03-01

In this paper, we develop a theory for the calculation of the surface diffusion coefficient for an arbitrarily curved fluid-fluid interface. The theory is valid for systems in hydrodynamic equilibrium, with zero mass-averaged velocities in the bulk and interfacial regions. We restrict our attention to systems with isotropic bulk phases, and an interfacial region that is isotropic in the plane parallel to the dividing surface. The dividing surface is assumed to be a simple interface, without memory effects or yield stresses. We derive an expression for the surface diffusion coefficient in terms of two parameters of the interfacial region: the coefficient for plane-parallel diffusion D (AB)aa(ξ) , and the driving force d(B)I||(ξ) . This driving force is the parallel component of the driving force for diffusion in the interfacial region. We derive an expression for this driving force using the entropy balance.

Fabrication of Fe1.1Se0.5Te0.5 bulk by a high energy ball milling technique

NASA Astrophysics Data System (ADS)

Liu, Jixing; Li, Chengshan; Zhang, Shengnan; Feng, Jianqing; Zhang, Pingxiang; Zhou, Lian

2017-11-01

Fe1.1Se0.5Te0.5 superconducting bulks were successfully synthesized by a high energy ball milling (HEBM) aided sintering technique. Two advantages of this new technique have been revealed compared with traditional solid state sintering method. One is greatly increased the density of sintered bulks. It is because the precursor powders with β-Fe(Se, Te) and δ-Fe(Se, Te) were obtained directly by the HEBM process and without formation of liquid Se (and Te), which could avoid the huge volume expansion. The other is the obvious decrease of sintering temperature and dwell time due to the effective shortened length of diffusion paths. The superconducting critical temperature Tc of 14.2 K in our sample is comparable with those in previous reports, and further optimization of chemical composition is on the way.

Effect of the magnetism of impurities on their diffusion in metals: Bulk diffusion of iron, cobalt, and rhodium in iridium single crystals

NASA Astrophysics Data System (ADS)

Klotsman, S. M.; Tatarinova, G. N.

2008-12-01

The coefficients and parameters of the temperature dependences of the coefficients of bulk diffusion of Fe, Co, Rh, and Au atomic probes (APs) in iridium single crystals (mono-Ir) have been determined from the diffusion profiles obtained using secondary-ion mass spectrometry of the diffusion zones. The enthalpies of activation of diffusion of Fe, Co, and Rh APs are considerably lower than the enthalpy of activation of selfdiffusion in mono-Ir. This is caused by the negative contributions of the intraatomic exchange energy and energy of relaxation of the environment of the d transition APs to the enthalpy of interaction of magnetically active APs with the vacancies in the iridium lattice. The interaction energy of partners in such complexes and the relationships between the magnetic moments of d transition APs in complexes with vacancies have been estimated. The Rh APs in complexes with vacancies in iridium possess stable magnetic moments.

Defect engineering and luminescence characterization in bulk and thin film polycrystalline silicon

NASA Astrophysics Data System (ADS)

Koshka, Yaroslav

The passivation of recombination centers and the monitoring of passivation efficiency are critical for successful utilization of polycrystalline silicon (poly-Si) in solar cells and in thin-film transistors. Two important classes of poly-Si-thin films and bulk wafers-can respond differently to passivation processes (hydrogenation efficiency, possibilities of extrinsic and intrinsic gettering, etc.) and demand different approaches to their characterization. The effect of photoluminescence (PL) enhancement using ultrasound treatment (UST) was studied in poly-Si and amorphous-Si films on glass. In addition to the previously documented growth of the 0.7 eV oxygen related band in poly-Si films, generation and dramatic enhancement of a new luminescence maximum at about 0.98 eV occurs in films containing a superposition of poly-Si and alpha-Si phases. A model of ultrasound stimulated hydrogen detrapping followed by hydrogen diffusion and passivation of non-radiative centers was developed. Room temperature photoluminescence (PL) mapping was used to monitor improvement of recombination properties in bulk photovoltaic poly-Si during solar cell fabrication. Analysis of the statistical distribution of the values of PL enhancement shows that the contribution of individual processing steps to the increasing PL are different in nature. A correlation between PL mapping and minority carrier diffusion length was performed and quantitatively described. A method of obtaining separate information about the recombination properties of the bulk and the p/n junction regions of solar cells was developed. The method is based on measurements of PL distribution under different biases applied to solar cells and under different intensities of the excitation light. A PL study at 0.8 eV spectral maximum and comparison with the band-to-band PL was performed. Influence of the defects responsible for the 0.8 eV defect band was insignificant in as-grown wafers. It was revealed, however, that these defects start to determine non-homogeneity of recombination properties in poly-Si after the solar cell processing. Room-T electroluminescence (EL) mapping is shown to be a complimentary approach to characterize the bulk and the p/n junction regions of poly-Si solar cells. The major advantage of the EL approach is the possibility of instantaneous mapping of solar-grade poly-Si.

The Measurement of Thermal Diffusivity in Conductor and Insulator by Photodeflection Technique

NASA Astrophysics Data System (ADS)

Achathongsuk, U.; Rittidach, T.; Tipmonta, P.; Kijamnajsuk, P.; Chotikaprakhan, S.

2017-09-01

The purpose of this study is to estimate thermal diffusivities of high thermal diffusivity bulk material as well as low thermal diffusivity bulk material by using many types of fluid such as Ethyl alcohol and water. This method is studied by measuring amplitude and phase of photodeflection signal in various frequency modulations. The experimental setup consists of two laser lines: 1) a pump laser beams through a modulator, varied frequency, controlled by lock-in amplifier and focused on sample surface by lens. 2) a probe laser which parallels with the sample surface and is perpendicular to the pump laser beam. The probe laser deflection signal is obtained by a position sensor which controlled by lock-in amplifier. Thermal diffusivity is calculated by measuring the amplitude and phase of the photodeflection signal and compared with the thermal diffusivity of a standard value. The thermal diffusivity of SGG agrees well with the literature but the thermal diffusivity of Cu is less than the literature value by a factor of ten. The experiment requires further improvement to measure the thermal diffusivity of Cu. However, we succeed in using ethyl alcohol as the coupling medium instead of CCl4 which is highly toxic.

Molecular dynamics simulation of diffusion and electrical conductivity in montmorillonite interlayers

DOE PAGES

Greathouse, Jeffery A.; Cygan, Randall T.; Fredrich, Joanne T.; ...

2016-01-20

In this study, the diffusion of water and ions in the interlayer region of smectite clay minerals represents a direct probe of the type and strength of clay–fluid interactions. Interlayer diffusion also represents an important link between molecular simulation and macroscopic experiments. Here we use molecular dynamics simulation to investigate trends in cation and water diffusion in montmorillonite interlayers, looking specifically at the effects of layer charge, interlayer cation and cation charge (sodium or calcium), water content, and temperature. For Na-montmorillonite, the largest increase in ion and water diffusion coefficients occurs between the one-layer and two-layer hydrates, corresponding to themore » transition from inner-sphere to outer-sphere surface complexes. Calculated activation energies for ion and water diffusion in Na-montmorillonite are similar to each other and to the water hydrogen bond energy, suggesting the breaking of water–water and water–clay hydrogen bonds as a likely mechanism for interlayer diffusion. A comparison of interlayer diffusion with that of bulk electrolyte solutions reveals a clear trend of decreasing diffusion coefficient with increasing electrolyte concentration, and in most cases the interlayer diffusion results are nearly coincident with the corresponding bulk solutions. Trends in electrical conductivities computed from the ion diffusion coefficients are also compared.« less

Thermodynamic Derivation of the Activation Energy for Ice Nucleation

NASA Technical Reports Server (NTRS)

Barahona, D.

2015-01-01

Cirrus clouds play a key role in the radiative and hydrological balance of the upper troposphere. Their correct representation in atmospheric models requires an understanding of the microscopic processes leading to ice nucleation. A key parameter in the theoretical description of ice nucleation is the activation energy, which controls the flux of water molecules from the bulk of the liquid to the solid during the early stages of ice formation. In most studies it is estimated by direct association with the bulk properties of water, typically viscosity and self-diffusivity. As the environment in the ice-liquid interface may differ from that of the bulk, this approach may introduce bias in calculated nucleation rates. In this work a theoretical model is proposed to describe the transfer of water molecules across the ice-liquid interface. Within this framework the activation energy naturally emerges from the combination of the energy required to break hydrogen bonds in the liquid, i.e., the bulk diffusion process, and the work dissipated from the molecular rearrangement of water molecules within the ice-liquid interface. The new expression is introduced into a generalized form of classical nucleation theory. Even though no nucleation rate measurements are used to fit any of the parameters of the theory the predicted nucleation rate is in good agreement with experimental results, even at temperature as low as 190 K, where it tends to be underestimated by most models. It is shown that the activation energy has a strong dependency on temperature and a weak dependency on water activity. Such dependencies are masked by thermodynamic effects at temperatures typical of homogeneous freezing of cloud droplets; however, they may affect the formation of ice in haze aerosol particles. The new model provides an independent estimation of the activation energy and the homogeneous ice nucleation rate, and it may help to improve the interpretation of experimental results and the development of parameterizations for cloud formation.

Interfacial layers in high-temperature-oxidized NiCrAl

NASA Technical Reports Server (NTRS)

Larson, L. A.; Browning, R.; Poppa, H.; Smialek, J.

1983-01-01

The utility of Auger electron spectroscopy combined with ball cratering for depth analysis of oxide and diffusion layers produced in a Ni-14Cr-24Al alloy by oxidation in air at 1180 C for 25 hr is demonstrated. During postoxidation cooling, the oxide layers formed by this alloy spalled profusely. The remaining very thin oxide was primarily Cr2O3 with a trace of Ni. The underlying metal substrate exhibited gamma/gamma-prime and beta phases with a metallic interfacial layer which was similar to the bulk gamma/gamma-prime phase but slightly enriched in Cr and Al. These data are compared to electron microprobe results from a nominally identical alloy. The diffusion layer thickness is modelled with a simple mass balance equation and compared to recent results on the diffusion process in NiCrAl alloys.

Kinetics of cellular dissolution in a Cu-Cd alloy

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

Nakkalil, R.; Gupta, S.P.

1989-07-01

Dissolution of the cellular precipitate by cell boundary migration has been studied in a Cu-2 at.% Cd alloy in the temperature range 777--878 K. Microstructural observations have revealed that the process of dissolution begins at the original position of the grain boundary as well as the cell boundary. The steady state rate of cell boundary migration decreased with decreasing temperature of dissolution and became zero at approximately 770 K, which is about 30 K below the equilibrium solves temperature. The boundary diffusivities were determined at a number of temperatures by using the theory of Petermann and Hornbogen modified for dissolution.more » The diffusivity values calculated from the experimental data are seven orders of magnitude higher than the corresponding volume diffusivities. From the temperature dependence of the diffusivity, an activation energy of 157 kJ mol{sup {minus} 1} is obtained, which is bout three-quarters of the activation energy for the bulk diffusion of Cd into Cu. From the diffusivity and activation energy values, it is concluded that the diffusion of Cd along the migrating grain boundaries control the dissolution of the cellular precipitate in this alloy.« less

Atomistic modeling of water diffusion in hydrolytic biomaterials.

PubMed

Gautieri, Alfonso; Mezzanzanica, Andrea; Motta, Alberto; Redealli, Alberto; Vesentini, Simone

2012-04-01

One of the most promising applications of hydrolytically degrading biomaterials is their use as drug release carriers. These uses, however, require that the degradation and diffusion of drug are reliably predicted, which is complex to achieve through present experimental methods. Atomistic modeling can help in the knowledge-based design of degrading biomaterials with tuned drug delivery properties, giving insights on the small molecules diffusivity at intermediate states of the degradation process. We present here an atomistic-based approach to investigate the diffusion of water (through which hydrolytic degradation occurs) in degrading bulk models of poly(lactic acid) or PLA. We determine the water diffusion coefficient for different swelling states of the polymeric matrix (from almost dry to pure water) and for different degrees of degradation. We show that water diffusivity is highly influenced by the swelling degree, while little or not influenced by the degradation state. This approach, giving water diffusivity for different states of the matrix, can be combined with diffusion-reaction analytical methods in order to predict the degradation path on longer time scales. Furthermore, atomistic approach can be used to investigate diffusion of other relevant small molecules, eventually leading to the a priori knowledge of degradable biomaterials transport properties, helping the design of the drug delivery systems.

Copper/solder intermetallic growth studies.

PubMed

Kirchner, K W; Lucey, G K; Geis, J

1993-08-01

Copper samples, hot solder (eutectic) dipped and thermally aged, were cross-sectioned and placed in an environmental scanning electronic microscope (ESEM). While in the ESEM the samples were heated for approximately 2.5 h at 170 degrees C to stimulate the growth of additional Cu/Sn intermetallic compound. The intent of the study was to obtain a continuous real-time videotape record of the diffusion process and compare the observations to static SEM images reported to represent long-term, naturally aged intermetallic growth. The video obtained allows the observation of the diffusion process and relativistic growth phenomena at the Cu, Cu3Sn, Cu6Sn5, and solder interfaces as well as effects on the bulk Cu and solder. Effects contrary to earlier reports were observed; for example, growth rates of Cu3Sn were found to greatly exceed those of Cu6Sn5.

Numerical Modeling of High-Temperature Corrosion Processes

NASA Technical Reports Server (NTRS)

Nesbitt, James A.

1995-01-01

Numerical modeling of the diffusional transport associated with high-temperature corrosion processes is reviewed. These corrosion processes include external scale formation and internal subscale formation during oxidation, coating degradation by oxidation and substrate interdiffusion, carburization, sulfidation and nitridation. The studies that are reviewed cover such complexities as concentration-dependent diffusivities, cross-term effects in ternary alloys, and internal precipitation where several compounds of the same element form (e.g., carbides of Cr) or several compounds exist simultaneously (e.g., carbides containing varying amounts of Ni, Cr, Fe or Mo). In addition, the studies involve a variety of boundary conditions that vary with time and temperature. Finite-difference (F-D) techniques have been applied almost exclusively to model either the solute or corrodant transport in each of these studies. Hence, the paper first reviews the use of F-D techniques to develop solutions to the diffusion equations with various boundary conditions appropriate to high-temperature corrosion processes. The bulk of the paper then reviews various F-D modeling studies of diffusional transport associated with high-temperature corrosion.

Modeling of adsorption dynamics at air-liquid interfaces using statistical rate theory (SRT).

PubMed

Biswas, M E; Chatzis, I; Ioannidis, M A; Chen, P

2005-06-01

A large number of natural and technological processes involve mass transfer at interfaces. Interfacial properties, e.g., adsorption, play a key role in such applications as wetting, foaming, coating, and stabilizing of liquid films. The mechanistic understanding of surface adsorption often assumes molecular diffusion in the bulk liquid and subsequent adsorption at the interface. Diffusion is well described by Fick's law, while adsorption kinetics is less understood and is commonly described using Langmuir-type empirical equations. In this study, a general theoretical model for adsorption kinetics/dynamics at the air-liquid interface is developed; in particular, a new kinetic equation based on the statistical rate theory (SRT) is derived. Similar to many reported kinetic equations, the new kinetic equation also involves a number of parameters, but all these parameters are theoretically obtainable. In the present model, the adsorption dynamics is governed by three dimensionless numbers: psi (ratio of adsorption thickness to diffusion length), lambda (ratio of square of the adsorption thickness to the ratio of adsorption to desorption rate constant), and Nk (ratio of the adsorption rate constant to the product of diffusion coefficient and bulk concentration). Numerical simulations for surface adsorption using the proposed model are carried out and verified. The difference in surface adsorption between the general and the diffusion controlled model is estimated and presented graphically as contours of deviation. Three different regions of adsorption dynamics are identified: diffusion controlled (deviation less than 10%), mixed diffusion and transfer controlled (deviation in the range of 10-90%), and transfer controlled (deviation more than 90%). These three different modes predominantly depend on the value of Nk. The corresponding ranges of Nk for the studied values of psi (10(-2)

Does Diffusion Sequester Heavy Metals in Old Contamination Soils?

NASA Astrophysics Data System (ADS)

Ma, J.; Jennings, A. A.

2002-12-01

Old soil contamination refers to soil contamination that has aged over a long period of time. For example, at some brownfields, the soil heavy metal contamination can be one hundred or more years old. When contamination is young, the heavy metals are bound relatively weakly to the soil. However, the speciation and/or mechanisms of association evolve with aging into much more stable forms. It also appears that the metals migrate deeper into the bulk soil matrix where they are less available to participate in surface-related phenomena. Previous research showed elevated heavy metal extraction result after the soil was pulverized, with all other experiment conditions remaining unchanged. This indicates the presence of sequestered heavy metal contamination within the large soil particles (aggregate). The mechanisms of sequestering are uncertain, but diffusion appears to be a major factor. There are two possible pathways of diffusion that can account for heavy metal sequestering: solid-state diffusion through the bulk aggregate or liquid-phase diffusion through micro-pores within the aggregate structure. The second diffusion mechanism can be coupled with sorption (or other surface-related phenomena) on the pore walls. The remediation of sequestered heavy metals is also impacted by diffusion. Grinding a soil significantly reduces its average particle size. This exposes more of its internal bulk volume to extraction and results in much shorter diffusion pathway for the sequestered heavy metals to be released. Evidence has illustrated that this both improves remediation efficiency and provides a method by which the degree of sequestering can be quantified. This paper will present the results of ongoing research that is developing methods to identify the mechanisms of, quantify the magnitude of and determine the relative importance of (i.e. risk analysis) heavy metals sequestered in old contamination soils.

Determination of gaseous fission product behavior near the cerium dioxide Σ 3 (111)/[11 bar0] tilt grain boundary via first-principles study

NASA Astrophysics Data System (ADS)

Xi, Jianqi; Liu, Bin; Xu, Haixuan; Zhang, Yanwen; Weber, William J.

2018-02-01

Grain boundaries (GBs) are the most abundant structural defects in nanostructured nuclear fuels and play an important role in determining fission product behavior, which further affects the performance of nuclear fuels. In this work, cerium dioxide (CeO2) is used as a surrogate material for mixed oxide fuels to understand gaseous fission product behavior, specifically Xe. First-principles calculations are employed to comprehensively study the behavior of Xe and trap sites for Xe near the Σ 3 (111)/[11 bar0] grain boundary in CeO2, which will provide guidance on overall trends for Xe stability and diffusion at grain boundaries vs in the bulk. Significant segregation behavior of trap sites, regardless of charge states, is observed near the GB. This is mainly ascribed to the local atomic structure near the GB, which results in weaker bond strength and more negative segregation energies. For Xe, however, the segregation profile near the GB is different. Our calculations show that, as the size of trap sites increases, the segregation propensity of Xe is reduced. In addition, under hyper-stoichiometric conditions, the solubility of Xe trapped at the GB is significantly higher than that in the bulk, suggesting higher Xe concentration than that in the bulk. The results of this work demonstrate that the diffusion mechanism of Xe in CeO2 is comparable to that in UO2. The diffusion activation energies of Xe atoms in the Σ 3 GB are lower than that in the bulk CeO2. These results suggest that the diffusivity of Xe atoms is higher along the GB than that in the bulk, which enhances the aggregation of Xe atoms near the GB.

Simulation studies of plasma waves in the electron foreshock - The generation of downshifted oscillations

NASA Technical Reports Server (NTRS)

Dum, C. T.

1990-01-01

The generation of waves with frequencies downshifted from the plasma frequency, as observed in the electron foreshock, is analyzed by particle simulation. Wave excitation differs fundamentally from the familiar excitation of the plasma eigenmodes by a gentle bump-on-tail electron distribution. Beam modes are destabilized by resonant interaction with bulk electrons, provided the beam velocity spread is very small. These modes are stabilized, starting with the higher frequencies, as the beam is broadened and slowed down by the interaction with the wave spectrum. Initially a very cold beam is also capable of exciting frequencies considerably above the plasma frequency, but such oscillations are quickly stabilized. Low-frequency modes persist for a long time, until the bump in the electron distribution is completely 'ironed' out. This diffusion process also is quite different from the familiar case of well-separated beam and bulk electrons. A quantitative analysis of these processes is carried out.

How does spallation microdamage nucleate in bulk amorphous alloys under shock loading?

NASA Astrophysics Data System (ADS)

Huang, X.; Ling, Z.; Zhang, H. S.; Ma, J.; Dai, L. H.

2011-11-01

Specially designed plate-impact experiments have been conducted on a Zr-based amorphous alloy using a single-stage light gas gun. To understand the microdamage nucleation process in the material, the samples are subjected to dynamic tensile loadings of identical amplitude (˜ 3.18 GPa) but with different durations (83-201 ns). A cellular pattern with an equiaxed shape is observed on the spallation surface, which shows that spallation in the tested amorphous alloy is a typical ductile fracture and that microvoids have been nucleated during the process. Based on the observed fracture morphologies of the spallation surface and free-volume theory, we propose a microvoid nucleation model of bulk amorphous alloys. It is found that nucleation of microvoids at the early stage of spallation in amorphous alloys results from diffusion and coalescence of free volume, and that high mean tensile stress plays a dominant role in microvoid nucleation.

DFT-derived reactive potentials for the simulation of activated processes: the case of CdTe and CdTe:S.

PubMed

Hu, Xiao Liang; Ciaglia, Riccardo; Pietrucci, Fabio; Gallet, Grégoire A; Andreoni, Wanda

2014-06-19

We introduce a new ab initio derived reactive potential for the simulation of CdTe within density functional theory (DFT) and apply it to calculate both static and dynamical properties of a number of systems (bulk solid, defective structures, liquid, surfaces) at finite temperature. In particular, we also consider cases with low sulfur concentration (CdTe:S). The analysis of DFT and classical molecular dynamics (MD) simulations performed with the same protocol leads to stringent performance tests and to a detailed comparison of the two schemes. Metadynamics techniques are used to empower both Car-Parrinello and classical molecular dynamics for the simulation of activated processes. For the latter, we consider surface reconstruction and sulfur diffusion in the bulk. The same procedures are applied using previously proposed force fields for CdTe and CdTeS materials, thus allowing for a detailed comparison of the various schemes.

OBJECT KINETIC MONTE CARLO SIMULATIONS OF RADIATION DAMAGE IN BULK TUNGSTEN

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

Nandipati, Giridhar; Setyawan, Wahyu; Heinisch, Howard L.

2015-09-22

We used our recently developed lattice based OKMC code; KSOME [1] to carryout simulations of radiation damage in bulk W. We study the effect of dimensionality of self interstitial atom (SIA) diffusion i.e. 1D versus 3D on the defect accumulation during irradiation with a primary knock-on atom (PKA) energy of 100 keV at 300 K for the dose rates of 10-5 and 10-6 dpa/s. As expected 3D SIA diffusion significantly reduces damage accumulation due to increased probability of recombination events. In addition, dose rate, over the limited range examined here, appears to have no effect in both cases of SIAmore » diffusion.« less

Localized diffusive motion on two different time scales in solid alkane nanoparticles

NASA Astrophysics Data System (ADS)

Wang, S.-K.; Mamontov, E.; Bai, M.; Hansen, F. Y.; Taub, H.; Copley, J. R. D.; García Sakai, V.; Gasparovic, G.; Jenkins, T.; Tyagi, M.; Herwig, K. W.; Neumann, D. A.; Montfrooij, W.; Volkmann, U. G.

2010-09-01

High-energy-resolution quasielastic neutron scattering on three complementary spectrometers has been used to investigate molecular diffusive motion in solid nano- to bulk-sized particles of the alkane n-C32H66. The crystalline-to-plastic and plastic-to-fluid phase transition temperatures are observed to decrease as the particle size decreases. In all samples, localized molecular diffusive motion in the plastic phase occurs on two different time scales: a "fast" motion corresponding to uniaxial rotation about the long molecular axis; and a "slow" motion attributed to conformational changes of the molecule. Contrary to the conventional interpretation in bulk alkanes, the fast uniaxial rotation begins in the low-temperature crystalline phase.

A computational method for the coupled solution of reaction-diffusion equations on evolving domains and manifolds: Application to a model of cell migration and chemotaxis.

PubMed

MacDonald, G; Mackenzie, J A; Nolan, M; Insall, R H

2016-03-15

In this paper, we devise a moving mesh finite element method for the approximate solution of coupled bulk-surface reaction-diffusion equations on an evolving two dimensional domain. Fundamental to the success of the method is the robust generation of bulk and surface meshes. For this purpose, we use a novel moving mesh partial differential equation (MMPDE) approach. The developed method is applied to model problems with known analytical solutions; these experiments indicate second-order spatial and temporal accuracy. Coupled bulk-surface problems occur frequently in many areas; in particular, in the modelling of eukaryotic cell migration and chemotaxis. We apply the method to a model of the two-way interaction of a migrating cell in a chemotactic field, where the bulk region corresponds to the extracellular region and the surface to the cell membrane.

A kinetic Monte Carlo simulation method of van der Waals epitaxy for atomistic nucleation-growth processes of transition metal dichalcogenides.

PubMed

Nie, Yifan; Liang, Chaoping; Cha, Pil-Ryung; Colombo, Luigi; Wallace, Robert M; Cho, Kyeongjae

2017-06-07

Controlled growth of crystalline solids is critical for device applications, and atomistic modeling methods have been developed for bulk crystalline solids. Kinetic Monte Carlo (KMC) simulation method provides detailed atomic scale processes during a solid growth over realistic time scales, but its application to the growth modeling of van der Waals (vdW) heterostructures has not yet been developed. Specifically, the growth of single-layered transition metal dichalcogenides (TMDs) is currently facing tremendous challenges, and a detailed understanding based on KMC simulations would provide critical guidance to enable controlled growth of vdW heterostructures. In this work, a KMC simulation method is developed for the growth modeling on the vdW epitaxy of TMDs. The KMC method has introduced full material parameters for TMDs in bottom-up synthesis: metal and chalcogen adsorption/desorption/diffusion on substrate and grown TMD surface, TMD stacking sequence, chalcogen/metal ratio, flake edge diffusion and vacancy diffusion. The KMC processes result in multiple kinetic behaviors associated with various growth behaviors observed in experiments. Different phenomena observed during vdW epitaxy process are analysed in terms of complex competitions among multiple kinetic processes. The KMC method is used in the investigation and prediction of growth mechanisms, which provide qualitative suggestions to guide experimental study.

Enhanced gas absorption in the ionic liquid 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores: a molecular simulation study.

PubMed

Shi, Wei; Luebke, David R

2013-05-07

Two-dimensional NPxyT and isostress-osmotic (N2PxyTf1) Monte Carlo simulations were used to compute the density and gas absorption properties of the ionic liquid (IL) 1-n-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([hmim][Tf2N]) confined in silica slit pores (25-45 Å). Self-diffusivity values for both gas and IL were calculated from NVE molecular dynamics simulations using both smooth and atomistic potential models for silica. The simulations showed that the molar volume of [hmim][Tf2N] confined in 25-45-Å silica slit pores is 12-31% larger than that of the bulk IL at 313-573 K and 1 bar. The amounts of CO2, H2, and N2 absorbed in the confined IL are 1.1-3 times larger than those in the bulk IL because of the larger molar volume of the confined IL compared to the bulk IL. The CO2, N2, and H2 molecules are generally absorbed close to the silica wall where the IL density is very low. This arrangement causes the self-diffusivities of these gases in the confined IL to be 2-8 times larger than those in the bulk IL at 298-573 K. The solubilities of water in the confined and bulk ILs are similar, which is likely due to strong water interactions with [hmim][Tf2N] through hydrogen bonding, so that the molar volume of the confined IL plays a less important role in determining the H2O solubility. Water molecules are largely absorbed in the IL-rich region rather than close to the silica wall. The self-diffusivities of water correlate with those of the confined IL. The confined IL exhibits self-diffusivities larger than those of the bulk IL at lower temperatures, but smaller than those of the bulk IL at higher temperatures. The findings from our simulations are consistent with available experimental data for similar confined IL systems.

Similar solutions of double-diffusive dissipative layers along free surfaces

NASA Astrophysics Data System (ADS)

Napolitano, L. G.; Viviani, A.; Savino, R.

1990-10-01

Free convection due to buoyant forces (natural convection) and surface tension gradients (Marangoni convection) generated by temperature and concentration gradients is discussed together with the formation of double-diffusive boundary layers along liquid-gas interfaces. Similarity solutions for each class of free convection are derived and the resulting nonlinear two-point problems are solved numerically using the quasi-linearization method. Velocity, temperature, concentration profiles, interfacial velocity, heat and mass transfer bulk coefficients for various Prandtl and Schmidt numbers, and different values of the similarity parameters are determined. The convective flows are of particular interest because they are considered to influence the processes of crystal growth, both on earth and in a microgravity environment.

Multistage adsorption of diffusing macromolecules and viruses

NASA Astrophysics Data System (ADS)

Chou, Tom; D'Orsogna, Maria R.

2007-09-01

We derive the equations that describe adsorption of diffusing particles onto a surface followed by additional surface kinetic steps before being transported across the interface. Multistage surface kinetics occurs during membrane protein insertion, cell signaling, and the infection of cells by virus particles. For example, viral entry into healthy cells is possible only after a series of receptor and coreceptor binding events occurs at the cellular surface. We couple the diffusion of particles in the bulk phase with the multistage surface kinetics and derive an effective, integrodifferential boundary condition that contains a memory kernel embodying the delay induced by the surface reactions. This boundary condition takes the form of a singular perturbation problem in the limit where particle-surface interactions are short ranged. Moreover, depending on the surface kinetics, the delay kernel induces a nonmonotonic, transient replenishment of the bulk particle concentration near the interface. The approach generalizes that of Ward and Tordai [J. Chem. Phys. 14, 453 (1946)] and Diamant and Andelman [Colloids Surf. A 183-185, 259 (2001)] to include surface kinetics, giving rise to qualitatively new behaviors. Our analysis also suggests a simple scheme by which stochastic surface reactions may be coupled to deterministic bulk diffusion.

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

Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversiblymore » reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.« less

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

DOE PAGES

Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla; ...

2017-12-15

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversiblymore » reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.« less

Growth Kinetics and Size Distribution Dynamics of Viscous Secondary Organic Aerosol

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

Zaveri, Rahul A.; Shilling, John E.; Zelenyuk, Alla

Low bulk diffusivity inside viscous semisolid atmospheric secondary organic aerosol (SOA) can prolong equilibration time scale, but its broader impacts on aerosol growth and size distribution dynamics are poorly understood. In this article, we present quantitative insights into the effects of bulk diffusivity on the growth and evaporation kinetics of SOA formed under dry conditions from photooxidation of isoprene in the presence of a bimodal aerosol consisting of Aitken (ammonium sulfate) and accumulation (isoprene or α-pinene SOA) mode particles. Aerosol composition measurements and evaporation kinetics indicate that isoprene SOA is composed of several semivolatile organic compounds (SVOCs), with some reversiblymore » reacting to form oligomers. Model analysis shows that liquid-like bulk diffusivities can be used to fit the observed evaporation kinetics of accumulation mode particles but fail to explain the growth kinetics of bimodal aerosol by significantly under-predicting the evolution of the Aitken mode. In contrast, the semisolid scenario successfully reproduces both evaporation and growth kinetics, with the interpretation that hindered partitioning of SVOCs into large viscous particles effectively promotes the growth of smaller particles that have shorter diffusion time scales. This effect has important implications for the growth of atmospheric ultrafine particles to climatically active sizes.« less

Density functional calculation of activation energies for lattice and grain boundary diffusion in alumina

NASA Astrophysics Data System (ADS)

Lei, Yinkai; Gong, Yu; Duan, Zhiyao; Wang, Guofeng

2013-06-01

To acquire knowledge on the lattice and grain boundary diffusion processes in alumina, we have determined the activation energies of elementary O and Al diffusive jumps in the bulk crystal, Σ3(0001) grain boundaries, and Σ3(101¯0) grain boundaries of α-Al2O3 using the first-principles density functional theory method. Specifically, we calculated the activation energies for four elementary jumps of both O and Al lattice diffusion in alumina. It was predicted that the activation energy of O lattice diffusion varied from 3.58 to 5.03 eV, while the activation energy of Al lattice diffusion ranged from 1.80 to 3.17 eV. As compared with experimental measurements, the theoretical predictions of the activation energy for lattice diffusion were lower and thus implied that there might be other high-energy diffusive jumps in the experimental alumina samples. Moreover, our results suggested that the Al lattice diffusion was faster than the O lattice diffusion in alumina, in agreement with experiment observations. Furthermore, it was found from our calculations for α-Al2O3 that the activation energies of O and Al grain boundary diffusion in the high-energy Σ3(0001) grain boundaries were significantly lower than those of the lattice diffusion. In contrast, the activation energies of O and Al grain boundary diffusion in the low-energy Σ3(101¯0) grain boundaries could be even higher than those of the lattice diffusion.

Molecular Design of High Performance Molecular Devices Based on Direct Ab-initio Molecular Dynamics Method: Diffusion of Lithium Ion on Fluorinated Amorphous Carbon

NASA Astrophysics Data System (ADS)

Kawabata, Hiroshi; Iyama, Tetsuji; Tachikawa, Hiroto

2008-01-01

Hybrid density functional theory (DFT) calculations have been carried out for the lithium adsorbed on a fluorinated graphene surface (F-graphene, C96F24) to elucidate the effect of fluorination of amorphous carbon on the diffusion mechanism of lithium ion. Also, direct molecular orbital-molecular dynamics (MO-MD) calculation [H. Tachikawa and A. Shimizu: J. Phys. Chem. B 109 (2005) 13255] was applied to diffusion processes of the Li+ ion on F-graphene. The B3LYP/LANL2MB calculation showed that the Li+ ion is most stabilized around central position of F-graphene, and the energy was gradually instabilized for the edge region. The direct MO-MD calculations showed that the Li+ ion diffuses on the bulk surface region of F-graphite at 300 K. The nature of the interaction between Li+ and F-graphene was discussed on the basis of theoretical results.

The Electron Diffusion Region: Forces and Currents

NASA Technical Reports Server (NTRS)

Hesse, Michael

2008-01-01

The dissipation mechanism of magnetic reconnection remains a subject of intense scientific interest. On one hand, one set of recent studies have shown that particle inertia-based processes, which include thermal and bulk inertial effects, provide the reconnection electric field in the diffusion region. On the other hand, a second set of studies emphasizes the role of wave-particle interactions in providing anomalous resistivity in the diffusion region. In this presentation, we present analytical theory results, as well as PIC simulations of guide-field magnetic reconnection. We will show that the thermal electron inertia-based dissipation mechanism, expressed through nongyrotropic electron pressure tensors, remains viable in three dimensions. We will demonstrate the thermal inertia effect through studies of electron distribution functions. Furthermore, we will show that the reconnection electric field provides a transient acceleration on particles traversing the inner reconnection region. This inertia1 effect can be described as a diffusion-like term of the current density, which matches key features of electron distribution functions.

The Electron Diffusion Region: Forces and Currents

NASA Technical Reports Server (NTRS)

Hesse, Michael

2009-01-01

The dissipation mechanism of magnetic reconnection remains a subject of intense scientific interest. On one hand, one set of recent studies have shown that particle inertia-based processes, which include thermal and bulk inertial effects, provide the reconnection electric field in the diffusion region. On the other hand, a second set of studies emphasizes the role of wave-particle interactions in providing anomalous resistivity in the diffusion region. In this presentation, we present analytical theory results, as well as PIC simulations of guide-field magnetic reconnection. We will show that the thermal electron inertia-based dissipation mechanism, expressed through nongyrotropic electron pressure tensors, remains viable in three dimensions. We will demonstrate the thermal inertia effect through studies of electron distribution functions. Furthermore, we will show that the reconnection electric field provides a transient acceleration on particles traversing the inner reconnection region. This inertial effect can be described as a diffusion-like term of the current density, which matches key features of electron distribution functions.

Nanowire Membrane-based Nanothermite: towards Processable and Tunable Interfacial Diffusion for Solid State Reactions

PubMed Central

Yang, Yong; Wang, Peng-peng; Zhang, Zhi-cheng; Liu, Hui-ling; Zhang, Jingchao; Zhuang, Jing; Wang, Xun

2013-01-01

Interfacial diffusion is of great importance in determining the performance of solid-state reactions. For nanometer sized particles, some solid-state reactions can be triggered accidently by mechanical stress owing to their large surface-to-volume ratio compared with the bulk ones. Therefore, a great challenge is the control of interfacial diffusion for solid state reactions, especially for energetic materials. Here we demonstrate, through the example of nanowire-based thermite membrane, that the thermite solid-state reaction can be easily tuned via the introduction of low-surface-energy coating layer. Moreover, this silicon-coated thermite membrane exhibit controlled wetting behavior ranging from superhydrophilic to superhydrophobic and, simultaneously, to significantly reduce the friction sensitivity of thermite membrane. This effect enables to increase interfacial resistance by increasing the amount of coating material. Indeed, our results described here make it possible to tune the solid-state reactions through the manipulation of interfacial diffusion between the reactants. PMID:23603809

Improving the prospects of cleavage-based nanopore sequencing engines

NASA Astrophysics Data System (ADS)

Brady, Kyle T.; Reiner, Joseph E.

2015-08-01

Recently proposed methods for DNA sequencing involve the use of cleavage-based enzymes attached to the opening of a nanopore. The idea is that DNA interacting with either an exonuclease or polymerase protein will lead to a small molecule being cleaved near the mouth of the nanopore, and subsequent entry into the pore will yield information about the DNA sequence. The prospects for this approach seem promising, but it has been shown that diffusion related effects impose a limit on the capture probability of molecules by the pore, which limits the efficacy of the technique. Here, we revisit the problem with the goal of optimizing the capture probability via a step decrease in the nucleotide diffusion coefficient between the pore and bulk solutions. It is shown through random walk simulations and a simplified analytical model that decreasing the molecule's diffusion coefficient in the bulk relative to its value in the pore increases the nucleotide capture probability. Specifically, we show that at sufficiently high applied transmembrane potentials (≥100 mV), increasing the potential by a factor f is equivalent to decreasing the diffusion coefficient ratio Dbulk/Dpore by the same factor f. This suggests a promising route toward implementation of cleavage-based sequencing protocols. We also discuss the feasibility of forming a step function in the diffusion coefficient across the pore-bulk interface.

Dependence of Exciton Diffusion Length and Diffusion Coefficient on Photophysical Parameters in Bulk Heterojunction Organic Solar Cells

NASA Astrophysics Data System (ADS)

Yeboah, Douglas; Singh, Jai

2017-11-01

Recently, the dependence of exciton diffusion length (LD ) on some photophysical parameters of organic solids has been experimentally demonstrated, however no systematic theoretical analysis of this phenomenon has been carried out. We have conducted a theoretical study by using the Förster resonance energy transfer and Dexter carrier transfer mechanisms together with the Einstein-Smoluchowski diffusion equation to derive analytical models for the diffusion lengths (LD ) and diffusion coefficients (D) of singlet (S) and triplet (T) excitons in organic solids as functions of spectral overlap integral (J) , photoluminescence (PL) quantum yield (φD ) , dipole moment (μT ) and refractive index (n) of the photoactive material. The exciton diffusion lengths and diffusion coefficients in some selected organic solids were calculated, and we found that the singlet exciton diffusion length (LDS ) increases with φD and J, and decreases with n. Also, the triplet exciton diffusion length (LDT ) increases with φD and decreases with μT . These may be achieved through doping the organic solids into broad optical energy gap host materials as observed in previous experiments. The calculated exciton diffusion lengths are compared with experimental values and a reasonably good agreement is found between them. The results presented are expected to provide insight relevant to the synthesis of new organic solids for fabrication of bulk heterojunction organic solar cells characterized by better power conversion efficiency.

Measurement of effective bulk and contact resistance of gas diffusion layer under inhomogeneous compression - Part I: Electrical conductivity

NASA Astrophysics Data System (ADS)

Vikram, Ajit; Chowdhury, Prabudhya Roy; Phillips, Ryan K.; Hoorfar, Mina

2016-07-01

This paper describes a measurement technique developed for the determination of the effective electrical bulk resistance of the gas diffusion layer (GDL) and the contact resistance distribution at the interface of the GDL and the bipolar plate (BPP). The novelty of this study is the measurement and separation of the bulk and contact resistance under inhomogeneous compression, occurring in an actual fuel cell assembly due to the presence of the channels and ribs on the bipolar plates. The measurement of the electrical contact resistance, contributing to nearly two-third of the ohmic losses in the fuel cell assembly, shows a non-linear distribution along the GDL/BPP interface. The effective bulk resistance of the GDL under inhomogeneous compression showed a decrease of nearly 40% compared to that estimated for homogeneous compression at different compression pressures. Such a decrease in the effective bulk resistance under inhomogeneous compression could be due to the non-uniform distribution of pressure under the ribs and the channels. This measurement technique can be used to identify optimum GDL, BPP and channel-rib structures based on minimum bulk and contact resistances measured under inhomogeneous compression.

Excited-State Proton Transfer on the Surface of a Therapeutic Protein, Protamine.

PubMed

Awasthi, Ankur A; Singh, Prabhat K

2017-11-16

Proton transfer reactions on biosurfaces play an important role in a myriad of biological processes. Herein, the excited-state proton transfer reaction of 8-hydroxypyrene-1,3,6-trisulfonate (HPTS) has been investigated in the presence of an important therapeutic protein, Protamine (PrS), using ground-state absorption, steady-state, and detailed time-resolved emission measurements. HPTS forms a 1:1 complex with Protamine with a high association constant of 2.6 × 10 4 M -1 . The binding of HPTS with Protamine leads to a significant modulation in the ground-state prototropic equilibrium causing a downward shift of 1.1 unit in the acidity constant (pK a ). In contrast to a large number of reports of slow proton transfer of HPTS on biosurfaces, interestingly, HPTS registers a faster proton transfer event in the presence of Protamine as compared to that of even the bulk aqueous buffer medium. Furthermore, the dimensionality of the proton diffusion process is also significantly reduced on the surface of Protamine that is in contrast to the behavior of HPTS in the bulk aqueous buffer medium, where the proton diffusion process is three-dimensional. The effect of ionic strength on the binding of HPTS toward PrS suggests a predominant role of electrostatic interaction between anionic HPTS and cationic Protamine, which is further supported by molecular docking simulations which predict that the most preferable binding site for HPTS on the surface of Protamine is surrounded by multiple cationic arginine residues.

Modeling cytoskeletal traffic: an interplay between passive diffusion and active transport.

PubMed

Neri, Izaak; Kern, Norbert; Parmeggiani, Andrea

2013-03-01

We introduce the totally asymmetric simple exclusion process with Langmuir kinetics on a network as a microscopic model for active motor protein transport on the cytoskeleton, immersed in the diffusive cytoplasm. We discuss how the interplay between active transport along a network and infinite diffusion in a bulk reservoir leads to a heterogeneous matter distribution on various scales: we find three regimes for steady state transport, corresponding to the scale of the network, of individual segments, or local to sites. At low exchange rates strong density heterogeneities develop between different segments in the network. In this regime one has to consider the topological complexity of the whole network to describe transport. In contrast, at moderate exchange rates the transport through the network decouples, and the physics is determined by single segments and the local topology. At last, for very high exchange rates the homogeneous Langmuir process dominates the stationary state. We introduce effective rate diagrams for the network to identify these different regimes. Based on this method we develop an intuitive but generic picture of how the stationary state of excluded volume processes on complex networks can be understood in terms of the single-segment phase diagram.

Electrolytic Deposition and Diffusion of Lithium onto Magnesium-9 Wt Pct Yttrium Bulk Alloy in Low-Temperature Molten Salt of Lithium Chloride and Potassium Chloride

NASA Astrophysics Data System (ADS)

Dong, Hanwu; Wu, Yaoming; Wang, Lidong; Wang, Limin

2009-10-01

The electrolytic deposition and diffusion of lithium onto bulk magnesium-9 wt pct yttrium alloy cathode in molten salt of 47 wt pct lithium chloride and 53 wt pct potassium chloride at 693 K were investigated. Results show that magnesium-yttrium-lithium ternary alloys are formed on the surface of the cathodes, and a penetration depth of 642 μm is acquired after 2 hours of electrolysis at the cathodic current density of 0.06 A·cm-2. The diffusion of lithium results in a great amount of precipitates in the lithium containing layer. These precipitates are the compound of Mg41Y5, which arrange along the grain boundaries and hinder the diffusion of lithium, and solid solution of yttrium in magnesium. The grain boundaries and the twins of the magnesium-9 wt pct yttrium substrate also have negative effects on the diffusion of lithium.

Molecular dynamics analysis of diffusion of uranium and oxygen ions in uranium dioxide

NASA Astrophysics Data System (ADS)

Arima, T.; Yoshida, K.; Idemitsu, K.; Inagaki, Y.; Sato, I.

2010-03-01

Diffusion behaviours of oxygen and uranium were evaluated for bulk and grain-boundaries of uranium dioxide using the molecular dynamics (MD) simulation. It elucidated that oxygen behaved like liquid in superionic state at high temperatures and migrated on sub-lattice sites accompanying formation of lattice defects such as Frenkel defects at middle temperatures. Formation energies of Frenkel and Shottky defects were compared to literature data, and migration energies of oxygen and uranium were estimated by introducing vacancies into the supercell. For grain-boundaries (GB) modelled by the coincidence-site lattice theory, MD calculations showed that GB energy and diffusivities of oxygen and uranium increased with the misorientation angle. By analysing GB structures such as pair-correlation functions, it also showed that the disordered phase was observed for uranium as well as oxygen in GBs especially for a large misorientation angle such as S5 GB. Hence, GB diffusion was much larger than bulk diffusion for oxygen and uranium.

Ag out-surface diffusion in crystalline SiC with an effective SiO 2 diffusion barrier

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

Xue, H.; Xiao, H. Y.; Zhu, Z.

2015-05-07

For applications of tristructural isotropic (TRISO) fuel particles in high temperature reactors, release of radioactive Ag isotope ( 110mAg) through the SiC coating layer is a safety concern. In order to understand the diffusion mechanism, Ag ion implantations near the surface and in the bulk were performed by utilizing different ion energies and energy-degrader foils. High temperature annealing was carried out on the as-irradiated samples to study the possible out-surface diffusion. Before and after annealing, Rutherford backscattering spectrometry (RBS) and secondary ion mass spectrometry (SIMS) measurements were employed to obtain the elemental profiles of the implanted samples. Our results suggestmore » little migration of buried Ag in the bulk, and an out-diffusion of the implanted Ag in the near-surface region of single crystal SiC. It is also found that a SiO 2 layer, which was formed during annealing, may serve as an effective barrier to reduce or prevent Ag out diffusion through the SiC coating layer.« less

Ag Out-surface Diffusion In Crystalline SiC With An Effective SiO2 Diffusion Barrier

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

Xue, H.; Xiao, Haiyan Y.; Zhu, Zihua

2015-09-01

For applications of tristructural isotropic (TRISO) fuel particles in high temperature reactors, release of radioactive Ag isotope (110mAg) through the SiC coating layer is a safety concern. To understand the diffusion mechanism, Ag ion implantations near the surface and in the bulk were performed by utilizing different ion energies and energy-degrader foils. High temperature annealing was carried out on the as-irradiated samples to study the possible out-surface diffusion. Before and after annealing, Rutherford backscattering spectrometry (RBS) and secondary ion mass spectrometry (SIMS) measurements were employed to obtain the elemental profiles of the implanted samples. The results suggest little migration ofmore » buried Ag in the bulk, and an out-diffusion of the implanted Ag in the near-surface region of single crystal SiC. It is also found that a SiO2 layer, which was formed during annealing, may serve as an effective barrier to reduce or prevent Ag out diffusion through the SiC coating layer.« less

Fundamentals of Tribology; Proceedings of the International Conference on the Fundamentals of Tribology held at The Massachusetts Institute of Technology, Cambridge, MA

DTIC Science & Technology

1978-06-01

HDL). The locus of electrical centers of hydrated ions in contact with the electrode surface is known as the outer Helmholtz plane ( OHP ) while the...and then a more Crdual exponential decay in the diffuse double layer. The difference in potential between the OHP and the bulk electrolyte, i.e., the...rnntribution of the diffuse double layer, is called the electrokinetic or iC 275 (a) Wc IHP OHP GCL- BULK + + ELECTRO YTE + + + + +G+ + eS+ J f -A -A

Analysis of the moisture diffusion transfer through fibrous porous membrane used for waterproof breathable fabrics

NASA Astrophysics Data System (ADS)

Zhu, Fanglong; Zhou, Yu; Liu, Suyan

2013-10-01

In this paper, we propose a new fractal model to determine the moisture effective diffusivity of porous membrane such as expanded polytetrafluorethylene membrane, by taking account of both parallel and perpendicular channels to diffusion flow direction. With the consideration of both the Knudsen and bulk diffusion effect, a relationship between micro-structural parameters and effective moisture diffusivity is deduced. The effective moisture diffusivities predicted by the present fractal model are compared with moisture diffusion experiment data and calculated values obtained from other theoretical models.

Upgraded metallurgical-grade silicon solar cells with efficiency above 20%

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

Zheng, P.; Rougieux, F. E.; Samundsett, C.

We present solar cells fabricated with n-type Czochralski–silicon wafers grown with strongly compensated 100% upgraded metallurgical-grade feedstock, with efficiencies above 20%. The cells have a passivated boron-diffused front surface, and a rear locally phosphorus-diffused structure fabricated using an etch-back process. The local heavy phosphorus diffusion on the rear helps to maintain a high bulk lifetime in the substrates via phosphorus gettering, whilst also reducing recombination under the rear-side metal contacts. The independently measured results yield a peak efficiency of 20.9% for the best upgraded metallurgical-grade silicon cell and 21.9% for a control device made with electronic-grade float-zone silicon. The presencemore » of boron-oxygen related defects in the cells is also investigated, and we confirm that these defects can be partially deactivated permanently by annealing under illumination.« less

Three-Dimensional Tracking of Interfacial Hopping Diffusion

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Wu, Haichao; Schwartz, Daniel K.

2017-12-01

Theoretical predictions have suggested that molecular motion at interfaces—which influences processes including heterogeneous catalysis, (bio)chemical sensing, lubrication and adhesion, and nanomaterial self-assembly—may be dominated by hypothetical "hops" through the adjacent liquid phase, where a diffusing molecule readsorbs after a given hop according to a probabilistic "sticking coefficient." Here, we use three-dimensional (3D) single-molecule tracking to explicitly visualize this process for human serum albumin at solid-liquid interfaces that exert varying electrostatic interactions on the biomacromolecule. Following desorption from the interface, a molecule experiences multiple unproductive surface encounters before readsorption. An average of approximately seven surface collisions is required for the repulsive surfaces, decreasing to approximately two and a half for surfaces that are more attractive. The hops themselves are also influenced by long-range interactions, with increased electrostatic repulsion causing hops of longer duration and distance. These findings explicitly demonstrate that interfacial diffusion is dominated by biased 3D Brownian motion involving bulk-surface coupling and that it can be controlled by influencing short- and long-range adsorbate-surface interactions.

First-Principles Study of MoO3/Graphene Composite as Cathode Material for High-Performance Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Cui, Yanhua; Zhao, Yu; Chen, Hong; Wei, Kaiyuan; Ni, Shuang; Cui, Yixiu; Shi, Siqi

2018-03-01

Using first-principles calculations, we have systematically investigated the adsorption and diffusion behavior of Li in MoO3 bulk, on MoO3 (010) surface and in MoO3/graphene composite. Our results indicate that, in case of MoO3 bulk, Li diffusion barriers in the interlayer and intralayer spaces are 0.55 eV and 0.58 eV respectively, which are too high to warrant fast Lithium-ion charge/discharge processes. While on MoO3 (010) surface, Li exhibits a diffusion barrier as low as 0.07 eV which guarantees an extremely fast Li diffusion rate during charge/discharge cycling. However, in MoO3/graphene monolayer, Li diffusion barrier is at the same level as that on MoO3 (010) surface, which also ensures a very rapid Li charge/discharge rate. The rapid Li charge/discharge rate in this system originates from the removal of the upper dangling O1 atoms which hinder the Li diffusion on the lower MoO3 layer. Besides this, due to the interaction between Li and graphene, the Li average binding energy increases to 0.14 eV compared to its value on MoO3 (010) surface which contributes to a higher voltage. Additionally, the increased ratio of surface area provides more space for Li storage and the capacity of MoO3/graphene composite increases up to 279.2 mAhg-1. The last but not the least, due to the high conductivity of graphene, the conductivity of MoO3/graphene composite enhances greatly which is beneficial for electrode materials. In the light of present results, MoO3/graphene composite exhibits higher voltage, good conductivity, large Li capacity and very rapid Li charge/discharge rate, which prove it as a promising cathode material for high-performance lithium-ion batteries (LIBs).

Comparison of Climatological Planetary Boundary Layer Depth Estimates Using the GEOS-5 AGCM

NASA Technical Reports Server (NTRS)

Mcgrath-Spangler, Erica Lynn; Molod, Andrea M.

2014-01-01

Planetary boundary layer (PBL) processes, including those influencing the PBL depth, control many aspects of weather and climate and accurate models of these processes are important for forecasting changes in the future. However, evaluation of model estimates of PBL depth are difficult because no consensus on PBL depth definition currently exists and various methods for estimating this parameter can give results that differ by hundreds of meters or more. In order to facilitate comparisons between the Goddard Earth Observation System (GEOS-5) and other modeling and observational systems, seven PBL depth estimation methods are used to produce PBL depth climatologies and are evaluated and compared here. All seven methods evaluate the same atmosphere so all differences are related solely to the definition chosen. These methods depend on the scalar diffusivity, bulk and local Richardson numbers, and the diagnosed horizontal turbulent kinetic energy (TKE). Results are aggregated by climate class in order to allow broad generalizations. The various PBL depth estimations give similar midday results with some exceptions. One method based on horizontal turbulent kinetic energy produces deeper PBL depths in the winter associated with winter storms. In warm, moist conditions, the method based on a bulk Richardson number gives results that are shallower than those given by the methods based on the scalar diffusivity. The impact of turbulence driven by radiative cooling at cloud top is most significant during the evening transition and along several regions across the oceans and methods sensitive to this cooling produce deeper PBL depths where it is most active. Additionally, Richardson number-based methods collapse better at night than methods that depend on the scalar diffusivity. This feature potentially affects tracer transport.

A comparison of partially specular radiosity and ray tracing for room acoustics modeling

NASA Astrophysics Data System (ADS)

Beamer, C. Walter; Muehleisen, Ralph T.

2005-04-01

Partially specular (PS) radiosity is an extended form of the general radiosity method. Acoustic radiosity is a form of bulk transfer of radiant acoustic energy. This bulk transfer is accomplished through a system of energy balance equations that relate the bulk energy transfer of each surface in the system to all other surfaces in the system. Until now acoustic radiosity has been limited to modeling only diffuse surface reflection. The new PS acoustic radiosity method can model all real surface types, diffuse, specular and everything in between. PS acoustic radiosity also models all real source types and distributions, not just point sources. The results of the PS acoustic radiosity method are compared to those of well known ray tracing programs. [Work supported by NSF.

Apparatus and method for excluding gas from a liquid

DOEpatents

Murphy, Jr., Robert J.

1985-01-01

The present invention is directed to an apparatus and method for preventing diffusion of a gas under high pressure into the bulk of a liquid filling a substantially closed chamber. This apparatus and method is particularly useful in connection with test devices for testing fluid characteristics under harsh conditions of extremely high pressure and high temperature. These devices typically pressurize the liquid by placing the liquid in pressure and fluid communication with a high pressure inert gas. The apparatus and method of the present invention prevent diffusion of the pressurizing gas into the bulk of the test liquid by decreasing the chamber volume at a rate sufficient to maintain the bulk of the liquid free of absorbed or dissolved gas by expelling that portion of the liquid which is contaminated by the pressurizing gas.

Diffuse Reflectance Infrared Fourier Transform Spectroscopy for the Determination of Asbestos Species in Bulk Building Materials

PubMed Central

Accardo, Grazia; Cioffi, Raffaeke; Colangelo, Francesco; d’Angelo, Raffaele; De Stefano, Luca; Paglietti, Fderica

2014-01-01

Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy is a well-known technique for thin film characterization. Since all asbestos species exhibit intense adsorptions peaks in the 4000–400 cm−1 region of the infrared spectrum, a quantitative analysis of asbestos in bulk samples by DRIFT is possible. In this work, different quantitative analytical procedures have been used to quantify chrysotile content in bulk materials produced by building requalification: partial least squares (PLS) chemometrics, the Linear Calibration Curve Method (LCM) and the Method of Additions (MoA). Each method has its own pros and cons, but all give affordable results for material characterization: the amount of asbestos (around 10%, weight by weight) can be determined with precision and accuracy (errors less than 0.1). PMID:28788467

Diffusion and related transport mechanisms in brain tissue

NASA Astrophysics Data System (ADS)

Nicholson, Charles

2001-07-01

Diffusion plays a crucial role in brain function. The spaces between cells can be likened to the water phase of a foam and many substances move within this complicated region. Diffusion in this interstitial space can be accurately modelled with appropriate modifications of classical equations and quantified from measurements based on novel micro-techniques. Besides delivering glucose and oxygen from the vascular system to brain cells, diffusion also moves informational substances between cells, a process known as volume transmission. Deviations from expected results reveal how local uptake, degradation or bulk flow may modify the transport of molecules. Diffusion is also essential to many therapies that deliver drugs to the brain. The diffusion-generated concentration distributions of well-chosen molecules also reveal the structure of brain tissue. This structure is represented by the volume fraction (void space) and the tortuosity (hindrance to diffusion imposed by local boundaries or local viscosity). Analysis of these parameters also reveals how the local geometry of the brain changes with time or under pathological conditions. Theoretical and experimental approaches borrow from classical diffusion theory and from porous media concepts. Earlier studies were based on radiotracers but the recent methods use a point-source paradigm coupled with micro-sensors or optical imaging of macromolecules labelled with fluorescent tags. These concepts and methods are likely to be applicable elsewhere to measure diffusion properties in very small volumes of highly structured but delicate material.

Quantitative experimental monitoring of molecular diffusion in clay with positron emission tomography

NASA Astrophysics Data System (ADS)

Kulenkampff, Johannes; Zakhnini, Abdelhamid; Gründig, Marion; Lippmann-Pipke, Johanna

2016-08-01

Clay plays a prominent role as barrier material in the geosphere. The small particle sizes cause extremely small pore sizes and induce low permeability and high sorption capacity. Transport of dissolved species by molecular diffusion, driven only by a concentration gradient, is less sensitive to the pore size. Heterogeneous structures on the centimetre scale could cause heterogeneous effects, like preferential transport zones, which are difficult to assess. Laboratory measurements with diffusion cells yield limited information on heterogeneity, and pore space imaging methods have to consider scale effects. We established positron emission tomography (PET), applying a high-resolution PET scanner as a spatially resolved quantitative method for direct laboratory observation of the molecular diffusion process of a PET tracer on the prominent scale of 1-100 mm. Although PET is rather insensitive to bulk effects, quantification required significant improvements of the image reconstruction procedure with respect to Compton scatter and attenuation. The experiments were conducted with 22Na and 124I over periods of 100 and 25 days, respectively. From the images we derived trustable anisotropic diffusion coefficients and, in addition, we identified indications of preferential transport zones. We thus demonstrated the unique potential of the PET imaging modality for geoscientific process monitoring under conditions where other methods fail, taking advantage of the extremely high detection sensitivity that is typical of radiotracer applications.

Equilibration of a polycation - anionic surfactant mixture at the water/vapor interface.

PubMed

Akanno, Andrew; Guzmán, Eduardo; Fernández-Peña, Laura; Llamas, Sara; Ortega, Francisco; Rubio, Ramon Gonzalez

2018-06-01

The adsorption of concentrated poly(diallyldimethylammonium chloride) (PDADMAC) - sodium lauryl ether sulfate (SLES) mixtures at the water / vapor interface has been studied by different surface tension techniques and dilational visco-elasticity measurements. This work tries to shed light on the way in which the formation of polyelectrolyte - surfactant complexes in the bulk affects to the interfacial properties of mixtures formed by a polycation and an oppositely charged surfactant. The results are discussed in terms of a two-step adsorption-equilibration of PDADMAC - SLES complexes at the interface, with the initial stages involving the diffusion of kinetically trapped aggregates formed in the bulk to the interface followed by the dissociation and spreading of such aggregates at the interface. This latter process becomes the main contribution to the surface tension decrease. This work helps on the understanding of the most fundamental bases of the physico-chemical behavior of concentrated polyelectrolyte - surfactant mixtures which present complex bulk and interfacial interactions with interest in both basic and applied sciences.

Homogenization Theory for the Prediction of Obstructed Solute Diffusivity in Macromolecular Solutions.

PubMed

Donovan, Preston; Chehreghanianzabi, Yasaman; Rathinam, Muruhan; Zustiak, Silviya Petrova

2016-01-01

The study of diffusion in macromolecular solutions is important in many biomedical applications such as separations, drug delivery, and cell encapsulation, and key for many biological processes such as protein assembly and interstitial transport. Not surprisingly, multiple models for the a-priori prediction of diffusion in macromolecular environments have been proposed. However, most models include parameters that are not readily measurable, are specific to the polymer-solute-solvent system, or are fitted and do not have a physical meaning. Here, for the first time, we develop a homogenization theory framework for the prediction of effective solute diffusivity in macromolecular environments based on physical parameters that are easily measurable and not specific to the macromolecule-solute-solvent system. Homogenization theory is useful for situations where knowledge of fine-scale parameters is used to predict bulk system behavior. As a first approximation, we focus on a model where the solute is subjected to obstructed diffusion via stationary spherical obstacles. We find that the homogenization theory results agree well with computationally more expensive Monte Carlo simulations. Moreover, the homogenization theory agrees with effective diffusivities of a solute in dilute and semi-dilute polymer solutions measured using fluorescence correlation spectroscopy. Lastly, we provide a mathematical formula for the effective diffusivity in terms of a non-dimensional and easily measurable geometric system parameter.

In situ study of emerging metallicity on ion-bombarded SrTiO3 surface

NASA Astrophysics Data System (ADS)

Gross, Heiko; Bansal, Namrata; Kim, Yong-Seung; Oh, Seongshik

2011-10-01

We report how argon bombardment induces metallic states on the surface of insulating SrTiO3 at different temperatures by combining in situ conductance measurements and model calculations. At cryogenic temperatures, ionic bombardment created a thin-but much thicker than the argon-penetration depth-steady-state oxygen-vacant layer, leading to a highly-concentric metallic state. Near room temperatures, however, significant thermal diffusion occurred and the metallic state continuously diffused into the bulk, leaving only low concentration of electron carriers on the surface. Analysis of the discrepancy between the experiments and the models also provided evidence for vacancy clustering, which seems to occur during any vacancy formation process and affects the observed conductance.

Diffusion and aggregation of subsurface radiation defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Martynovich, E. F.; Stupak, A. P.; Runets, L. P.

2015-09-01

Lithium fluoride nanocrystals were irradiated by gamma rays at a temperature below the temperature corresponding to the mobility of anion vacancies. The kinetics of the aggregation of radiation-induced defects in subsurface layers of nanocrystals during annealing after irradiation was elucidated. The processes that could be used to determine the activation energy of the diffusion of anion vacancies were revealed. The value of this energy in subsurface layers was obtained. For subsurface layers, the concentrations ratio of vacancies and defects consisting of one vacancy and two electrons was found. The factors responsible for the differences in the values of the activation energies and concentration ratios in subsurface layers and in the bulk of the crystals were discussed.

Diffusion, sorption, and retardation processes of anions in bentonite and organo-bentonites for multibarrier systems

NASA Astrophysics Data System (ADS)

Schampera, Birgit; Dultz, Stefan

2013-04-01

The low permeability, high cation exchange capacity (CEC) and plasticity of bentonites favor their use in multibarrier systems of waste deposits [1]. Bentonites have a high CEC but their ability to sorb anions is very low. There is, however, need for retardation of anions and organic pollutants in many applications. Bentonites, modified with certain organic cations, have the capacity to sorb anions and non-polar organic compounds in addition to cations. Investigations on organically modified clays address a wide variety of applications including immobilization of pollutants in contaminated soils, waste water treatment and in situ placement for the protection of ground water [2]. Many experiments on anion and cation sorption of organo-clays were conducted in the batch mode which does not reflect solid-liquid ratios and material densities in barrier systems. Diffusion experiments on compacted clays allow the evaluation of transport processes and sorption of pollutants at conditions relevant for repositories. For organo-clays only few diffusion studies are published e.g. [3] measured the diffusion of tritium and [4] the diffusion of H2O in bentonite and organo-bentonites. The organic cation hexadecylpyridinium (HDPy) was added to Wyoming bentonite (MX-80) in amounts corresponding to 2-400 % of the CEC. The uptake of organic cations was determined by the C-content, XRD and IR-spectroscopy. Wettability was analyzed by the contact angle. Physical, chemical and mineralogical properties of clays were characterized. Diffusion experiments were carried out in situ in a cell attached to the ATR-unit of a FTIR-spectrometer. For H2O-diffusion the compacted organo-clays are saturated first with D2O, afterwards H2O is supplied to the surface at the top of the clay platelet. Anion-diffusion was conducted with NO3--solution instead of H2O only having characteristic IR band positions at 1350 cm-1. Three different concentrations (0.25M, 0.5M and 1M) were used. Additional batch experiments with NO3- will support the understanding of sorption behavior of the anions. All hydrophilic samples have a higher retardation capacity, indicated by diffusion coefficients of 2.44 x 10-11 m/s2 for original bentonite and ˜2.1 x 10-11m/s2 for hydrophilic organo-clays. For hydrophobic organo-clays the H2O diffusion can be higher and is increased at high bulk density (1-1.5 g/m3) up to 2.76 x 10-10m2/s. Experiments with NO3- at bulk density of 1.5 g/m3 reveal that the apparent diffusion coefficients of nitrate are with results up to 5.61 x 1012 m2/s distinctively lower than free diffusion of nitrate in pure water (6.46 x 1010 m2/s at experimental conditions) and nitrate diffusion in natural bentonite (2.63 x 1011 m2/s). The measurements allow the interpretation of the different sorption mechanisms, retardation capacity and diffusion behavior of the analyzed clays at different anion concentrations. Ongoing molecular dynamic simulations will contribute understanding of diffusion processes in organo-clays including the conditions at the interface of the clay minerals and in solution. References: [1] Shackelford, C.D., Moore S.M. (2013) Fickian diffusion of radionuclides for engineered containment barriers: Diffusion coefficients, porosities, and complicating issues. Engineering Geology, 152, 133-147. [2] Rytwo, G., Nir, S., Shuali, U. (2012) Clay and water treatment. Applied Clay Science, 67-68, 117-118. [3] Lorenzetti, R.L., Bartelt-Hunt, S.L., Burns, S.E., Smith, J.A. (2005) Hydraulic conductivities and effective diffusion coefficients of geosynthetic clay liners with organobentonite amendments. Geotextiles and Geomembranes, 23, 385-400. [4] Schampera, B., Dultz, S. (2011) H2O self-diffusion in compacted clays as influenced by surface charge and wettability - obstruction effects of bound H2O layers. Clay and Clay Minerals,59, 42-57.

Non-universal tracer diffusion in crowded media of non-inert obstacles.

PubMed

Ghosh, Surya K; Cherstvy, Andrey G; Metzler, Ralf

2015-01-21

We study the diffusion of a tracer particle, which moves in continuum space between a lattice of excluded volume, immobile non-inert obstacles. In particular, we analyse how the strength of the tracer-obstacle interactions and the volume occupancy of the crowders alter the diffusive motion of the tracer. From the details of partitioning of the tracer diffusion modes between trapping states when bound to obstacles and bulk diffusion, we examine the degree of localisation of the tracer in the lattice of crowders. We study the properties of the tracer diffusion in terms of the ensemble and time averaged mean squared displacements, the trapping time distributions, the amplitude variation of the time averaged mean squared displacements, and the non-Gaussianity parameter of the diffusing tracer. We conclude that tracer-obstacle adsorption and binding triggers a transient anomalous diffusion. From a very narrow spread of recorded individual time averaged trajectories we exclude continuous type random walk processes as the underlying physical model of the tracer diffusion in our system. For moderate tracer-crowder attraction the motion is found to be fully ergodic, while at stronger attraction strength a transient disparity between ensemble and time averaged mean squared displacements occurs. We also put our results into perspective with findings from experimental single-particle tracking and simulations of the diffusion of tagged tracers in dense crowded suspensions. Our results have implications for the diffusion, transport, and spreading of chemical components in highly crowded environments inside living cells and other structured liquids.

Ordered mesoporous silica prepared by quiescent interfacial growth method - effects of reaction chemistry

PubMed Central

2013-01-01

Acidic interfacial growth can provide a number of industrially important mesoporous silica morphologies including fibers, spheres, and other rich shapes. Studying the reaction chemistry under quiescent (no mixing) conditions is important for understanding and for the production of the desired shapes. The focus of this work is to understand the effect of a number of previously untested conditions: acid type (HCl, HNO3, and H2SO4), acid content, silica precursor type (TBOS and TEOS), and surfactant type (CTAB, Tween 20, and Tween 80) on the shape and structure of products formed under quiescent two-phase interfacial configuration. Results show that the quiescent growth is typically slow due to the absence of mixing. The whole process of product formation and pore structuring becomes limited by the slow interfacial diffusion of silica source. TBOS-CTAB-HCl was the typical combination to produce fibers with high order in the interfacial region. The use of other acids (HNO3 and H2SO4), a less hydrophobic silica source (TEOS), and/or a neutral surfactant (Tweens) facilitate diffusion and homogenous supply of silica source into the bulk phase and give spheres and gyroids with low mesoporous order. The results suggest two distinct regions for silica growth (interfacial region and bulk region) in which the rate of solvent evaporation and local concentration affect the speed and dimension of growth. A combined mechanism for the interfacial bulk growth of mesoporous silica under quiescent conditions is proposed. PMID:24237719

A novel broadband impedance method for detection of cell-derived microparticles

PubMed Central

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L.

2010-01-01

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per µL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent - β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼ 10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding −100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that that a relatively low conductivity Tyrode’s buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2 to 40. PMID:20729061

N vacancy, self-interstitial diffusion, and Frenkel-pair formation/dissociation in TiN studied by ab-initio and classical molecular dynamics

NASA Astrophysics Data System (ADS)

Sangiovanni, Davide G.; Alling, Björn; Hultman, Lars; Abrikosov, Igor A.

2015-03-01

We use ab-initio and classical molecular dynamics (AIMD, CMD) to simulate diffusion of N vacancy and N self-interstitial point-defects in B1 TiN. The physical properties of TiN, important material system for thin film and coatings applications, are largely dictated by concentration and mobility of point defects. We determine N dilute-point-defect diffusion pathways, activation energies, attempt frequencies, and diffusion coefficients as a function of temperature. In addition, MD simulations reveal an unanticipated atomistic process, which controls the spontaneous formation of N-self-interstitial/N-vacancy pairs (Frenkel pairs) in defect-free TiN. This entails that a N lattice atom leaves its bulk position and bonds to a neighboring N lattice atom. In most cases, Frenkel-pair NI and NV recombine within a fraction of ns; 50% of these processes result in the exchange of two nitrogen lattice atoms. Occasionally, however, Frenkel-pair N-interstitial atoms permanently escape from the anion vacancy site, thus producing unpaired NI and NV point defects. The Knut and Alice Wallenberg foundation (Isotope Project, 2011.0094), the Swedish Research Council (VR) Linköping Linnaeus Initiative LiLi-NFM (Grant 2008-6572), and the Swedish Government Strategic Research (Grant MatLiU 2009-00971).

Nitrogen vacancy, self-interstitial diffusion, and Frenkel-pair formation/dissociation in B 1 TiN studied by ab initio and classical molecular dynamics with optimized potentials

NASA Astrophysics Data System (ADS)

Sangiovanni, D. G.; Alling, B.; Steneteg, P.; Hultman, L.; Abrikosov, I. A.

2015-02-01

We use ab initio and classical molecular dynamics (AIMD and CMD) based on the modified embedded-atom method (MEAM) potential to simulate diffusion of N vacancy and N self-interstitial point defects in B 1 TiN. TiN MEAM parameters are optimized to obtain CMD nitrogen point-defect jump rates in agreement with AIMD predictions, as well as an excellent description of Ti Nx(˜0.7

Magnesium and iron isotopes in 2.7 Ga Alexo komatiites: Mantle signatures, no evidence for Soret diffusion, and identification of diffusive transport in zoned olivine

NASA Astrophysics Data System (ADS)

Dauphas, Nicolas; Teng, Fang-Zhen; Arndt, Nicholas T.

2010-06-01

Komatiites from Alexo, Canada, are well preserved and represent high-degree partial mantle melts (˜50%). They are thus well suited for investigating the Mg and Fe isotopic compositions of the Archean mantle and the conditions of magmatic differentiation in komatiitic lavas. High precision Mg and Fe isotopic analyses of 22 samples taken along a 15-m depth profile in a komatiite flow are reported. The δ 25Mg and δ 26Mg values of the bulk flow are -0.138 ± 0.021‰ and -0.275 ± 0.042‰, respectively. These values are indistinguishable from those measured in mantle peridotites and chondrites, and represent the best estimate of the composition of the silicate Earth from analysis of volcanic rocks. Excluding the samples affected by secondary Fe mobilization, the δ 56Fe and δ 57Fe values of the bulk flow are +0.044 ± 0.030‰, and +0.059 ± 0.044‰, respectively. These values are consistent with a near-chondritic Fe isotopic composition of the silicate Earth and minor fractionation during komatiite magma genesis. In order to explain the early crystallization of pigeonite relative to augite in slowly cooled spinifex lavas, it was suggested that magmas trapped in the crystal mush during spinifex growth differentiated by Soret effect, which should be associated with large and coupled variations in the isotopic compositions of Mg and Fe. The lack of variations in Mg and Fe isotopic ratios either rules out the Soret effect in the komatiite flow or the effect is effaced as the solidification front migrates downward through the flow crust. Olivine separated from a cumulate sample has light δ 56Fe and slightly heavy δ 26Mg values relative to the bulk flow, which modeling shows can be explained by kinetic isotope fractionation associated with Fe-Mg inter-diffusion in olivine. Such variations can be used to identify diffusive processes involved in the formation of zoned minerals.

A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic

DOE PAGES

Popovic, M. P.; Chen, K.; Shen, H.; ...

2018-03-29

At elevated temperatures, heavy liquid metals and their alloys are known to create a highly corrosive environment that causes irreversible degradation of most iron-based materials. In this paper, it has been found that an appropriate concentration of oxygen in the liquid alloy can significantly reduce this issue by creating a passivating oxide scale that controls diffusion, especially if Al is present in Fe-based materials (by Al-oxide formation). However, the increase of the temperature and of oxygen content in liquid phase leads to the increase of oxygen diffusion into bulk, and to promotion of the internal Al oxidation. This can causemore » a strain in bulk near the oxide layer, due either to mismatch between the thermal expansion coefficients of the oxides and bulk material, or to misfit of the crystal lattices (bulk vs. oxides). This work investigates the strain induced into proximal bulk of a Fe-Cr-Al alloy by oxide layers formation in liquid lead-bismuth eutectic utilizing synchrotron X-ray Laue microdiffraction. Finally, it is found that internal oxidation is the most likely cause for the strain in the metal rather than thermal expansion mismatch as a two-layer problem.« less

A study of deformation and strain induced in bulk by the oxide layers formation on a Fe-Cr-Al alloy in high-temperature liquid Pb-Bi eutectic

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

Popovic, M. P.; Chen, K.; Shen, H.

At elevated temperatures, heavy liquid metals and their alloys are known to create a highly corrosive environment that causes irreversible degradation of most iron-based materials. In this paper, it has been found that an appropriate concentration of oxygen in the liquid alloy can significantly reduce this issue by creating a passivating oxide scale that controls diffusion, especially if Al is present in Fe-based materials (by Al-oxide formation). However, the increase of the temperature and of oxygen content in liquid phase leads to the increase of oxygen diffusion into bulk, and to promotion of the internal Al oxidation. This can causemore » a strain in bulk near the oxide layer, due either to mismatch between the thermal expansion coefficients of the oxides and bulk material, or to misfit of the crystal lattices (bulk vs. oxides). This work investigates the strain induced into proximal bulk of a Fe-Cr-Al alloy by oxide layers formation in liquid lead-bismuth eutectic utilizing synchrotron X-ray Laue microdiffraction. Finally, it is found that internal oxidation is the most likely cause for the strain in the metal rather than thermal expansion mismatch as a two-layer problem.« less

Determination of gaseous fission product behavior near the cerium dioxide Σ 3 (111)/[1 1 ¯ 0] tilt grain boundary via first-principles study

DOE PAGES

Xi, Jianqi; Liu, Bin; Xu, Haixuan; ...

2017-12-02

We presenmore » t that grain boundaries (GBs) are the most abundant structural defects in nanostructured nuclear fuels and play an important role in determining fission product behavior, which further affects the performance of nuclear fuels. In this work, cerium dioxide (CeO 2) is used as a surrogate material for mixed oxide fuels to understand gaseous fission product behavior, specifically Xe. First-principles calculations are employed to comprehensively study the behavior of Xe and trap sites for Xe near the Σ 3 (111)/[1 1 ¯ 0] grain boundary in CeO 2, which will provide guidance on overall trends for Xe stability and diffusion at grain boundaries vs in the bulk. Significant segregation behavior of trap sites, regardless of charge states, is observed near the GB. This is mainly ascribed to the local atomic structure near the GB, which results in weaker bond strength and more negative segregation energies. For Xe, however, the segregation profile near the GB is different. Our calculations show that, as the size of trap sites increases, the segregation propensity of Xe is reduced. In addition, under hyper-stoichiometric conditions, the solubility of Xe trapped at the GB is significantly higher than that in the bulk, suggesting higher Xe concentration than that in the bulk. The results of this work demonstrate that the diffusion mechanism of Xe in CeO 2 is comparable to that in UO 2. The diffusion activation energies of Xe atoms in the Σ3GB are lower than that in the bulk CeO 2. Lastly, these results suggest that the diffusivity of Xe atoms is higher along the GB than that in the bulk, which enhances the aggregation of Xe atoms near the GB.« less

Determination of gaseous fission product behavior near the cerium dioxide Σ 3 (111)/[1 1 ¯ 0] tilt grain boundary via first-principles study

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

Xi, Jianqi; Liu, Bin; Xu, Haixuan

We presenmore » t that grain boundaries (GBs) are the most abundant structural defects in nanostructured nuclear fuels and play an important role in determining fission product behavior, which further affects the performance of nuclear fuels. In this work, cerium dioxide (CeO 2) is used as a surrogate material for mixed oxide fuels to understand gaseous fission product behavior, specifically Xe. First-principles calculations are employed to comprehensively study the behavior of Xe and trap sites for Xe near the Σ 3 (111)/[1 1 ¯ 0] grain boundary in CeO 2, which will provide guidance on overall trends for Xe stability and diffusion at grain boundaries vs in the bulk. Significant segregation behavior of trap sites, regardless of charge states, is observed near the GB. This is mainly ascribed to the local atomic structure near the GB, which results in weaker bond strength and more negative segregation energies. For Xe, however, the segregation profile near the GB is different. Our calculations show that, as the size of trap sites increases, the segregation propensity of Xe is reduced. In addition, under hyper-stoichiometric conditions, the solubility of Xe trapped at the GB is significantly higher than that in the bulk, suggesting higher Xe concentration than that in the bulk. The results of this work demonstrate that the diffusion mechanism of Xe in CeO 2 is comparable to that in UO 2. The diffusion activation energies of Xe atoms in the Σ3GB are lower than that in the bulk CeO 2. Lastly, these results suggest that the diffusivity of Xe atoms is higher along the GB than that in the bulk, which enhances the aggregation of Xe atoms near the GB.« less

Two-stage bulk electron heating in the diffusion region of anti-parallel symmetric reconnection

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

Le, Ari Yitzchak; Egedal, Jan; Daughton, William Scott

2016-10-13

Electron bulk energization in the diffusion region during anti-parallel symmetric reconnection entails two stages. First, the inflowing electrons are adiabatically trapped and energized by an ambipolar parallel electric field. Next, the electrons gain energy from the reconnection electric field as they undergo meandering motion. These collisionless mechanisms have been described previously, and they lead to highly structured electron velocity distributions. Furthermore, a simplified control-volume analysis gives estimates for how the net effective heating scales with the upstream plasma conditions in agreement with fully kinetic simulations and spacecraft observations.

X ray absorption by dark nebulae (HEAO-2 guest investigator program)

NASA Technical Reports Server (NTRS)

Sanders, W. T.

1991-01-01

A study is described of data obtained from the Imaging Proportional Counter (IPC) x ray detector aboard the HEAO-2 satellite (Einstein Observatory). The research project involved a search for absorption of diffuse low energy x ray background emission by galactic dark nebulae. The commonly accepted picture that the bulk of the C band emission originates locally, closer that a few hundred parsec, and the bulk of the M band emission originates farther away than a few hundred parsec, was tested. The idea was to look for evidence of absorption of the diffuse background radiation by nearby interstellar clouds.

Phosphorus Diffusion Gettering Efficacy in Upgraded Metallurgical-Grade Solar Silicon

NASA Astrophysics Data System (ADS)

Jiménez, A.; del Cañizo, C.; Cid, C.; Peral, A.

2018-05-01

In the context of the continuous price reduction in photovoltaics (PV) in recent years, Si feedstock continues to be a relevant component in the cost breakdown of a PV module, highlighting the need for low-cost, low-capital expenditure (CAPEX) silicon technologies to further reduce this cost component. Upgraded metallurgical-grade silicon (UMG Si) has recently received much attention, improving its quality and even attaining, in some cases, solar cell efficiencies similar to those of conventional material. However, some technical challenges still have to be addressed when processing this material to compensate efficiently for the high content of impurities and contaminants. Adaptation of a conventional solar cell process to monocrystalline UMG Si wafers has been studied in this work. In particular, a tailored phosphorus diffusion gettering step followed by a low-temperature anneal at 700°C was implemented, resulting in enhanced bulk lifetime and emitter recombination properties. In spite of the need for further research and material optimization, UMG Si wafers were successfully processed, achieving efficiencies in the range of 15% for a standard laboratory solar cell process with aluminum back surface field.

Determination of charge-carrier diffusion length in the photosensing layer of HgCdTe n-on-p photovoltaic infrared focal plane array detectors

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

Vishnyakov, A. V.; Stuchinsky, V. A., E-mail: stuchin@isp.nsc.ru; Brunev, D. V.

2014-03-03

In the present paper, we propose a method for evaluating the bulk diffusion length of minority charge carriers in the photosensing layer of photovoltaic focal plane array (FPA) photodetectors. The method is based on scanning a strip-shaped illumination spot with one of the detector diodes at a low level of photocurrents j{sub ph} being registered; such scanning provides data for subsequent analysis of measured spot-scan profiles within a simple diffusion model. The asymptotic behavior of the effective (at j{sub ph} ≠ 0) charge-carrier diffusion length l{sub d} {sub eff} as a function of j{sub ph} for j{sub ph} → 0 inferred frommore » our experimental data proved to be consistent with the behavior of l{sub d} {sub eff} vs j{sub ph} as predicted by the model, while the obtained values of the bulk diffusion length of minority carriers (electrons) in the p-HgCdTe film of investigated HgCdTe n-on-p FPA photodetectors were found to be in a good agreement with the previously reported carrier diffusion-length values for HgCdTe.« less

Laser depth profiling studies of helium diffusion in Durango fluorapatite

NASA Astrophysics Data System (ADS)

van Soest, Matthijs C.; Monteleone, Brian D.; Hodges, Kip V.; Boyce, Jeremy W.

2011-05-01

Ultraviolet lasers coupled with sensitive mass spectrometers provide a useful way to measure laboratory-induced noble gas diffusion profiles in minerals, thus enabling the calculation of diffusion parameters. We illustrate this laser ablation depth profiling (LADP) technique for a previously well-studied mineral-isotopic system: 4He in Durango fluorapatite. LADP studies were conducted on oriented, polished slabs from a single crystal that were heated under vacuum to a variety of temperatures between 300 and 450 °C for variable times. The resolved 4He profiles exhibited error-function loss as predicted by previous bulk 4He diffusion studies. All of the slabs, regardless of crystallographic orientation, yielded modeled diffusivities that are statistically co-linear on an Arrhenius diagram, suggesting no diffusional anisotropy of 4He in this material. The data indicate an activation energy of 142.2 ± 5.0 (2 σ) kJ/mol and diffusivity at infinite temperature - reported as ln( D0) - of -4.71 ± 0.94 (2 σ) m 2/s. These values imply a bulk closure temperature for 4He in Durango fluorapatite of 74 °C for a 50 μm radius grain, infinite cylinder geometry, and a cooling rate of 10 °C/Myr.

Diffuse X-ray Emission from M101

NASA Technical Reports Server (NTRS)

Kuntz, K. D.; Snowden, S. L.; Pence, W. D.; Mukai, K.; White, Nicholas E. (Technical Monitor)

2002-01-01

The total 0.45-2.0 keV luminosity of M101 is 3.1 x 10(exp 39) ergs/s, of which 2.2 x 10(exp 39) ergs/s is due to diffuse emission. Of the diffuse emission, no more than 6% can be due to unresolved point sources such as X-ray binaries, and approx. 11% is due to dwarf stars. The diffuse emission traces the spiral arms and is roughly correlated with the H alpha and FUV (far ultraviolet) emission. The radial distribution closely follows the optical profile. The bulk of the diffuse emission is characterized by a two thermal component spectrum with kT = 0.20,0.75 keV, and the ratios of the emission measures of the two components is roughly constant as a function of both radius and surface brightness. The softer component has a sufficiently large covering factor that the bulk of the emission is likely extra-planar. We find no evidence of an extended axisymmetric X-ray halo, suggesting that any such halo has a strength much smaller than current predictions.

Lithium ion solvation and diffusion in bulk organic electrolytes from first-principles and classical reactive molecular dynamics.

PubMed

Ong, Mitchell T; Verners, Osvalds; Draeger, Erik W; van Duin, Adri C T; Lordi, Vincenzo; Pask, John E

2015-01-29

Lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF6(-) anion. Li(+) prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li(+) solvation. Corresponding analysis for the PF6(-) anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. These results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.

Converting Y(OH){sub 3} nanofiber bundles to YVO{sub 4} polyhedrons for photodegradation of dye contaminants

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

Li, Li; School of Chemical Engineering and Materials Engineering, Huainan Normal University, Huainan 232038; Zou, Lei

2015-08-15

Highlights: • YVO{sub 4} polyhedrons were prepared from Y(OH){sub 3} nanofiber bundles through a hydrothermal conversion process. • In contrast to the bulk oxide, the photocatalytic performance of the polyhedrons was much improved. • The main active species involved in photocatalytic oxidative reaction were also investigated. - Abstract: This paper reports a hydrothermal conversion process of rare earth microstructures, Y(OH){sub 3} nanofiber bundles, into YVO{sub 4} polyhedrons, together with the investigation on the related photocatalytic properties. The as-synthesized samples were characterized by a variety of techniques, including XRD, SEM, TEM and UV–vis diffuse reflectance spectroscopy. The photocatalytic activities of YVO{submore » 4} polyhedrons were comparatively evaluated by the photodegradation of Rhodamine B and methylene blue. In contrast to the bulk oxide, the photocatalytic performance of the polyhedrons was much improved. The mechanism and the main active species involved in photocatalytic oxidative reaction were also investigated through the carriers trapping experiments.« less

Process Research On Polycrystalline Silicon Material (PROPSM). [flat plate solar array project

NASA Technical Reports Server (NTRS)

Culik, J. S.

1983-01-01

The performance-limiting mechanisms in large-grain (greater than 1 to 2 mm in diameter) polycrystalline silicon solar cells were investigated by fabricating a matrix of 4 sq cm solar cells of various thickness from 10 cm x 10 cm polycrystalline silicon wafers of several bulk resistivities. Analysis of the illuminated I-V characteristics of these cells suggests that bulk recombination is the dominant factor limiting the short-circuit current. The average open-circuit voltage of the polycrystalline solar cells is 30 to 70 mV lower than that of co-processed single-crystal cells; the fill-factor is comparable. Both open-circuit voltage and fill-factor of the polycrystalline cells have substantial scatter that is not related to either thickness or resistivity. This implies that these characteristics are sensitive to an additional mechanism that is probably spatial in nature. A damage-gettering heat-treatment improved the minority-carrier diffusion length in low lifetime polycrystalline silicon, however, extended high temperature heat-treatment degraded the lifetime.

Vacuum ultraviolet photolysis of hydrogenated amorphous carbons. III. Diffusion of photo-produced H2 as a function of temperature

NASA Astrophysics Data System (ADS)

Martín-Doménech, R.; Dartois, E.; Muñoz Caro, G. M.

2016-06-01

Context. Hydrogenated amorphous carbon (a-C:H) has been proposed as one of the carbonaceous solids detected in the interstellar medium. Energetic processing of the a-C:H particles leads to the dissociation of the C-H bonds and the formation of hydrogen molecules and small hydrocarbons. Photo-produced H2 molecules in the bulk of the dust particles can diffuse out to the gas phase and contribute to the total H2 abundance. Aims: We have simulated this process in the laboratory with plasma-produced a-C:H and a-C:D analogs under astrophysically relevant conditions to investigate the dependence of the diffusion as a function of temperature. Methods: Experimental simulations were performed in a high-vacuum chamber, with complementary experiments carried out in an ultra-high-vacuum chamber. Plasma-produced a-C:H and a-C:D analogs were UV-irradiated using a microwave-discharged hydrogen flow lamp. Molecules diffusing to the gas-phase were detected by a quadrupole mass spectrometer, providing a measurement of the outgoing H2 or D2 flux. By comparing the experimental measurements with the expected flux from a one-dimensional diffusion model, a diffusion coefficient D could be derived for experiments carried out at different temperatures. Results: Dependence on the diffusion coefficient D with the temperature followed an Arrhenius-type equation. The activation energy for the diffusion process was estimated (ED(H2) = 1660 ± 110 K, ED(D2) = 2090 ± 90 K), as well as the pre-exponential factor (D0(H2) = 0.0007 cm2 s-1, D0(D2) = 0.0045 cm2 s-1). Conclusions: The strong decrease of the diffusion coefficient at low dust particle temperatures exponentially increases the diffusion times in astrophysical environments. Therefore, transient dust heating by cosmic rays needs to be invoked for the release of the photo-produced H2 molecules in cold photon-dominated regions, where destruction of the aliphatic component in hydrogenated amorphous carbons most probably takes place.

Under What Conditions Can Equilibrium Gas-Particle Partitioning Be Expected to Hold in the Atmosphere?

PubMed

Mai, Huajun; Shiraiwa, Manabu; Flagan, Richard C; Seinfeld, John H

2015-10-06

The prevailing treatment of secondary organic aerosol formation in atmospheric models is based on the assumption of instantaneous gas-particle equilibrium for the condensing species, yet compelling experimental evidence indicates that organic aerosols can exhibit the properties of highly viscous, semisolid particles, for which gas-particle equilibrium may be achieved slowly. The approach to gas-particle equilibrium partitioning is controlled by gas-phase diffusion, interfacial transport, and particle-phase diffusion. Here we evaluate the controlling processes and the time scale to achieve gas-particle equilibrium as a function of the volatility of the condensing species, its surface accommodation coefficient, and its particle-phase diffusivity. For particles in the size range of typical atmospheric organic aerosols (∼50-500 nm), the time scale to establish gas-particle equilibrium is generally governed either by interfacial accommodation or particle-phase diffusion. The rate of approach to equilibrium varies, depending on whether the bulk vapor concentration is constant, typical of an open system, or decreasing as a result of condensation into the particles, typical of a closed system.

Excitation-dependent carrier lifetime and diffusion length in bulk CdTe determined by time-resolved optical pump-probe techniques

NASA Astrophysics Data System (ADS)

Ščajev, Patrik; Miasojedovas, Saulius; Mekys, Algirdas; Kuciauskas, Darius; Lynn, Kelvin G.; Swain, Santosh K.; JarašiÅ«nas, Kestutis

2018-01-01

We applied time-resolved pump-probe spectroscopy based on free carrier absorption and light diffraction on a transient grating for direct measurements of the carrier lifetime and diffusion coefficient D in high-resistivity single crystal CdTe (codoped with In and Er). The bulk carrier lifetime τ decreased from 670 ± 50 ns to 60 ± 10 ns with increase of excess carrier density N from 1016 to 5 × 1018 cm-3 due to the excitation-dependent radiative recombination rate. In this N range, the carrier diffusion length dropped from 14 μm to 6 μm due to lifetime decrease. Modeling of in-depth (axial) and in-plane (lateral) carrier diffusion provided the value of surface recombination velocity S = 6 × 105 cm/s for the untreated surface. At even higher excitations, in the 1019-3 × 1020 cm-3 density range, D increase from 5 to 20 cm2/s due to carrier degeneracy was observed.

Account of the intratrack radiolytic processes for interpretation of the AMOC spectrum of liquid water

NASA Astrophysics Data System (ADS)

Zvezhinskiy, D. S.; Butterling, M.; Wagner, A.; Krause-Rehberg, R.; Stepanov, S. V.

2013-06-01

Recent development of the Gamma-induced Positron Spectroscopy (GiPS) setup significantly extends applicability of the Age-Momentum Correlation technique (AMOC) for studies of the bulk samples. It also provides many advantages comparing with conventional positron annihilation experiments in liquids, such as extremely low annihilation fraction in vessel walls, absence of a positron source and positron annihilations in it. We have developed a new approach for processing and interpretation of the AMOC-GiPS data based on the diffusion recombination model of the intratrack radiolytic processes. This approach is verified in case of liquid water, which is considered as a reference medium in the positron and positronium chemistry.

A temperature-programmed X-ray photoelectron spectroscopy (TPXPS) study of chlorine adsorption and diffusion on Ag(1 1 1)

NASA Astrophysics Data System (ADS)

Piao, H.; Adib, K.; Barteau, Mark A.

2004-05-01

Synchrotron-based temperature programmed X-ray photoelectron spectroscopy (TPXPS) has been used to investigate the surface chloridation of Ag(1 1 1) to monolayer coverages. At 100 K both atomic and molecular chlorine species are present on the surface; adsorption at 300 K or annealing the adlayer at 100 K to this temperature generates adsorbed Cl atoms. As the surface is heated from 300 to 600 K, chlorine atoms diffuse below the surface, as demonstrated by attenuation of the Cl2p signals in TPXPS experiments. Quantitative analysis of the extent of attenuation is consistent with chlorine diffusion below the topmost silver layer. For coverages in the monolayer and sub-monolayer regime, chlorine diffusion to and from the bulk appears not to be significant, in contrast to previous results obtained at higher chlorine loadings. Chlorine is removed from the surface at 650-780 K by desorption as AgCl. These results demonstrate that chlorine diffusion beneath the surface does occur at coverages and temperatures relevant to olefin epoxidation processes carried out on silver catalysts with chlorine promoters. The surface sensitivity advantages of synchrotron-based XPS experiments were critical to observing Cl diffusion to the sub-surface at low coverages.

Using tobacco mosaic virus to probe enhanced surface diffusion of molecular glasses.

PubMed

Zhang, Yue; Potter, Richard; Zhang, William; Fakhraai, Zahra

2016-11-09

Recent studies have shown that diffusion on the surface of organic glasses can be many orders of magnitude faster than bulk diffusion. Developing new probes that can readily measure surface diffusion can help study the effect of parameters such as chemical structure, intermolecular interaction, molecules' shape and size on the enhanced surface diffusion. In this study, we develop a novel probe that significantly simplifies these types of studies. Tobacco mosaic virus (TMV) is used as probe particle to measure surface diffusion coefficient of molecular glass N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD). The evolution of the meniscus formed around TMV is probed as a function of time at various temperatures. TMV has a well-defined, mono-dispersed, cylindrical shape, with a large aspect-ratio (average diameter of 16.6 nm, length of 300 nm). As such, the shape of the meniscus around the center of TMV is semi-two dimensional, which compared to using a nanosphere as probe, increases the driving force for meniscus formation and simplifies the analysis of surface diffusion. We show that under these conditions, after a short transient time the shape of the meniscus is self-similar, allowing accurate determination of the surface diffusion coefficient. Measurements at various temperatures are then performed to investigate the temperature dependence of the surface diffusion coefficient. It is found that surface diffusion is greatly enhanced in TPD and has a lower activation barrier compared to the bulk counterpart. These observations are consistent with previous studies of surface diffusion on molecular glasses, demonstrating the accuracy of this method.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

DOE PAGES

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; ...

2014-07-25

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface.more » The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is signifcantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. When the strength of the interface saturates, the number of interfacial entanglements scales with the corresponding bulk entanglement density. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.« less

Local Interactions of Hydrometeors by Diffusion in Mixed-Phase Clouds

NASA Astrophysics Data System (ADS)

Baumgartner, Manuel; Spichtinger, Peter

2017-04-01

Mixed-phase clouds, containing both ice particles and liquid droplets, are important for the Earth-Atmosphere system. They modulate the radiation budget by a combination of albedo effect and greenhouse effect. In contrast to liquid water clouds, the radiative impact of clouds containing ice particles is still uncertain. Scattering and absorption highly depends in microphysical properties of ice crystals, e.g. size and shape. In addition, most precipitation on Earth forms via the ice phase. Thus, better understanding of ice processes as well as their representation in models is required. A key process for determining shape and size of ice crystals is diffusional growth. Diffusion processes in mixed-phase clouds are highly uncertain; in addition they are usually highly simplified in cloud models, especially in bulk microphysics parameterizations. The direct interaction between cloud droplets and ice particles, due to spatial inhomogeneities, is ignored; the particles can only interact via their environmental conditions. Local effects as supply of supersaturation due to clusters of droplets around ice particles are usually not represented, although they form the physical basis of the Wegener-Bergeron-Findeisen process. We present direct numerical simulations of the interaction of single ice particles and droplets, especially their local competition for the available water vapor. In addition, we show an approach to parameterize local interactions by diffusion. The suggested parameterization uses local steady-state solutions of the diffusion equations for water vapor for an ice particle as well as a droplet. The individual solutions are coupled together to obtain the desired interaction. We show some results of the scheme as implemented in a parcel model.

Relationships between self-diffusivity, packing fraction, and excess entropy in simple bulk and confined fluids.

PubMed

Mittal, Jeetain; Errington, Jeffrey R; Truskett, Thomas M

2007-08-30

Static measures such as density and entropy, which are intimately connected to structure, have featured prominently in modern thinking about the dynamics of the liquid state. Here, we explore the connections between self-diffusivity, density, and excess entropy for two of the most widely used model "simple" liquids, the equilibrium Lennard-Jones and square-well fluids, in both bulk and confined environments. We find that the self-diffusivity data of the Lennard-Jones fluid can be approximately collapsed onto a single curve (i) versus effective packing fraction and (ii) in appropriately reduced form versus excess entropy, as suggested by two well-known scaling laws. Similar data collapse does not occur for the square-well fluid, a fact that can be understood on the basis of the nontrivial effects that temperature has on its static structure. Nonetheless, we show that the implications of confinement for the self-diffusivity of both of these model fluids, over a broad range of equilibrium conditions, can be predicted on the basis of knowledge of the bulk fluid behavior and either the effective packing fraction or the excess entropy of the confined fluid. Excess entropy is perhaps the most preferable route due to its superior predictive ability and because it is a standard, unambiguous thermodynamic quantity that can be readily predicted via classical density functional theories of inhomogeneous fluids.

Surface-structure dependence of healing radiation-damage mechanism in nanoporous tungsten

NASA Astrophysics Data System (ADS)

Duan, Guohua; Li, Xiangyan; Sun, Jingjing; Hao, Congyu; Xu, Yichun; Zhang, Yange; Liu, Wei; Liu, C. S.

2018-01-01

Under nuclear fusion environments, displacement damage in tungsten (W) is usually caused by neutrons irradiation through producing large quantities of vacancies (Vs) and self-interstitial atoms (SIAs). These defects not only affect the mechanical properties of W, but also act as the trap sites for implanted hydrogen isotopes and helium. Nano-porous (NP) W with a high fraction of free surfaces has been developed to mitigate the radiation damage. However, the mechanism of the surface reducing defects accumulation is not well understood. By using multi-scale simulation methods, we investigated the interaction of the SIA and V with different surfaces on across length and time scales. We found that, at a typical operation temperature of 1000 K, surface (1 1 0) preferentially heals radiation damage of W compared with surface (1 0 0) and boundary (3 1 0). On surface (1 1 0), the diffusion barrier for the SIA is only 0.68 eV. The annihilation of the SIA-V happens via the coupled motion of the V segregation towards the surface from the bulk and the two-dimensional diffusion of the SIA on the surface. Such mechanism makes the surface (1 1 0) owe better healing capability. On surface (1 0 0), the diffusion energy barrier for the SIA is 2.48 eV, higher than the diffusion energy barrier of the V in bulk. The annihilation of the SIA-V occurs via the V segregation and recombination. The SIA was found to migrate one-dimensionally along a boundary (3 1 0) with a barrier of 0.21 eV, leading to a lower healing efficiency in the boundary. This study suggested that the on-surface process plays an important role in healing radiation damage of NP W in addition to surface-enhanced diffusion and annihilation near the surface. A certain surface structure renders nano-structured W more radiation-tolerant.

Can we develop pathology-specific MRI contrast for "MR-negative" epilepsy?

PubMed

Feindel, Kirk W

2013-05-01

Recent improvements in magnetic resonance imaging (MRI) hardware, software, and analysis routines are helping to put cases of "MR-negative" epilepsy on the decline. However, most standard-of-care MRI relies on careful manipulation and presentation of T1, T2, and diffusion-weighted contrast, which characterize the behavior of water in "bulk" tissue rather than providing pathology-specific contrast. Research efforts in MR physics continue to identify and develop novel theory, and methods such as diffusional kurtosis imaging (DKI) and temporal diffusion spectroscopy that can better characterize tissue substructure, and chemical exchange saturation transfer (CEST) that can target underlying biochemical processes. The potential role of each technique in targeting pathologies implicated in "MR-negative" epilepsy is outlined herein. Wiley Periodicals, Inc. © 2013 International League Against Epilepsy.

Spatial organization of surface nanobubbles and its implications in their formation process.

PubMed

Lhuissier, Henri; Lohse, Detlef; Zhang, Xuehua

2014-02-21

We study the size and spatial distribution of surface nanobubbles formed by the solvent exchange method to gain insight into the mechanism of their formation. The analysis of Atomic Force Microscopy (AFM) images of nanobubbles formed on a hydrophobic surface reveals that the nanobubbles are not randomly located, which we attribute to the role of the history of nucleation during the formation. Moreover, the size of each nanobubble is found to be strongly correlated with the area of the bubble-depleted zone around it. The precise correlation suggests that the nanobubbles grow by diffusion of the gas from the bulk rather than by diffusion of the gas adsorbed on the surface. Lastly, the size distribution of the nanobubbles is found to be well described by a log-normal distribution.

Effect of turbulence on the dissipation of the space-charge wave in a bounded turbulent plasma column

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

Lee, Myoung-Jae; Jung, Young-Dae, E-mail: ydjung@hanyang.ac.kr; Department of Applied Physics and Department of Bionanotechnology, Hanyang University, Ansan, Kyunggi-Do 15588

The dispersion relation and the dissipation process of the space-charge wave propagating in a bounded plasma such as a cylindrical waveguide are investigated by employing the longitudinal dielectric permittivity that contains the diffusivity based on the Dupree theory of turbulent plasma. We derived the dispersion relation for space-charge wave in terms of the radius of cylindrical waveguide and the roots of the Bessel function of the first kind which appears as the boundary condition. We find that the wave frequency for a lower-order root of the Bessel function is higher than that of a higher-order root. We also find thatmore » the dissipation is greatest for the lowest-order root, but it is suppressed significantly as the order of the root increases. The wave frequency and the dissipation process are enhanced as the radius of cylindrical waveguide increases. However, they are always smaller than the case of bulk plasma. We find that the diffusivity of turbulent plasma would enhance the damping of space-charge waves, especially, in the range of small wave number. For a large wave number, the diffusivity has little effect on the damping.« less

Homogenization Theory for the Prediction of Obstructed Solute Diffusivity in Macromolecular Solutions

PubMed Central

Donovan, Preston; Chehreghanianzabi, Yasaman; Rathinam, Muruhan; Zustiak, Silviya Petrova

2016-01-01

The study of diffusion in macromolecular solutions is important in many biomedical applications such as separations, drug delivery, and cell encapsulation, and key for many biological processes such as protein assembly and interstitial transport. Not surprisingly, multiple models for the a-priori prediction of diffusion in macromolecular environments have been proposed. However, most models include parameters that are not readily measurable, are specific to the polymer-solute-solvent system, or are fitted and do not have a physical meaning. Here, for the first time, we develop a homogenization theory framework for the prediction of effective solute diffusivity in macromolecular environments based on physical parameters that are easily measurable and not specific to the macromolecule-solute-solvent system. Homogenization theory is useful for situations where knowledge of fine-scale parameters is used to predict bulk system behavior. As a first approximation, we focus on a model where the solute is subjected to obstructed diffusion via stationary spherical obstacles. We find that the homogenization theory results agree well with computationally more expensive Monte Carlo simulations. Moreover, the homogenization theory agrees with effective diffusivities of a solute in dilute and semi-dilute polymer solutions measured using fluorescence correlation spectroscopy. Lastly, we provide a mathematical formula for the effective diffusivity in terms of a non-dimensional and easily measurable geometric system parameter. PMID:26731550

Superdiffusive motion of membrane-targeting C2 domains

NASA Astrophysics Data System (ADS)

Campagnola, Grace; Nepal, Kanti; Schroder, Bryce W.; Peersen, Olve B.; Krapf, Diego

2015-12-01

Membrane-targeting domains play crucial roles in the recruitment of signalling molecules to the plasma membrane. For most peripheral proteins, the protein-to-membrane interaction is transient. After proteins dissociate from the membrane they have been observed to rebind following brief excursions in the bulk solution. Such membrane hops can have broad implications for the efficiency of reactions on membranes. We study the diffusion of membrane-targeting C2 domains using single-molecule tracking in supported lipid bilayers. The ensemble-averaged mean square displacement (MSD) exhibits superdiffusive behaviour. However, traditional time-averaged MSD analysis of individual trajectories remains linear and does not reveal superdiffusion. Our observations are explained in terms of bulk excursions that introduce jumps with a heavy-tail distribution. These hopping events allow proteins to explore large areas in a short time. The experimental results are shown to be consistent with analytical models of bulk-mediated diffusion and numerical simulations.

Analysis of Decomposition for Structure I Methane Hydrate by Molecular Dynamics Simulation

NASA Astrophysics Data System (ADS)

Wei, Na; Sun, Wan-Tong; Meng, Ying-Feng; Liu, An-Qi; Zhou, Shou-Wei; Guo, Ping; Fu, Qiang; Lv, Xin

2018-05-01

Under multi-nodes of temperatures and pressures, microscopic decomposition mechanisms of structure I methane hydrate in contact with bulk water molecules have been studied through LAMMPS software by molecular dynamics simulation. Simulation system consists of 482 methane molecules in hydrate and 3027 randomly distributed bulk water molecules. Through analyses of simulation results, decomposition number of hydrate cages, density of methane molecules, radial distribution function for oxygen atoms, mean square displacement and coefficient of diffusion of methane molecules have been studied. A significant result shows that structure I methane hydrate decomposes from hydrate-bulk water interface to hydrate interior. As temperature rises and pressure drops, the stabilization of hydrate will weaken, decomposition extent will go deep, and mean square displacement and coefficient of diffusion of methane molecules will increase. The studies can provide important meanings for the microscopic decomposition mechanisms analyses of methane hydrate.

Atomistic models of Cu diffusion in CuInSe2 under variations in composition

NASA Astrophysics Data System (ADS)

Sommer, David E.; Dunham, Scott T.

2018-03-01

We construct an analytic model for the composition dependence of the vacancy-mediated Cu diffusion coefficient in undoped CuInSe2 using parameters from density functional theory. The applicability of this model is supported numerically with kinetic lattice Monte Carlo and Onsager transport tensors. We discuss how this model relates to experimental measurements of Cu diffusion, arguing that our results can account for significant contributions to the bulk diffusion of Cu tracers in non-stoichiometric CuInSe2.

Photocharge accumulation and recombination in perovskite solar cells regarding device performance and stability

NASA Astrophysics Data System (ADS)

Li, Yusheng; Li, Yiming; Shi, Jiangjian; Li, Hongshi; Zhang, Huiyin; Wu, Jionghua; Li, Dongmei; Luo, Yanhong; Wu, Huijue; Meng, Qingbo

2018-01-01

Photocharge accumulation and recombination in perovskite solar cells have been systematically investigated in this paper by electrochemical spectroscopy and transient photocurrent/photovoltage methods. It is found that the non-equilibrium photocharges stored in the selective charge transport layers follow a backward recombination mechanism. That is, the photocharges are first captured by the interface defects corresponding to the fast photovoltage decay, while the bulk charge recombination instead of the diffusion process dominates the slow photovoltage decay process. Further investigation reveals that the device degradation preferentially takes place at the interface under working conditions, which thus can confirm the importance of interface engineering to enhance the device stability.

Sodium doping in ZnO crystals

NASA Astrophysics Data System (ADS)

Parmar, N. S.; Lynn, K. G.

2015-01-01

ZnO bulk single crystals were doped with sodium by thermal diffusion. Positron annihilations spectroscopy confirms the filling of zinc vacancies, to >6 μm deep in the bulk. Secondary-ion mass spectrometry measurement shows the diffusion of sodium up to 8 μm with concentration (1-3.5) × 1017 cm-3. Broad photoluminescence excitation peak at 3.1 eV, with onset appearance at 3.15 eV in Na:ZnO, is attributed to an electronic transition from a NaZn level at ˜(220-270) meV to the conduction band. Resistivity in Na doped ZnO crystals increases up to (4-5) orders of magnitude at room temperature.

Aqueous pathways dominate permeation of solutes across Pisum sativum seed coats and mediate solute transport via diffusion and bulk flow of water.

PubMed

Niemann, Sylvia; Burghardt, Markus; Popp, Christian; Riederer, Markus

2013-05-01

The permeability of seed coats to solutes either of biological or anthropogenic origin plays a major role in germination, seedling growth and seed treatment by pesticides. An experimental set-up was designed for investigating the mechanisms of seed coat permeation, which allows steady-state experiments with isolated seed coats of Pisum sativum. Permeances were measured for a set of organic model compounds with different physicochemical properties and sizes. The results show that narrow aqueous pathways dominate the diffusion of solutes across pea seed coats, as indicated by a correlation of permeances with the molecular sizes of the compounds instead of their lipophilicity. Further indicators for an aqueous pathway are small size selectivity and a small effect of temperature on permeation. The application of an osmotic water potential gradient across isolated seed coats leads to an increase in solute transfer, indicating that the aqueous pathways form a water-filled continuum across the seed coat allowing the bulk flow of water. Thus, the uptake of organic solutes across pea testae has two components: (1) by diffusion and (2) by bulk water inflow, which, however, is relevant only during imbibition. © 2012 Blackwell Publishing Ltd.

Spatial Variation in Mobility-Lifetime Product in Bulk TlBr and CZT

NASA Astrophysics Data System (ADS)

Phillips, David; Haegel, Nancy; Blaine, Kevin; Kim, Hadong; Ciampi, Guido; Cirignano, Len

2012-02-01

The energy resolution of a semiconductor radiation detector depends on the charge transport properties of the semiconductor, and the mobility-lifetime (μτ) product is a key figure of merit for charge transport. In this work, we investigate the effects of two impurities, Na and Cu, on the μτ product in bulk thallium bromide (TlBr) using cathodoluminescence (CL) and transport imaging. Transport imaging uses a scanning electron microscope to generate a line of charge carriers on the surface of a bulk sample, and the intensity and spatial distribution of the recombination luminescence are recorded. A Green's function approach is used to model the generation, diffusion, and recombination of charge carriers under steady-state conditions. The luminescence distribution is fit to the model to extract the ambipolar diffusion length and the μτ product, providing a high-resolution correlation between the luminescence variations due to dopants/defects and the quantitative transport behavior. The μτ product has been mapped across a 40 μm segment of TlBr at a resolution of 2 μm. Additionally, this approach has been used to locally map variations in ambipolar diffusion length and μτ product due to extended defects in cadmium zinc telluride (CZT).

Profiling of Current Transients in Capacitor Type Diamond Sensors.

PubMed

Gaubas, Eugenijus; Ceponis, Tomas; Meskauskaite, Dovile; Kazuchits, Nikolai

2015-06-08

The operational characteristics of capacitor-type detectors based on HPHT and CVD diamond have been investigated using perpendicular and parallel injection of carrier domain regimes. Simulations of the drift-diffusion current transients have been implemented by using dynamic models based on Shockley-Ramo's theorem, under injection of localized surface domains and of bulk charge carriers. The bipolar drift-diffusion regimes have been analyzed for the photo-induced bulk domain (packet) of excess carriers. The surface charge formation and polarization effects dependent on detector biasing voltage have been revealed. The screening effects ascribed to surface charge and to dynamics of extraction of the injected bulk excess carrier domain have been separated and explained. The parameters of drift mobility of the electrons μ(e) = 4000 cm2/Vs and holes μ(h) = 3800 cm2/Vs have been evaluated for CVD diamond using the perpendicular profiling of currents. The coefficient of carrier ambipolar diffusion D(a) = 97 cm2/s and the carrier recombination lifetime τ(R,CVD) ≌ 110 ns in CVD diamond were extracted by combining analysis of the transients of the sensor current and the microwave probed photoconductivity. The carrier trapping with inherent lifetime τR,HPHT ≌ 2 ns prevails in HPHT diamond.

Velocity relaxation of a particle in a confined compressible fluid

NASA Astrophysics Data System (ADS)

Tatsumi, Rei; Yamamoto, Ryoichi

2013-05-01

The velocity relaxation of an impulsively forced spherical particle in a fluid confined by two parallel plane walls is studied using a direct numerical simulation approach. During the relaxation process, the momentum of the particle is transmitted in the ambient fluid by viscous diffusion and sound wave propagation, and the fluid flow accompanied by each mechanism has a different character and affects the particle motion differently. Because of the bounding walls, viscous diffusion is hampered, and the accompanying shear flow is gradually diminished. However, the sound wave is repeatedly reflected and spreads diffusely. As a result, the particle motion is governed by the sound wave and backtracks differently in a bulk fluid. The time when the backtracking of the particle occurs changes non-monotonically with respect to the compressibility factor ɛ = ν/ac and is minimized at the characteristic compressibility factor. This factor depends on the wall spacing, and the dependence is different at small and large wall spacing regions based on the different mechanisms causing the backtracking.

An improved procedure for determining grain boundary diffusion coefficients from averaged concentration profiles

NASA Astrophysics Data System (ADS)

Gryaznov, D.; Fleig, J.; Maier, J.

2008-03-01

Whipple's solution of the problem of grain boundary diffusion and Le Claire's relation, which is often used to determine grain boundary diffusion coefficients, are examined for a broad range of ratios of grain boundary to bulk diffusivities Δ and diffusion times t. Different reasons leading to errors in determining the grain boundary diffusivity (DGB) when using Le Claire's relation are discussed. It is shown that nonlinearities of the diffusion profiles in lnCav-y6/5 plots and deviations from "Le Claire's constant" (-0.78) are the major error sources (Cav=averaged concentration, y =coordinate in diffusion direction). An improved relation (replacing Le Claire's constant) is suggested for analyzing diffusion profiles particularly suited for small diffusion lengths (short times) as often required in diffusion experiments on nanocrystalline materials.

A novel broadband impedance method for detection of cell-derived microparticles.

PubMed

Lvovich, Vadim; Srikanthan, Sowmya; Silverstein, Roy L

2010-10-15

A novel label-free method is presented to detect and quantify cell-derived microparticles (MPs) by the electrochemical potential-modulated electrochemical impedance spectroscopy (EIS). MPs are present in elevated concentrations during pathological conditions and play a major role in the establishment and pathogenesis of many diseases. Considering this, accurate detection and quantification of MPs is very important in clinical diagnostics and therapeutics. A combination of bulk solution electrokinetic sorting and interfacial impedance responses allows achieving detection limits as low as several MPs per μL. By fitting resulting EIS spectra with an equivalent electrical circuit, the bulk solution electrokinetic and interfacial impedance responses were characterized. In the bulk solution two major relaxations were prominent-β-relaxation in low MHz region due to the MP capacitive membrane bridging, and α-relaxation at ∼10 kHz due to counter ions diffusion. At low frequencies (10-0.1 Hz) at electrochemical potentials exceeding -100 mV, a facile interfacial Faradaic process of oxidation in MPs coupled with diffusion and non-Faradaic double layer charging dominate, probably due to oxidation of phospholipids and/or proteins on the MP surface and MP lysis. Buffer influence on the MP detection demonstrated that a relatively low conductivity Tyrode's buffer background solution is preferential for the MP electrokinetic separation and characterization. This study also demonstrated that standard laboratory methods such as flow cytometry underestimate MP concentrations, especially those with smaller average sizes, by as much as a factor of 2-40. Copyright © 2010 Elsevier B.V. All rights reserved.

The Laser ablation of a metal foam: The role of electron-phonon coupling and electronic heat diffusivity

NASA Astrophysics Data System (ADS)

Rosandi, Yudi; Grossi, Joás; Bringa, Eduardo M.; Urbassek, Herbert M.

2018-01-01

The incidence of energetic laser pulses on a metal foam may lead to foam ablation. The processes occurring in the foam may differ strongly from those in a bulk metal: The absorption of laser light, energy transfer to the atomic system, heat conduction, and finally, the atomistic processes—such as melting or evaporation—may be different. In addition, novel phenomena take place, such as a reorganization of the ligament network in the foam. We study all these processes in an Au foam of average porosity 79% and an average ligament diameter of 2.5 nm, using molecular dynamics simulation. The coupling of the electronic system to the atomic system is modeled by using the electron-phonon coupling, g, and the electronic heat diffusivity, κe, as model parameters, since their actual values for foams are unknown. We show that the foam coarsens under laser irradiation. While κe governs the homogeneity of the processes, g mainly determines their time scale. The final porosity reached is independent of the value of g.

Review on first-principles study of defect properties of CdTe as a solar cell absorber

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

Yang, Ji-Hui; Yin, Wan-Jian; Park, Ji-Sang

2016-07-15

CdTe is one of the leading materials for high-efficiency, low-cost, and thin-film solar cells. In this work, we review the recent first-principles study of defect properties of CdTe and present that: (1) When only intrinsic defects are present, p-type doping in CdTe is weak and the hole density is low due to the relatively deep acceptor levels of Cd vacancy. (2) When only intrinsic defects present, the dominant non-radiative recombination center in p-type CdTe is Te-2+/Cd, which limits the carrier lifetime to be around 200 ns. (3) Extrinsic p-type doping in CdTe by replacing Te with group V elements generallymore » will be limited by the formation of AX centers. This could be overcome through a non-equilibrium cooling process and the hole density can achieve 10^17 cm-3. However, the long-term stability will be a challenging issue. (4) Extrinsic p-type doping by replacing Cd with alkaline group I elements is limited by alkaline interstitials and a non-equilibrium cooling process can efficiently enhance the hole density to the order of 10^17 cm-3. (5) Cu and Cl treatments are discussed. In bulk CdTe, Cu can enhance p-type doping, but Cl is found to be unsuitable for this. Both Cu and Cl show segregation at grain boundaries, especially at those with Te-Te wrong bonds. (6) External impurities are usually incorporated by diffusion. Therefore, the diffusion processes in CdTe are investigated. We find that cation interstitial (Nai, Cui) diffusion follows relatively simple diffusion paths, but anion diffusion (Cli, Pi) follows more complicated paths due to the degenerated defect wavefunctions.« less

Lithium Ion Solvation and Diffusion in Bulk Organic Electrolytes from First-Principles and Classical Reactive Molecular Dynamics

DOE PAGES

Ong, Mitchell T.; Verners, Osvalds; Draeger, Erik W.; ...

2014-12-19

We report that lithium-ion battery performance is strongly influenced by the ionic conductivity of the electrolyte, which depends on the speed at which Li ions migrate across the cell and relates to their solvation structure. The choice of solvent can greatly impact both the solvation and diffusivity of Li ions. In this work, we used first-principles molecular dynamics to examine the solvation and diffusion of Li ions in the bulk organic solvents ethylene carbonate (EC), ethyl methyl carbonate (EMC), and a mixture of EC and EMC. We found that Li ions are solvated by either carbonyl or ether oxygen atoms of the solvents and sometimes by the PF more » $$\\bar{6}$$ anion. Li + prefers a tetrahedrally coordinated first solvation shell regardless of which species are involved, with the specific preferred solvation structure dependent on the organic solvent. In addition, we calculated Li diffusion coefficients in each electrolyte, finding slightly larger diffusivities in the linear carbonate EMC compared to the cyclic carbonate EC. The magnitude of the diffusion coefficient correlates with the strength of Li + solvation. Corresponding analysis for the PF $$\\bar{6}$$ anion shows greater diffusivity associated with a weakly bound, poorly defined first solvation shell. In conclusion, these results can be used to aid in the design of new electrolytes to improve Li-ion battery performance.« less

Experimental and theoretical aspects of studying themodynamics and mass transport in polymer-solvent systems

NASA Astrophysics Data System (ADS)

Davis, Peter Kennedy

Mass transport and thermodynamics in polymer-solvent systems are two key areas of importance to the polymer industry. Numerous processes including polymerization reactors, membrane separations, foam production, devolatilization processes, film and coating drying, supercritical extractions, drug delivery, and even nano-technology require fundamental phase equilibria and diffusion information. Although such information is vital in equipment design and optimization, acquisition and modeling of these data are still in the research and development stages. This thesis is rather diverse as it addresses many realms of this broad research area. From high pressure to low pressure, experimental to theoretical, and infinite dilution to finite concentration, the thesis covers a wide range of topics that are of current importance to the industrial and academic polymer community. Chapter 1 discusses advances in the development of a new volumetric sorption pressure decay technique to make phase equilibrium and diffusion measurements in severe temperature-pressure environments. Chapter 2 provides the derivations and results of a new completely predictive Group Contribution Lattice Fluid Equation of State for multi-component polymer-solvent systems. The remaining four chapters demonstrate advances in the modeling of inverse gas chromatography (IGC) experiments. IGC has been used extensively of the last 50 years to make low pressure sorption and diffusion measurements at infinitely dilute and finite solvent concentrations. Chapter 3 proposes a new IGC experiment capable of obtaining ternary vapor-liquid equilibria in polymer-solvent-solvent systems. Also in that chapter, an extensive derivation is provided for a continuum model capable of describing the results of such an experiment. Chapter 4 presents new data collected on a packed column IGC experiment and a new model that can be used with those experimental data to obtain diffusion and partition coefficients. Chapter 5 addresses a rather controversial topic about IGC experiments near the polymer glass transition temperature. Using a new IGC model capable of describing both bulk absorption and surface adsorption, IGC behavior around the glass transition was able to be better understood. Finally, Chapter 6 presents an IGC model that can be used to separate bulk effects from surface effects in capillary column IGC experiments.

Modeling condensation with a noncondensable gas for mixed convection flow

NASA Astrophysics Data System (ADS)

Liao, Yehong

2007-05-01

This research theoretically developed a novel mixed convection model for condensation with a noncondensable gas. The model developed herein is comprised of three components: a convection regime map; a mixed convection correlation; and a generalized diffusion layer model. These components were developed in a way to be consistent with the three-level methodology in MELCOR. The overall mixed convection model was implemented into MELCOR and satisfactorily validated with data covering a wide variety of test conditions. In the development of the convection regime map, two analyses with approximations of the local similarity method were performed to solve the multi-component two-phase boundary layer equations. The first analysis studied effects of the bulk velocity on a basic natural convection condensation process and setup conditions to distinguish natural convection from mixed convection. It was found that the superimposed velocity increases condensation heat transfer by sweeping away the noncondensable gas accumulated at the condensation boundary. The second analysis studied effects of the buoyancy force on a basic forced convection condensation process and setup conditions to distinguish forced convection from mixed convection. It was found that the superimposed buoyancy force increases condensation heat transfer by thinning the liquid film thickness and creating a steeper noncondensable gas concentration profile near the condensation interface. In the development of the mixed convection correlation accounting for suction effects, numerical data were obtained from boundary layer analysis for the three convection regimes and used to fit a curve for the Nusselt number of the mixed convection regime as a function of the Nusselt numbers of the natural and forced convection regimes. In the development of the generalized diffusion layer model, the driving potential for mass transfer was expressed as the temperature difference between the bulk and the liquid-gas interface using the Clausius-Clapeyron equation. The model was developed on a mass basis instead of a molar basis to be consistent with general conservation equations. It was found that vapor diffusion is not only driven by a gradient of the molar fraction but also a gradient of the mixture molecular weight at the diffusion layer.

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

PubMed Central

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Jürgen

2011-01-01

The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550–700 °C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300–400 °C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum – most likely along Pt grain boundaries – as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum. PMID:22210951

Observations on the structural degradation of silver during simultaneous exposure to oxidizing and reducing environments

NASA Astrophysics Data System (ADS)

Singh, Prabhakar; Yang, Zhenguo; Viswanathan, Vish; Stevenson, Jeff W.

2004-06-01

The structural stability of silver (Ag) in dual atmosphere exposure conditions, which are representative of solid oxide fuel cell (SOFC) current collector and gas seals, has been examined in the 600 800 °C temperature range. Experiments conducted on Ag tubular sections exposed to flowing H2-3% H2O (inside the tube) and air (outside the tube) showed extensive porosity formation along the grain boundaries in the bulk metal. Similar tubular sections, when exposed to air only (both inside and outside the tube), showed no bulk porosity or structural changes. It is postulated that the porosity formation in the bulk metal is related to the formation of gaseous H2O bubbles due to simultaneous diffusion of hydrogen and oxygen followed by subsequent interaction resulting in the formation of steam. Thermochemical processes that are responsible for structural degradation are presented and discussed. Based on experimental observations, it is concluded that Ag metal may not provide adequate long-term structural stability under a dual-environment condition that is typical of interconnects or gas seals in intermediate temperature SOFCs.

Tin doped PrBaFe 2O 5+δ anode material for solid oxide fuel cells

DOE PAGES

Dong, Guohui; Yang, Chunyang; He, Fei; ...

2017-04-25

Ceramic anodes have many advantages over cermet anodes for solid oxide fuel cells. We report the synthesis and characterization of Sn doped double perovskite PrBaFe (2-x)Sn xO 5+δ (x = 0–0.3) anode materials. Different crystal structures were observed depending on the Sn doping level and gas atmosphere. The materials demonstrated excellent stability in both reducing and redox atmospheres at elevated temperatures. The oxygen content in the as-prepared PrBaFe (2-x)Sn xO 5+δ was nonlinearly correlated to the Sn doping level and reached maximum values around x = 0.1. After the reducing treatment, the oxygen content linearly decreased with increasing Sn dopingmore » level. The electrical conductivity of bulk PrBaFe (2-x)Sn xO 5+δ (x = 0.1) reached 63.6 S cm -1 at 800 °C in humidified hydrogen. At 750 °C, the surface exchange coefficient and bulk diffusivity of PrBaFe (2-x)Sn xO 5+δ reached the maximum values of 4.42 × 10 -6 m s -1 and 6.04 × 10 -7 m 2 s -1, respectively, in the reducing process when the Sn doping level was x = 0.1. The activation energies of surface exchange coefficient and bulk diffusivity of PrBaFe (2-x)Sn xO 5+δ (x = 0.1) were 0.22 eV and 0.16 eV, respectively, in the reducing process. The area specific resistance of the PrBaFe (2-x)Sn xO 5+δ (x = 0.1) anode was 0.095–0.285 Ω cm 2 from 850–750 °C in humidified hydrogen, better than or comparable to the best ceramic anodes in the literature.« less

A study of interdiffusion in beta + gamma/gamma + gamma prime Ni-Cr-Al. M.S. Thesis. Final Report

NASA Technical Reports Server (NTRS)

Carol, L. A.

1985-01-01

Ternary diffusion in the NiCrAl system at 1200 C was studied with beta + gamma/gamma + gamma prime infinite diffusion couples. Interdiffusion resulted in the formation of complex, multiphase diffusion zones. Concentration/distance profiles for Cr and Al in the phases present in the diffusion zone were measured after 200 hr. The Ni-rich portion of the NiCrAl phase diagram (1200 C) was also determined. From these data, bulk Cr and Al profiles were calculated and translated to diffusion paths on the ternary isotherm. Growth layer kinetics of the layers present in the diffusion zone were also measured.

Diffuse neutrino supernova background as a cosmological test

NASA Astrophysics Data System (ADS)

Barranco, J.; Bernal, A.; Delepine, D.

2018-05-01

The future detection and measurement of the diffuse neutrino supernova background will provide us with information about supernova neutrino emission and the cosmic core-collapse supernova rate. Little has been said about the information that this measurement could give us about the expansion history of the Universe. The purpose of this article is to study the change of the predicted diffuse supernova neutrino background as a function of the cosmological model. In particular, we study three different models: the Λ–Cold Dark Matter model, the Logotropic universe and a bulk viscous matter-dominated universe. By fitting the free parameters of each model with the supernova Ia probe, we calculate the predicted number of events in these three models. We found that the spectra and number of events for the Λ–Cold dark matter model and the Logotropic model are almost indistinguishable, while a bulk viscous matter-dominated cosmological model predicts more events.

Mathematical modeling of hydrolysate diffusion and utilization in cellulolytic biofilms of the extreme thermophile Caldicellulosiruptor obsidiansis.

PubMed

Wang, Zhi-Wu; Hamilton-Brehm, Scott D; Lochner, Adriane; Elkins, James G; Morrell-Falvey, Jennifer L

2011-02-01

In this study, a hydrolysate diffusion and utilization model was developed to examine factors influencing cellulolytic biofilm morphology. Model simulations using Caldicellulosiruptor obsidiansis revealed that the cellulolytic biofilm needs to generate more hydrolysate than it consumes to establish a higher than bulk solution intra-biofilm substrate concentration to support its growth. This produces a hydrolysate surplus that diffuses through the thin biofilm structure into the bulk solution, which gives rise to a uniform growth rate and hence the homogeneous morphology of the cellulolytic biofilm. Model predictions were tested against experimental data from a cellulose-fermenting bioreactor and the results were consistent with the model prediction and indicated that only a small fraction (10-12%) of the soluble hydrolysis products are utilized by the biofilm. The factors determining the rate-limiting step of cellulolytic biofilm growth are also analyzed and discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

The aggregation and characteristics of radiation-induced defects in lithium fluoride nanocrystals

NASA Astrophysics Data System (ADS)

Voitovich, A. P.; Kalinov, V. S.; Korzhik, M. V.; Martynovich, E. F.; Runets, L. P.; Stupak, A. P.

2013-02-01

It has been established that diffusion activation energies for anion vacancies and centres ? in lithium fluoride nanocrystals are higher than those in bulk crystals. In nanocrystals, ? centres migrating in the range of the temperature close to room temperature is not observed and these centres remain stable. The ratio of centres ? and F 2 concentrations in nanocrystals is higher than in bulk crystals. A new type of colour centres, which is absent in bulk crystals, is discovered in nanocrystals.

Thermal diffusivity of electrical insulators at high temperatures: Evidence for diffusion of bulk phonon-polaritons at infrared frequencies augmenting phonon heat conduction

NASA Astrophysics Data System (ADS)

Hofmeister, Anne M.; Dong, Jianjun; Branlund, Joy M.

2014-04-01

We show that laser-flash analysis measurements of the temperature (T) dependence of thermal diffusivity (D) for diverse non-metallic (e.g., silicates) single-crystals is consistently represented by D(T) = FT-G + HT above 298 K, with G ranging from 0.3 to 2, depending on structure, and H being ˜10-4 K-1 for 51 single-crystals, 3 polycrystals, and two glasses unaffected by disorder or reconstructive phase transitions. Materials exhibiting this behavior include complex silicates with variable amounts of cation disorder, perovskite structured materials, and graphite. The high-temperature term HT becomes important by ˜1300 K, above which temperature its contribution to D(T) exceeds that of the FT-G term. The combination of the FT-G and HT terms produces the nearly temperature independent high-temperature region of D previously interpreted as the minimal phonon mean free path being limited by the finite interatomic spacing. Based on the simplicity of the fit and large number of materials it represents, this finding has repercussions for high-temperature models of heat transport. One explanation is that the two terms describing D(T) are associated with two distinct microscopic mechanisms; here, we explore the possibility that the thermal diffusivity of an electrical insulator could include both a contribution of lattice phonons (the FT-G term) and a contribution of diffusive bulk phonon-polaritons (BPP) at infrared (IR) frequencies (the HT term). The proposed BPP diffusion exists over length scales smaller than the laboratory sample sizes, and transfers mixed light and vibrational energy at a speed significantly smaller than the speed of light. Our diffusive IR-BPP hypothesis is consistent with other experimental observations such as polarization behavior, dependence of D on the number of IR peaks, and H = 0 for Ge and Si, which lack IR fundamentals. A simple quasi-particle thermal diffusion model is presented to begin understanding the contribution from bulk phonon-polaritons to overall heat conduction.

Combined measurement of surface, grain boundary and lattice diffusion coefficients on olivine bi-crystals

NASA Astrophysics Data System (ADS)

Marquardt, Katharina; Dohmen, Ralf; Wagner, Johannes

2014-05-01

Diffusion along interface and grain boundaries provides an efficient pathway and may control chemical transport in rocks as well as their mechanical strength. Besides the significant relevance of these diffusion processes for various geologic processes, experimental data are still very limited (e.g., Dohmen & Milke, 2010). Most of these data were measured using polycrystalline materials and the formalism of LeClaire (1951) to fit integrated concentration depth profiles. To correctly apply this formalism, certain boundary conditions of the diffusion problem need to be fulfilled, e.g., surface diffusion is ignored, and furthermore the lattice diffusion coefficient has to be known from other studies or is an additional fitting parameter, which produces some ambiguity in the derived grain boundary diffusion coefficients. We developed an experimental setup where we can measure the lattice and grain boundary diffusion coefficients simultaneously but independent and demonstrate the relevance of surface diffusion for typical grain boundary diffusion experiments. We performed Mg2SiO4 bicrystal diffusion experiments, where a single grain boundary is covered by a thin-film of pure Ni2SiO4 acting as diffusant source, produced by pulsed laser deposition. The investigated grain boundary is a 60° (011)/[100]. This specific grain boundary configuration was modeled using molecular dynamics for comparison with the experimental observations in the transmission electron microscope (TEM). Both, experiment and model are in good agreement regarding the misorientation, whereas there are still some disagreements regarding the strain fields along the grain boundary that are of outmost importance for the strengths of the material. The subsequent diffusion experiments were carried out in the temperature range between 800° and 1450° C. The inter diffusion profiles were measured using the TEMs energy dispersive x-ray spectrometer standardized using the Cliff-Lorimer equation and EMPA measurements. To evaluate the obtained diffusion profiles we adapted the isolated grain boundary model, first proposed by Fisher (1951) to match several observations: (i) Anisotropic diffusion in forsterite, (ii) fast diffusion along the grain boundary, (iii) fast diffusion on the surface of the sample. The latter process is needed to explain an additional flux of material from the surface into the grain boundary. Surface and grain boundary diffusion coefficients are on the order of 10000 times faster than diffusion in the lattice. Another observation was that in some regions the diffusion profiles in the lattice were greatly extended. TEM observations suggest here that surface defects (nano-cracks, ect.) have been present, which apparently enhanced the diffusion through the bulk lattice. Dohmen, R., & Milke, R. (2010). Diffusion in Polycrystalline Materials: Grain Boundaries, Mathematical Models, and Experimental Data. Reviews in Mineralogy and Geochemistry, 72(1), 921-970. Fisher, J. C. (1951). Calculations of Diffusion Penetration Curves for Surface and Grain Boundary Diffusion. Journal of Applied Physics, 22(1), 74-77. Le Claire, A. D. (1951). Grain boundary diffusion in metals. Philosophical Magazine A, 42(328), 468-474.

Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil

PubMed Central

Milani, Narges; Hettiarachchi, Ganga M.; Kirby, Jason K.; Beak, Douglas G.; Stacey, Samuel P.; McLaughlin, Mike J.

2015-01-01

Zinc oxide (ZnO) nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk) particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP) and urea) using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ–XRF) mapping and absorption fine structure spectroscopy (μ–XAFS). Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO4)2.2H2O) and zinc ammonium phosphate (Zn(NH4)PO4) species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO) at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength) of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH)2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers) was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be the same as bulk sources of ZnO. PMID:25965385

Laser depth profiling of diffusion and alpha ejection profiles in Durango apatite: testing the fundamental parameters of apatite (U-Th)/He dating

NASA Astrophysics Data System (ADS)

van Soest, M. C.; Monteleone, B. D.; Boyce, J. W.; Hodges, K.

2009-12-01

Since its development (e.g. Zeitler et al., 1987, Lippolt et al., 1994, Farley et al., 1996, Wolf et al., 1996) as a viable low temperature thermochronological method (U-Th)/He dating of apatite has become a popular and widely applied low temperature thermochronometer. The method has been applied with success to a great variety of geological problems, and the fundamental parameters of the method: the bulk diffusion parameters of helium in apatite, and the calculated theoretical helium stopping distance in apatite used to correct the ages for the effects of alpha ejection appear sound. However, the development of the UV laser microprobe technique for the (U-Th)/He method (Boyce et al., 2006) allows for in-situ testing of the helium bulk diffusion parameters (Farley, 2000) and can provide a direct measurement of the alpha ejection distance in apatite. So, with the ultimate goal of further developing the in-situ (U-Th)/He dating method and micro-analytical depth profiling techniques to constrain cooling histories in natural grains, we conducted a helium depth profiling study of induced diffusion and natural alpha ejection profiles in Durango apatite. For the diffusion depth profiling, a Durango crystal was cut in slabs oriented parallel and perpendicular to the crystal c-axis. The slabs were polished and heated using different temperature and time schedules to induce predictable diffusion profiles based on the bulk helium diffusion parameters in apatite. Depth profiling of the 4He diffusion profiles was done using an ArF excimer laser. The measured diffusion depth profiles at 350°, 400°, and 450° C coincide well with the predicted bulk diffusion curves, independent of slab orientation, but the 300° C profiles consistently deviate significantly. The possible cause for this deviation is currently being investigated. Alpha ejection profiling was carried out on crystal margins from two different Durango apatite crystals, several faces from each crystal were analyzed to evaluate the potential effects of crystallographic orientation on alpha ejection. The results from both crystals were very reproducible irrespective of crystal surface used and confirm the findings of Monteleone et al. (2008) that the measured alpha ejection profiles deviate significantly from and are shorter than the calculated theoretical average value. Efforts are currently underway to better constrain the measured alpha ejection distance and measure alpha ejection profiles in apatite crystals other than Durango apatite. References: Boyce, J. et al. (2006) GCA 70, pp. 3031-3039. Farley, K. et al. (1996) GCA 60, pp. 4223-4229. Farley, K. (2006) JGR SE 105, p. 2903-2914. Lippolt, H. et al. (1994) Chem Geol 112, pp. 179-191. Monteleone, B. et al. (2008) Eos Trans AGU, 89 Fall Meeting V53B-2162. Wolf, R. et al. (1996) GCA 60, pp. 4231-4240. Zeitler, P. et al. (1987) GCA 51, pp. 2865-2868.

Mathematical modelling of the Phloem: the importance of diffusion on sugar transport at osmotic equilibrium.

PubMed

Payvandi, S; Daly, K R; Zygalakis, K C; Roose, T

2014-11-01

Plants rely on the conducting vessels of the phloem to transport the products of photosynthesis from the leaves to the roots, or to any other organs, for growth, metabolism, and storage. Transport within the phloem is due to an osmotically-generated pressure gradient and is hence inherently nonlinear. Since convection dominates over diffusion in the main bulk flow, the effects of diffusive transport have generally been neglected by previous authors. However, diffusion is important due to boundary layers that form at the ends of the phloem, and at the leaf-stem and stem-root boundaries. We present a mathematical model of transport which includes the effects of diffusion. We solve the system analytically in the limit of high Münch number which corresponds to osmotic equilibrium and numerically for all parameter values. We find that the bulk solution is dependent on the diffusion-dominated boundary layers. Hence, even for large Péclet number, it is not always correct to neglect diffusion. We consider the cases of passive and active sugar loading and unloading. We show that for active unloading, the solutions diverge with increasing Péclet. For passive unloading, the convergence of the solutions is dependent on the magnitude of loading. Diffusion also permits the modelling of an axial efflux of sugar in the root zone which may be important for the growing root tip and for promoting symbiotic biological interactions in the soil. Therefore, diffusion is an essential mechanism for transport in the phloem and must be included to accurately predict flow.

First Principles Calculations on the Diffusion of Cu, Ag and Au Atoms or Aggregates on the Bulk and Surface of Titania

DTIC Science & Technology

2011-04-01

filament. The filament may be composed of the metal electrode which is transported into the insulator or due to the formation of sub-oxides. During the...possibility that ionic transport and red-ox processes are at the basis of the resistive switching. The idea is that the oxidation of the active metal...oxide layer and subsequent discard at the inert metal counter-electrode. This mechanism should lead to the formation of metal dendrimers inside the

Generation and Sustainment of Plasma Rotation by ICRF Heating

NASA Astrophysics Data System (ADS)

Perkins, F. W.

2000-10-01

When tokamak plasmas are heated by the fundamental minority ion-cyclotron process, they are observed to rotate toroidally, even though this heating process introduces negligable angular momentum. This work proposes and evaluates a physics mechanism which resolves this apparent conflict. The argument has two elements. First, it is assumed that angular momentum transport is governed by a diffusion equation with a v_tor = 0 boundary condition at the plasma surface and a torque-density source. When the source consists of separated regions of positive and negative torque density, a finite central rotation velocity results, even though the volume integrated torque density - the angular momentum input - vanishes. Secondly, ions energized by the ICRF process can generate separated regions of positive and negative torque density. Heating increases their banana widths which leads to radial energetic-particle transport that must be balanced by neutralizing radial currents and a j_rB_pR torque density in the bulk plasma. Additional, comparable torque density results from collisional transfer of mechanical angular momentum from energetic particles to the bulk plasma and particle loss through banana particles impacting the wall. Monte-Carlo calculations utilizing the ORBIT code evaluate all sources of torque density and rigorously assure that no net angular momentum is introduced. Two models of ICRF heating, diffusive and instantaneous, give similar results. When the resonance location is on the LFS, the calculated rotation has the magnitude, profile, and co-current sense of Alcator C-Mod observations. For HFS resonance locations, the model predicts counter-current rotation. Scans of rotational profiles vs. resonance location, initial energy, particle loss, pitch, and qm will be presented as will the location of the velocity shear layer its scaling to a reactor.

Strong Asymmetric Limit of the Quasi-Potential of the Boundary Driven Weakly Asymmetric Exclusion Process

NASA Astrophysics Data System (ADS)

Bertini, Lorenzo; Gabrielli, Davide; Landim, Claudio

2009-07-01

We consider the weakly asymmetric exclusion process on a bounded interval with particles reservoirs at the endpoints. The hydrodynamic limit for the empirical density, obtained in the diffusive scaling, is given by the viscous Burgers equation with Dirichlet boundary conditions. In the case in which the bulk asymmetry is in the same direction as the drift due to the boundary reservoirs, we prove that the quasi-potential can be expressed in terms of the solution to a one-dimensional boundary value problem which has been introduced by Enaud and Derrida [16]. We consider the strong asymmetric limit of the quasi-potential and recover the functional derived by Derrida, Lebowitz, and Speer [15] for the asymmetric exclusion process.

Thermodynamics and Kinetics of Prenucleation Clusters, Classical and Non-Classical Nucleation

PubMed Central

Zahn, Dirk

2015-01-01

Recent observations of prenucleation species and multi-stage crystal nucleation processes challenge the long-established view on the thermodynamics of crystal formation. Here, we review and generalize extensions to classical nucleation theory. Going beyond the conventional implementation as has been used for more than a century now, nucleation inhibitors, precursor clusters and non-classical nucleation processes are rationalized as well by analogous concepts based on competing interface and bulk energy terms. This is illustrated by recent examples of species formed prior to/instead of crystal nucleation and multi-step nucleation processes. Much of the discussed insights were obtained from molecular simulation using advanced sampling techniques, briefly summarized herein for both nucleation-controlled and diffusion-controlled aggregate formation. PMID:25914369

Exploration of bulk and interface behavior of gas molecules and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid using equilibrium and nonequilibrium molecular dynamics simulation and quantum chemical calculation.

PubMed

Yang, Quan; Achenie, Luke E K

2018-04-18

Ionic liquids (ILs) show brilliant performance in separating gas impurities, but few researchers have performed an in-depth exploration of the bulk and interface behavior of penetrants and ILs thoroughly. In this research, we have performed a study on both molecular dynamics (MD) simulation and quantum chemical (QC) calculation to explore the transport of acetylene and ethylene in the bulk and interface regions of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]-[BF4]). The diffusivity, solubility and permeability of gas molecules in the bulk were researched with MD simulation first. The subdiffusion behavior of gas molecules is induced by coupling between the motion of gas molecules and the ions, and the relaxation processes of the ions after the disturbance caused by gas molecules. Then, QC calculation was performed to explore the optical geometry of ions, ion pairs and complexes of ions and penetrants, and interaction potential for pairs and complexes. Finally, nonequilibrium MD simulation was performed to explore the interface structure and properties of the IL-gas system and gas molecule behavior in the interface region. The research results may be used in the design of IL separation media.

Surface diffusion of Sb on Ge(111) investigated by second harmonic microscopy

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

Schultz, K.A.

Surface diffusion of Sb on Ge(111) has been measured with the newly-developed technique of second harmonic microscopy. In this method, concentration profiles at submonolayer coverage are imaged directly by second harmonic generation with 5 [mu]m spatial resolution. A Boltzmann-Matano analysis of the concentration profiles yields the coverage dependence of the diffusivity D without parameterization. Experiments were performed at roughly 70% of the bulk melting temperature T[sub m]. In the coverage range of 0 < [theta] < 0.6, the activation energy E[sub diff] remains constant at 47.5 [+-] 1.5 kcal/mol. The corresponding pre-exponential factor decreases from 8.7 [times] 10[sup 3[+-]0.4] tomore » 1.6 [times] 10[sup 2[+-]0.4] cm[sup 2]/sec. The results are explained in terms of a new vacancy model for surface diffusion at high-temperatures. The model accounts semiquantitatively for the large values of E[sub diff] and D[sub o], and suggest that these quantities may be manipulated by bulk doping levels and photon illumination of the surface.« less

Excitation-dependent carrier lifetime and diffusion length in bulk CdTe determined by time-resolved optical pump-probe techniques

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

Ščajev, Patrik; Miasojedovas, Saulius; Mekys, Algirdas

We applied time-resolved pump-probe spectroscopy based on free carrier absorption and light diffraction on a transient grating for direct measurements of the carrier lifetime and diffusion coefficient D in high-resistivity single crystal CdTe (codoped with In and Er). The bulk carrier lifetime t decreased from 670 +/-50 ns to 60 +/- 10 ns with increase of excess carrier density N from 10 16 to 5 x 10 18cm -3 due to the excitation-dependent radiative recombination rate. In this N range, the carrier diffusion length dropped from 14 um to 6 um due to lifetime decrease. Modeling of in-depth (axial) andmore » in-plane (lateral) carrier diffusion provided the value of surface recombination velocity S = 6 x 10 5 cm/s for the untreated surface. At even higher excitations, in the 10 19-3 x 10 20 cm -3 density range, D increase from 5 to 20 cm^2/s due to carrier degeneracy was observed.« less

Excitation-dependent carrier lifetime and diffusion length in bulk CdTe determined by time-resolved optical pump-probe techniques

DOE PAGES

Ščajev, Patrik; Miasojedovas, Saulius; Mekys, Algirdas; ...

2018-01-14

We applied time-resolved pump-probe spectroscopy based on free carrier absorption and light diffraction on a transient grating for direct measurements of the carrier lifetime and diffusion coefficient D in high-resistivity single crystal CdTe (codoped with In and Er). The bulk carrier lifetime t decreased from 670 +/-50 ns to 60 +/- 10 ns with increase of excess carrier density N from 10 16 to 5 x 10 18cm -3 due to the excitation-dependent radiative recombination rate. In this N range, the carrier diffusion length dropped from 14 um to 6 um due to lifetime decrease. Modeling of in-depth (axial) andmore » in-plane (lateral) carrier diffusion provided the value of surface recombination velocity S = 6 x 10 5 cm/s for the untreated surface. At even higher excitations, in the 10 19-3 x 10 20 cm -3 density range, D increase from 5 to 20 cm^2/s due to carrier degeneracy was observed.« less

Materials corrosion and protection from first principles

NASA Astrophysics Data System (ADS)

Johnson, Donald F.

Materials erode under environmental stresses such as high temperature, high pressure, and mechanical shock/stress, but erosion is often exacerbated by chemical corrosion. In this dissertation, periodic density functional theory (DFT) is employed to simulate interfacial adhesion, absorption kinetics, bulk diffusion, and other material phenomena (e.g., hydrogen-enhanced decohesion and shock-induced phase changes) with the intention of understanding corrosion and subsequent failure processes and guiding the design of new protective coatings. This work examines corrosion and/or protection of materials ( i.e., Fe, Ni, W) with important applications: structural steel, gun tubes, high-pressure oil recovery vessels, jet engine turbine blades, and fusion reactor walls. We use DFT to model the pressure-induced, bcc-to-hcp phase transformation in Fe, in which a new low energy pathway is predicted exhibiting nonadiabatic behavior coupling magnetic and structural changes. Protection of steel is addressed in two aspects: interfacial adhesion of protective coatings and assessment of corrosion resistance provided by a surface alloy. First, the current chrome-coated steel system is examined where extremely strong adhesion is predicted at the Cr/Fe interface originating in strong spin correlations. A ceramic coating, SiC, is considered as a possible replacement for Cr. Strong adhesion is predicted, especially for C-Fe interfacial bonds. To assess corrosion resistance, we model ingress of two common corrosive elements, H and C, into two Fe alloys, FeAl and Fe3Si. Adsorption and absorption thermodynamics and kinetics, as well as bulk dissolution and diffusion are calculated in order to determine whether these two alloys can inhibit uptake of H and C. Relative to pure Fe, dissolved H and C are less stable in the alloys, as the dissolution enthalpy is predicted to be more endothermic. Overall, the energy barriers and rate constants for adsorbed H/C diffusing into Fe3Si subsurface layers suggests that alloying Fe with Si can be an effective means to limit uptake of these elements into steel. Spallation of protective layers on jet engine turbine blades is a problem that arises during thermal cycling. An alternative thermal barrier coating system involving MoSi2 is considered and calculations predict strong adhesion at the MoSi2/Ni interface. The interfacial bonding structure reveals a mixture of metallic and covalent cross-interface bonds. The adhesion energy is similar across all three MoSi2 facets studied. Upon exposure to oxygen, this MoSi2 alloy will form a strongly adhered oxide scale, which in turn may strongly adhere the heat shield material (yttria-stabilized zirconia), thereby potentially extending the lifetime of the barrier coating. Lastly, the interaction of hydrogen isotopes (fusion fuel) with tungsten (a proposed fusion reactor wall material) is examined. Exothermic dissociative adsorption is predicted, along with endothermic absorption and dissolution. Surface-to-subsurface diffusion energy barriers for H incorporation into bulk W are large and the corresponding outward diffusion barriers are very small. In bulk W, deep energetic traps (trapping multiple H atoms) are predicted at vacancy defects. Thus, under high neutron fluxes that will produce vacancies in W, H are predicted to collect at these vacancies. In turn, locally high concentrations of H at such vacancies will enhance decohesion of bulk W, consistent with observed blistering under deuterium implantation. Limiting vacancy formation may be key to the survival of W as a fusion reactor wall material.

Modeling intragranular diffusion in low-connectivity granular media

NASA Astrophysics Data System (ADS)

Ewing, Robert P.; Liu, Chongxuan; Hu, Qinhong

2012-03-01

Characterizing the diffusive exchange of solutes between bulk water in an aquifer and water in the intragranular pores of the solid phase is still challenging despite decades of study. Many disparities between observation and theory could be attributed to low connectivity of the intragranular pores. The presence of low connectivity indicates that a useful conceptual framework is percolation theory. The present study was initiated to develop a percolation-based finite difference (FD) model, and to test it rigorously against both random walk (RW) simulations of diffusion starting from nonequilibrium, and data on Borden sand published by Ball and Roberts (1991a,b) and subsequently reanalyzed by Haggerty and Gorelick (1995) using a multirate mass transfer (MRMT) approach. The percolation-theoretical model is simple and readily incorporated into existing FD models. The FD model closely matches the RW results using only a single fitting parameter, across a wide range of pore connectivities. Simulation of the Borden sand experiment without pore connectivity effects reproduced the MRMT analysis, but including low pore connectivity effects improved the fit. Overall, the theory and simulation results show that low intragranular pore connectivity can produce diffusive behavior that appears as if the solute had undergone slow sorption, despite the absence of any sorption process, thereby explaining some hitherto confusing aspects of intragranular diffusion.

Flexible Hybrid Battery/Pseudocapacitor

NASA Technical Reports Server (NTRS)

Tucker, Dennis S.; Paley, Steven

2015-01-01

Batteries keep devices working by utilizing high energy density, however, they can run down and take tens of minutes to hours to recharge. For rapid power delivery and recharging, high-power density devices, i.e., supercapacitors, are used. The electrochemical processes which occur in batteries and supercapacitors give rise to different charge-storage properties. In lithium ion (Li+) batteries, the insertion of Li+, which enables redox reactions in bulk electrode materials, is diffusion controlled and can be slow. Supercapacitor devices, also known as electrical double-layer capacitors (EDLCs) store charge by adsorption of electrolyte ions onto the surface of electrode materials. No redox reactions are necessary, so the response to changes in potential without diffusion limitations is rapid and leads to high power. However, the charge in EDLCs is confined to the surface, so the energy density is lower than that of batteries.

Vacuum ultra-violet damage and damage mitigation for plasma processing of highly porous organosilicate glass dielectrics

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

Marneffe, J.-F. de, E-mail: marneffe@imec.be; Lukaszewicz, M.; Porter, S. B.

2015-10-07

Porous organosilicate glass thin films, with k-value 2.0, were exposed to 147 nm vacuum ultra-violet (VUV) photons emitted in a Xenon capacitive coupled plasma discharge. Strong methyl bond depletion was observed, concomitant with a significant increase of the bulk dielectric constant. This indicates that, besides reactive radical diffusion, photons emitted during plasma processing do impede dielectric properties and therefore need to be tackled appropriately during patterning and integration. The detrimental effect of VUV irradiation can be partly suppressed by stuffing the low-k porous matrix with proper sacrificial polymers showing high VUV absorption together with good thermal and VUV stability. In addition,more » the choice of an appropriate hard-mask, showing high VUV absorption, can minimize VUV damage. Particular processing conditions allow to minimize the fluence of photons to the substrate and lead to negligible VUV damage. For patterned structures, in order to reduce VUV damage in the bulk and on feature sidewalls, the combination of both pore stuffing/material densification and absorbing hard-mask is recommended, and/or the use of low VUV-emitting plasma discharge.« less

Partitioning of tritium between surface and bulk of 316 stainless steel at room temperature

DOE PAGES

Sharpe, M. D.; Fagan, C.; Shmayda, W. T.; ...

2018-03-28

The distribution of tritium between the near surface and the bulk of 316 stainless steel has been measured using two independent techniques: pulsed-plasma exposures and a zinc-chloride wash. Between 17% and 20% of the total inventory absorbed into a stainless-steel sample during a 24-h exposure to DT gas at room temperature resides in the water layers present on the metal surface. Redistribution of tritium between the surface and the bulk of stainless steel, if it occurs, is very slow. Finally, tritium does not appear to enter into the bulk at a rate defined solely by lattice diffusivity.

Partitioning of tritium between surface and bulk of 316 stainless steel at room temperature

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

Sharpe, M. D.; Fagan, C.; Shmayda, W. T.

The distribution of tritium between the near surface and the bulk of 316 stainless steel has been measured using two independent techniques: pulsed-plasma exposures and a zinc-chloride wash. Between 17% and 20% of the total inventory absorbed into a stainless-steel sample during a 24-h exposure to DT gas at room temperature resides in the water layers present on the metal surface. Redistribution of tritium between the surface and the bulk of stainless steel, if it occurs, is very slow. Finally, tritium does not appear to enter into the bulk at a rate defined solely by lattice diffusivity.

Interface Pattern Selection in Directional Solidification

NASA Technical Reports Server (NTRS)

Trivedi, Rohit; Tewari, Surendra N.

2001-01-01

The central focus of this research is to establish key scientific concepts that govern the selection of cellular and dendritic patterns during the directional solidification of alloys. Ground-based studies have established that the conditions under which cellular and dendritic microstructures form are precisely where convection effects are dominant in bulk samples. Thus, experimental data can not be obtained terrestrially under pure diffusive regime. Furthermore, reliable theoretical models are not yet possible which can quantitatively incorporate fluid flow in the pattern selection criterion. Consequently, microgravity experiments on cellular and dendritic growth are designed to obtain benchmark data under diffusive growth conditions that can be quantitatively analyzed and compared with the rigorous theoretical model to establish the fundamental principles that govern the selection of specific microstructure and its length scales. In the cellular structure, different cells in an array are strongly coupled so that the cellular pattern evolution is controlled by complex interactions between thermal diffusion, solute diffusion and interface effects. These interactions give infinity of solutions, and the system selects only a narrow band of solutions. The aim of this investigation is to obtain benchmark data and develop a rigorous theoretical model that will allow us to quantitatively establish the physics of this selection process.

Modeling Deuterium Release from Plasma Implanted Surfaces

NASA Astrophysics Data System (ADS)

Grossman, A. A.; Doerner, R.; Hirooka, Y.; Luckhardt, S. C.; Sze, F. C.

1997-11-01

When energetic ions or atoms of hydrogen isotopes interact with a solid surface, they may either be reflected or they may be implanted, a slowing down process within the subsurface layer of the energetic particles to thermal velocities. Subsequent interactions of the thermalized particles are those of diffusion and trapping within the material and the possibility of re-emission from the solid via desorption. The diffusion equation and its boundary conditions govern the transport of this thermalized hydrogen within the material. Diffusivities obey an Arrhenius law over as much as fourteen orders of magnitude for the temperature range of interest for a fusion reactor first wall and divertor plate. Using TMAP4, a variety of diffusion models are set up for comparison with experiments on PISCES which involve implantation and desorption of deuterium from beryllium, tungsten, carbon and boron carbide. The parameters and characteristics of the models which give the closest fit to the experimental data are reported. At the high fluences of these experiments, it is necessary to take into account saturation effects during implantation using a separate implantation layer with thickness given by TRIM and a higher trapping to lattice ratio than in the bulk in order to model the experimental data.

Numerical investigations on the characteristics of thermomagnetic instability in MgB2 bulks

NASA Astrophysics Data System (ADS)

Xia, Jing; Li, Maosheng; Zhou, Youhe

2017-07-01

This paper presents the characteristics of thermomagnetic instability in MgB2 bulks by numerically solving the macroscopic dynamics of thermomagnetic interaction governed by the coupled magnetic and heat diffusion equations in association with a modified E-J power-law relationship. The finite element method is used to discretize the system of partial differential equations. The calculated magnetization loops with flux jumps are consistent with the experimental results for MgB2 slabs bathed in a wide range of ambient temperatures. We reveal the evolution process of the thermomagnetic instability and present the distributions of the magnetic field, temperature, and current density before and after flux jumps. A 2D axisymmetric model is used to study the thermomagnetic instability in cylindrical MgB2 bulks. It is found that the number of flux jumps monotonously reduces as the ambient temperature rises and no flux jump appears when the ambient temperature exceeds a certain value. Moreover, the flux-jump phenomenon exists in a wide range of the ramp rate of the applied external field, i.e. 10-2-102 T s-1. Furthermore, the dependences of the first flux-jump field on the ambient temperature, ramp rate, and bulk thickness are investigated. The critical bulk thicknesses for stability are obtained for different ambient temperatures and sample radii. In addition, the influence of the capability of the interfacial heat transfer on the temporal response of the bulk temperature is discussed. We also find that the prediction of thermomagnetic instability is sensitive to the employment of the flux creep exponent in the simulations.

Investigation of Thermal Interface Materials Using Phase-Sensitive Transient Thermoreflectance Technique: Preprint

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

Feng, X.; King, C.; DeVoto, D.

2014-08-01

With increasing power density in electronics packages/modules, thermal resistances at multiple interfaces are a bottleneck to efficient heat removal from the package. In this work, the performance of thermal interface materials such as grease, thermoplastic adhesives and diffusion-bonded interfaces are characterized using the phase-sensitive transient thermoreflectance technique. A multi-layer heat conduction model was constructed and theoretical solutions were derived to obtain the relation between phase lag and the thermal/physical properties. This technique enables simultaneous extraction of the contact resistance and bulk thermal conductivity of the TIMs. With the measurements, the bulk thermal conductivity of Dow TC-5022 thermal grease (70 tomore » 75 um bondline thickness) was 3 to 5 W/(m-K) and the contact resistance was 5 to 10 mm2-K/W. For the Btech thermoplastic material (45 to 80 μm bondline thickness), the bulk thermal conductivity was 20 to 50 W/(m-K) and the contact resistance was 2 to 5 mm2-K/W. Measurements were also conducted to quantify the thermal performance of diffusion-bonded interface for power electronics applications. Results with the diffusion-bonded sample showed that the interfacial thermal resistance is more than one order of magnitude lower than those of traditional TIMs, suggesting potential pathways to efficient thermal management.« less

Profiling of Current Transients in Capacitor Type Diamond Sensors

PubMed Central

Gaubas, Eugenijus; Ceponis, Tomas; Meskauskaite, Dovile; Kazuchits, Nikolai

2015-01-01

The operational characteristics of capacitor-type detectors based on HPHT and CVD diamond have been investigated using perpendicular and parallel injection of carrier domain regimes. Simulations of the drift-diffusion current transients have been implemented by using dynamic models based on Shockley-Ramo’s theorem, under injection of localized surface domains and of bulk charge carriers. The bipolar drift-diffusion regimes have been analyzed for the photo-induced bulk domain (packet) of excess carriers. The surface charge formation and polarization effects dependent on detector biasing voltage have been revealed. The screening effects ascribed to surface charge and to dynamics of extraction of the injected bulk excess carrier domain have been separated and explained. The parameters of drift mobility of the electrons μe = 4000 cm2/Vs and holes μh = 3800 cm2/Vs have been evaluated for CVD diamond using the perpendicular profiling of currents. The coefficient of carrier ambipolar diffusion Da = 97 cm2/s and the carrier recombination lifetime τR,CVD ≌ 110 ns in CVD diamond were extracted by combining analysis of the transients of the sensor current and the microwave probed photoconductivity. The carrier trapping with inherent lifetime τR,HPHT ≌ 2 ns prevails in HPHT diamond. PMID:26061200

Optical and Magnetic Resonance Studies of Na-Diffused ZnO Bulk Single Crystals

NASA Astrophysics Data System (ADS)

Glaser, E. R.; Garces, N. Y.; Parmar, N. S.; Lynn, K. G.

2013-03-01

Photoluminescence (PL) and optically-detected magnetic resonance (ODMR) at 24 GHz were performed on bulk ZnO crystals after diffusion of Na impurities that were explored as an alternate doping source for p-type conductivity. PL at 2K revealed strong bandedge excitonic recombination at 3.361 eV and a broad ``orange'' PL band at 2.17 eV with FWHM of ~0.5 eV. This ``orange'' emission is very similar to that reported previously[1] from thermoluminescence measurements of intentionally Na-doped bulk ZnO and, thus, strongly suggests the incorporation and activation of the Na-diffused impurities. ODMR performed on this ``orange'' PL revealed two signals. The first was a sharp feature with g-value of ~1.96 and is a well-known ``fingerprint'' of shallow donors in ZnO. The second signal consisted of a pair of lines with an intensity ratio of ~3:1 and with g-tensors (g∥,g⊥ ~2.008-2.029) very similar to ESR signals attributed previously[2] to holes bound to Na impurities located at the axial and non-axial Zn host lattice sites in Na-doped ZnO. Thus, the ``orange'' PL can be tentatively assigned to radiative recombination between residual shallow donors and deep Na-related hole traps.

MoO3 Thickness, Thermal Annealing and Solvent Annealing Effects on Inverted and Direct Polymer Photovoltaic Solar Cells

PubMed Central

Chambon, Sylvain; Derue, Lionel; Lahaye, Michel; Pavageau, Bertrand; Hirsch, Lionel; Wantz, Guillaume

2012-01-01

Several parameters of the fabrication process of inverted polymer bulk heterojunction solar cells based on titanium oxide as an electron selective layer and molybdenum oxide as a hole selective layer were tested in order to achieve efficient organic photovoltaic solar cells. Thermal annealing treatment is a common process to achieve optimum morphology, but it proved to be damageable for the performance of this kind of inverted solar cells. We demonstrate using Auger analysis combined with argon etching that diffusion of species occurs from the MoO3/Ag top layers into the active layer upon thermal annealing. In order to achieve efficient devices, the morphology of the bulk heterojunction was then manipulated using the solvent annealing technique as an alternative to thermal annealing. The influence of the MoO3 thickness was studied on inverted, as well as direct, structure. It appeared that only 1 nm-thick MoO3 is enough to exhibit highly efficient devices (PCE = 3.8%) and that increasing the thickness up to 15 nm does not change the device performance.

Scalable planar fabrication processes for chalcogenide-based topological insulators

NASA Astrophysics Data System (ADS)

Sharma, Peter; Henry, M. David; Douglas, Erica; Wiwi, Michael; Lima Sharma, Ana; Lewis, Rupert; Sugar, Joshua; Salehi, Maryam; Koirala, Nikesh; Oh, Seongshik

Surface currents in topological insulators are expected to have long spin diffusion lengths, which could lead to numerous applications. Experiments that show promising transport properties were conducted on exfoliated flakes from bulk material, thin films on substrates of limited dimensions, or bulk material, with limited yield. A planar thin film-based technology is needed to make topological insulator devices at scale and could also lead to new device designs. We address two problems related to fabricating chalcogenide-based topological insulator devices on 3'' wafers in the Sandia Microfabrication Facility using Bi2Te3 films. (2) Implantation damage and its subsequent mitigation through annealing is characterized. (2) The degradation in dielectric layers used to manipulate surface potential for elucidating topological surface state transport is characterized under different processing conditions. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000. Funded by the Office of Naval Research (N0001416IP00098-0).

Understanding Solvent Manipulation of Morphology in Bulk-Heterojunction Organic Solar Cells.

PubMed

Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

2016-10-06

Film morphology greatly influences the performance of bulk-heterojunction (BHJ)-structure-based solar cells. It is known that an interpenetrating bicontinuous network with nanoscale-separated donor and acceptor phases for charge transfer, an ordered molecular packing for exciton diffusion and charge transport, and a vertical compositionally graded structure for charge collection are prerequisites for achieving highly efficient BHJ organic solar cells (OSCs). Therefore, control of the morphology to obtain an ideal structure is a key problem. For this solution-processing BHJ system, the solvent participates fully in film processing. Its involvement is critical in modifying the nanostructure of BHJ films. In this review, we discuss the effects of solvent-related methods on the morphology of BHJ films, including selection of the casting solvent, solvent mixture, solvent vapor annealing, and solvent soaking. On the basis of a discussion on interaction strength and time between solvent and active materials, we believe that the solvent-morphology-performance relationship will be clearer and that solvent selection as a means to manipulate the morphology of BHJ films will be more rational. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Strategies for increasing the efficiency of heterojunction organic solar cells: material selection and device architecture.

PubMed

Heremans, Paul; Cheyns, David; Rand, Barry P

2009-11-17

Thin-film blends or bilayers of donor- and acceptor-type organic semiconductors form the core of heterojunction organic photovoltaic cells. Researchers measure the quality of photovoltaic cells based on their power conversion efficiency, the ratio of the electrical power that can be generated versus the power of incident solar radiation. The efficiency of organic solar cells has increased steadily in the last decade, currently reaching up to 6%. Understanding and combating the various loss mechanisms that occur in processes from optical excitation to charge collection should lead to efficiencies on the order of 10% in the near future. In organic heterojunction solar cells, the generation of photocurrent is a cascade of four steps: generation of excitons (electrically neutral bound electron-hole pairs) by photon absorption, diffusion of excitons to the heterojunction, dissociation of the excitons into free charge carriers, and transport of these carriers to the contacts. In this Account, we review our recent contributions to the understanding of the mechanisms that govern these steps. Starting from archetype donor-acceptor systems of planar small-molecule heterojunctions and solution-processed bulk heterojunctions, we outline our search for alternative materials and device architectures. We show that non-planar phthalocynanines have appealing absorption characteristics but also have reduced charge carrier transport. As a result, the donor layer needs to be ultrathin, and all layers of the device have to be tuned to account for optical interference effects. Using these optimization techniques, we illustrate cells with 3.1% efficiency for the non-planar chloroboron subphthalocyanine donor. Molecules offering a better compromise between absorption and carrier mobility should allow for further improvements. We also propose a method for increasing the exciton diffusion length by converting singlet excitons into long-lived triplets. By doping a polymer with a phosphorescent molecule, we demonstrate an increase in the exciton diffusion length of a polymer from 4 to 9 nm. If researchers can identify suitable phosphorescent dopants, this method could be employed with other materials. The carrier transport from the junction to the contacts is markedly different for a bulk heterojunction cell than for planar junction cells. Unlike for bulk heterojunction cells, the open-circuit voltage of planar-junction cells is independent of the contact work functions, as a consequence of the balance of drift and diffusion currents in these systems. This understanding helps to guide the development of new materials (particularly donor materials) that can further boost the efficiency of single-junction cells to 10%. With multijunction architectures, we expect that efficiencies of 12-16% could be attained, at which point organic photovoltaic cells could become an important renewable energy source.

Plasma Jet Interactions with Liquids in Partial Fulfillment of an NRL Karles Fellowship

DTIC Science & Technology

2015-11-30

water (DI H2O) as the reference solution, two concentrations of NaCl mixtures (0.6 Molar, and 1.0 Molar saturated NaCl), and three electroless solutions...by diffusion) to the bulk surface in net excess; that oxygen ions/radicals are being consumed from the bulk by an electrolysis path way; or that the

Numerical simulation of ozone concentration profile and flow characteristics in paddy bulks.

PubMed

Pandiselvam, Ravi; Chandrasekar, Veerapandian; Thirupathi, Venkatachalam

2017-08-01

Ozone has shown the potential to control stored product insect pests. The high reactivity of ozone leads to special problems when it passes though an organic medium such as stored grains. Thus, there is a need for a simulation study to understand the concentration profile and flow characteristics of ozone in stored paddy bulks as a function of time. Simulation of ozone concentration through the paddy grain bulks was explained by applying the principle of the law of conservation along with a continuity equation. A higher ozone concentration value was observed at regions near the ozone diffuser whereas a lower concentration value was observed at regions away from the ozone diffuser. The relative error between the experimental and predicted ozone concentration values for the entire bin geometry was less than 42.8%. The simulation model described a non-linear change of ozone concentration in stored paddy bulks. Results of this study provide a valuable source for estimating the parameters needed for effectively designing a storage bin for fumigation of paddy grains in a commercial scale continuous-flow ozone fumigation system. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Development of a kinetic model of hydrogen absorption and desorption in magnesium and analysis of the rate-determining step

NASA Astrophysics Data System (ADS)

Kitagawa, Yuta; Tanabe, Katsuaki

2018-05-01

Mg is promising as a new light-weight and low-cost hydrogen-storage material. We construct a numerical model to represent the hydrogen dynamics on Mg, comprising dissociative adsorption, desorption, bulk diffusion, and chemical reaction. Our calculation shows a good agreement with experimental data for hydrogen absorption and desorption on Mg. Our model clarifies the evolution of the rate-determining processes as absorption and desorption proceed. Furthermore, we investigate the optimal condition and materials design for efficient hydrogen storage in Mg. By properly understanding the rate-determining processes using our model, one can determine the design principle for high-performance hydrogen-storage systems.

Electrokinetics of diffuse soft interfaces. 1. Limit of low Donnan potentials.

PubMed

Duval, Jérôme F L; van Leeuwen, Herman P

2004-11-09

The current theoretical approaches to electrokinetics of gels or polyelectrolyte layers are based on the assumption that the position of the very interface between the aqueous medium and the gel phase is well defined. Within this assumption, spatial profiles for the volume fraction of polymer segments (phi), the density of fixed charges in the porous layer (rho fix), and the coefficient modeling the friction to hydrodynamic flow (k) follow a step-function. In reality, the "fuzzy" nature of the charged soft layer is intrinsically incompatible with the concept of a sharp interface and therefore necessarily calls for more detailed spatial representations for phi, rho fix, and k. In this paper, the notion of diffuse interface is introduced. For the sake of illustration, linear spatial distributions for phi and rho fix are considered in the interfacial zone between the bulk of the porous charged layer and the bulk electrolyte solution. The corresponding distribution for k is inferred from the Brinkman equation, which for low phi reduces to Stokes' equation. Linear electrostatics, hydrodynamics, and electroosmosis issues are analytically solved within the context of streaming current and streaming potential of charged surface layers in a thin-layer cell. The hydrodynamic analysis clearly demonstrates the physical incorrectness of the concept of a discrete slip plane for diffuse interfaces. For moderate to low electrolyte concentrations and nanoscale spatial transition of phi from zero (bulk electrolyte) to phi o (bulk gel), the electrokinetic properties of the soft layer as predicted by the theory considerably deviate from those calculated on the basis of the discontinuous approximation by Ohshima.

Bulk properties and velocity distributions of water group ions at Comet Halley - Giotto measurements

NASA Astrophysics Data System (ADS)

Coates, A. J.; Wilken, B.; Johnstone, A. D.; Jockers, K.; Glassmeier, K.-H.; Huddleston, D. E.

1990-07-01

In the region upstream of Comet Halley, pickup heavy ions of cometary origin were directly observed by the implanted ion spectrometer on Giotto. Diffusion of this population in pitch angle and in energy, during the approach to the comet and on the outbound leg is discussed. The two data sets are compared and qualitative ideas on scattering timescales are inferred. In addition the bulk parameters of these distributions have been computed and a comparison of the observed speed in the solar wind frame and the observed density with expectations is presented. Pitch angle scattering occurs more slowly than expected with filled shells appearing at 2,500,000 km, and significant energy diffusion does not occur until the bow shock region. Also the shell distributions downstream of the shock flow at the bispherical bulk speed (related to the Alfven speed) along the magnetic field with respect to the solar wind in accordance with conservation of energy between the pickup ions and the wave turbulence.

Physics of beer tapping.

PubMed

Rodríguez-Rodríguez, Javier; Casado-Chacón, Almudena; Fuster, Daniel

2014-11-21

The popular bar prank known in colloquial English as beer tapping consists in hitting the top of a beer bottle with a solid object, usually another bottle, to trigger the foaming over of the former within a few seconds. Despite the trick being known for a long time, to the best of our knowledge, the phenomenon still lacks scientific explanation. Although it seems natural to think that shock-induced cavitation enhances the diffusion of CO2 from the supersaturated bulk liquid into the bubbles by breaking them up, the subtle mechanism by which this happens remains unknown. Here, we show that the overall foaming-over process can be divided into three stages where different physical phenomena take place in different time scales: namely, the bubble-collapse (or cavitation) stage, the diffusion-driven stage, and the buoyancy-driven stage. In the bubble-collapse stage, the impact generates a train of expansion-compression waves in the liquid that leads to the fragmentation of preexisting gas cavities. Upon bubble fragmentation, the sudden increase of the interface-area-to-volume ratio enhances mass transfer significantly, which makes the bubble volume grow by a large factor until CO2 is locally depleted. At that point buoyancy takes over, making the bubble clouds rise and eventually form buoyant vortex rings whose volume grows fast due to the feedback between the buoyancy-induced rising speed and the advection-enhanced CO2 transport from the bulk liquid to the bubble. The physics behind this explosive process sheds insight into the dynamics of geological phenomena such as limnic eruptions.

Physics of Beer Tapping

NASA Astrophysics Data System (ADS)

Rodríguez-Rodríguez, Javier; Casado-Chacón, Almudena; Fuster, Daniel

2014-11-01

The popular bar prank known in colloquial English as beer tapping consists in hitting the top of a beer bottle with a solid object, usually another bottle, to trigger the foaming over of the former within a few seconds. Despite the trick being known for a long time, to the best of our knowledge, the phenomenon still lacks scientific explanation. Although it seems natural to think that shock-induced cavitation enhances the diffusion of CO2 from the supersaturated bulk liquid into the bubbles by breaking them up, the subtle mechanism by which this happens remains unknown. Here, we show that the overall foaming-over process can be divided into three stages where different physical phenomena take place in different time scales: namely, the bubble-collapse (or cavitation) stage, the diffusion-driven stage, and the buoyancy-driven stage. In the bubble-collapse stage, the impact generates a train of expansion-compression waves in the liquid that leads to the fragmentation of preexisting gas cavities. Upon bubble fragmentation, the sudden increase of the interface-area-to-volume ratio enhances mass transfer significantly, which makes the bubble volume grow by a large factor until CO2 is locally depleted. At that point buoyancy takes over, making the bubble clouds rise and eventually form buoyant vortex rings whose volume grows fast due to the feedback between the buoyancy-induced rising speed and the advection-enhanced CO2 transport from the bulk liquid to the bubble. The physics behind this explosive process sheds insight into the dynamics of geological phenomena such as limnic eruptions.

Increased rate of solvent diffusion in a prototypical supramolecular gel measured on the picosecond timescale.

PubMed

Seydel, Tilo; Edkins, Robert M; Jones, Christopher D; Foster, Jonathan A; Bewley, Robert; Aguilar, Juan A; Edkins, Katharina

2018-06-14

Solvent diffusion in a prototypical supramolecular gel probed by quasi-elastic neutron scattering on the picosecond timescale is faster than that in the respective bulk solvent. This phenomenon is hypothesized to be due to disruption of the hydrogen bonding of the solvent by the large hydrophobic surface of the gel network.

Damage coefficients in low resistivity silicon. [solar cells

NASA Technical Reports Server (NTRS)

Srour, J. R.; Othmer, S.; Chiu, K. Y.; Curtis, O. L., Jr.

1975-01-01

Electron and proton damage coefficients are determined for low resistivity silicon based on minority-carrier lifetime measurements on bulk material and diffusion length measurements on solar cells. Irradiations were performed on bulk samples and cells fabricated from four types of boron-doped 0.1 ohm-cm silicon ingots, including the four possible combinations of high and low oxygen content and high and low dislocation density. Measurements were also made on higher resistivity boron-doped bulk samples and solar cells. Major observations and conclusions from the investigation are discussed.

A numerical analysis of the performance of unpumped SBE 41 sensors at low flushing rates

NASA Astrophysics Data System (ADS)

Alvarez, A.

2018-05-01

The thermal and hydrodynamic response of a Sea-Bird unpumped CTD SBE 41, is numerically modeled to assess the biases occurring at the slow flushing rates typical of glider operations. Based on symmetry considerations, the sensor response is approximated by coupling the incompressible Navier-Stokes and the thermal advection-diffusion equations in two dimensions. Numerical results illustrate three regimes in the thermal response of the SBE 41 sensor, when crossing water layers with different thermal signatures. A linear decay in time of the bulk temperature of the conductivity cell is initially found. This is induced by the transit of the inflow through the conductivity cell in the form of a relatively narrow jet. Water masses with new thermal signatures do not immediately fill the sensor chambers, where the cross-section widens. Thermal equilibrium of these water masses is then achieved, in a second regime, via a cross-flow thermal diffusion between the boundary of the jet and the walls. Consequently, the evolution of the bulk temperature scales with the square root of time. In a third regime, the evolution of the bulk temperature depends on the thermal gradient between the fluid and the coating material. This results on an exponential decay of the bulk temperature with time. A comprehensive analytical model of the time evolution of the bulk temperature inside a cell is proposed based on these results.

Measurement of effective bulk and contact resistance of gas diffusion layer under inhomogeneous compression - Part II: Thermal conductivity

NASA Astrophysics Data System (ADS)

Roy Chowdhury, Prabudhya; Vikram, Ajit; Phillips, Ryan K.; Hoorfar, Mina

2016-07-01

The gas diffusion layer (GDL) is a thin porous layer sandwiched between a bipolar plate (BPP) and a catalyst coated membrane in a fuel cell. Besides providing passage for water and gas transport from and to the catalyst layer, it is responsible for electron and heat transfer from and to the BPP. In this paper, a method has been developed to measure the GDL bulk thermal conductivity and the contact resistance at the GDL/BPP interface under inhomogeneous compression occurring in an actual fuel cell assembly. Toray carbon paper GDL TGP-H-060 was tested under a range of compression pressure of 0.34 to 1.71 MPa. The results showed that the thermal contact resistance decreases non-linearly (from 3.8 × 10-4 to 1.17 × 10-4 Km2 W-1) with increasing pressure due to increase in microscopic contact area between the GDL and BPP; while the effective bulk thermal conductivity increases (from 0.56 to 1.42 Wm-1 K-1) with increasing the compression pressure. The thermal contact resistance was found to be greater (by a factor of 1.6-2.8) than the effective bulk thermal resistance for all compression pressure ranges applied here. This measurement technique can be used to identify optimum GDL based on minimum bulk and contact resistances measured under inhomogeneous compression.

Reduction in Recombination Current Density in Boron Doped Silicon Using Atomic Hydrogen

NASA Astrophysics Data System (ADS)

Young, Matthew Garett

The solar industry has grown immensely in recent years and has reached a point where solar energy has now become inexpensive enough that it is starting to emerge as a mainstream electrical generation source. However, recent economic analysis has suggested that for solar to become a truly wide spread source of electricity, the costs still need to plummet by a factor of 8x. This demands new and innovative concepts to help lower such cost. In pursuit of this goal, this dissertation examines the use of atomic hydrogen to lessen the recombination current density in the boron doped region of n-type silicon solar cells. This required the development of a boron diffusion process that maintained the bulk lifetime of n-type silicon such that the recombination current density could be extracted by photoconductance spectroscopy. It is demonstrated that by hydrogenating boron diffusions, the majority carrier concentration can be controlled. By using symmetrically diffused test structures with quinhydrone-methanol surface passivation the recombination current density of a hydrogenated boron profile is shown to be less than that of a standard boron profile, by as much as 30%. This is then applied to a modified industrial silicon solar cell process to demonstrate an efficiency enhancement of 0.4%.

Dynamics of a Room Temperature Ionic Liquid in Supported Ionic Liquid Membranes vs the Bulk Liquid: 2D IR and Polarized IR Pump-Probe Experiments.

PubMed

Shin, Jae Yoon; Yamada, Steven A; Fayer, Michael D

2017-01-11

Supported ionic liquid membranes (SILMs) are membranes that have ionic liquids impregnated in their pores. SILMs have been proposed for advanced carbon capture materials. Two-dimensional infrared (2D IR) and polarization selective IR pump-probe (PSPP) techniques were used to investigate the dynamics of reorientation and spectral diffusion of the linear triatomic anion, SeCN - , in poly(ether sulfone) (PES) membranes and room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimNTf 2 ). The dynamics in the bulk EmimNTf 2 were compared to its dynamics in the SILM samples. Two PES membranes, PES200 and PES30, have pores with average sizes, ∼300 nm and ∼100 nm, respectively. Despite the relatively large pore sizes, the measurements reveal that the reorientation of SeCN - and the RTIL structural fluctuations are substantially slower in the SILMs than in the bulk liquid. The complete orientational randomization, slows from 136 ps in the bulk to 513 ps in the PES30. 2D IR measurements yield three time scales for structural spectral diffusion (SSD), that is, the time evolution of the liquid structure. The slowest decay constant increases from 140 ps in the bulk to 504 ps in the PES200 and increases further to 1660 ps in the PES30. The results suggest that changes at the interface propagate out and influence the RTIL structural dynamics even more than a hundred nanometers from the polymer surface. The differences between the IL dynamics in the bulk and in the membranes suggest that studies of bulk RTIL properties may be poor guides to their use in SILMs in carbon capture applications.

Is the surface oxygen exchange rate linked to bulk ion diffusivity in mixed conducting Ruddlesden–Popper phases?

DOE PAGES

Tomkiewicz, Alex C.; Tamimi, Mazin A.; Huq, Ashfia; ...

2015-03-02

There is a possible link between oxygen surface exchange rate and bulk oxygen anion diffusivity in mixed ionic and electronic conducting oxides; it is a topic of great interest and debate. While a large body of experimental evidence and theoretical analyses support a link, observed differences between bulk and surface composition of these materials are hard to reconcile with this observation. This is further compounded by potential problems with simultaneous measurement of both parameters. Here we utilize separate techniques, in situ neutron diffraction and pulsed isotopic surface exchange, to examine bulk ion mobility and surface oxygen exchange rates of threemore » Ruddlesden-Popper phases, general form A n-1A 2'BnO 3n+1, A n-1A 2'BnX 3n+1; LaSrCo 0.5Fe 0.5O 4-δ (n = 1), La 0.3Sr 2.7CoFeO 7-δ (n = 2) and LaSr 3Co 1.5Fe 1.5O 10-δ (n = 3). These measurements are complemented by surface composition determination via high sensitivity-low energy ion scattering. We observe a correlation between bulk ion mobility and surface exchange rate between materials. The surface exchange rates vary by more than one order of magnitude with high anion mobility in the bulk of an oxygen vacancy-rich n = 2 Ruddlesden-Popper material correlating with rapid oxygen exchange. Furthermore this is in contrast with the similar surface exchange rates which we may expect due to similar surface compositions across all three samples. This paper conclude that experimental limitations lead to inherent convolution of surface and bulk rates, and that surface exchange steps are not likely to be rate limiting in oxygen incorporation.« less

Observations of Ag diffusion in ion implanted SiC

DOE PAGES

Gerczak, Tyler J.; Leng, Bin; Sridharan, Kumar; ...

2015-03-17

The nature and magnitude of Ag diffusion in SiC has been a topic of interest in connection with the performance of tristructural isotropic (TRISO) coated particle fuel for high temperature gas-cooled nuclear reactors. Ion implantation diffusion couples have been revisited to continue developing a more complete understanding of Ag fission product diffusion in SiC. Ion implantation diffusion couples fabricated from single crystal 4H-SiC and polycrystalline 3C-SiC substrates and exposed to 1500–1625°C, were investigated in this study by transmission electron microscopy and secondary ion mass spectrometry (SIMS). The high dynamic range of SIMS allowed for multiple diffusion régimes to be investigated,more » including enhanced diffusion by implantation-induced defects and grain boundary (GB) diffusion in undamaged SiC. Lastly, estimated diffusion coefficients suggest GB diffusion in bulk SiC does not properly describe the release observed from TRISO fuel.« less

Structure and Dynamics of Ionic Liquid [MMIM][Br] Confined in Hydrophobic and Hydrophilic Porous Matrices: A Molecular Dynamics Simulation Study.

PubMed

Sharma, Anirban; Ghorai, Pradip Kr

2016-11-17

The effects of confinement on the structural and dynamical properties of the ionic liquid (IL) 1,3-dimethylimidazolium bromide ([MMIM][Br]) have been investigated by molecular dynamics simulations. We used zeolite faujasite (NaY) as a hydrophilic confinement and dealuminated faujasite (DAY) as a hydrophobic confinement. The presence of an extra framework cation, [Na + ], in NaY makes the host hydrophilic, whereas DAY, with no extra framework cation, is hydrophobic. Although both NaY and DAY have almost similar structures, the IL showed markedly different structural and dynamical properties in these confinements and in bulk. In the confinements, the cation-cation radial distribution function, which strongly depends on temperature, exhibits a layer-like structure, whereas in bulk, it shows a liquid-like structure that hardly depends on temperature. Although the interaction between [MMIM] + and Br - in DAY is stronger than that in both NaY and bulk, the strength of the interaction between them is almost invariant with temperature. Both [MMIM] + and Br - strongly interact with Na + of the host, and their interaction strongly depends on temperature, whereas the interaction of the IL with Si and O is very weak and invariant with temperature. In bulk, the self-diffusion coefficient, [D], of both [MMIM] + and Br - increases exponentially with temperature, and the D of the cation is slightly higher than that of the anion at all studied temperatures, whereas in the confinements, [MMIM] + moves much faster than Br - . For example, in the hydrophilic confinement, the D of the cation is 20-30 times higher than that of the anion. The D of both the ions decreases significantly in the confinements as compared to that in bulk. During diffusion, [MMIM] + diffuses closer to the inner surface in the hydrophilic confinement than that in the hydrophobic confinement. The diffusion pathway imperceptibly depends on temperature but strongly depends on the nature of the confinement. The self part of the time-dependent van Hoove correlation function of [MMIM] + in the hydrophilic confinement shows a larger deviation from its Gaussian form than that in the hydrophobic confinement at all temperatures, indicating that the long-time dynamics of [MMIM] + in NaY is more heterogeneous than that in DAY. Although the orientational relaxation time scales of [MMIM] + in the confinements significantly slowed as compared to those in bulk, confinement does not affect the librational motion of the collective hydrogen-bond network present in the IL.

Enhanced ionic liquid mobility induced by confinement in 1D CNT membranes

NASA Astrophysics Data System (ADS)

Berrod, Q.; Ferdeghini, F.; Judeinstein, P.; Genevaz, N.; Ramos, R.; Fournier, A.; Dijon, J.; Ollivier, J.; Rols, S.; Yu, D.; Mole, R. A.; Zanotti, J.-M.

2016-04-01

Water confined within carbon nanotubes (CNT) exhibits tremendous enhanced transport properties. Here, we extend this result to ionic liquids (IL) confined in vertically aligned CNT membranes. Under confinement, the IL self-diffusion coefficient is increased by a factor 3 compared to its bulk reference. This could lead to high power battery separators.Water confined within carbon nanotubes (CNT) exhibits tremendous enhanced transport properties. Here, we extend this result to ionic liquids (IL) confined in vertically aligned CNT membranes. Under confinement, the IL self-diffusion coefficient is increased by a factor 3 compared to its bulk reference. This could lead to high power battery separators. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01445c

Controlling mechanisms of metals release form cement-based waste form in acetic acid solution

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

Cheng, Kuang Ye.

1991-01-01

The purpose of this dissertation is to identify the individual leaching mechanisms of metals by knowing the pH profile within the leached specimen and the physical and chemical properties of the leached material. Leaching of cement-based waste form in acetic acid solutions with different acidic strengths has been investigated in this work. The pH profile along the acid penetration route in the cement-based waste form was identified by various pH color indicators. The pH in the surface altered layer varies from 5.0 to 6.0, which is very close to the pH in the bulk leachate. A reacting zone, where themore » pH abruptly changes from 6 to 12, sharply divides the altered surface layer from the remaining unleached waste form or kernel. Leaching of metals is controlled by the acidity available in the leachant. Dissolution of alkaline materials leaves a silica-rich layer on the surface of the cement-based waste form. This surface layer exhibits different properties than those of the unleached material. The surface layer has a higher water content, is lighter weight, and is soft and friable. Furthermore, the abundant silicate content on the solid surface detains portion of the leached metals, while they are moving through the leached layer into bulk solution. The leaching of metals is a consequence of acid penetration. The distance from the solid/solution interface to the front of the leaching boundary can be regarded as the depth of leaching zone, where the metals dissolve and diffuse out of the waste form. The metal ions diffuse through the leached layer may be retarded on the solid surface by the pH-dependent adsorption reactions. It is found that the leaching process through the leached layer is diffusion-controlled for calcium and cadmium, whereas diffusion and adsorption occur simultaneously in the leached layer for lead and arsenic.« less

Diffusion length measurements using the scanning electron microscope. [in semiconductor devices

NASA Technical Reports Server (NTRS)

Weizer, V. G.

1975-01-01

A measurement technique employing the scanning electron microscope is described in which values of the true bulk diffusion length are obtained. It is shown that surface recombination effects can be eliminated through the application of highly doped surface field layers. The influence of high injection level effects and low-high junction current generation on the resulting measurement was investigated. Close agreement is found between the diffusion lengths measured by this method and those obtained using a penetrating radiation technique.

Reverse-Selective Diffusion in Nanocomposite Membranes

NASA Astrophysics Data System (ADS)

Hill, Reghan J.

2006-06-01

The permeability of certain polymer membranes with impenetrable nanoinclusions increases with the particle volume fraction [T. C. Merkel , Science 296, 519 (2002)SCIEAS0036-807510.1126/science.1069580]. The discovery contradicts qualitative expectations based on Maxwell’s classical theory of conduction or diffusion in composites with homogeneous phases. This Letter presents a theory based on an hypothesis that polymer chains are repelled from the inclusions during membrane casting. The accompanying increase in free volume, and hence solute diffusivity, yields bulk transport properties that are in good agreement with experiments.

An unusual slowdown of fast diffusion in a room temperature

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

Chathoth,; Mamontov, Eugene; Fulvio, Pasquale F

2013-01-01

Using quasielastic neutron scattering in the temperature range from 290 to 350 K, we show that the diffusive motions in a room temperature ionic liquid [H2NC(dma)2][BETI] become faster for a fraction of cations when the liquid is confined in a mesoporous carbon. This applies to both the localized and long-range translational diffusive motions of the highly mobile cations, although the former exhibit an unusual trend of slowing-down as the temperature is increased, until the localized diffusivity is reduced to the bulk ionic liquid value at a temperature of 350 K.

Spatial Modeling of Iron Transformations Within Artificial Soil Aggregates

NASA Astrophysics Data System (ADS)

Kausch, M.; Meile, C.; Pallud, C.

2008-12-01

Structured soils exhibit significant variations in transport characteristics at the aggregate scale. Preferential flow occurs through macropores while predominantly diffusive exchange takes place in intra-aggregate micropores. Such environments characterized by mass transfer limitations are conducive to the formation of small-scale chemical gradients and promote strong spatial variation in processes controlling the fate of redox-sensitive elements such as Fe. In this study, we present a reactive transport model used to spatially resolve iron bioreductive processes occurring within a spherical aggregate at the interface between advective and diffusive domains. The model is derived from current conceptual models of iron(hydr)oxide (HFO) transformations and constrained by literature and experimental data. Data were obtained from flow-through experiments on artificial soil aggregates inoculated with Shewanella putrefaciens strain CN32, and include the temporal evolution of the bulk solution composition, as well as spatial information on the final solid phase distribution within aggregates. With all iron initially in the form of ferrihydrite, spatially heterogeneous formation of goethite/lepidocrocite, magnetite and siderite was observed during the course of the experiments. These transformations were reproduced by the model, which ascribes a central role to divalent iron as a driver of HFO transformations and master variable in the rate laws of the considered reaction network. The predicted dissolved iron breakthrough curves also match the experimental ones closely. Thus, the computed chemical concentration fields help identify factors governing the observed trends in the solid phase distribution patterns inside the aggregate. Building on a mechanistic description of transformation reactions, fluid flow and solute transport, the model was able to describe the observations and hence illustrates the importance of small-scale gradients and dynamics of bioreductive processes for assessing bulk iron cycling. As HFOs are ubiquitous in soils, such process-level understanding of aggregate-scale iron dynamics has broad implications for the prediction of the subsurface fate of nutrients and contaminants that interact strongly with HFO surfaces.

An International Round-Robin Study, Part II: Thermal Diffusivity, Specific Heat and Thermal Conductivity

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

Wang, Hsin; Porter, Wallace D; Bottner, Harold

2013-01-01

For bulk thermoelectrics, figure-of-merit, ZT, still needs to improve from the current value of 1.0 - 1.5 to above 2 to be competitive to other alternative technologies. In recent years, the most significant improvements in ZT were mainly due to successful reduction of thermal conductivity. However, thermal conductivity cannot be measured directly at high temperatures. The combined measurements of thermal diffusivity and specific heat and density are required. It has been shown that thermal conductivity is the property with the greatest uncertainty and has a direct influence on the accuracy of the figure of merit. The International Energy Agency (IEA)more » group under the implementing agreement for Advanced Materials for Transportation (AMT) has conducted two international round-robins since 2009. This paper is Part II of the international round-robin testing of transport properties of bulk bismuth telluride. The main focuses in Part II are on thermal diffusivity, specific heat and thermal conductivity.« less

Diffusion length measurements of thin GaAs solar cells by means of energetic electrons

NASA Technical Reports Server (NTRS)

Vonross, O.

1980-01-01

A calculation of the short circuit current density (j sub sc) of a thin GaAs solar cell induced by fast electrons is presented. It is shown that in spite of the disparity in thickness between the N-type portion of the junction and the P-type portion of the junction, the measurement of the bulk diffusion length L sub p of the N-type part of the junction is seriously hampered due to the presence of a sizable contribution to the j sub sc from the P-type region of the junction. Corrections of up to 50% had to be made in order to interpret the data correctly. Since these corrections were not amenable to direct measurements it is concluded that the electron beam method for the determination of the bulk minority carrier diffusion length, which works so well for Si solar cells, is a poor method when applied to thin GaAs cells.

Molecular dynamics and quasidynamics simulations of the annealing of bulk and near-surface interstitials formed in molecular-beam epitaxial Si due to low-energy particle bombardment during deposition

NASA Technical Reports Server (NTRS)

Kitabatake, M.; Fons, P.; Greene, J. E.

1991-01-01

The relaxation, diffusion, and annihilation of split and hexagonal interstitials resulting from 10 eV Si irradiation of (2x1)-terminated Si(100) are investigated. Molecular dynamics and quasidynamics simulations, utilizing the Tersoff many-body potential are used in the investigation. The interstitials are created in layers two through six, and stable atomic configurations and total potential energies are derived as a function of site symmetry and layer depth. The interstitial Si atoms are allowed to diffuse, and the total potential energy changes are calculated. Lattice configurations along each path, as well as the starting configurations, are relaxed, and minimum energy diffusion paths are derived. The results show that the minimum energy paths are toward the surface and generally involved tetrahedral sites. The calculated interstitial migration activation energies are always less than 1.4 eV and are much lower in the near-surface region than in the bulk.

Aminopolymer Mobility and Support Interactions in Silica-PEI Composites for CO 2 Capture Applications: A Quasielastic Neutron Scattering Study

DOE PAGES

Holewinski, Adam; Sakwa-Novak, Miles A.; Carrillo, Jan-Michael Y.; ...

2017-05-30

Composite gas sorbents, formed from an active polymer phase and a porous support, are promising materials for the separation of acid gases from a variety of gas streams. Significant changes in sorption performance (capacity, rate, stability etc.) can be achieved by tuning the properties of the polymer and the nature of interactions between polymer and support. We utilize quasielastic neutron scattering (QENS) and coarse-grained molecular dynamics (MD) simulations to characterize the dynamic behavior of the most commonly reported polymer in such materials, poly(ethylenimine) (PEI), both in bulk form and when supported in a mesoporous silica framework. The polymer chain dynamicsmore » (rotational and translational diffusion) are characterized using two neutron backscattering spectrometers that have overlapping time scales, ranging from picoseconds to a few nanoseconds. Two modes of motion are detected for the PEI molecule in QENS. At low energy transfers, a “slow process” on the time scale of ~200 ps is found and attributed to jump-mediated, center-of-mass diffusion. Second, a “fast process” at ~20 ps scale is also found and is attributed to a locally confined, jump-diffusion. Characteristic data (time scale and spectral weight) of these processes are compared to those characterized by MD, and reasonable agreement is found. For the nanopore-confined PEI, we observe a significant reduction in the time scale of polymer motion as compared to the bulk. The impacts of silica surface functionalization and of polymer fill fraction in the silica pores (controlling the portion of polymer molecules in contact with the pore walls), are both studied in detail. Hydrophobic functionalization of the silica leads to an increase of the PEI mobility above that in native silanol-terminated silica, but the dynamics are still slower than those in bulk PEI. Sorbents with faster PEI dynamics are also found to be more efficient for CO 2 capture, possibly because sorption sites are more accessible than those in systems with slower PEI dynamics. Therefore, this work supports the existence of a link between the affinity of the support for PEI and the accessibility of active sorbent functional groups.« less

Biologically tunable reactivity of energetic nanomaterials using protein cages.

PubMed

Slocik, Joseph M; Crouse, Christopher A; Spowart, Jonathan E; Naik, Rajesh R

2013-06-12

The performance of aluminum nanomaterial based energetic formulations is dependent on the mass transport, diffusion distance, and stability of reactive components. Here we use a biologically inspired approach to direct the assembly of oxidizer loaded protein cages onto the surface of aluminum nanoparticles to improve reaction kinetics by reducing the diffusion distance between the reactants. Ferritin protein cages were loaded with ammonium perchlorate (AP) or iron oxide and assembled with nAl to create an oxidation-reduction based energetic reaction and the first demonstration of a nanoscale biobased thermite material. Both materials showed enhanced exothermic behavior in comparison to nanothermite mixtures of bulk free AP or synthesized iron oxide nanopowders prepared without the use of ferritin. In addition, by utilizing a layer-by-layer (LbL) process to build multiple layers of protein cages containing iron oxide and iron oxide/AP on nAl, stoichiometric conditions and energetic performance can be optimized.

Statistical mechanics of an ideal active fluid confined in a channel

NASA Astrophysics Data System (ADS)

Wagner, Caleb; Baskaran, Aparna; Hagan, Michael

The statistical mechanics of ideal active Brownian particles (ABPs) confined in a channel is studied by obtaining the exact solution of the steady-state Smoluchowski equation for the 1-particle distribution function. The solution is derived using results from the theory of two-way diffusion equations, combined with an iterative procedure that is justified by numerical results. Using this solution, we quantify the effects of confinement on the spatial and orientational order of the ensemble. Moreover, we rigorously show that both the bulk density and the fraction of particles on the channel walls obey simple scaling relations as a function of channel width. By considering a constant-flux steady state, an effective diffusivity for ABPs is derived which shows signatures of the persistent motion that characterizes ABP trajectories. Finally, we discuss how our techniques generalize to other active models, including systems whose activity is modeled in terms of an Ornstein-Uhlenbeck process.

The behaviour of tributyl phosphate in an organic diluent

NASA Astrophysics Data System (ADS)

Leay, Laura; Tucker, Kate; Del Regno, Annalaura; Schroeder, Sven L. M.; Sharrad, Clint A.; Masters, Andrew J.

2014-09-01

Tributyl phosphate (TBP) is used as a complexing agent in the Plutonium Uranium Extraction (PUREX) liquid-liquid phase extraction process for recovering uranium and plutonium from spent nuclear reactor fuel. Here, we address the molecular and microstructure of the organic phases involved in the extraction process, using molecular dynamics to show that when TBP is mixed with a paraffinic diluent, the TBP self-assembles into a bi-continuous phase. The underlying self-association of TBP is driven by intermolecular interaction between its polar groups, resulting in butyl moieties radiating out into the organic solvent. Simulation predicts a TBP diffusion constant that is anomalously low compared to what might normally be expected for its size; experimental nuclear magnetic resonance (NMR) studies also indicate an extremely low diffusion constant, consistent with a molecular aggregation model. Simulation of TBP at an oil/water interface shows the formation of a bilayer system at low TBP concentrations. At higher concentrations, a bulk bi-continuous structure is observed linking to this surface bilayer. We suggest that this structure may be intimately connected with the surprisingly rapid kinetics of the interfacial mass transport of uranium and plutonium from the aqueous to the organic phase in the PUREX process.

Iterative absolute electroanalytical approach to characterization of bulk redox conducting systems.

PubMed

Lewera, Adam; Miecznikowski, Krzysztof; Chojak, Malgorzata; Makowski, Oktawian; Golimowski, Jerzy; Kulesza, Pawel J

2004-05-15

A novel electroanalytical approach is proposed here, and it is demonstrated with the direct and simultaneous determination of two unknowns: the concentration of redox sites and the apparent diffusion coefficient for charge propagation in a single crystal of dodecatungstophosphoric acid. This Keggin-type polyoxometalate serves as a model bulk redox conducting inorganic material for solid-state voltammetry. The system has been investigated using an ultramicrodisk working electrode in the absence of external liquid supporting electrolyte. The analytical method requires numerical solution of the combination of two equations in which the first one describes current (or charge) in a well-defined (either spherical or linear) diffusional regime and the second general equation describes chronoamperometric (or normal pulse voltammetric current) under mixed (linear-spherical) conditions. The iterative approach is based on successive approximations through calculation and minimizing the least-squares error function. The method is fairly universal, and in principle, it can be extended to the investigation of other bulk systems including sol-gel processed materials, redox melts, and solutions on condition that they are electroactive and well behaved, they contain redox centers at sufficiently high level, and a number of electrons for the redox reaction considered is known.

Estimation of CO2 diffusion coefficient at 0-10 cm depth in undisturbed and tilled soils

USDA-ARS?s Scientific Manuscript database

Diffusion coefficients (D) of CO2 at 0 – 10 cm layers in undisturbed and tilled soil conditions were estimated using Penman, Millington-Quirk, Ridgwell et al. (1999), Troeh et al., and Moldrup et al. models. Soil bulk density and volumetric soil water content ('v) at 0 – 10 cm were measured on April...

Persistent wind-induced enhancement of diffusive CO2 transport in a mountain forest snowpack

Treesearch

D. R. Bowling; W. J. Massman

2011-01-01

Diffusion dominates the transport of trace gases between soil and the atmosphere. Pressure gradients induced by atmospheric flow and wind interacting with topographical features cause a small but persistent bulk flow of air within soil or snow. This forcing, called pressure pumping or wind pumping, leads to a poorly quantified enhancement of gas transport beyond the...

Phosphorus ionization in silicon doped by self-assembled macromolecular monolayers

NASA Astrophysics Data System (ADS)

Wu, Haigang; Li, Ke; Gao, Xuejiao; Dan, Yaping

2017-10-01

Individual dopant atoms can be potentially controlled at large scale by the self-assembly of macromolecular dopant carriers. However, low concentration phosphorus dopants often suffer from a low ionization rate due to defects and impurities introduced by the carrier molecules. In this work, we demonstrated a nitrogen-free macromolecule doping technique and investigated the phosphorus ionization process by low temperature Hall effect measurements. It was found that the phosphorus dopants diffused into the silicon bulk are in nearly full ionization. However, the electrons ionized from the phosphorus dopants are mostly trapped by deep level defects that are likely carbon interstitials.

Morphological characterization of microspheres, films and implants prepared from poly(lactide-co-glycolide) and ABA triblock copolymers: is the erosion controlled by degradation, swelling or diffusion?

PubMed

Witt, C; Kissel, T

2001-05-01

Erosion of biodegradable parenteral delivery systems (PDS) based on ABA copolymers consisting of poly(L-lactide-co-glycolide) (PLGA) A-blocks attached to polyethylene oxide (PEO) B-blocks, or PLGA is important for the release of macromolecular drugs. The degradation behavior of four types of PDS, namely extruded rods, tablets, films and microspheres, was studied with respect to molecular weight, mass, polymer composition and shape and microstructure of the PDS. For each device the onset time of bulk erosion (t(on)) and the apparent rate of mass loss (k(app)) were calculated. In the case of PLGA, the t(on) was 16.2 days for microspheres, 19.2 days for films and 30.1 days for cylindrical implants and tablets. The k(app) was 0.04 days(-1) for microspheres, 0.09 days(-1) for films, 0.11 days(-1) for implants and 0.10 days(-1) for tablets. The degradation rates were in the same range irrespective of the geometry and the micrographs of eroding PDS demonstrated pore formation; therefore, a complex pore diffusion mechanism seems to control the erosion of PLGA devices. In contrast, PDS based on ABA copolymers showed swelling, followed by a parallel process of molecular weight degradation and polymer erosion, independent of the geometry. The contact angles of ABA films increased either with decreasing PEO content or with increasing chain length of the PEO B-blocks. In summary, the insertion of a hydrophilic B-block leads to an erosion controlled by degradation of ABA copolymers, whereas for PLGA a complex pore diffusion of degradation products controls the rate of bulk erosion.

Healing of polymer interfaces: Interfacial dynamics, entanglements, and strength

NASA Astrophysics Data System (ADS)

Ge, Ting; Robbins, Mark O.; Perahia, Dvora; Grest, Gary S.

2014-07-01

Self-healing of polymer films often takes place as the molecules diffuse across a damaged region, above their melting temperature. Using molecular dynamics simulations we probe the healing of polymer films and compare the results with those obtained for thermal welding of homopolymer slabs. These two processes differ from each other in their interfacial structure since damage leads to increased polydispersity and more short chains. A polymer sample was cut into two separate films that were then held together in the melt state. The recovery of the damaged film was followed as time elapsed and polymer molecules diffused across the interface. The mass uptake and formation of entanglements, as obtained from primitive path analysis, are extracted and correlated with the interfacial strength obtained from shear simulations. We find that the diffusion across the interface is significantly faster in the damaged film compared to welding because of the presence of short chains. Though interfacial entanglements increase more rapidly for the damaged films, a large fraction of these entanglements are near chain ends. As a result, the interfacial strength of the healing film increases more slowly than for welding. For both healing and welding, the interfacial strength saturates as the bulk entanglement density is recovered across the interface. However, the saturation strength of the damaged film is below the bulk strength for the polymer sample. At saturation, cut chains remain near the healing interface. They are less entangled and as a result they mechanically weaken the interface. Chain stiffness increases the density of entanglements, which increases the strength of the interface. Our results show that a few entanglements across the interface are sufficient to resist interfacial chain pullout and enhance the mechanical strength.

Limit theorems for Lévy walks in d dimensions: rare and bulk fluctuations

NASA Astrophysics Data System (ADS)

Fouxon, Itzhak; Denisov, Sergey; Zaburdaev, Vasily; Barkai, Eli

2017-04-01

We consider super-diffusive Lévy walks in d≥slant 2 dimensions when the duration of a single step, i.e. a ballistic motion performed by a walker, is governed by a power-law tailed distribution of infinite variance and finite mean. We demonstrate that the probability density function (PDF) of the coordinate of the random walker has two different scaling limits at large times. One limit describes the bulk of the PDF. It is the d-dimensional generalization of the one-dimensional Lévy distribution and is the counterpart of the central limit theorem (CLT) for random walks with finite dispersion. In contrast with the one-dimensional Lévy distribution and the CLT this distribution does not have a universal shape. The PDF reflects anisotropy of the single-step statistics however large the time is. The other scaling limit, the so-called ‘infinite density’, describes the tail of the PDF which determines second (dispersion) and higher moments of the PDF. This limit repeats the angular structure of the PDF of velocity in one step. A typical realization of the walk consists of anomalous diffusive motion (described by anisotropic d-dimensional Lévy distribution) interspersed with long ballistic flights (described by infinite density). The long flights are rare but due to them the coordinate increases so much that their contribution determines the dispersion. We illustrate the concept by considering two types of Lévy walks, with isotropic and anisotropic distributions of velocities. Furthermore, we show that for isotropic but otherwise arbitrary velocity distributions the d-dimensional process can be reduced to a one-dimensional Lévy walk. We briefly discuss the consequences of non-universality for the d  >  1 dimensional fractional diffusion equation, in particular the non-uniqueness of the fractional Laplacian.

Electro-fenton and photoelectro-fenton degradation of sulfanilic acid using a boron-doped diamond anode and an air diffusion cathode.

PubMed

El-Ghenymy, Abdellatif; Garrido, José Antonio; Centellas, Francesc; Arias, Conchita; Cabot, Pere Lluís; Rodríguez, Rosa María; Brillas, Enric

2012-04-05

The mineralization of sulfanilic acid has been studied by electro-Fenton (EF) and photoelectro-Fenton (PEF) reaction with UVA light using an undivided electrochemical cell with a boron-doped diamond (BDD) anode and an air diffusion cathode able to generate H(2)O(2). Organics were then oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton's reaction between generated H(2)O(2) and added Fe(2+). The UVA irradiation in PEF enhanced the production of hydroxyl radicals in the bulk, accelerating the removal of organics and photodecomposed intermediates like Fe(III)-carboxylate complexes. Partial decontamination of 1.39 mM sulfanilic acid solutions was achieved by EF until 100 mA cm(-2) at optimum conditions of 0.4 mM Fe(2+) and pH 3.0. The increase in current density and substrate content led to an almost total mineralization. In contrast, the PEF process was more powerful, yielding almost complete mineralization in less electrolysis time under comparable conditions. The kinetics for sulfanilic acid decay always followed a pseudo-first-order reaction. Hydroquinone and p-benzoquinone were detected as aromatic intermediates, whereas acetic, maleic, formic, oxalic, and oxamic acids were identified as generated carboxylic acids. NH(4)(+) ion was preferentially released in both treatments, along with NO(3)(-) ion in smaller proportion.

Temperature Dependence of Nonelectrolyte Permeation across Red Cell Membranes

PubMed Central

Galey, W. R.; Owen, J. D.; Solomon, A. K.

1973-01-01

The temperature dependence of permeation across human red cell membranes has been determined for a series of hydrophilic and lipophilic solutes, including urea and two methyl substituted derivatives, all the straight-chain amides from formamide through valeramide and the two isomers, isobutyramide and isovaleramide. The temperature coefficient for permeation by all the hydrophilic solutes is 12 kcal mol-1 or less, whereas that for all the lipophilic solutes is 19 kcal mol-1 or greater. This difference is consonant with the view that hydrophilic molecules cross the membrane by a path different from that taken by the lipophilic ones. The thermodynamic parameters associated with lipophile permeation have been studied in detail. ΔG is negative for adsorption of lipophilic amides onto an oil-water interface, whereas it is positive for transfer of the polar head from the aqueous medium to bulk lipid solvent. Application of absolute reaction rate theory makes it possible to make a clear distinction between diffusion across the water-red cell membrane interface and diffusion within the membrane. Diffusion coefficients and apparent activation enthalpies and entropies have been computed for each process. Transfer of the polar head from the solvent into the interface is characterized by ΔG ‡ = 0 kcal mol-1 and ΔS ‡ negative, whereas both of these parameters have large positive values for diffusion within the membrane. Diffusion within the membrane is similar to what is expected for diffusion through a highly associated viscous fluid. PMID:4708405

Dynamic surface tension and adsorption mechanism of surfactin biosurfactant at the air-water interface.

PubMed

Onaizi, Sagheer A

2018-03-01

The dynamic adsorption of the anionic biosurfactant, surfactin, at the air-water interface has been investigated in this work and compared to those of two synthetic surfactants: the anionic sodium dodecylbenzenesulfonate (SDBS) and the nonionic octaethylene glycol monotetradecyl ether (C 14 E 8 ). The results revealed that surfactin adsorption at the air-water interface is purely controlled by diffusion mechanism at the initial stage of the adsorption process (i.e., [Formula: see text]), but shifts towards a mixed diffusion-barrier mechanism when surface tension approaches equilibrium (i.e., [Formula: see text]) due to the development of an energy barrier for adsorption. Such energy barrier has been found to be a function of the surfactin bulk concentration (increases with increasing surfactin concentration) and it is estimated to be in the range of 1.8-9.5 kJ/mol. Interestingly, such a trend (pure diffusion-controlled mechanism at [Formula: see text] and mixed diffusion-barrier mechanism at [Formula: see text]) has been also observed for the nonionic C 14 E 8 surfactant. Unlike the pure diffusion-controlled mechanism of the initial surfactin adsorption, which was the case in the presence and the absence of the sodium ion (Na + ), SDBS showed a mixed diffusion-barrier controlled at both short and long time, with an energy barrier of 3.0-9.0 and 3.8-18.0 kJ/mol, respectively. Such finding highlights the nonionic-like adsorption mechanism of surfactin despite its negative charge.

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents

NASA Technical Reports Server (NTRS)

Jambon, A.; Zhang, Y.; Stolper, E. M.

1992-01-01

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

Experimental dehydration of natural obsidian and estimation of DH2O at low water contents.

PubMed

Jambon, A; Zhang, Y; Stolper, E M

1992-01-01

Water diffusion experiments were carried out by dehydrating rhyolitic obsidian from Valles Caldera (New Mexico, USA) at 510-980 degrees C. The starting glass wafers contained approximately 0.114 wt% total water, lower than any glasses previously investigated for water diffusion. Weight loss due to dehydration was measured as a function of experiment duration, which permits determination of mean bulk water diffusivity, mean Dw. These diffusivities are in the range of 2.6 to 18 X 10(-14) m2/s and can be fit with the following Arrhenius equation: ln mean Dw (m2/s) = -(25.10 +/- 1.29) - (46,480 +/- 11,400) (J/mol) / RT, except for two replicate runs at 510 degrees C which give mean Dw values much lower than that defined by the above equation. When interpreted according to a model of water speciation in which molecular H2O is the diffusing species with concentration-independent diffusivity while OH units do not contribute to the transport but react to provide H2O, the data (except for the 510 degrees C data) are in agreement with extrapolation from previous results and hence extend the previous data base and provide a test of the applicability of the model to very low water contents. Mean bulk water diffusivities are about two orders of magnitude less than molecular H2O diffusivities because the fraction of molecular H2O out of total water is very small at 0.114 wt% total water and less. The 510 degrees C experimental results can be interpreted as due to slow kinetics of OH to H2O interconversion at low temperatures.

Interface or bulk scattering in the semiclassical theory for spin valves

NASA Astrophysics Data System (ADS)

Wang, L.; McMahon, W. J.; Liu, B.; Wu, Y. H.; Chong, C. T.

2004-06-01

By taking into account spin asymmetries of the interface transmissions and the bulk mean free paths, we have treated pure interface, non-pure interface, bulk, and interface plus bulk scattering within the semiclassical Boltzmann theory. First, the optimizations of NOL (nano-oxide-layers) insertions in bottom, synthetic, and dual spin valves and the variations of the giant magnetoresistance (GMR) with the thickness of the free layer have been examined. For non-pure interface, bulk, and interface plus bulk scattering, qualitative trends of GMR versus NOL positions in spin valves are similar to each other. For pure interface scattering, there is no optimized NOL insertion positions and the blocking effect of the NOL inserted in the spacer remains effective as other three kinds of scattering. The GMR ratio for bulk scattering simply approaches zero when the free layer thickness becomes short; in contrast, for interface scattering or interface plus bulk scattering, the GMR ratio is nonzero at zero thickness of the free layer. Second, the relationships between GMR and specular and diffusive scattering have been explored. As far as specular reflection is concerned, our results imply that for a realistic bottom spin filter spin valve, Ta/NiFe/IrMn/CoFe/Cu/CoFe/Cu/Ta, roughness of the surfaces of Ta and the interfaces of Ta/NiFe, NiFe/IrMn, pinned layer/spacer, and spacer/free layer may lead to large GMR. We also find that the enhancement of GMR due to surface specular reflection is only a pure interface effect. The dependences of GMR on the specular transmissions roughly follow square relations. The trends of GMR against the spin-down diffusive scattering depend on the values of the spin-up transmission. Finally, impurity scattering was investigated and our semiclassical results are in qualitative agreement with the experiments and the quantum theory.

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

Nuclear spin warm up in bulk n -GaAs

NASA Astrophysics Data System (ADS)

Kotur, M.; Dzhioev, R. I.; Vladimirova, M.; Jouault, B.; Korenev, V. L.; Kavokin, K. V.

2016-08-01

We show that the spin-lattice relaxation in n -type insulating GaAs is dramatically accelerated at low magnetic fields. The origin of this effect, which cannot be explained in terms of well-known diffusion-limited hyperfine relaxation, is found in the quadrupole relaxation, induced by fluctuating donor charges. Therefore, quadrupole relaxation, which governs low field nuclear spin relaxation in semiconductor quantum dots, but was so far supposed to be harmless to bulk nuclei spins in the absence of optical pumping, can be studied and harnessed in the much simpler model environment of n -GaAs bulk crystal.

Mixed ionic and electronic conducting membranes for hydrogen generation and separation

NASA Astrophysics Data System (ADS)

Cui, Hengdong

Dense mixed ionic and electronic conducting (MIEC) membranes are receiving increasing attention due to their potential for application as gas separation membranes to separate oxygen from air. The objective of this work is to study a novel, chemically-assisted separation process that utilizes oxygen-ion and electron-conducting MIECs for generating and separating hydrogen from steam. This research aims at exploring new routes and materials for high-purity hydrogen production for use in fuel cells and hydrogen-based internal combustion (IC) engines. In this approach, hydrocarbon fuel such as methane is fed to one side of the membrane, while steam is fed to the other side. The MIEC membrane separation process involves steam dissociation and oxidation of the fuel. The oxygen ions formed as a result of steam dissociation are transported across the membrane in a coupled transport process with electrons being transported in the opposite direction. Upon reaching the fuel side of the membrane, the oxygen ions oxidize the hydrocarbon. This process results in hydrogen production on the steam side of the membrane. The oxygen partial pressure gradient across the membrane is the driving force for this process. In this work, a novel, dual-phase composite MIEC membrane system comprising of rare-earth doped ceria with high oxygen ion conductivity and donor-doped strontium titanate with high electronic conductivity were investigated. The chemical diffusion coefficient and surface exchange coefficient have been measured using the electrical conductivity relaxation (ECR) technique. These two parameters control the rate of oxygen permeation across the membrane. The permeation data have been fit with a kinetic model that incorporates oxygen surface exchange on two sides of the membrane and bulk transport of oxygen through the membrane. This material has higher bulk diffusion coefficient and surface exchange reaction rate compared to other known MIEC conductors under the process conditions of interest. Over 10 mumol·cm-2·s-1 (micromoles per square cm per second) of area specific hydrogen flux has been achieved employing a membrane of this material with thickness of 0.2 mm. This flux is several orders of magnitude higher than the hydrogen generation rates reported using other MIEC materials under similar operating conditions.

Predicting vertical phase segregation in polymer-fullerene bulk heterojunction solar cells by free energy analysis.

PubMed

Clark, Michael D; Jespersen, Michael L; Patel, Romesh J; Leever, Benjamin J

2013-06-12

Blends of poly(3-hexylthiophene) (P3HT) and C61-butyric acid methyl ester (PCBM) are widely used as a model system for bulk heterojunction active layers developed for solution-processable, flexible solar cells. In this work, vertical concentration profiles within the P3HT:PCBM active layer are predicted based on a thermodynamic analysis of the constituent materials and typical solvents. Surface energies of the active layer components and a common transport interlayer blend, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), are first extracted using contact angle measurements coupled with the acid-base model. From this data, intra- and interspecies interaction free energies are calculated, which reveal that the thermodynamically favored arrangement consists of a uniformly blended "bulk" structure capped with a P3HT-rich air interface and a slightly PCBM-rich buried interface. Although the "bulk" composition is solely determined by P3HT:PCBM ratio, composition near the buried interface is dependent on both the blend ratio and interaction free energy difference between solvated P3HT and PCBM deposition onto PEDOT:PSS. In contrast, the P3HT-rich overlayer is independent of processing conditions, allowing kinetic formation of a PCBM-rich sublayer during film casting due to limitations in long-range species diffusion. These thermodynamic calculations are experimentally validated by angle-resolved X-ray photoelectron spectroscopy (XPS) and low energy XPS depth profiling, which show that the actual composition profiles of the cast and annealed films closely match the predicted behavior. These experimentally derived profiles provide clear evidence that typical bulk heterojunction active layers are predominantly characterized by thermodynamically stable composition profiles. Furthermore, the predictive capabilities of the comprehensive free energy approach are demonstrated, which will enable investigation of structurally integrated devices and novel active layer systems including low band gap polymers, ternary systems, and small molecule blends.

Plasma-gun-assisted field-reversed configuration formation in a conical θ-pinch

NASA Astrophysics Data System (ADS)

Weber, T. E.; Intrator, T. P.; Smith, R. J.

2015-04-01

Injection of plasma via an annular array of coaxial plasma guns during the pre-ionization phase of field-reversed configuration (FRC) formation is shown to catalyze the bulk ionization of a neutral gas prefill in the presence of a strong axial magnetic field and change the character of outward flux flow during field-reversal from a convective process to a much slower resistive diffusion process. This approach has been found to significantly improve FRC formation in a conical θ-pinch, resulting in a ˜350% increase in trapped flux at typical operating conditions, an expansion of accessible formation parameter space to lower densities and higher temperatures, and a reduction or elimination of several deleterious effects associated with the pre-ionization phase.

Polymer diffusion in the interphase between surface and solution.

PubMed

Weger, Lukas; Weidmann, Monika; Ali, Wael; Hildebrandt, Marcus; Gutmann, Jochen Stefan; Hoffmann-Jacobsen, Kerstin

2018-05-22

Total internal reflection fluorescence correlation spectroscopy (TIR-FCS) is applied to study the self-diffusion of polyethylene glycol solutions in the presence of weakly attractive interfaces. Glass coverslips modified with aminopropyl- and propyl-terminated silanes are used to study the influence of solid surfaces on polymer diffusion. A model of three phases of polymer diffusion allows to describe the experimental fluorescence autocorrelation functions. Besides the two-dimensional diffusion of adsorbed polymer on the substrate and three-dimensional free diffusion in bulk solution, a third diffusion time scale is observed with intermediate diffusion times. This retarded three-dimensional diffusion in solution is assigned to long range effects of solid surfaces on diffusional dynamics of polymers. The respective diffusion constants show Rouse scaling (D~N -1 ) indicating a screening of hydrodynamic interactions by the presence of the surface. Hence, the presented TIR-FCS method proves to be a valuable tool to investigate the effect of surfaces on polymer diffusion beyond the first adsorbed polymer layer on the 100 nm length scale.

Structural relaxation driven increase in elastic modulus for a bulk metallic glass

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

Arora, Harpreet Singh; Aditya, Ayyagari V.; Mukherjee, Sundeep, E-mail: sundeep.mukherjee@unt.edu

2015-01-07

The change in elastic modulus as a function of temperature was investigated for a zirconium-based bulk metallic glass. High temperature nano-indentation was done over a wide temperature range from room temperature to the glass-transition. At higher temperature, there was a transition from inhomogeneous to homogeneous deformation, with a decrease in serrated flow and an increase in creep displacement. Hardness was found to decrease, whereas elastic modulus was found to increase with temperature. The increase in elastic modulus for metallic glass at higher temperature was explained by diffusive rearrangement of atoms resulting in free volume annihilation. This is in contrast tomore » elastic modulus increase with temperature for silicate glasses due to compaction of its open three dimensional coordinated structure without any atomic diffusion.« less

Kinetics of DNA-mediated docking reactions between vesicles tethered to supported lipid bilayers

PubMed Central

Chan, Yee-Hung M.; Lenz, Peter; Boxer, Steven G.

2007-01-01

Membrane–membrane recognition and binding are crucial in many biological processes. We report an approach to studying the dynamics of such reactions by using DNA-tethered vesicles as a general scaffold for displaying membrane components. This system was used to characterize the docking reaction between two populations of tethered vesicles that display complementary DNA. Deposition of vesicles onto a supported lipid bilayer was performed by using a microfluidic device to prevent mixing of the vesicles in bulk during sample preparation. Once tethered onto the surface, vesicles mixed via two-dimensional diffusion. DNA-mediated docking of two reacting vesicles results in their colocalization after collision and their subsequent tandem motion. Individual docking events and population kinetics were observed via epifluorescence microscopy. A lattice-diffusion simulation was implemented to extract from experimental data the probability, Pdock, that a collision leads to docking. For individual vesicles displaying small numbers of docking DNA, Pdock shows a first-order relationship with copy number as well as a strong dependence on the DNA sequence. Both trends are explained by a model that includes both tethered vesicle diffusion on the supported bilayer and docking DNA diffusion over each vesicle's surface. These results provide the basis for the application of tethered vesicles to study other membrane reactions including protein-mediated docking and fusion. PMID:18025472

Dopants Diffusion in Silicon during Molecular Oxygen/nitrogen Trifluoride Oxidation and Related Phenomena

NASA Astrophysics Data System (ADS)

Kim, U. S.

1990-01-01

To date, chlorine has been used as useful additives in silicon oxidation. However, rapid scaling of device dimensions motivates the development of a new dielectric layer or modification of the silicon dioxide itself. More recently, chemically enhanced thermal oxidation by the use of fluorine containing species has been introduced to verify the potential of fluorine in the silicon oxidation process. In this study, gaseous nitrogen trifluoride (NF _3) was selected as the fluorine oxidizing source based on ease of use and was compared with the dichlorofluoroethane (C_2H _3Cl_2F) source. Two different kinds of boron marker samples were prepared and oxidized in O_2/NF_3 ambient for the comparison of surface vs bulk oxidation enhanced/retarded diffusion (OED/ORD). The phosphorus, arsenic and antimony diffusion in silicon during fluorine oxidation has been studied using the various covering layers such as SiO_2, Si_3 N_4, and SiO_2 + Si_3N_4 layers. The oxidation related phenomena, i.e. enhanced silicon and silicon nitride oxidation in fluorine ambient were studied and correlated with the point defect balance at the oxidizing interface. The results of this investigation were discussed with special emphasis on the effect of fluorine on enhanced oxidation and dopant diffusion.

Acceleration of metal-atom diffusion in electric field at metal/insulator interfaces: First-principles study

NASA Astrophysics Data System (ADS)

Nagasawa, Riki; Asayama, Yoshihiro; Nakayama, Takashi

2018-04-01

Metal-atom diffusion from metal electrodes into SiO2 in electric fields was studied using first-principles calculations. It was shown in the case without electric field that the diffusion barrier of a metal atom is mainly made of the cohesive energy of bulk metal layers, while the shape of the diffusion potential reflects the hybridization of the metal-atom state with metal-induced gap states (MIGSs) and the electron transfer between the metal atom and the electrode. We found that the metal-atom diffusion is markedly accelerated by the applied electric field, such that the diffusion barrier ϕB(E) decreases almost linearly with increasing electric field strength E. By analyzing the physical origins of the metal-atom diffusion, we derived the universal formula to estimate the diffusion barrier in the electric field, which is closely related to MIGSs.

Influence of moisture content and temperature on thermal conductivity and thermal diffusivity of rice flours

USDA-ARS?s Scientific Manuscript database

The thermal conductivity and thermal diffusivity of four types of rice flours and one type of rice protein were determine at temperatures ranging from 4.8 to 36.8 C, bulk densities 535 to 875.8 kg/m3, and moisture contents 2.6 to 16.7 percent (w.b.), using a KD2 Thermal Properties Analyzer. It was ...

Interfacial reactions between metal and gallium arsenide

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

Lin, J.C.; Schulz, K.J.; Hsieh, K.C.

1989-10-01

The phase formation sequence for GaAs/metal ternary diffusion couples is discussed. The diffusion path concept is introduced and is used with the phase diagram to understand interfacial reactions between GaAs and metal. The correlation between growth kinetics and interface morphology is discussed. Studies of bulk and thin film couples in two systems, GaAs/Pd and GaAs/Pt, are given to illustrate these concepts.

Microscale anechoic architecture: acoustic diffusers for ultra low power microparticle separation via traveling surface acoustic waves.

PubMed

Behrens, Jan; Langelier, Sean; Rezk, Amgad R; Lindner, Gerhard; Yeo, Leslie Y; Friend, James R

2015-01-07

We present a versatile and very low-power traveling SAW microfluidic sorting device able to displace and separate particles of different diameter in aqueous suspension; the travelling wave propagates through the fluid bulk and diffuses via a Schröder diffuser, adapted from its typical use in concert hall acoustics to be the smallest such diffuser to be suitable for microfluidics. The effective operating power range is two to three orders of magnitude less than current SAW devices, uniquely eliminating the need for amplifiers, and by using traveling waves to impart forces directly upon suspended microparticles, they can be separated by size.

A fully coupled 3D transport model in SPH for multi-species reaction-diffusion systems

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

Adami, Stefan; Hu, X. Y.; Adams, N. A.

2011-08-23

Abstract—In this paper we present a fully generalized transport model for multiple species in complex two and threedimensional geometries. Based on previous work [1] we have extended our interfacial reaction-diffusion model to handle arbitrary numbers of species allowing for coupled reaction models. Each species is tracked independently and we consider different physics of a species with respect to the bulk phases in contact. We use our SPH model to simulate the reaction-diffusion problem on a pore-scale level of a solid oxide fuel cell (SOFC) with special emphasize on the effect of surface diffusion.

An Alternative Hypothesis for How Microgravity Improves Macromolecular Crystal Quality

NASA Technical Reports Server (NTRS)

Pusey, Marc

2003-01-01

There is a substantial body of experimental evidence, from this and other laboratories, that strongly suggests that for many proteins crystal nucleation and growth is by addition of associated species that are preformed by reversible concentration-driven self association processes in the bulk solution. We have developed a self-association model for the crystal nucleation and growth of the protein chicken egg lysozyme. The model accounts for the obtained crystal symmetry, explains the observed surface structures, and shows the importance of the symmetry obtained by self-association in solution to the process as a whole. This model also offers a possible mechanism for fluid flow effects on the growth process and how microgravity may affect it. While a single lysozyme molecule is relatively small an octamer in the 43 helix configuration (the proposed average sized growth unit) would have a M.W. approx. 115,000 and dimensions of 5.6 x 5.6 x 7.6 nm. Direct AFM measurements of growth unit incorporation indicate that units as wide as 11.2 nm and as long as 11.4 nm (a 24-mer) commonly attach to the crystal. AFM results from Weichmann et al. (Ultramicroscopy 86, 159-166, 2001) suggest that associated species of up to 40-mers in size add to the (101) faces. These measurements reflect the sizes of units that both added and desorbed from the crystal surface. The larger and less isotropic the associated species the more likely that it will be oriented to some degree in a flowing boundary layer, even at the low flow velocities measured about macromolecule crystals. On Earth, concentration gradient driven flow will maintain a high interfacial concentration, i.e., a high level (essentially that of the bulk solution) of solute association at the interface and higher growth rate. Higher growth rates mean an increased probability that misaligned growth units are trapped by subsequent growth layers before they can be desorbed and try again, or that the desorbing species is more likely to be smaller than the adsorbing species. In microgravity the extended diffusive boundary layer will lower the interfacial concentration. This results in a net dissociation of aggregated species that diffuse in from the bulk solution, i.e., smaller associated species, which are more likely able to make multiple attempts to correctly bind, yielding higher quality crystals.

Vapour-Phase Processes Control Liquid-Phase Isotope Profiles in Unsaturated Sphagnum Moss

NASA Astrophysics Data System (ADS)

Edwards, T. W.; Yi, Y.; Price, J. S.; Whittington, P. N.

2009-05-01

Seminal work in the early 1980s clearly established the basis for predicting patterns of heavy-isotope enrichment of pore waters in soils undergoing evaporation. A key feature of the process under steady-state conditions is the development of stable, convex-upward profiles whose shape is controlled by the balance between downward-diffusing heavy isotopologues concentrated by evaporative enrichment at the surface and the upward capillary flow of bulk water that maintains the evaporative flux. We conducted an analogous experiment to probe evaporation processes within 20-cm columns of unsaturated, living and dead (but undecomposed) Sphagnum moss evaporating under controlled conditions, while maintaining a constant water table. The experiment provided striking evidence of the importance of vapour-liquid mass and isotope exchange in the air-filled pores of the Sphagnum columns, as evidenced by the rapid development of hydrologic and isotopic steady-state within hours, rather than days, i.e., an order of magnitude faster than possible by liquid-phase processes alone. This is consistent with the notion that vapour-phase processes effectively "short-circuit" mass and isotope fluxes within the Sphagnum columns, as proposed also in recent characterizations of water dynamics in transpiring leaves. Additionally, advection-diffusion modelling of our results supports independent estimates of the effective liquid-phase diffusivities of the respective heavy water isotopologues, 2.380 x 10-5 cm2 s-1 for 1H1H18O and 2.415 x 10-5 cm2 s-1 for 1H2H16O, which are in notably good agreement with the "default" values that are typically assumed in soil and plant water studies.

Effect of dead layer and strain on diffuse phase transition of PLZT relaxor thin films.

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

Tong, S.; Narayanan, M.; Ma, B.

2011-02-01

Bulk relaxor ferroelectrics exhibit excellent permittivity compared to their thin film counterpart, although both show diffuse phase transition (DPT) behavior unlike normal ferroelectrics. To better understand the effect of dead layer and strain on the observed anomaly in the dielectric properties, we have developed relaxor PLZT (lead lanthanum zirconate titanate) thin films with different thicknesses and measured their dielectric properties as a function of temperature and frequency. The effect of dead layer on thin film permittivity has been found to be independent of temperature and frequency, and is governed by the Schottky barrier between the platinum electrode and PLZT. Themore » total strain (thermal and intrinsic) in the film majorly determines the broadening, dielectric peak and temperature shift in the relaxor ferroelectric. The Curie-Weiss type law for relaxors has been further modified to incorporate these two effects to accurately predict the DPT behavior of thin film and bulk relaxor ferroelectrics. The dielectric behavior of thin film is predicted by using the bulk dielectric data from literature in the proposed equation, which agree well with the measured dielectric behavior.« less

Calibration-free concentration analysis for an analyte prone to self-association.

PubMed

Imamura, Hiroshi; Honda, Shinya

2017-01-01

Calibration-free concentration analysis (CFCA) based on surface plasmon resonance uses the diffusion coefficient of an analyte to determine the concentration of that analyte in a bulk solution. In general, CFCA is avoided when investigating analytes prone to self-association, as the heterogeneous diffusion coefficient results in a loss of precision. The derivation for self-association of the analyte was presented here. By using the diffusion coefficient for the monomeric state, CFCA provides the lowest possible concentration even though the analyte is self-associated. Copyright © 2016 Elsevier Inc. All rights reserved.

Particle-size segregation and diffusive remixing in shallow granular avalanches

NASA Astrophysics Data System (ADS)

Gray, J. M. N. T.; Chugunov, V. A.

2006-12-01

Segregation and mixing of dissimilar grains is a problem in many industrial and pharmaceutical processes, as well as in hazardous geophysical flows, where the size-distribution can have a major impact on the local rheology and the overall run-out. In this paper, a simple binary mixture theory is used to formulate a model for particle-size segregation and diffusive remixing of large and small particles in shallow gravity-driven free-surface flows. This builds on a recent theory for the process of kinetic sieving, which is the dominant mechanism for segregation in granular avalanches provided the density-ratio and the size-ratio of the particles are not too large. The resulting nonlinear parabolic segregation remixing equation reduces to a quasi-linear hyperbolic equation in the no-remixing limit. It assumes that the bulk velocity is incompressible and that the bulk pressure is lithostatic, making it compatible with most theories used to compute the motion of shallow granular free-surface flows. In steady-state, the segregation remixing equation reduces to a logistic type equation and the ‘S’-shaped solutions are in very good agreement with existing particle dynamics simulations for both size and density segregation. Laterally uniform time-dependent solutions are constructed by mapping the segregation remixing equation to Burgers equation and using the Cole Hopf transformation to linearize the problem. It is then shown how solutions for arbitrary initial conditions can be constructed using standard methods. Three examples are investigated in which the initial concentration is (i) homogeneous, (ii) reverse graded with the coarse grains above the fines, and, (iii) normally graded with the fines above the coarse grains. Time-dependent two-dimensional solutions are also constructed for plug-flow in a semi-infinite chute.

Crystallization process of a three-dimensional complex plasma

NASA Astrophysics Data System (ADS)

Steinmüller, Benjamin; Dietz, Christopher; Kretschmer, Michael; Thoma, Markus H.

2018-05-01

Characteristic timescales and length scales for phase transitions of real materials are in ranges where a direct visualization is unfeasible. Therefore, model systems can be useful. Here, the crystallization process of a three-dimensional complex plasma under gravity conditions is considered where the system ranges up to a large extent into the bulk plasma. Time-resolved measurements exhibit the process down to a single-particle level. Primary clusters, consisting of particles in the solid state, grow vertically and, secondarily, horizontally. The box-counting method shows a fractal dimension of df≈2.72 for the clusters. This value gives a hint that the formation process is a combination of local epitaxial and diffusion-limited growth. The particle density and the interparticle distance to the nearest neighbor remain constant within the clusters during crystallization. All results are in good agreement with former observations of a single-particle layer.

Shear-Assisted Production of Few-Layer Boron Nitride Nanosheets by Supercritical CO2 Exfoliation and Its Use for Thermally Conductive Epoxy Composites.

PubMed

Tian, Xiaojuan; Li, Yun; Chen, Zhuo; Li, Qi; Hou, Liqiang; Wu, Jiaye; Tang, Yushu; Li, Yongfeng

2017-12-19

Boron nitride nanosheets (BNNS) hold the similar two-dimensional structure as graphene and unique properties complementary to graphene, which makes it attractive in application ranging from electronics to energy storage. The exfoliation of boron nitride (BN) still remains challenge and hinders the applications of BNNS. In this work, the preparation of BNNS has been realized by a shear-assisted supercritical CO 2 exfoliation process, during which supercritical CO 2 intercalates and diffuses between boron nitride layers, and then the exfoliation of BN layers is obtained in the rapid depressurization process by overcoming the van der Waals forces. Our results indicate that the bulk boron nitride has been successfully exfoliated into thin nanosheets with an average 6 layers. It is found that the produced BNNS is well-dispersed in isopropyl alcohol (IPA) with a higher extinction coefficient compared with the bulk BN. Moreover, the BNNS/epoxy composite used as thermal interface materials has been prepared. The introduction of BNNS results in a 313% enhancement in thermal conductivity. Our results demonstrate that BNNS produced by supercritical CO 2 exfoliation show great potential applications for heat dissipation of high efficiency electronics.

Novel method for minority-carrier mobility measurement using photoconductance decay with chemically passivated and plasma damaged surfaces

NASA Astrophysics Data System (ADS)

Stephens, A. W.; Green, M. A.

1996-10-01

A method for measuring minority-carrier mobility using microwave-detected photoconductance decay without requiring bulk lifetime, estimates is presented. Three different measurements on a single sample yield values for surface recombination velocity, bulk lifetime, and diffusivity. For each measurement the surface conditions of the sample are changed, allowing extraction of different parameters. The usefulness of 0.08 molar ethanol/iodine solution as a means of achieving such good surface passivation is demonstrated. The following procedure was used to achieve high surface recombination. A CF4 plasma surface etch was shown to achieve the same level of surface damage as mechanical abrasion. The advantage of the new method is that it completely eliminates the chance of breaking samples during the abrasion process, which is of particular advantage for thin samples. The new experimental method for minority-carrier mobility measurement is evaluated using carrier lifetime measurements made on a commercially available Leo Giken ``Wafer-τ'' lifetime tester.

Particle-based modeling of heterogeneous chemical kinetics including mass transfer.

PubMed

Sengar, A; Kuipers, J A M; van Santen, Rutger A; Padding, J T

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

Particle-based modeling of heterogeneous chemical kinetics including mass transfer

NASA Astrophysics Data System (ADS)

Sengar, A.; Kuipers, J. A. M.; van Santen, Rutger A.; Padding, J. T.

2017-08-01

Connecting the macroscopic world of continuous fields to the microscopic world of discrete molecular events is important for understanding several phenomena occurring at physical boundaries of systems. An important example is heterogeneous catalysis, where reactions take place at active surfaces, but the effective reaction rates are determined by transport limitations in the bulk fluid and reaction limitations on the catalyst surface. In this work we study the macro-micro connection in a model heterogeneous catalytic reactor by means of stochastic rotation dynamics. The model is able to resolve the convective and diffusive interplay between participating species, while including adsorption, desorption, and reaction processes on the catalytic surface. Here we apply the simulation methodology to a simple straight microchannel with a catalytic strip. Dimensionless Damkohler numbers are used to comment on the spatial concentration profiles of reactants and products near the catalyst strip and in the bulk. We end the discussion with an outlook on more complicated geometries and increasingly complex reactions.

Effect of gold nanoparticles on structure and dynamics of binary Lennard-Jones liquid: direct space analysis.

PubMed

Separdar, L; Davatolhagh, S

2013-02-01

We investigate the static structure and diffusive dynamics of binary Lennard-Jones mixture upon supercooling in the presence of gold nanoparticle within the framework of the mode-coupling theory of the dynamic glass transition in the direct space by means of constant-NVT molecular dynamics simulations. It is found that the presence of gold nanoparticle causes the energy per particle and the pressure of this system to decrease with respect to the bulk binary Lennard-Jones mixture. Furthermore, the presence of nanoparticle has a direct effect on the liquid structure and causes the peaks of the radial distribution functions to become shorter with respect to the bulk binary Lennard-Jones liquid. The dynamics of the liquid at a given density is found to be consistent with the mode-coupling theory (MCT) predictions in a certain range at low temperatures. In accordance with the idealized MCT, the diffusion constants D(T) show a power-law behavior at low temperatures for both types of binary Lennard-Jones (BLJ) particles as well as the gold atoms comprising the nanoparticle. The mode-coupling crossover temperature T(c) is the same for all particle types; however, T(c)=0.4 is reduced with respect to that of the bulk BLJ liquid, and the γ exponent is found to depend on the particle type. The existence of the nanoparticle causes the short-time β-relaxation regime to shorten and the range of validity of the MCT shrinks with respect to the bulk BLJ. It is also found that at intermediate and low temperatures the curves of the mean-squared displacements (MSDs) versus tD(T) fall onto a master curve. The MSDs follow the master curve in an identical time range with the long-time α-relaxation regime of the mode-coupling theory. By obtaining the viscosity, it is observed that the Stokes-Einstein relation remains valid at high and intermediate temperatures but breaks down as the temperatures approach T(c) as a result of the cooperative motion or activated processes.

High-precision measurements of the compressibility of chalcogenide glasses at a hydrostatic pressure up to 9 GPa

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

Brazhkin, V. V., E-mail: brazhkin@hppi.troitsk.ru; Bychkov, E.; Tsiok, O. B.

2016-08-15

The volumes of glassy germanium chalcogenides GeSe{sub 2}, GeS{sub 2}, Ge{sub 17}Se{sub 83}, and Ge{sub 8}Se{sub 92} are precisely measured at a hydrostatic pressure up to 8.5 GPa. The stoichiometric GeSe{sub 2} and GeS{sub 2} glasses exhibit elastic behavior in the pressure range up to 3 GPa, and their bulk modulus decreases at pressures higher than 2–2.5 GPa. At higher pressures, inelastic relaxation processes begin and their intensity is proportional to the logarithm of time. The relaxation rate for the GeSe{sub 2} glasses has a pronounced maximum at 3.5–4.5 GPa, which indicates the existence of several parallel structural transformation mechanisms.more » The nonstoichiometric glasses exhibit a diffuse transformation and inelastic behavior at pressures above 1–2 GPa. The maximum relaxation rate in these glasses is significantly lower than that in the stoichiometric GeSe{sub 2} glasses. All glasses are characterized by the “loss of memory” of history: after relaxation at a fixed pressure, the further increase in the pressure returns the volume to the compression curve obtained without a stop for relaxation. After pressure release, the residual densification in the stoichiometric glasses is about 7% and that in the Ge{sub 17}Se{sub 83} glasses is 1.5%. The volume of the Ge{sub 8}Se{sub 92} glass returns to its initial value within the limits of experimental error. As the pressure decreases, the effective bulk moduli of the Ge{sub 17}Se{sub 83} and Ge{sub 8}Se{sub 92} glasses coincide with the moduli after isobaric relaxation at the stage of increasing pressure, and the bulk modulus of the stoichiometric GeSe{sub 2} glass upon decreasing pressure noticeably exceeds the bulk modulus after isobaric relaxation at the stage of increasing pressure. Along with the reported data, our results can be used to draw conclusions regarding the diffuse transformations in glassy germanium chalcogenides during compression.« less

Kinetic multi-layer model of the epithelial lining fluid (KM-ELF): Reactions of ozone and OH with antioxidants and surfactant molecules

NASA Astrophysics Data System (ADS)

Lakey, Pascale; Pöschl, Ulrich; Shiraiwa, Manabu

2015-04-01

Oxidants cause damage to biosurfaces such as the lung epithelium unless they are effectively scavenged. The respiratory tract is covered in a thin layer of fluid which extends from the nasal cavity to the alveoli and contain species that scavenge ozone and other incoming oxidants. The kinetic multi-layer model of the epithelial lining fluid (KM-ELF) has been developed in order to investigate the reactions of ozone and OH with antioxidants (ascorbate, uric acid, glutathione and α-tocopherol) and surfactant lipids and proteins within the epithelial lining fluid (ELF). The model incorporates different processes: gas phase diffusion, adsorption and desorption from the surface, bulk phase diffusion and known reactions at the surface and in the bulk. The ELF is split into many layers: a sorption layer, a surfactant layer, a near surface bulk layer and several bulk layers. Initial results using KM-ELF indicate that at ELF thicknesses of 80 nm and 1 × 10-4cm the ELF would become rapidly saturated with ozone with saturation occurring in less than a second. However, at an ELF thickness of 1 × 10-3cm concentration gradients were observed throughout the ELF and the presence of antioxidants reduced the O3 reaching the lung cells and tissues by 40% after 1 hour of exposure. In contrast, the antioxidants were efficient scavengers of OH radicals, although the large rate constants of OH reacting with the antioxidants resulted in the antioxidants decaying away rapidly. The chemical half-lives of the antioxidants and surface species were also calculated using KM-ELF as a function of O3 and OH concentration and ELF thickness. Finally, the pH dependence of the products of reactions between antioxidants and O3 were investigated. The KM-ELF model predicted that a harmful ascorbate ozonide product would increase from 1.4 × 1011cm-3at pH 7.4 to 1.1 × 1014 cm-3 at pH 4after 1 hour although a uric acid ozonide product would decrease from 2.0 × 1015cm-3to 5.9 × 1012cm-3.

Understanding the Effect of Na in Improving the Performance of CuInSe 2 Based Photovoltaics

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

Dobson, Kevin D.

Cu(In,Ga)Se 2 (CIGS) thin film photovoltaic technology is in the early stages of commercialization with an annual manufacturing capacity over 1 GW and has demonstrated the highest module efficiency of any of the thin film technologies. However there still is a lack of fundamental understanding of the relationship between the material properties and solar cell device operation. It is well known that the incorporation of a small amount of Na into the CIGS film during processing is essential for high efficiency devices. However, there are conflicting explanations for how Na behaves at the atomic scale. This report investigates how Namore » is incorporated into the CIGS device structure and evaluates the diffusion of Na into CIGS grain boundaries (GBs) and bulk crystallites. Participants: This project was carried out at the Institute of Energy Conversion at the University of Delaware, collaborating with the Rockett group at the University of Illinois Urbana-Champagne. Significant Findings: The significant outcomes of this project for each task include; Task 1.0: Effect of Na in Devices Fabricated on PVD Deposited CIGS; Na diffusion occurs through the Mo back contact via GBs driven by the presence of oxygen; Na reversibly compensates donor defects in CIGS GBs,Task 2.0: Na Incorporation in Single Crystal CIGS; and bulk Na diffusion proceeds rapidly such that grains are Na-saturated immediately following CIGS thin film manufacture. Industry Guidance: The presented results offer interesting concepts for modification of manufacturing processes of CIGS-based PV modules. Possible approaches to improve control of Na uptake and uniformly increase levels in CIGS films are highlighted for processes that employ either soda-lime glass or NaF as the Na source. Concepts include the potential of O 2 or oxidative based treatments of Mo back contacts to improve Na diffusion through the metal film and increase Na uptake into the growing CIGS. This project has also offered fundamental understanding of the behavior of Na in CIGS grains and GBs, particularly the confirmation that CIGS grains will be saturated with Na immediately following manufacture Summary of Results: Most commercially available CIGS modules are fabricated on soda-lime glass coated with Mo as the back electric contact, and Na in the glass diffuses through the Mo layer into the CIGS during film growth. In Task 1 the transport of Na through Mo was evaluated using x-ray photoelectron surface spectroscopy along with diffusion modeling to obtain diffusion coefficients at several temperatures. It was determined that Na diffusion in Mo only occurs along GBs and that oxygen provides an additional driving force to enhance Na transport. Device data revealed that older Mo substrates with a greater amount of surface oxide resulted in slightly higher efficiencies due to enhanced Na incorporation caused by the oxide. This finding shows that Mo substrates could potentially undergo an oxidation treatment prior to CIGS deposition to further improve and control the incorporation of Na. To determine if in-grain Na affects device performance, in Task 1 Na was selectively removed from GBs using heat/rinse cycles. Due to the low temperature of this treatment, Na at GBS remained mobile while diffusion within the bulk was too slow for Na removal from the grain interiors. Changes in electrical properties were evaluated using conductivity and Seebeck coefficient measurements, with both decreasing as Na was removed to reach values similar to Na-free controls samples. This can be explained by the compensation of donor defects by Na, causing an increase in the free carrier concentration. Devices showed a decrease in open-circuit voltage after Na removal confirming that the beneficial effects of GB Na. The findings of this project will provide guidance for rational optimization of Na incorporation procedures in the manufacturing of CIGS solar cells. While it is known that Na segregates at CIGS GBs, the nature and role of Na diffusion into grain interiors was less clear. In Task 2, single crystal CuInSe 2 was used as a model system to represent the grain interiors of CIGS. Crystals processed by two different methods of different compositions and dislocation densities, were evaluated. Diffusion coefficients were obtained at two temperatures after Na diffusion, giving near identical values, ~2x10 11 cm 2/s and ~6x10 11 cm2/s at 420°C and 480°C, respectively, for each crystal. Characterization confirmed that dislocation densities were too low to significantly impact the effective diffusion coefficient. The Cu-poor crystal had a higher solubility suggesting that Na diffusion is mediated by Cu-vacancies, but was not accompanied by an expected increase in diffusion coefficient. The activation energy for diffusion was similar to values expected for interstitial diffusion, but the large size of Na + ions should result in a solubility that is much lower than what was experimentally measured. A hybrid interstitial-substitutional mechanism is proposed that combines the fast diffusion of interstitial atoms with the high solubility common for substitutional impurities. Lattice diffusion of Na proceeds fast enough that CIGS grain interiors will have Na concentrations near the solubility limit of 1018 cm -3 when manufactured under standard conditions. Na and K treated epitaxial CIS films showed a significant increase in cathodoluminescence emission intensity, indicating a reduction of non-radiative recombination pathways, which is consistent with improvements in CIGS device performance, though the mechanism is not clear. Pathways forward: Despite the success of this project, there are a number of questions remaining related to further the understanding of the chemistry of Na in CIGS films and devices. These include further elucidation of the mechanisms of Na passivation in CIGS GBs, with identification of which defects are involved and confirmation of the possible effects of in-grain Na on device performance. To complete analysis of the cell structure, conformation of the presence and possible chemistries of Na at the CIGS/CdS junction and/or in the front transparent contacts, and its effects on device performance, is needed.« less

Mapping Ionic Currents and Reactivity on the Nanoscale: Electrochemical Strain Microscopy

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

Kalinin, S.V.

2010-10-19

Solid-state electrochemical processes in oxides underpin a broad spectrum of energy and information storage devices, ranging from Li-ion and Li-air batteries, to solid oxide fuel cells (SOFC) to electroresistive and memristive systems. These functionalities are controlled by the bias-driven diffusive and electromigration transport of mobile ionic species, as well as intricate a set of electrochemical and defect-controlled reactions at interfaces and in bulk. Despite the wealth of device-level and atomistic studies, little is known on the mesoscopic mechanisms of ion diffusion and electronic transport on the level of grain clusters, individual grains, and extended defects. The development of the capabilitymore » for probing ion transport on the nanometer scale is a key to deciphering complex interplay between structure, functionality, and performance in these systems. Here we introduce Electrochemical Strain Microscopy, a scanning probe microscopy technique based on strong strain-bias coupling in the systems in which local ion concentrations are changed by electrical fields. The imaging capability, as well as time- and voltage spectroscopies analogous to traditional current based electrochemical characterization methods are developed. The reversible intercalation of Li and mapping electrochemical activity in LiCoO2 is demonstrated, illustrating higher Li diffusivity at non-basal planes and grain boundaries. In Si-anode device structure, the direct mapping of Li diffusion at extended defects and evolution of Li-activity with charge state is explored. The electrical field-dependence of Li mobility is studied to determine the critical bias required for the onset of electrochemical transformation, allowing reaction and diffusion processes in the battery system to be separated at each location. Finally, the applicability of ESM for probing oxygen vacancy diffusion and oxygen reduction/evolution reactions is illustrated, and the high resolution ESM maps are correlated with aberration corrected scanning transmission electron microscopy imaging. The future potential for deciphering mechanisms of electrochemical transformations on an atomically-defined single-defect level is discussed.« less

Stress studies in edge-defined film-fed growth of silicon ribbons

NASA Technical Reports Server (NTRS)

Kalejs, J.

1985-01-01

Stress and efficiency studies on sheet silicon are reported. It was found that the bulk diffusion length of stressed float zone and Czochralski silicon is limited by point defect recombination to about 20 micrometers in dislocation free regions after high temperature heat treatment and stress application. If in-diffusion by iron occurs, dislocations, carbon and oxygen, do not produce significant gettering with annealing. Further work ideas are suggested.

Solutions for the diurnally forced advection-diffusion equation to estimate bulk fluid velocity and diffusivity in streambeds from temperature time series

Treesearch

Charles H. Luce; Daniele Tonina; Frank Gariglio; Ralph Applebee

2013-01-01

Work over the last decade has documented methods for estimating fluxes between streams and streambeds from time series of temperature at two depths in the streambed. We present substantial extension to the existing theory and practice of using temperature time series to estimate streambed water fluxes and thermal properties, including (1) a new explicit analytical...

A novel approach to interpretation of the time-dependent self-diffusion coefficient as a probe of porous media geometry.

PubMed

Loskutov, V V; Sevriugin, V A

2013-05-01

This article presents a new approximation describing fluid diffusion in porous media. Time dependence of the self-diffusion coefficient D(t) in the permeable porous medium is studied based on the assumption that diffusant molecules move randomly. An analytical expression for time dependence of the self-diffusion coefficient was obtained in the following form: D(t)=(D0-D∞)exp(-D0t/λ)+D∞, where D0 is the self-diffusion coefficient of bulk fluid, D∞ is the asymptotic value of the self-diffusion coefficient in the limit of long time values (t→∞), λ is the characteristic parameter of this porous medium with dimensionality of length. Applicability of the solution obtained to the analysis of experimental data is shown. The possibility of passing to short-time and long-time regimes is discussed. Copyright © 2013 Elsevier Inc. All rights reserved.

Modulation of Crystal Surface and Lattice by Doping: Achieving Ultrafast Metal-Ion Insertion in Anatase TiO2.

PubMed

Wang, Hsin-Yi; Chen, Han-Yi; Hsu, Ying-Ya; Stimming, Ulrich; Chen, Hao Ming; Liu, Bin

2016-10-26

We report that an ultrafast kinetics of reversible metal-ion insertion can be realized in anatase titanium dioxide (TiO 2 ). Niobium ions (Nb 5+ ) were carefully chosen to dope and drive anatase TiO 2 into very thin nanosheets standing perpendicularly onto transparent conductive electrode (TCE) and simultaneously construct TiO 2 with an ion-conducting surface together with expanded ion diffusion channels, which enabled ultrafast metal ions to diffuse across the electrolyte/solid interface and into the bulk of TiO 2 . To demonstrate the superior metal-ion insertion rate, the electrochromic features induced by ion intercalation were examined, which exhibited the best color switching speed of 4.82 s for coloration and 0.91 s for bleaching among all reported nanosized TiO 2 devices. When performed as the anode for the secondary battery, the modified TiO 2 was capable to deliver a highly reversible capacity of 61.2 mAh/g at an ultrahigh specific current rate of 60 C (10.2 A/g). This fast metal-ion insertion behavior was systematically investigated by the well-controlled electrochemical approaches, which quantitatively revealed both the enhanced surface kinetics and bulk ion diffusion rate. Our study could provide a facile methodology to modulate the ion diffusion kinetics for metal oxides.

Combined effects of the drug distribution and mucus diffusion properties of self-microemulsifying drug delivery systems on the oral absorption of fenofibrate.

PubMed

Sunazuka, Yushi; Ueda, Keisuke; Higashi, Kenjirou; Tanaka, Yusuke; Moribe, Kunikazu

2018-05-24

We present the absorption improvement mechanism of fenofibrate (FFB), a Biopharmaceutics Classification System (BCS) class II drug, from self-microemulsifying drug delivery systems (SMEDDS), centered on improving the diffusion of FFB through the unstirred water layer (UWL). Four SMEDDS formulations containing Labrafac™ lipophile WL 1349 (WL1349) or Labrafil ® M 1944CS (M1944) oils and NIKKOL HCO-40 (HCO40) or NIKKOL HCO-60 (HCO60) surfactants were prepared. Every SMEDDS formulation formed microemulsion droplets of approximately 30 nm. In vitro tests showed that the microemulsion droplets containing M1944 had relatively small FFB solubilization capacities, causing larger amounts of FFB to be dissolved in the bulk water phase, compared to the droplets containing WL1349. The diffusivity of the microemulsion droplets through the mucin solution layer was enhanced when using HCO40 compared to HCO60. The oral absorption in rats was the highest when using the SMEDDS formulation containing M1944 and HCO40. High FFB distribution in the bulk water phase and fast diffusion of microemulsion droplets through the mucus layer contributed to the efficient delivery of FFB molecules through the UWL to the epithelial cells, leading to enhanced FFB absorption. Copyright © 2018 Elsevier B.V. All rights reserved.

Diffusion weighted imaging: a comprehensive evaluation of a fast spin echo DWI sequence with BLADE (PROPELLER) k-space sampling at 3 T, using a 32-channel head coil in acute brain ischemia.

PubMed

Attenberger, Ulrike I; Runge, Val M; Stemmer, Alto; Williams, Kenneth D; Naul, L Gill; Michaely, Henrik J; Schoenberg, Stefan O; Reiser, Maximilian F; Wintersperger, Bernd J

2009-10-01

To evaluate the signal-to-noise ratio (SNR) and diagnostic quality of diffusion weighted imaging (DWI) using a fast spin echo (FSE) sequence with BLADE k-space trajectory at 3 T in combination with a 32-channel head coil. The scan was compared with a standard spin echo (SE) echo-planar imaging (EPI) DWI and a high resolution SE EPI DWI sequence. Fourteen patients with acute brain ischemia were included in this Institutional Review Board approved study. All patients were evaluated with 3 different image sequences, using a 3 T scanner and a 32-channel head coil: (a) a standard SE EPI DWI (matrix size 192 x 192), (b) a high resolution SE EPI DWI (matrix size of 256 x 256) and (c) a FSE DWI BLADE (matrix size 192 x 192). The SNR of the 3 scans was compared in 10 healthy volunteers by a paired student t test. Image quality was evaluated with 4 dedicated questions in a blinded read: (1) The scans were ranked in terms of bulk susceptibility artifact. (2) The scan preference for diagnosis of any diffusion abnormality that might occur and (3) the preference for visualization of the diffusion abnormality actually present was determined. (4) The influence of bulk susceptibility on image evaluation for the diffusion abnormality present was assessed. For visualization of the diffusion abnormality present, BLADE DWI was the scan sequence preferred most by both readers (reader 1: 41.7%, reader 2: 35.7%). For visualization of any diffusion abnormality present, BLADE DWI was the preferred scan in 13 of 14 cases for reader 1 (93%) and in 11 of 14 cases for reader 2 (78.6%). No high resolution SE EPI DWI scan was rated best by reader 1. Reader 2 rated the high resolution SE EPI DWI scan superior in only 1 of 56 judgments. The standard EPI DWI sequence (21.8 +/- 5.3) had in comparison to the high resolution EPI DWI (11.9 +/- 2.6) and the BLADE DWI scans (11.3 +/- 3.8) significantly higher SNR mean values. Our preliminary data demonstrates the feasibility of a FSE EPI DWI scan with radial-like k-space sampling, using a 32-channel coil at 3 T in acute brain ischemia. The BLADE DWI was the preferred scan for the detection of acute diffusion abnormalities because of the lack of bulk susceptibility artifacts.

C Diffusion in Fe: Isotope Effects and Other Complexities

NASA Astrophysics Data System (ADS)

Watson, E. B.; Muller, T.; Trail, D.; Van Orman, J. A.; Papineau, D.

2011-12-01

Carbon is a minor but significant component of iron meteorites, and probably also of planetary cores, including that of Earth. Given the dynamical nature of core-forming processes, C diffusion in the metal phase may play a role in C equilibration between Fe-Ni metal and silicate, carbide or oxide at some stage. Despite its relevance to steel-making, C diffusion in Fe is not well characterized over the range of conditions of interest in planetary bodies, and the likelihood of an isotope mass effect on C diffusion has not been explored. The prospect of incomplete diffusive equilibration of carbon in Fe-Ni raises the possibility that carbon isotopes might be fractionated by diffusion during core formation and evolution-perhaps to an extent that could affect the C isotope ratio of the bulk silicate Earth. Here we report results of preliminary experiments addressing the isotopic mass effect on C diffusion in Fe. Initial low-pressure experiments were conducted by placing a layer of ^{13}C-enriched graphite ( 20% ^{13}C) at the end of a high-purity, polycrystalline Fe cylinder in a silica glass container. These diffusion couples were run in a piston-cylinder apparatus at 1.5 GPa and 1000-1100^{o}C for several hours, and the resulting C-uptake profiles in the Fe cylinders were measured by EPMA and SIMS. In traverses moving away from the original C-Fe interface, total carbon decreases monotonically and becomes significantly lighter, indicating that ^{12}C diffuses faster than ^{13}C. Preliminary estimates of β in the relative isotope diffusivity relation D_{1}/D_{2} = [M_{2}/M_{1}]^{β} (where D is diffusivity and M is mass of isotopes 1 and 2) suggest values as high as 0.5, corresponding to predictions for gaseous diffusion. Isotope mass effects approaching this magnitude have been observed previously for diffusion in metals, and are expected to be highest for interstitial diffusion. Such a high β value will lead to major C isotope fractionation in some partial equilibration scenarios in planets and meteorite parent bodies. Caution is warranted at this point, however, because D_{carbon} is sensitive to carbon concentration, complicating quantification of the isotope effect.

Electrolyte transport in neutral polymer gels embedded with charged inclusions

NASA Astrophysics Data System (ADS)

Hill, Reghan

2005-11-01

Ion permeable membranes are the basis of a variety of molecular separation technologies, including ion exchange, gel electrophoresis and dialysis. This work presents a theoretical model of electrolyte transport in membranes comprised of a continuous polymer gel embedded with charged spherical inclusions, e.g., biological cells and synthetic colloids. The microstructure mimics immobilized cell cultures, where electric fields have been used to promote nutrient transport. Because several important characteristics can, in principle, be carefully controlled, the theory provides a quantitative framework to help tailor the bulk properties for enhanced molecular transport, microfluidic pumping, and physicochemical sensing applications. This talk focuses on the electroosmotic flow driven by weak electric fields and electrolyte concentration gradients. Also of importance is the influence of charge on the effective ion diffusion coefficients, bulk electrical conductivity, and membrane diffusion potential.

Investigation on Explosive Welding of Zr53Cu35Al12 Bulk Metallic Glass with Crystalline Copper

NASA Astrophysics Data System (ADS)

Feng, Jianrui; Chen, Pengwan; Zhou, Qiang

2018-05-01

A Zr53Cu35Al12 bulk metallic glass (BMG) was welded to a crystalline Cu using explosive welding technique. The morphology and the composition of the composite were characterized using optical microscopy, scanning electron microscopy, energy-dispersive x-ray spectroscopy and transmission electron microscopy. The investigation indicated that the BMG and Cu were tightly joined together without visible defects, and a thin diffusion layer appeared at the interface. The captured jet at the end of the welding region mostly comes from the Cu side. Amorphous and partially crystallized structures have been observed within the diffusion layer, but the BMG in close proximity to the interface still retains its amorphous state. Nanoindentation tests reveal that the interface exhibits an increment in hardness compared with the matrix on both sides.

Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

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

Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.

2016-07-28

Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relativemore » to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.« less

Phototransformation Rate Constants of PAHs Associated with Soot Particles

PubMed Central

Kim, Daekyun; Young, Thomas M.; Anastasio, Cort

2013-01-01

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k0p), the effective diffusion coefficients (Deff), and the light penetration depths (z0.5) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z0.5 is more sensitive to the soot layer thickness than the k0p value. As the thickness of the soot layer increases, the z0.5 values increase, but the k0p values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k0p and z0.5 in thinner layers, Deff should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. PMID:23247292

Production of Open Cell Bulk Metallic Glass Foam Structures via Electromechanical Forming

DTIC Science & Technology

2011-07-20

brazing of aluminium alloys using liquid gallium (UKpatent application 0128623.6). Science and Technology of Welding and Joining, 2003. 8(2): p. 149-153...interface approaches V2 the bulk strength of the alloy . Recent efforts have focused on varying the stress state at the interface in order to evaluate...gallium surface treatments have shown promise in the successful diffusion bonding of aluminum alloys and stainless steel alloys [1]. However, in the

Reconstructing thermal properties of firn at Summit, Greenland from a temperature profile

NASA Astrophysics Data System (ADS)

Giese, A. L.; Hawley, R. L.

2013-12-01

Thermodynamic properties of firn are important factors when considering energy balance and temperature-dependent physical processes in the near-surface of glaciers. Of particular interest is thermal diffusivity, which can take a range of values and which governs both the temperature gradient and its evolution through time. Given that temperature is a well-established driver of firn densification, a better understanding of heat transfer will permit greater accuracy in the compaction models essential for interpreting inter-annual and seasonal ice surface elevation changes detected by airborne and satellite altimetry. Due to its dependence on microstructure, diffusivity can vary significantly by location. Rather than directly measuring diffusivity or one of its proxies (e.g. density, hardness, shear strength), this study inverts the heat equation to reconstruct diffusivity values. This is a less logistically-intensive approach which circumvents many of the challenges associated with imperfect proxies and snow metamorphism during measurement. Hourly records (May 2004 - July 2008) from 8 thermistors placed in the top 10 m at Summit, Greenland provide temperature values for Summit's firn, which is broadly representative of firn across the ice sheet's dry snow zone. In this study, we use both physical analysis and a finite-difference numerical model to determine a diffusivity magnitude and gradient; we find that diffusivity of Summit firn falls in the lower end of the range expected from local density and temperature conditions alone (i.e. 15 - 36 m^2/a for firn at -30C). Further, we assess the utility of our modeling approach, explore the validity of assuming bulk conductive heat transfer when modeling temperature changes in non-homogeneous firn, and investigate the implications of a low-end diffusivity value for surface compaction modeling in Greenland.

Numerical simulation of artificial microswimmers driven by Marangoni flow

NASA Astrophysics Data System (ADS)

Stricker, L.

2017-10-01

In the present paper the behavior of a single artificial microswimmer is addressed, namely an active droplet moving by Marangoni flow. We provide a numerical treatment for the main factors playing a role in real systems, such as advection, diffusion and the presence of chemical species with different behaviors. The flow field inside and outside the droplet is modeled to account for the two-way coupling between the surrounding fluid and the motion of the swimmer. Mass diffusion is also taken into account. In particular, we consider two concentration fields: the surfactant concentration in the bulk, i.e. in the liquid surrounding the droplet, and the surfactant concentration on the surface. The latter is related to the local surface tension, through an equation of state (Langmuir equation). We examine different interaction mechanisms between the bulk and the surface concentration fields, namely the case of insoluble surfactants attached to the surface (no exchange between the bulk and the surface) and soluble surfactants with adsorption/desorption at the surface. We also consider the case where the bulk concentration field is in equilibrium with the content of the droplet. The numerical results are validated through comparison with analytical calculations. We show that our model can reproduce the typical pusher/puller behavior presented by squirmers. It is also able to capture the self-propulsion mechanism of droplets driven by Belousov-Zhabotinsky (BZ) reactions, as well as a typical chemotactic behavior.

Nucleation of rotating crystals by Thiovulum majus bacteria

NASA Astrophysics Data System (ADS)

Petroff, A. P.; Libchaber, A.

2018-01-01

Thiovulum majus self-organize on glass surfaces into active two-dimensional crystals of rotating cells. Unlike classical crystals, these bacterial crystallites continuously rotate and reorganize as the power of rotating cells is dissipated by the surrounding flow. In this article, we describe the earliest stage of crystallization, the attraction of two bacteria into a hydrodynamically-bound dimer. This process occurs in three steps. First a free-swimming cell collides with the wall and becomes hydrodynamically bound to the two-dimensional surface. We present a simple model to understand how viscous forces localize cells near the chamber walls. Next, the cell diffuses over the surface for an average of 63+/- 6 s before escaping to the bulk fluid. The diffusion coefficient {D}{{eff}}=7.98 +/- 0.1 μ {{{m}}}2 {{{s}}}-1 of these 8.5 μ {{m}} diameter cells corresponds to a temperature of (4.16+/- 0.05)× {10}4 K, and thus cannot be explained by equilibrium fluctuations. Finally, two cells coalesce into a rotating dimer when the convergent flow created by each cell overwhelms their active Brownian motion. This occurs when cells diffuse to within a distance of 13.3 ± 0.2 μm of each other.

Connecting the Kinetics and Energy Landscape of tRNA Translocation on the Ribosome

PubMed Central

Whitford, Paul C.; Blanchard, Scott C.; Cate, Jamie H. D.; Sanbonmatsu, Karissa Y.

2013-01-01

Functional rearrangements in biomolecular assemblies result from diffusion across an underlying energy landscape. While bulk kinetic measurements rely on discrete state-like approximations to the energy landscape, single-molecule methods can project the free energy onto specific coordinates. With measures of the diffusion, one may establish a quantitative bridge between state-like kinetic measurements and the continuous energy landscape. We used an all-atom molecular dynamics simulation of the 70S ribosome (2.1 million atoms; 1.3 microseconds) to provide this bridge for specific conformational events associated with the process of tRNA translocation. Starting from a pre-translocation configuration, we identified sets of residues that collectively undergo rotary rearrangements implicated in ribosome function. Estimates of the diffusion coefficients along these collective coordinates for translocation were then used to interconvert between experimental rates and measures of the energy landscape. This analysis, in conjunction with previously reported experimental rates of translocation, provides an upper-bound estimate of the free-energy barriers associated with translocation. While this analysis was performed for a particular kinetic scheme of translocation, the quantitative framework is general and may be applied to energetic and kinetic descriptions that include any number of intermediates and transition states. PMID:23555233

Connecting the kinetics and energy landscape of tRNA translocation on the ribosome.

PubMed

Whitford, Paul C; Blanchard, Scott C; Cate, Jamie H D; Sanbonmatsu, Karissa Y

2013-01-01

Functional rearrangements in biomolecular assemblies result from diffusion across an underlying energy landscape. While bulk kinetic measurements rely on discrete state-like approximations to the energy landscape, single-molecule methods can project the free energy onto specific coordinates. With measures of the diffusion, one may establish a quantitative bridge between state-like kinetic measurements and the continuous energy landscape. We used an all-atom molecular dynamics simulation of the 70S ribosome (2.1 million atoms; 1.3 microseconds) to provide this bridge for specific conformational events associated with the process of tRNA translocation. Starting from a pre-translocation configuration, we identified sets of residues that collectively undergo rotary rearrangements implicated in ribosome function. Estimates of the diffusion coefficients along these collective coordinates for translocation were then used to interconvert between experimental rates and measures of the energy landscape. This analysis, in conjunction with previously reported experimental rates of translocation, provides an upper-bound estimate of the free-energy barriers associated with translocation. While this analysis was performed for a particular kinetic scheme of translocation, the quantitative framework is general and may be applied to energetic and kinetic descriptions that include any number of intermediates and transition states.

Plasma-gun-assisted field-reversed configuration formation in a conical θ-pinch

DOE PAGES

Weber, T. E.; Intrator, T. P.; Smith, R. J.

2015-04-29

We show through injection of plasma via an annular array of coaxial plasma guns, during the pre-ionization phase of field-reversed configuration (FRC) formation how to catalyze the bulk ionization of a neutral gas prefill in the presence of a strong axial magnetic field and change the character of outward flux flow during field-reversal from a convective process to a much slower resistive diffusion process. Our approach has been found to significantly improve FRC formation in a conical θ-pinch, resulting in a ~350% increase in trapped flux at typical operating conditions, an expansion of accessible formation parameter space to lower densitiesmore » and higher temperatures, and a reduction or elimination of several deleterious effects associated with the pre-ionization phase.« less

Effect of oxygen on dislocation multiplication in silicon crystals

NASA Astrophysics Data System (ADS)

Fukushima, Wataru; Harada, Hirofumi; Miyamura, Yoshiji; Imai, Masato; Nakano, Satoshi; Kakimoto, Koichi

2018-03-01

This paper aims to clarify the effect of oxygen on dislocation multiplication in silicon single crystals grown by the Czochralski and floating zone methods using numerical analysis. The analysis is based on the Alexander-Haasen-Sumino model and involves oxygen diffusion from the bulk to the dislocation cores during the annealing process in a furnace. The results show that after the annealing process, the dislocation density in silicon single crystals decreases as a function of oxygen concentration. This decrease can be explained by considering the unlocking stress caused by interstitial oxygen atoms. When the oxygen concentration is 7.5 × 1017 cm-3, the total stress is about 2 MPa and the unlocking stress is less than 1 MPa. As the oxygen concentration increases, the unlocking stress also increases; however, the dislocation velocity decreases.

Plasma-gun-assisted field-reversed configuration formation in a conical θ-pinch

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

Weber, T. E., E-mail: tweber@lanl.gov; Intrator, T. P.; Smith, R. J.

2015-04-15

Injection of plasma via an annular array of coaxial plasma guns during the pre-ionization phase of field-reversed configuration (FRC) formation is shown to catalyze the bulk ionization of a neutral gas prefill in the presence of a strong axial magnetic field and change the character of outward flux flow during field-reversal from a convective process to a much slower resistive diffusion process. This approach has been found to significantly improve FRC formation in a conical θ-pinch, resulting in a ∼350% increase in trapped flux at typical operating conditions, an expansion of accessible formation parameter space to lower densities and highermore » temperatures, and a reduction or elimination of several deleterious effects associated with the pre-ionization phase.« less

CdCl2 passivation of polycrystalline CdMgTe and CdZnTe absorbers for tandem photovoltaic cells

NASA Astrophysics Data System (ADS)

Swanson, Drew E.; Reich, Carey; Abbas, Ali; Shimpi, Tushar; Liu, Hanxiao; Ponce, Fernando A.; Walls, John M.; Zhang, Yong-Hang; Metzger, Wyatt K.; Sampath, W. S.; Holman, Zachary C.

2018-05-01

As single-junction silicon solar cells approach their theoretical limits, tandems provide the primary path to higher efficiencies. CdTe alloys can be tuned with magnesium (CdMgTe) or zinc (CdZnTe) for ideal tandem pairing with silicon. A II-VI/Si tandem holds the greatest promise for inexpensive, high-efficiency top cells that can be quickly deployed in the market using existing polycrystalline CdTe manufacturing lines combined with mature silicon production lines. Currently, all high efficiency polycrystalline CdTe cells require a chloride-based passivation process to passivate grain boundaries and bulk defects. This research examines the rich chemistry and physics that has historically limited performance when extending Cl treatments to polycrystalline 1.7-eV CdMgTe and CdZnTe absorbers. A combination of transmittance, quantum efficiency, photoluminescence, transmission electron microscopy, and energy-dispersive X-ray spectroscopy clearly reveals that during passivation, Mg segregates and out-diffuses, initially at the grain boundaries but eventually throughout the bulk. CdZnTe exhibits similar Zn segregation behavior; however, the onset and progression is localized to the back of the device. After passivation, CdMgTe and CdZnTe can render a layer that is reduced to predominantly CdTe electro-optical behavior. Contact instabilities caused by inter-diffusion between the layers create additional complications. The results outline critical issues and paths for these materials to be successfully implemented in Si-based tandems and other applications.

Effect of Annealing on Exciton Diffusion in a High Performance Small Molecule Organic Photovoltaic Material.

PubMed

Long, Yun; Hedley, Gordon J; Ruseckas, Arvydas; Chowdhury, Mithun; Roland, Thomas; Serrano, Luis A; Cooke, Graeme; Samuel, Ifor D W

2017-05-03

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh 2 ) 2 . Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton-exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10 -3 to 3.6 × 10 -3 cm 2 s -1 , resulting in an enhancement of the mean two-dimensional exciton diffusion length (L D = (4Dτ) 1/2 ) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions.

Effect of Annealing on Exciton Diffusion in a High Performance Small Molecule Organic Photovoltaic Material

PubMed Central

2017-01-01

Singlet exciton diffusion was studied in the efficient organic photovoltaic electron donor material DTS(FBTTh2)2. Three complementary time-resolved fluorescence measurements were performed: quenching in planar heterojunctions with an electron acceptor, exciton–exciton annihilation, and fluorescence depolarization. The average exciton diffusivity increases upon annealing from 1.6 × 10–3 to 3.6 × 10–3 cm2 s–1, resulting in an enhancement of the mean two-dimensional exciton diffusion length (LD = (4Dτ)1/2) from 15 to 27 nm. About 30% of the excitons get trapped very quickly in as-cast films. The high exciton diffusion coefficient of the material leads to it being able to harvest excitons efficiently from large donor domains in bulk heterojunctions. PMID:28358189

Thermal diffusivity of diamond nanowires studied by laser assisted atom probe tomography

NASA Astrophysics Data System (ADS)

Arnoldi, L.; Spies, M.; Houard, J.; Blum, I.; Etienne, A.; Ismagilov, R.; Obraztsov, A.; Vella, A.

2018-04-01

The thermal properties of single-crystal diamond nanowires (NWs) have been calculated from first principles but have never been measured experimentally. Taking advantage of the sharp geometry of samples analyzed in a laser assisted atom probe, this technique is used to measure the thermal diffusivity of a single NW at low temperature (<300 K). The obtained value is in good agreement with the ab-initio calculations and confirms that thermal diffusivity in nanoscale samples is lower than in bulk samples. The results impact the design and integration of diamond NWs and nanoneedles in nanoscale devices for heat dissipation.

Diffusion of multi-isotopic chemical species in molten silicates

NASA Astrophysics Data System (ADS)

Watkins, James M.; Liang, Yan; Richter, Frank; Ryerson, Frederick J.; DePaolo, Donald J.

2014-08-01

Diffusion experiments in a simplified Na2O-CaO-SiO2 liquid system are used to develop a general formulation for the fractionation of Ca isotopes during liquid-phase diffusion. Although chemical diffusion is a well-studied process, the mathematical description of the effects of diffusion on the separate isotopes of a chemical element is surprisingly underdeveloped and uncertain. Kinetic theory predicts a mass dependence on isotopic mobility, but it is unknown how this translates into a mass dependence on effective binary diffusion coefficients, or more generally, the chemical diffusion coefficients that are housed in a multicomponent diffusion matrix. Our experiments are designed to measure Ca mobility, effective binary diffusion coefficients, the multicomponent diffusion matrix, and the effects of chemical diffusion on Ca isotopes in a liquid of single composition. We carried out two chemical diffusion experiments and one self-diffusion experiment, all at 1250 °C and 0.7 GPa and using a bulk composition for which other information is available from the literature. The self-diffusion experiment is used to determine the mobility of Ca in the absence of diffusive fluxes of other liquid components. The chemical diffusion experiments are designed to determine the effect on Ca isotope fractionation of changing the counter-diffusing component from fast-diffusing Na2O to slow-diffusing SiO2. When Na2O is the main counter-diffusing species, CaO diffusion is fast and larger Ca isotopic effects are generated. When SiO2 is the main counter-diffusing species, CaO diffusion is slow and smaller Ca isotopic effects are observed. In both experiments, the liquid is initially isotopically homogeneous, and during the experiment Ca isotopes become fractionated by diffusion. The results are used as a test of a new general expression for the diffusion of isotopes in a multicomponent liquid system that accounts for both self diffusion and the effects of counter-diffusing species. Our results show that (1) diffusive isotopic fractionations depend on the direction of diffusion in composition space, (2) diffusive isotopic fractionations scale with effective binary diffusion coefficient, as previously noted by Watkins et al. (2011), (3) self-diffusion is not decoupled from chemical diffusion, (4) self diffusion can be faster than or slower than chemical diffusion and (5) off-diagonal terms in the chemical diffusion matrix have isotopic mass-dependence. The results imply that relatively large isotopic fractionations can be generated by multicomponent diffusion even in the absence of large concentration gradients of the diffusing element. The new formulations for isotope diffusion can be tested with further experimentation and provide an improved framework for interpreting mass-dependent isotopic variations in natural liquids.

Bulk diffusion in a kinetically constrained lattice gas

NASA Astrophysics Data System (ADS)

Arita, Chikashi; Krapivsky, P. L.; Mallick, Kirone

2018-03-01

In the hydrodynamic regime, the evolution of a stochastic lattice gas with symmetric hopping rules is described by a diffusion equation with density-dependent diffusion coefficient encapsulating all microscopic details of the dynamics. This diffusion coefficient is, in principle, determined by a Green-Kubo formula. In practice, even when the equilibrium properties of a lattice gas are analytically known, the diffusion coefficient cannot be computed except when a lattice gas additionally satisfies the gradient condition. We develop a procedure to systematically obtain analytical approximations for the diffusion coefficient for non-gradient lattice gases with known equilibrium. The method relies on a variational formula found by Varadhan and Spohn which is a version of the Green-Kubo formula particularly suitable for diffusive lattice gases. Restricting the variational formula to finite-dimensional sub-spaces allows one to perform the minimization and gives upper bounds for the diffusion coefficient. We apply this approach to a kinetically constrained non-gradient lattice gas in two dimensions, viz. to the Kob-Andersen model on the square lattice.

Diffusion mechanism in the sodium-ion battery material sodium cobaltate.

PubMed

Willis, T J; Porter, D G; Voneshen, D J; Uthayakumar, S; Demmel, F; Gutmann, M J; Roger, M; Refson, K; Goff, J P

2018-02-16

High performance batteries based on the movement of Li ions in Li x CoO 2 have made possible a revolution in mobile electronic technology, from laptops to mobile phones. However, the scarcity of Li and the demand for energy storage for renewables has led to intense interest in Na-ion batteries, including structurally-related Na x CoO 2 . Here we have determined the diffusion mechanism for Na 0.8 CoO 2 using diffuse x-ray scattering, quasi-elastic neutron scattering and ab-initio molecular dynamics simulations, and we find that the sodium ordering provides diffusion pathways and governs the diffusion rate. Above T ~ 290 K the so-called partially disordered stripe superstructure provides channels for quasi-1D diffusion, and melting of the sodium ordering leads to 2D superionic diffusion above T ~ 370 K. We obtain quantitative agreement between our microscopic study of the hopping mechanism and bulk self-diffusion measurements. Our approach can be applied widely to other Na- or Li-ion battery materials.

The photochemical trapping rate from red spectral states in PSI-LHCI is determined by thermal activation of energy transfer to bulk chlorophylls.

PubMed

Jennings, Robert C; Zucchelli, Giuseppe; Croce, Roberta; Garlaschi, Flavio M

2003-03-06

The average fluorescence decay lifetimes, due to reaction centre photochemical trapping, were calculated for wavelengths in the 690- to 770-nm interval from the published fluorescence decay-associated emission spectra for Photosystem I (PSI)-light-harvesting complex of Photosystem I (LHCI) [Biochemistry 39 (2000) 6341] at 280 and 170 K. For 280 K, the overall trapping time at 690 nm is 81 ps and increases with wavelength to reach 103 ps at 770 nm. For 170 K, the 690-nm value is 115 ps, increasing to 458 ps at 770 nm. This underlines the presence of kinetically limiting processes in the PSI antenna (diffusion limited). The explanation of these nonconstant values for the overall trapping time band is sought in terms of thermally activated transfer from the red absorbing states to the "bulk" acceptor chlorophyll (chl) states in the framework of the Arrhenius-Eyring theory. It is shown that the wavelength-dependent "activation energies" come out in the range between 1.35 and 2.7 kcal mol(-1), increasing with the emission wavelength within the interval 710-770 nm. These values are in good agreement with the Arrhenius activation energy determined for the steady-state fluorescence yield over the range 130-280 K for PSI-LHCI. We conclude that the variable trapping time in PSI-LHCI can be accounted for entirely by thermally activated transfer from the low-energy chl states to the bulk acceptor states and therefore that the position of the various red states in the PSI antenna seems not to be of significant importance. The analysis shows that the bulk antenna acceptor states are on the low-energy side of the bulk antenna absorption band.

Microdialysis of Soil P: A means to mimic root uptake?

NASA Astrophysics Data System (ADS)

Schack-Kirschner, Helmer; Demand, Dominic; Lang, Friederike

2017-04-01

Standard procedures to assess P availability in soils are based on batch experiments with various extractants. However, in most soils P nutrition is less limited by bulk stocks but by slow diffusion of phosphate through the soil solution. More comparable to the root's approach is to strip phosphate locally from the solid phase by lowering the soil-solution concentration, which can be achieved by establishing an infinite diffusional sink, such as DGT. An alternative diffusive sampling technique is microdialysis (MD), well established in pharmacokinetics. Briefly, this method uses miniaturized flow-through probes where the perfusate gets in diffusive contact to the external solution by a semipermeable membrane. Important aspects of P supply to roots resemble MD sampling. This is not only the mostly diffusive transport, but also an elongated capillary tube-like geometry of absorption. The diameter of typical commercial MD probes is around 500μm. One additional inherent feature of microdialysis is the possibility to release low-molecular substances from the perfusate by diffusion into the matrix, such as carboxylates. However, microdialysis has yet not been used for P in soils. We tested microdialysis in topsoils of an acid beech forest, of an unfertilized grassland and of a fertilized crop site. Three perfusates have been used: 1 mM KNO3, electrolyte + 0.1 mM citric acid, and electrolyte + 1 mM citric acid. We observed rates of uptake into the probes in a range between 1.5*10-15 and 6.7*10-14 mol s-1cm-1 in case of no citrate addition. Surprisingly, these uptake rates were mostly independent of the bulk stocks. Citrate addition increased P yields only in the higher concentration but not in the forest soil. The order of magnitude of MD uptake rates from the soil samples matched root-length related uptake rates from other studies. The micro-radial citrate release in MD reflects the processes controlling phosphate mobilization in the rhizosphere better than measurements based on "flooding" of soil samples with citric acid in batch experiments. Important challenges in MD with phosphate are small volumes of dialysate with extremely low concentrations and a high variability of results due to soil heterogeneity and between-probe variability. We conclude that MD is a promising tool to complement existing P-analytical procedures, especially when spatial aspects or the release of mobilizing substances are in focus.

Thin film solar cells grown by organic vapor phase deposition

NASA Astrophysics Data System (ADS)

Yang, Fan

Organic solar cells have the potential to provide low-cost photovoltaic devices as a clean and renewable energy resource. In this thesis, we focus on understanding the energy conversion process in organic solar cells, and improving the power conversion efficiencies via controlled growth of organic nanostructures. First, we explain the unique optical and electrical properties of organic materials used for photovoltaics, and the excitonic energy conversion process in donor-acceptor heterojunction solar cells that place several limiting factors of their power conversion efficiency. Then, strategies for improving exciton diffusion and carrier collection are analyzed using dynamical Monte Carlo models for several nanostructure morphologies. Organic vapor phase deposition is used for controlling materials crystallization and film morphology. We improve the exciton diffusion efficiency while maintaining good carrier conduction in a bulk heterojunction solar cell. Further efficiency improvement is obtained in a novel nanocrystalline network structure with a thick absorbing layer, leading to the demonstration of an organic solar cell with 4.6% efficiency. In addition, solar cells using simultaneously active heterojunctions with broad spectral response are presented. We also analyze the efficiency limits of single and multiple junction organic solar cells, and discuss the challenges facing their practical implementations.

Tailoring characteristic thermal stability of Ni-Au binary nanocrystals via structure and composition engineering: theoretical insights into structural evolution and atomic inter-diffusion

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

Li, Bangquan; Wang, Hailong; Xing, Guozhong

We report on the structural evolution and atomic inter-diffusion characteristics of the bimetallic Ni-Au nanocrystals (NCs) by molecular dynamics simulations studies. Our results reveal that the thermal stability dynamics of Ni-Au NCs strongly depends on the atomic configurations. By engineering the structural construction with Ni:Au = 1:1 atomic composition, compared with core-shell Au@Ni and alloy NCs, the melting point of core-shell Ni@Au NCs is significantly enhanced up to 1215 K. Unexpectedly, with atomic ratio of Au:Ni= 1:9, the melting process initiates from the atoms in the shell of Ni@Au and alloy NCs, while starts from the core of Au@Ni NCs.more » The corresponding features and evolution process of structural motifs, mixing and segregation are illustrated via a series of dynamic simulations videos. Moreover, our results revealed that the face centered cubic phase Au{sub 0.75}Ni{sub 0.25} favorably stabilizes in NCs form but does not exist in the bulk counterpart, which elucidates the anomalies of previously reported experimental results on such bimetallic NCs.« less

Fluctuating hydrodynamics, current fluctuations, and hyperuniformity in boundary-driven open quantum chains

NASA Astrophysics Data System (ADS)

Carollo, Federico; Garrahan, Juan P.; Lesanovsky, Igor; Pérez-Espigares, Carlos

2017-11-01

We consider a class of either fermionic or bosonic noninteracting open quantum chains driven by dissipative interactions at the boundaries and study the interplay of coherent transport and dissipative processes, such as bulk dephasing and diffusion. Starting from the microscopic formulation, we show that the dynamics on large scales can be described in terms of fluctuating hydrodynamics. This is an important simplification as it allows us to apply the methods of macroscopic fluctuation theory to compute the large deviation (LD) statistics of time-integrated currents. In particular, this permits us to show that fermionic open chains display a third-order dynamical phase transition in LD functions. We show that this transition is manifested in a singular change in the structure of trajectories: while typical trajectories are diffusive, rare trajectories associated with atypical currents are ballistic and hyperuniform in their spatial structure. We confirm these results by numerically simulating ensembles of rare trajectories via the cloning method, and by exact numerical diagonalization of the microscopic quantum generator.

Fluctuating hydrodynamics, current fluctuations, and hyperuniformity in boundary-driven open quantum chains.

PubMed

Carollo, Federico; Garrahan, Juan P; Lesanovsky, Igor; Pérez-Espigares, Carlos

2017-11-01

We consider a class of either fermionic or bosonic noninteracting open quantum chains driven by dissipative interactions at the boundaries and study the interplay of coherent transport and dissipative processes, such as bulk dephasing and diffusion. Starting from the microscopic formulation, we show that the dynamics on large scales can be described in terms of fluctuating hydrodynamics. This is an important simplification as it allows us to apply the methods of macroscopic fluctuation theory to compute the large deviation (LD) statistics of time-integrated currents. In particular, this permits us to show that fermionic open chains display a third-order dynamical phase transition in LD functions. We show that this transition is manifested in a singular change in the structure of trajectories: while typical trajectories are diffusive, rare trajectories associated with atypical currents are ballistic and hyperuniform in their spatial structure. We confirm these results by numerically simulating ensembles of rare trajectories via the cloning method, and by exact numerical diagonalization of the microscopic quantum generator.

Atomistics of vapour–liquid–solid nanowire growth

PubMed Central

Wang, Hailong; Zepeda-Ruiz, Luis A.; Gilmer, George H.; Upmanyu, Moneesh

2013-01-01

Vapour–liquid–solid route and its variants are routinely used for scalable synthesis of semiconducting nanowires, yet the fundamental growth processes remain unknown. Here we employ atomic-scale computations based on model potentials to study the stability and growth of gold-catalysed silicon nanowires. Equilibrium studies uncover segregation at the solid-like surface of the catalyst particle, a liquid AuSi droplet, and a silicon-rich droplet–nanowire interface enveloped by heterogeneous truncating facets. Supersaturation of the droplets leads to rapid one-dimensional growth on the truncating facets and much slower nucleation-controlled two-dimensional growth on the main facet. Surface diffusion is suppressed and the excess Si flux occurs through the droplet bulk which, together with the Si-rich interface and contact line, lowers the nucleation barrier on the main facet. The ensuing step flow is modified by Au diffusion away from the step edges. Our study highlights key interfacial characteristics for morphological and compositional control of semiconducting nanowire arrays. PMID:23752586

Smart membranes: Hydroxypropyl cellulose for flavor delivery

NASA Astrophysics Data System (ADS)

Heitfeld, Kevin A.

2007-12-01

This work focuses on the use of temperature responsive gels (TRGs) (polymeric hydrogels with a large temperature-dependent change in volume) for flavor retention at cooking temperatures. Specifically, we have studied a gel with a lower critical solution temperature (LCST) that swells at low temperatures and collapses at high temperatures. In the collapsed state, the polymer acts as a transport barrier, keeping the volatile flavors inside. An encapsulation system was designed to utilize the solution (phase separation) behavior of a temperature responsive gel. The gel morphology was understood and diffusive properties were tailored through morphology manipulation. Heterogeneous and homogeneous gels were processed by understanding the effect of temperature on gel morphology. A morphology model was developed linking bulk diffusive properties to molecular morphology. Flavor was encapsulated within the gel and the emulsifying capability was determined. The capsules responded to temperature similarly to the pure polymer. The release kinetcs were compared to commercial gelatin capsules and the temperature responsive polymer took longer to release.

Tuning the density profile of surface-grafted hyaluronan and the effect of counter-ions.

PubMed

Berts, Ida; Fragneto, Giovanna; Hilborn, Jöns; Rennie, Adrian R

2013-07-01

The present paper investigates the structure and composition of grafted sodium hyaluronan at a solid-liquid interface using neutron reflection. The solvated polymer at the surface could be described with a density profile that decays exponentially towards the bulk solution. The density profile of the polymer varied depending on the deposition protocol. A single-stage deposition resulted in denser polymer layers, while layers created with a two-stage deposition process were more diffuse and had an overall lower density. Despite the diffuse density profile, two-stage deposition leads to a higher surface excess. Addition of calcium ions causes a strong collapse of the sodium hyaluronan chains, increasing the polymer density near the surface. This effect is more pronounced on the sample prepared by two-stage deposition due to the initial less dense profile. This study provides an understanding at a molecular level of how surface functionalization alters the structure and how surface layers respond to changes in calcium ions in the solvent.

Thin silicon solar cell performance characteristics

NASA Technical Reports Server (NTRS)

Gay, C. F.

1978-01-01

Refined techniques for surface texturizing, back surface field and back surface reflector formation were evaluated for use with shallow junction, single-crystal silicon solar cells. Each process was characterized individually and collectively as a function of device thickness and bulk resistivity. Among the variables measured and reported are open circuit voltage, short circuit current and spectral response. Substantial improvements were obtained by the utilization of a low cost aluminum paste process to simultaneously remove the unwanted n(+) diffused region, form the back surface field and produce an ohmic contact metallization. The highly effective BSF which results from applying this process has allowed fabrication of cells 0.05 mm thick with initial outputs as high as 79.5 mW/4 sq cm (28 C, AM0) and superior electron radiation tolerance. Cells of 0.02 mm to 0.04 mm thickness have been fabricated with power to mass ratios well in excess of 2 watts per gram.

Diffusion in Jammed Particle Packs.

PubMed

Bolintineanu, Dan S; Grest, Gary S; Lechman, Jeremy B; Silbert, Leonardo E

2015-08-21

Using random walk simulations we explore diffusive transport through monodisperse sphere packings over a range of packing fractions ϕ in the vicinity of the jamming transition at ϕ(c). Various diffusion properties are computed over several orders of magnitude in both time and packing pressure. Two well-separated regimes of normal "Fickian" diffusion, where the mean squared displacement is linear in time, are observed. The first corresponds to diffusion inside individual spheres, while the latter is the long-time bulk diffusion. The intermediate anomalous diffusion regime and the long-time value of the diffusion coefficient are both shown to be controlled by particle contacts, which in turn depend on proximity to ϕ(c). The time required to recover normal diffusion t* scales as (ϕ-ϕ(c))(-0.5) and the long-time diffusivity D(∞)∼(ϕ-ϕ(c))0.5, or D(∞)∼1/t*. It is shown that the distribution of mean first passage times associated with the escape of random walkers between neighboring particles controls both t* and D(∞) in the limit ϕ→ϕ(c).

Cs diffusion in SiC high-energy grain boundaries

NASA Astrophysics Data System (ADS)

Ko, Hyunseok; Szlufarska, Izabela; Morgan, Dane

2017-09-01

Cesium (Cs) is a radioactive fission product whose release is of concern for Tristructural-Isotropic fuel particles. In this work, Cs diffusion through high energy grain boundaries (HEGBs) of cubic-SiC is studied using an ab-initio based kinetic Monte Carlo (kMC) model. The HEGB environment was modeled as an amorphous SiC, and Cs defect energies were calculated using the density functional theory (DFT). From defect energies, it was suggested that the fastest diffusion mechanism is the diffusion of Cs interstitial in an amorphous SiC. The diffusion of Cs interstitial was simulated using a kMC model, based on the site and transition state energies sampled from the DFT. The Cs HEGB diffusion exhibited an Arrhenius type diffusion in the range of 1200-1600 °C. The comparison between HEGB results and the other studies suggests not only that the GB diffusion dominates the bulk diffusion but also that the HEGB is one of the fastest grain boundary paths for the Cs diffusion. The diffusion coefficients in HEGB are clearly a few orders of magnitude lower than the reported diffusion coefficients from in- and out-of-pile samples, suggesting that other contributions are responsible, such as radiation enhanced diffusion.

The Burrell Schmidt Deep Virgo Survey: Tidal Debris, Galaxy Halos, and Diffuse Intracluster Light in the Virgo Cluster

NASA Astrophysics Data System (ADS)

Mihos, J. Christopher; Harding, Paul; Feldmeier, John J.; Rudick, Craig; Janowiecki, Steven; Morrison, Heather; Slater, Colin; Watkins, Aaron

2017-01-01

We present the results of a deep imaging survey of the Virgo cluster of galaxies, concentrated around the cores of Virgo subclusters A and B. The goal of this survey was to detect and study very low surface brightness features present in Virgo, including discrete tidal features, the faint halos of luminous galaxies, and the diffuse intracluster light (ICL). Our observations span roughly 16 degrees2 in two filters, reaching a 3σ limiting depth of {μ }B = 29.5 and {μ }V = 28.5 mag arcsec-2. At these depths, our limiting systematic uncertainties are astrophysical: variations in faint background sources as well as scattered light from galactic dust. We show that this dust-scattered light is well traced by deep far-infrared imaging, making it possible to separate it from true diffuse light in Virgo. We use our imaging to trace and measure the color of the diffuse tidal streams and ICL in the Virgo core near M87, in fields adjacent to the core including the M86/M84 region, and to the south of the core around M49 and subcluster B, along with the more distant W{}\\prime cloud around NGC 4365. Overall, the bulk of the projected ICL is found in the Virgo core and within the W{}\\prime cloud; we find little evidence for an extensive ICL component in the field around M49. The bulk of the ICL we detect is fairly red in color (B - V = 0.7-0.9), indicative of old, evolved stellar populations. Based on the luminosity of the observed ICL features in the cluster, we estimate a total Virgo ICL fraction of 7%-15%. This value is somewhat smaller than that expected for massive, evolved clusters, suggesting that Virgo is still in the process of growing its extended ICL component. We also trace the shape of M87's extremely boxy outer halo out to ˜150 kpc, and show that the current tidal stripping rate from low luminosity galaxies is insufficient to have built M87's outer halo over a Hubble time. We identify a number of previously unknown low surface brightness structures around galaxies projected close to M86 and M84. The extensive diffuse light seen in the infalling W{}\\prime cloud around NGC 4365 is likely to be subsumed in the general Virgo ICL component once the group enters the cluster, illustrating the importance of group infall in generating ICL. Finally, we also identify another large and extremely low surface brightness ultradiffuse galaxy, likely in the process of being shredded by the cluster tidal field. With the survey complete, the full imaging data set is now available for public release.

Hydration of Rhyolitic Glasses: Comparison Between High- and Low-Temperature Processes

NASA Astrophysics Data System (ADS)

Anovitz, L.; Fayek, M.; Cole, D. R.; Carter, T.

2012-12-01

While a great deal is known about the interaction between water and rhyolitic glasses and melts at temperatures above the glass transition, the nature of this interaction at lower temperatures is more obscure. Comparisons between high- and low-temperature diffusive studies suggest that several factors play an important role under lower-temperatures conditions that are not significant at higher temperatures. Surface concentrations, which equilibrate quickly at high temperature, change far more slowly as temperatures decrease, and may not equilibrate at room temperature for hundreds or thousands of years. Coupled with temperature-dependent diffusion coefficients this complicates calculation of diffusion profiles as a function of time. A key factor in this process appears to be the inability of "self-stress", caused by the in-diffusing species, to relax at lower temperatures, a result expected below the glass transition. Regions of the glass hydrated at low temperatures are strongly optically anisotropic, and preliminary calculations suggest that the magnitude of stress involved may be very high. On the microstuctural scale, extrapolations of high-temperature FTIR data to lower temperatures suggests there should be little or no hydroxyl present in glasses "hydrated" at low temperatures. Analyses of both block and powder samples suggest that this is generally true in the bulk of the hydrated glass, excluding hydroxyl groups that formed during the initial cooling of the melt. However, hydroxyl do groups appear to be present at the glass surface, where both SIMS and neutron reflectometry data suggest hydration levels may be higher than projected from the bulk of the glass. Isotopic exchange experiments also suggest that bonding is relatively weak, as hydration water exchanges readily with the enviroment. All of these observations lead to the conclusion that the observed stress is due to the presence of interstructural, rather than bonded, water. This likely explains the "onion-skin" texture observed in weathered obsdians, with large hydration stresses leading to spheroidal fracture. Long-term experiments derived from archaeological samples, however, suggest that there remain significant uncertainties. Analysis of younger samples (< 2500 years) from the Chalco site in Mexico yield results consistent with laboratory experients where diffusion rates are proportional to t0.4235, and suggest small changes in the average paleo-hydration temperature. Older samples, however, from the complexly stratified site of Çatalhöyük, central Anatolia, Turkey, suggest near linear-with-time rates. This is consistent with other observations of realtively old samples. The two trends observed in the latter, however, do not necessarily correlate with sourcing data. The origin of these differences remains unexplained. Effort by LMA and DRC was supported by research sponsored by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, U.S. Department of Energy.

Heat treatment of bulk gallium arsenide using a phosphosilicate glass cap

NASA Technical Reports Server (NTRS)

Mathur, G.; Wheaton, M. L.; Borrego, J. M.; Ghandhi, S. K.

1985-01-01

n-type bulk GaAs crystals, capped with chemically vapor-deposited phosphosilicate glass, were heat treated at temperatures in the range of 600 to 950 C. Measurements on Schottky diodes and solar cells fabricated on the heat-treated material, after removal of a damaged surface layer, show an increase in free-carrier concentration, in minority-carrier-diffusion length, and in solar-cell short-circuit current. The observed changes are attributed to a removal of lifetime-reducing acceptorlike impurities, defects, or their complexes.

Water at hydrophobic interfaces delays proton surface-to-bulk transfer and provides a pathway for lateral proton diffusion

PubMed Central

Zhang, Chao; Knyazev, Denis G.; Vereshaga, Yana A.; Ippoliti, Emiliano; Nguyen, Trung Hai; Carloni, Paolo; Pohl, Peter

2012-01-01

Fast lateral proton migration along membranes is of vital importance for cellular energy homeostasis and various proton-coupled transport processes. It can only occur if attractive forces keep the proton at the interface. How to reconcile this high affinity to the membrane surface with high proton mobility is unclear. Here, we tested whether a minimalistic model interface between an apolar hydrophobic phase (n-decane) and an aqueous phase mimics the biological pathway for lateral proton migration. The observed diffusion span, on the order of tens of micrometers, and the high proton mobility were both similar to the values previously reported for lipid bilayers. Extensive ab initio simulations on the same water/n-decane interface reproduced the experimentally derived free energy barrier for the excess proton. The free energy profile GH+ adopts the shape of a well at the interface, having a width of two water molecules and a depth of 6 ± 2RT. The hydroniums in direct contact with n-decane have a reduced mobility. However, the hydroniums in the second layer of water molecules are mobile. Their in silico diffusion coefficient matches that derived from our in vitro experiments, (5.7 ± 0.7) × 10-5 cm2 s-1. Conceivably, these are the protons that allow for fast diffusion along biological membranes. PMID:22675120

Simulations of Xe and U diffusion in UO2

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

Andersson, Anders D.; Vyas, Shyam; Tonks, Michael R.

2012-09-10

Diffusion of xenon (Xe) and uranium (U) in UO{sub 2} is controlled by vacancy mechanisms and under irradiation the formation of mobile vacancy clusters is important. Based on the vacancy and cluster diffusion mechanisms established from density functional theory (DFT) calculations, we derive continuum thermodynamic and diffusion models for Xe and U in UO{sub 2}. In order to capture the effects of irradiation, vacancies (Va) are explicitly coupled to the Xe and U dynamics. Segregation of defects to grain boundaries in UO{sub 2} is described by combining the bulk diffusion model with models of the interaction between Xe atoms andmore » vacancies with grain boundaries, which were derived from atomistic calculations. The diffusion and segregation models were implemented in the MOOSE-Bison-Marmot (MBM) finite element (FEM) framework and the Xe/U redistribution was simulated for a few simple microstructures.« less

Low temperature hot air drying of potato cubes subjected to osmotic dehydration and intermittent microwave: drying kinetics, energy consumption and product quality indexes

NASA Astrophysics Data System (ADS)

Dehghannya, Jalal; Bozorghi, Somayyeh; Heshmati, Maryam Khakbaz

2018-04-01

Hot-air drying is a slow energy-extensive process. Use of intermittent microwave (IM) in hot-air (HA) drying of food products is characterized with advantages including reduced process time, energy saving, and improved final quality. In this study, the effect of IM-HA drying following an osmotic dehydration (OD) pretreatment was analyzed on qualitative and quantitative properties of the output (i.e. effective moisture diffusion coefficient (Deff), shrinkage, bulk density, rehydration and energy consumption). Temperature and airflow velocity were fixed at 40°C and 1 m/s, respectively. The process variables included sucrose solution concentration at five levels (0 or control, 10, 30, 50 and 70 w/w%), microwave output power at four levels (0 or control, 360, 600 and 900 W), and pulse ratio at four levels (1, 2, 3 and 4). Use of osmotic dehydration in combination with IM-HA drying reduced the drying time by up to about 54%. Increasing the osmotic solution concentration to 30% and using higher pulse ratios increased the Deff. The lowest shrinkage and bulk density as well as the highest rehydration belonged to the 900 W microwave power and pulse ratio of 4. The lowest energy consumption was observed when using the 900 W power level, showing 63.27% less consumption than the HA drying method.

Scaling behaviour for the water transport in nanoconfined geometries

PubMed Central

Chiavazzo, Eliodoro; Fasano, Matteo; Asinari, Pietro; Decuzzi, Paolo

2014-01-01

The transport of water in nanoconfined geometries is different from bulk phase and has tremendous implications in nanotechnology and biotechnology. Here molecular dynamics is used to compute the self-diffusion coefficient D of water within nanopores, around nanoparticles, carbon nanotubes and proteins. For almost 60 different cases, D is found to scale linearly with the sole parameter θ as D(θ)=DB[1+(DC/DB−1)θ], with DB and DC the bulk and totally confined diffusion of water, respectively. The parameter θ is primarily influenced by geometry and represents the ratio between the confined and total water volumes. The D(θ) relationship is interpreted within the thermodynamics of supercooled water. As an example, such relationship is shown to accurately predict the relaxometric response of contrast agents for magnetic resonance imaging. The D(θ) relationship can help in interpreting the transport of water molecules under nanoconfined conditions and tailoring nanostructures with precise modulation of water mobility. PMID:24699509

ToF-SIMS characterization of robust window material for use in diode pumped alkali lasers

NASA Astrophysics Data System (ADS)

Fletcher, Aaron; Turner, David; Fairchild, Steven; Rice, Christopher; Pitz, Gregory

2018-03-01

Developments in diode pumped alkali laser (DPAL) systems have been impeded because of the catastrophic failure of laser windows. The window's failure is caused by localized laser-induced heating of window material. This heating is believed to occur due to increases in absorption on or near the surface of the window. This increase is believed to be caused by either adsorption of carbon-based soot from the collisional gas or by the diffusion of rubidium into the bulk material. The work presented here will focus on the diffusion of Rb into the bulk window materials and will strive to identify a superior material to use as windows. The results of this research indicate that aluminum oxynitride (ALON), sapphire, MgAl2O4 (spinel), and ZrO2 are resistant to alkali-induced changes in optical properties.

Bulk Heterojunction versus Diffused Bilayer: The Role of Device Geometry in Solution p-Doped Polymer-Based Solar Cells.

PubMed

Loiudice, Anna; Rizzo, Aurora; Biasiucci, Mariano; Gigli, Giuseppe

2012-07-19

We exploit the effect of molecular p-type doping of P3HT in diffused bilayer (DB) polymer solar cells. In this alternative device geometry, the p-doping is accomplished in solution by blending the F4-TCNQ with P3HT. The p-doping both increases the film conductivity and reduces the potential barrier at the interface with the electrode. This results in an excellent power conversion efficiency of 4.02%, which is an improvement of ∼48% over the p-doped standard bulk heterojunction (BHJ) device. Combined VOC-light intensity dependence measurements and Kelvin probe force microscopy reveal that the DB device configuration is particularly advantageous, if compared to the conventional BHJ, because it enables optimization of the donor and acceptor layers independently to minimize the effect of trapping and to fully exploit the improved transport properties.

Simulations of induced-charge electro-osmosis in microfluidic devices

NASA Astrophysics Data System (ADS)

Ben, Yuxing

2005-03-01

Theories of nonlinear electrokinetic phenomena generally assume a uniform, neutral bulk electroylte in contact with a polarizable thin double layer near a metal or dielectric surface, which acts as a "capacitor skin". Induced-charge electro-osmosis (ICEO) is the general effect of nonlinear electro-osmotic slip, when an applied electric field acts on its own induced (diffuse) double-layer charge. In most theoretical and experimental work, ICEO has been studied in very simple geometries, such as colloidal spheres and planar, periodic micro-electrode arrays. Here we use finite-element simulations to predict how more complicated geometries of polarizable surfaces and/or electrodes yield flow profiles with subtle dependence on the amplitude and frequency of the applied voltage. We also consider how the simple model equations break down, due to surface conduction, bulk diffusion, and concentration polarization, for large applied voltages (as in most experiments).

Benefits of a 4th Ice Class in the Simulated Radar Reflectivities of Convective Systems Using a Bulk Microphysics Scheme

NASA Technical Reports Server (NTRS)

Lang, Stephen E.; Tao, Wei-Kuo; Chern, Jiun-Dar; Wu, Di; Li, Xiaowen

2015-01-01

Numerous cloud microphysical schemes designed for cloud and mesoscale models are currently in use, ranging from simple bulk to multi-moment, multi-class to explicit bin schemes. This study details the benefits of adding a 4th ice class (hail) to an already improved 3-class ice bulk microphysics scheme developed for the Goddard Cumulus Ensemble model based on Rutledge and Hobbs (1983,1984). Besides the addition and modification of several hail processes from Lin et al. (1983), further modifications were made to the 3-ice processes, including allowing greater ice super saturation and mitigating spurious evaporationsublimation in the saturation adjustment scheme, allowing graupelhail to become snow via vapor growth and hail to become graupel via riming, and the inclusion of a rain evaporation correction and vapor diffusivity factor. The improved 3-ice snowgraupel size-mapping schemes were adjusted to be more stable at higher mixing rations and to increase the aggregation effect for snow. A snow density mapping was also added. The new scheme was applied to an intense continental squall line and a weaker, loosely-organized continental case using three different hail intercepts. Peak simulated reflectivities agree well with radar for both the intense and weaker case and were better than earlier 3-ice versions when using a moderate and large intercept for hail, respectively. Simulated reflectivity distributions versus height were also improved versus radar in both cases compared to earlier 3-ice versions. The bin-based rain evaporation correction affected the squall line case more but did not change the overall agreement in reflectivity distributions.

Helium diffusion in carbonates

NASA Astrophysics Data System (ADS)

Amidon, W. H.; Cherniak, D. J.; Watson, E. B.; Hobbs, D.

2013-12-01

The abundance and large grain size of carbonate minerals make them a potentially attractive target for 4He thermochronology and 3He cosmogenic dating, although the diffusive properties of helium in carbonates remain poorly understood. This work characterizes helium diffusion in calcite and dolomite to better understand the crystal-chemical factors controlling He transport and retentivity. Slabs of cleaved natural calcite and dolomite, and polished sections of calcite cut parallel or normal to c, were implanted with 3He at 3 MeV with a dose of 5x1015/cm2. Implanted carbonates were heated in 1-atm furnaces, and 3He distributions following diffusion anneals were profiled with Nuclear Reaction Analysis using the reaction 3He(d,p)4He. For 3He transport normal to cleavage surfaces in calcite, we obtain the following Arrhenius relation over the temperature range 78-300°C: Dcalcite = 9.0x10-9exp(-55 × 6 kJ mol-1/RT) m2sec-1. Diffusion in calcite exhibits marked anisotropy, with diffusion parallel to c about two orders of magnitude slower than diffusion normal to cleavage faces. He diffusivities for transport normal to the c-axis are similar in value to those normal to cleavage surfaces. Our findings are broadly consistent with helium diffusivities from step-heating measurements of calcite by Copeland et al. (2007); these bulk degassing data may reflect varying effects of diffusional anisotropy. Helium diffusion normal to cleavage surfaces in dolomite is significantly slower than diffusion in calcite, and has a much higher activation energy for diffusion. For dolomite, we obtain the following Arrhenius relation for He diffusion over the temperature range 150-400°C: Ddolomite = 9.0x10-8exp(-92 × 9 kJ mol-1/RT) m2sec-1. The role of crystallographic structure in influencing these differences among diffusivities was evaluated using the maximum aperture approach of Cherniak and Watson (2011), in which crystallographic structures are sectioned along possible diffusion directions and the maximum interstitial apertures in each 'slice' in the structure are identified. Preliminary results show that observed differences in diffusivities are consistent with the size of the smallest maximum aperture along each diffusion direction. In calcite, the smallest maximum apertures are ~0.92 and ~0.66 angstroms for cleavage-normal and c-axis parallel directions respectively. In dolomite, the smallest maximum aperture is ~0.78 angstroms for the cleavage normal direction. Work is in progress on characterizing helium diffusion for other orientations in dolomite, and in other carbonates, including aragonite and magnesite, and in implementing these diffusion findings in the interpretation and modeling of bulk volume diffusion in heterogeneous calcite crystals common in many geologic applications. Copeland et al. (2007) GCA 71, 4488-4511 Cherniak and Watson, (2011) Chem. Geo. 288, 149-161

Nanoscale charge transfer and diffusion at the MoS2/SiO2 interface by atomic force microscopy: contact injection versus triboelectrification.

PubMed

Xu, Rui; Ye, Shili; Xu, Kunqi; Lei, Le; Hussain, Sabir; Zheng, Zhiyue; Pang, Fei; Xing, Shuya; Liu, Xinmeng; Ji, Wei; Cheng, Zhihai

2018-08-31

Understanding the process of charge generation, transfer, and diffusion between two-dimensional (2D) materials and their supporting substrates is very important for potential applications of 2D materials. Compared with the systematic studies of triboelectric charging in a bulk sample, a fundamental understanding of the triboelectrification of the 2D material/insulator system is rather limited. Here, the charge transfer and diffusion of both the SiO 2 surface and MoS 2 /SiO 2 interface through contact electrification and frictional electrification are investigated systematically in situ by scanning Kelvin probe microscopy and dual-harmonic electrostatic force microscopy. Different from the simple static charge transfer between SiO 2 and the PtSi alloy atomic force microscope (AFM) tip, the charge transfer between the tip and the MoS 2 /SiO 2 system is complicated. Triboelectric charges, generated by contact or frictional electrification with the AFM tip, are trapped at the MoS 2 /SiO 2 interface and act as floating gates. The local charge discharge processes can be obtained by monitoring the surface potential. The charge decay time (τ) of the MoS 2 /SiO 2 interface is one (or two) orders of magnitude larger than the decay time τ of the SiO 2 surface. This work facilitates an understanding of the triboelectric and de-electrification of the interface between 2D materials and substrates. In addition to the charge transfer and diffusion, we demonstrate the nanopatterns of surface and interfacial charges, which have great potential for the application of self-assembly of charged nanostructures.

Oxygen self-diffusion in ThO 2 under pressure: Connecting point defect parameters with bulk properties

DOE PAGES

Cooper, Michael William D.; Fitzpatrick, M. E.; Tsoukalas, L. H.; ...

2016-06-06

ThO 2 is a candidate material for use in nuclear fuel applications and as such it is important to investigate its materials properties over a range of temperatures and pressures. In the present study molecular dynamics calculations are used to calculate elastic and expansivity data. These are used in the framework of a thermodynamic model, the cBΩ model, to calculate the oxygen self-diffusion coefficient in ThO 2 over a range of pressures (–10–10 GPa) and temperatures (300–1900 K). As a result, increasing the hydrostatic pressure leads to a significant reduction in oxygen self-diffusion. Conversely, negative hydrostatic pressure significantly enhances oxygenmore » self-diffusion.« less

On the Role of Built-in Electric Fields on the Ignition of Oxide Coated NanoAluminum: Ion Mobility versus Fickian Diffusion

DTIC Science & Technology

2010-01-01

on Al ion diffu- sion can be computed using the Nernst –Planck equation . The Nernst –Plank equation is given in Eq. 4,22 J = − D dC dx − zFDC RT d dx...The use of the bulk diffusion equation is reason- able since during the time scales considered the movement of only the atoms initially on the surface

Formation and Migration Energies of Interstitials in Silicon Under Strain Conditions

NASA Technical Reports Server (NTRS)

Halicioglu, Timur; Barnett, David M.

1999-01-01

Simulation calculations are conducted for Si substrates to analyze formation and diffusion energies of interstitials under strain condition using statics methods .based on a Stillinger-Weber type potential function. Defects in the vicinity of the surface region and in the bulk are examined, and the role played by compressive and tensile strains on the energetics of interstitials is investigated. Results indicate that strain alters defect energetics which, in turn, modifies their diffusion characteristics.

Three-dimensional charge coupled device

DOEpatents

Conder, Alan D.; Young, Bruce K. F.

1999-01-01

A monolithic three dimensional charged coupled device (3D-CCD) which utilizes the entire bulk of the semiconductor for charge generation, storage, and transfer. The 3D-CCD provides a vast improvement of current CCD architectures that use only the surface of the semiconductor substrate. The 3D-CCD is capable of developing a strong E-field throughout the depth of the semiconductor by using deep (buried) parallel (bulk) electrodes in the substrate material. Using backside illumination, the 3D-CCD architecture enables a single device to image photon energies from the visible, to the ultra-violet and soft x-ray, and out to higher energy x-rays of 30 keV and beyond. The buried or bulk electrodes are electrically connected to the surface electrodes, and an E-field parallel to the surface is established with the pixel in which the bulk electrodes are located. This E-field attracts charge to the bulk electrodes independent of depth and confines it within the pixel in which it is generated. Charge diffusion is greatly reduced because the E-field is strong due to the proximity of the bulk electrodes.

Hydrogen bonded structure, polarity, molecular motion and frequency fluctuations at liquid-vapor interface of a water-methanol mixture: an ab initio molecular dynamics study.

PubMed

Choudhuri, Jyoti Roy; Chandra, Amalendu

2014-10-07

We have performed ab initio molecular dynamics simulations of a liquid-vapor interfacial system consisting of a mixture of water and methanol molecules. Detailed results are obtained for the structural and dynamical properties of the bulk and interfacial regions of the mixture. Among structural properties, we have looked at the inhomogeneous density profiles of water and methanol molecules, hydrogen bond distributions and also the orientational profiles of bulk and interfacial molecules. The methanol molecules are found to have a higher propensity to be at the interface than water molecules. It is found that the interfacial molecules show preference for specific orientations so as to form water-methanol hydrogen bonds at the interface with the hydrophobic methyl group pointing towards the vapor side. It is also found that for both types of molecules, the dipole moment decreases at the interface. It is also found that the local electric field of water influences the dipole moment of methanol molecules. Among the dynamical properties, we have calculated the diffusion, orientational relaxation, hydrogen bond dynamics, and vibrational frequency fluctuations in bulk and interfacial regions. It is found that the diffusion and orientation relaxation of the interfacial molecules are faster than those of the bulk. However, the hydrogen bond lifetimes are longer at the interface which can be correlated with the time scales found from the decay of frequency time correlations. The slower hydrogen bond dynamics for the interfacial molecules with respect to bulk can be attributed to diminished cooperative effects at the interface due to reduced density and number of hydrogen bonds.

Characterization of iron in silicon by low-temperature photoluminescence and deep-level transient spectroscopy

NASA Astrophysics Data System (ADS)

Nakamura, Minoru; Murakami, Susumu; Udono, Haruhiko

2018-03-01

We investigate the relationship between the intensity of band-edge (BDE) photoluminescence (PL) from 10 to 70 K and the concentration of iron diffused in boron-doped p-type silicon. Because of the nonradiative recombination activity of the interstitial iron-boron complex (FeiB center), the BDE-PL intensity at each temperature varies distinctively and systematically with the iron concentration, which means that this method has the potential to make the accurate measurements of a wide range of interstitial iron concentrations in silicon. The iron precipitates formed in the bulk and/or at the surface are found to exert much weaker recombination activity for excess carriers than FeiB center by exploiting both PL and deep-level transient spectroscopy (DLTS) measurements. The unexpected enhancement in BDE-PL intensity from iron-diffused silicon between 20 and 50 K is attributed to the passivation of the Si-oxide/Si interface by iron. For the samples diffused with trace amounts of iron, the iron concentration within 20 μm of the surface is significantly greater than that in the bulk, as measured by DLTS. This result is tentatively attributed to the affinity of iron with the Si-oxide.

Frequency bandwidth limitation of external pulse electric fields in cylindrical micro-channel electrophoresis with analyte velocity modulation.

PubMed

Wang, Shau-Chun; Chen, Hsiao-Ping; Lee, Chia-Yu; Yeo, Leslie Y

2005-04-15

In capillary electrophoresis, effective optical signal quality improvement is obtained when high frequency (>100 Hz) external pulse fields modulate analyte velocities with synchronous lock-in detection. However, the pulse frequency is constrained under a critical value corresponding to the time required for the bulk viscous flow, which arises due to viscous momentum diffusion from the electro-osmotic slip in the Debye layer, to reach steady-state. By solving the momentum diffusion equation for transient bulk flow in the micro-channel, we show that this set-in time to steady-state and hence, the upper limit for the pulse frequency is dependent on the characteristic diffusion length scale and therefore the channel geometry; for cylindrical capillaries, the set-in time is approximately one half of that for rectangular slot channels. From our estimation of the set-in time and hence the upper frequency modulation limit, we propose that the half width of planar channels does not exceed 100 microm and that the radii of cylindrical channels be limited to 140 microm such that there is a finite working bandwidth range above 100 Hz and below the upper limit in order for flicker noise to be effectively suppressed.

Effect of precipitation inhibitors on indomethacin supersaturation maintenance: mechanisms and modeling.

PubMed

Patel, Dhaval D; Anderson, Bradley D

2014-05-05

This study quantitatively explores the mechanisms underpinning the effects of model pharmaceutical polymeric precipitation inhibitors (PPIs) on the crystal growth and, in turn, maintenance of supersaturation of indomethacin, a model poorly water-soluble drug. A recently developed second-derivative UV spectroscopy method and a first-order empirical crystal growth model were used to determine indomethacin crystal growth rates in the presence of model PPIs. All three model PPIs including HP-β-CD, PVP, and HPMC inhibited indomethacin crystal growth at both high and low degrees of supersaturation (S). The bulk viscosity changes in the presence of model PPIs could not explain their crystal growth inhibitory effects. At 0.05% w/w, PVP (133-fold) and HPMC (28-fold) were better crystal growth inhibitors than HP-β-CD at high S. The inhibitory effect of HP-β-CD on the bulk diffusion-controlled indomethacin crystal growth at high S was successfully modeled using reactive diffusion layer theory, which assumes reversible complexation in the diffusion layer. Although HP-β-CD only modestly inhibited indomethacin crystal growth at either high S (∼15%) or low S (∼2-fold), the crystal growth inhibitory effects of PVP and HPMC were more dramatic, particularly at high S (0.05% w/w). The superior crystal growth inhibitory effects of PVP and HPMC as compared with HP-β-CD at high S were attributed to a change in the indomethacin crystal growth rate-limiting step from bulk diffusion to surface integration. Indomethacin crystal growth inhibitory effects of all three model PPIs at low S were attributed to retardation of the rate of surface integration of indomethacin, a phenomenon that may reflect the adsorption of PPIs onto the growing crystal surface. The quantitative approaches outlined in this study should be useful in future studies to develop tools to predict supersaturation maintenance effects of PPIs.

Kinetic Parameters of Secondary Carbide Precipitation in High-Cr White Iron Alloyed by Mn-Ni-Mo-V Complex

NASA Astrophysics Data System (ADS)

Efremenko, V. G.; Chabak, Yu. G.; Brykov, M. N.

2013-05-01

This study presents kinetics of precipitation of secondary carbides in 14.55%Cr-Mn-Ni-Mo-V white cast iron during the destabilization heat treatment. The as-cast iron was heat treated at temperatures in the range of 800-1100 °C with soaking up to 6 h. Investigation was carried out by optical and electron microscopy, dilatometric analysis, Ms temperature measurement, and bulk hardness evaluation. TTT-curve of precipitation process of secondary carbides (M7C3, M23C6, M3C2) has been constructed in this study. It was determined that the precipitation occurs at the maximum rate at 950 °C where the process is started after 10 s and completed within 160 min further. The precipitation leads to significant increase of Ms temperature and bulk hardness; large soaking times at destabilization temperatures cause coarsening of secondary carbides and decrease in particles number, followed by decrease in hardness. The results obtained are discussed in terms of solubility of carbon in the austenite and diffusion activation of Cr atoms. The precipitation was found to consist of two stages with activation energies of 196.5 kJ/g-mole at the first stage and 47.1 kJ/g-mole at the second stage.

A study of suppressed formation of low-conductivity phases in doped Li 7La 3Zr 2O 12 garnets by in situ neutron diffraction

DOE PAGES

Chen, Yan; Rangasamy, Ezhiylmurugan; dela Cruz, Clarina R.; ...

2015-09-28

Doped Li 7La 3Zr 2O 12 garnets, oxide-based solids with good Li + conductivity and compatibility, show great potential as leading electrolyte material candidates for all-solid-state lithium ion batteries. Still yet, the conductive bulk usually suffers from the presence of secondary phases and the transition towards a low-conductivity tetragonal phase during synthesis. Dopants are designed to stabilize the high-conductive cubic phase and suppress the formation of the low-conductivity phases. In situ neutron diffraction enables a direct observation of the doping effects by monitoring the phase evolutions during garnet synthesis. It reveals the reaction mechanism involving the temporary presence of intermediatemore » phases. The off-stoichiometry due to the liquid Li 2CO 3 evaporation leads to the residual of the low-conductivity intermediate phase in the as-synthesized bulk. Appropriate doping of an active element may alter the component of the intermediate phases and promote the completion of the reaction. While the dopants aid to stabilize most of the cubic phase, a small amount of tetragonal phase tends to form under a diffusion process. Lastly, the in situ observations provide the guideline of process optimization to suppress the formation of unwanted low-conductivity phases.« less

Multi-Scale Modeling of the Gamma Radiolysis of Nitrate Solutions.

PubMed

Horne, Gregory P; Donoclift, Thomas A; Sims, Howard E; Orr, Robin M; Pimblott, Simon M

2016-11-17

A multiscale modeling approach has been developed for the extended time scale long-term radiolysis of aqueous systems. The approach uses a combination of stochastic track structure and track chemistry as well as deterministic homogeneous chemistry techniques and involves four key stages: radiation track structure simulation, the subsequent physicochemical processes, nonhomogeneous diffusion-reaction kinetic evolution, and homogeneous bulk chemistry modeling. The first three components model the physical and chemical evolution of an isolated radiation chemical track and provide radiolysis yields, within the extremely low dose isolated track paradigm, as the input parameters for a bulk deterministic chemistry model. This approach to radiation chemical modeling has been tested by comparison with the experimentally observed yield of nitrite from the gamma radiolysis of sodium nitrate solutions. This is a complex radiation chemical system which is strongly dependent on secondary reaction processes. The concentration of nitrite is not just dependent upon the evolution of radiation track chemistry and the scavenging of the hydrated electron and its precursors but also on the subsequent reactions of the products of these scavenging reactions with other water radiolysis products. Without the inclusion of intratrack chemistry, the deterministic component of the multiscale model is unable to correctly predict experimental data, highlighting the importance of intratrack radiation chemistry in the chemical evolution of the irradiated system.

Bulk purification and deposition methods for selective enrichment in high aspect ratio single-walled carbon nanotubes.

PubMed

Bhatt, Nidhi P; Vichchulada, Pornnipa; Lay, Marcus D

2012-06-06

Aqueous batch processing methods for the concurrent purification of single-walled carbon nanotube (SWNT) soot and enrichment in high aspect ratio nanotubes are essential to their use in a wide variety of electronic, structural, and mechanical applications. This manuscript presents a new route to the bulk purification and enrichment of unbundled SWNTs having average lengths in excess of 2 μm. Iterative centrifugation cycles at low centripetal force not only removed amorphous C and catalyst nanoparticles but also allowed the enhanced buoyancy of surfactant encapsulated, unbundled, high aspect ratio SWNTs to be used to isolate them in the supernatant. UV-vis-NIR and Raman spectroscopy were used to verify the removal of residual impurities from as-produced (AP-grade) arc discharge soot and the simultaneous enrichment in unbundled, undamaged, high aspect ratio SWNTs. The laminar flow deposition process (LFD) used to form two-dimensional networks of SWNTs prevented bundle formation during network growth. Additionally, it further enhanced the quality of deposits by taking advantage of the inverse relationship between the translational diffusion coefficient and length for suspended nanoparticles. This resulted in preferential deposition of pristine, unbundled, high aspect ratio SWNTs over residual impurities, as observed by Raman spectroscopy and atomic force microscopy (AFM).

Effect of Ca substitution on some physical properties of nano-structured and bulk Ni-ferrite samples

NASA Astrophysics Data System (ADS)

Assar, S. T.; Abosheiasha, H. F.

2015-01-01

Nanoparticles of Ni1-xCaxFe2O4 (x=0.0, 0.02, 0.04, 0.06 and 0.10) were prepared by citrate precursor method. A part of these samples was sintered at 600 °C for 2 h in order to keep the particles within the nano-size while the other part was sintered at 1000 °C to let the particles to grow to the bulk size. The effect of Ca2+ ion substitution in nickel ferrite on some structural, magnetic, electrical and thermal properties was investigated. All samples were characterized by using X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR) and vibrating sample magnetometer (VSM). A two probe method was used to measure the dc electrical conductivity whereas the photoacoustic (PA) technique was used to determine the thermal diffusivity of the samples. To interpret different experimental results for nano and bulk samples some cation distributions were assumed based on the VSM and XRD data. These suggested cation distributions give logical explanations for other experimental results such as the observed values of the absorption bands in FTIR spectra and the dc conductivity results. Finally, in the thermal measurements it was found that increasing the Ca2+ ion content causes a decrease in the thermal diffusivity of both nano and bulk samples. The explanation of this behavior is ascribed to the phonon-phonon scattering.

Phototransformation rate constants of PAHs associated with soot particles.

PubMed

Kim, Daekyun; Young, Thomas M; Anastasio, Cort

2013-01-15

Photodegradation is a key process governing the residence time and fate of polycyclic aromatic hydrocarbons (PAHs) in particles, both in the atmosphere and after deposition. We have measured photodegradation rate constants of PAHs in bulk deposits of soot particles illuminated with simulated sunlight. The photodegradation rate constants at the surface (k(p)(0)), the effective diffusion coefficients (D(eff)), and the light penetration depths (z(0.5)) for PAHs on soot layers of variable thickness were determined by fitting experimental data with a model of coupled photolysis and diffusion. The overall disappearance rates of irradiated low molecular weight PAHs (with 2-3 rings) on soot particles were influenced by fast photodegradation and fast diffusion kinetics, while those of high molecular weight PAHs (with 4 or more rings) were apparently controlled by either the combination of slow photodegradation and slow diffusion kinetics or by very slow diffusion kinetics alone. The value of z(0.5) is more sensitive to the soot layer thickness than the k(p)(0) value. As the thickness of the soot layer increases, the z(0.5) values increase, but the k(p)(0) values are almost constant. The effective diffusion coefficients calculated from dark experiments are generally higher than those from the model fitting method for illumination experiments. Due to the correlation between k(p)(0) and z(0.5) in thinner layers, D(eff) should be estimated by an independent method for better accuracy. Despite some limitations of the model used in this study, the fitted parameters were useful for describing empirical results of photodegradation of soot-associated PAHs. Copyright © 2012 Elsevier B.V. All rights reserved.

Hybrid MD-Nernst Planck Model of Alpha-hemolysin Conductance Properties

NASA Technical Reports Server (NTRS)

Cozmuta, Ioana; O'Keefer, James T.; Bose, Deepak; Stolc, Viktor

2006-01-01

Motivated by experiments in which an applied electric field translocates polynucleotides through an alpha-hemolysin protein channel causing ionic current transient blockade, a hybrid simulation model is proposed to predict the conductance properties of the open channel. Time scales corresponding to ion permeation processes are reached using the Poisson-Nemst-Planck (PNP) electro-diffusion model in which both solvent and local ion concentrations are represented as a continuum. The diffusion coefficients of the ions (K(+) and Cl(-)) input in the PNP model are, however, calculated from all-atom molecular dynamics (MD). In the MD simulations, a reduced representation of the channel is used. The channel is solvated in a 1 M KCI solution, and an external electric field is applied. The pore specific diffusion coefficients for both ionic species are reduced 5-7 times in comparison to bulk values. Significant statistical variations (17-45%) of the pore-ions diffusivities are observed. Within the statistics, the ionic diffusivities remain invariable for a range of external applied voltages between 30 and 240mV. In the 2D-PNP calculations, the pore stem is approximated by a smooth cylinder of radius approx. 9A with two constriction blocks where the radius is reduced to approx. 6A. The electrostatic potential includes the contribution from the atomistic charges. The MD-PNP model shows that the atomic charges are responsible for the rectifying behaviour and for the slight anion selectivity of the a-hemolysin pore. Independent of the hierarchy between the anion and cation diffusivities, the anionic contribution to the total ionic current will dominate. The predictions of the MD-PNP model are in good agreement with experimental data and give confidence in the present approach of bridging time scales by combining a microscopic and macroscopic model.

Multiscale diffusion of a molecular probe in a crowded environment: a concept

NASA Astrophysics Data System (ADS)

Currie, Megan; Thao, Chang; Timerman, Randi; Welty, Robb; Berry, Brenden; Sheets, Erin D.; Heikal, Ahmed A.

2015-08-01

Living cells are crowded with macromolecules and organelles. Yet, it is not fully understood how macromolecular crowding affects the myriad of biochemical reactions, transport and the structural stability of biomolecules that are essential to cellular function and survival. These molecular processes, with or without electrostatic interactions, in living cells are therefore expected to be distinct from those carried out in test tube in dilute solutions where excluded volumes are absent. Thus there is an urgent need to understand the macromolecular crowding effects on cellular and molecular biophysics towards quantitative cell biology. In this report, we investigated how biomimetic crowding affects both the rotational and translation diffusion of a small probe (rhodamine green, RhG). For biomimetic crowding agents, we used Ficoll-70 (synthetic polymer), bovine serum albumin and ovalbumin (proteins) at various concentrations in a buffer at room temperature. As a control, we carried out similar measurements on glycerolenriched buffer as an environment with homogeneous viscosity as a function of glycerol concentration. The corresponding bulk viscosity was measured independently to test the validity of the Stokes-Einstein model of a diffusing species undergoing a random walk. For rotational diffusion (ps-ns time scale), we used time-resolved anisotropy measurements to examine potential binding of RhG as a function of the crowding agents (surface structure and size). For translational diffusion (μs-s time scale), we used fluorescence correlation spectroscopy for single-molecule fluctuation analysis. Our results allow us to examine the diffusion model of a molecular probe in crowded environments as a function of concentration, length scale, homogeneous versus heterogeneous viscosity, size and surface structures. These biomimetic crowding studies, using non-invasive fluorescence spectroscopy methods, represent an important step towards understanding cellular biophysics and quantitative cell biology.

Photochemical oxidation of water and reduction of polyoxometalate anions at interfaces of water with ionic liquids or diethylether

PubMed Central

Bernardini, Gianluca; Wedd, Anthony G.; Zhao, Chuan; Bond, Alan M.

2012-01-01

Photoreduction of [P2W18O62]6-, [S2Mo18O62]4-, and [S2W18O62]4- polyoxometalate anions (POMs) and oxidation of water occurs when water–ionic liquid and water–diethylether interfaces are irradiated with white light (275–750 nm) or sunlight. The ionic liquids (ILs) employed were aprotic ([Bmim]X; Bmim = (1-butyl-3-methylimidazolium,X = BF4,PF6) and protic (DEAS = diethanolamine hydrogen sulphate; DEAP = diethanolamine hydrogen phosphate). Photochemical formation of reduced POMs at both thermodynamically stable and unstable water–IL interfaces led to their initial diffusion into the aqueous phase and subsequent extraction into the IL phase. The mass transport was monitored visually by color change and by steady-state voltammetry at microelectrodes placed near the interface and in the bulk solution phases. However, no diffusion into the organic phase was observed when [P2W18O62]6- was photo-reduced at the water–diethylether interface. In all cases, water acted as the electron donor to give the overall process: 4POM + 2H2O + hν → 4POM- + 4H+ + O2. However, more highly reduced POM species are likely to be generated as intermediates. The rate of diffusion of photo-generated POM- was dependent on the initial concentration of oxidized POM and the viscosity of the IL (or mixed phase system produced in cases in which the interface is thermodynamically unstable). In the water-DEAS system, the evolution of dioxygen was monitored in situ in the aqueous phase by using a Clark-type oxygen sensor. Differences in the structures of bulk and interfacial water are implicated in the activation of water. An analogous series of reactions occurred upon irradiation of solid POM salts in the presence of water vapor. PMID:22753501

Monte Carlo Modeling of VLWIR HgCdTe Interdigitated Pixel Response

NASA Astrophysics Data System (ADS)

D'Souza, A. I.; Stapelbroek, M. G.; Wijewarnasuriya, P. S.

2010-07-01

Increasing very long-wave infrared (VLWIR, λ c ≈ 15 μm) pixel operability was approached by subdividing each pixel into four interdigitated subpixels. High response is maintained across the pixel, even if one or two interdigitated subpixels are deselected (turned off), because interdigitation provides that the preponderance of minority carriers photogenerated in the pixel are collected by the selected subpixels. Monte Carlo modeling of the photoresponse of the interdigitated subpixel simulates minority-carrier diffusion from carrier creation to recombination. Each carrier generated at an appropriately weighted random location is assigned an exponentially distributed random lifetime τ i, where < τ i> is the bulk minority-carrier lifetime. The minority carrier is allowed to diffuse for a short time d τ, and the fate of the carrier is decided from its present position and the boundary conditions, i.e., whether the carrier is absorbed in a junction, recombined at a surface, reflected from a surface, or recombined in the bulk because it lived for its designated lifetime. If nothing happens, the process is then repeated until one of the boundary conditions is attained. The next step is to go on to the next carrier and repeat the procedure for all the launches of minority carriers. For each minority carrier launched, the original location and boundary condition at fatality are recorded. An example of the results from Monte Carlo modeling is that, for a 20- μm diffusion length, the calculated quantum efficiency (QE) changed from 85% with no subpixels deselected, to 78% with one subpixel deselected, 67% with two subpixels deselected, and 48% with three subpixels deselected. Demonstration of the interdigitated pixel concept and verification of the Monte Carlo modeling utilized λ c(60 K) ≈ 15 μm HgCdTe pixels in a 96 × 96 array format. The measured collection efficiency for one, two, and three subelements selected, divided by the collection efficiency for all four subelements selected, matched that calculated using Monte Carlo modeling.

Simulations of Model Microswimmers with Fully Resolved Hydrodynamics

NASA Astrophysics Data System (ADS)

Oyama, Norihiro; Molina, John J.; Yamamoto, Ryoichi

2017-10-01

Swimming microorganisms, which include bacteria, algae, and spermatozoa, play a fundamental role in most biological processes. These swimmers are a special type of active particle, that continuously convert local energy into propulsive forces, thereby allowing them to move through their surrounding fluid medium. While the size, shape, and propulsion mechanism vary from one organism to the next, they share certain general characteristics: they exhibit force-free motion and they swim at a small Reynolds number. To study the dynamics of such systems, we use the squirmer model, which provides an ideal representation of swimmers as spheroidal particles that propel owing to a modified boundary condition at their surface. We have considered the single-particle and many-particle dynamics of swimmers in bulk and confined systems using the smoothed profile method, which allows us to efficiently solve the coupled particle-fluid problem. For the single-particle dynamics, we studied the diffusive behavior caused by the swimming of the particles. At short-time scales, the diffusion is caused by the hydrodynamic interactions, whereas at long-time scales, it is determined by the particle-particle collisions. Thus, the short-time diffusion will be the same for both swimmers and inert tracer particles. We then investigated the dynamics of confined microswimmers using cylindrical and parallel-plate confining walls. For the cylindrical confinement, we find evidence of an order/disorder phase transition which depends on the specific type of swimmers and the size of the cylinder. Under parallel-plane walls, some swimmers exhibit wavelike modes, which lead to traveling density waves that bounce back and forth between the walls. From an analysis of the bulk systems, we can show that this wavelike motion can be understood as a pseudoacoustic mode and is a consequence of the intrinsic swimming properties of the particles. The results presented here, together with the simulation method that we have developed, allow us to better understand the complex hydrodynamic interactions in microswimmer dispersions.

Bifunctional catalytic electrode

NASA Technical Reports Server (NTRS)

Cisar, Alan (Inventor); Murphy, Oliver J. (Inventor); Clarke, Eric (Inventor)

2005-01-01

The present invention relates to an oxygen electrode for a unitized regenerative hydrogen-oxygen fuel cell and the unitized regenerative fuel cell having the oxygen electrode. The oxygen electrode contains components electrocatalytically active for the evolution of oxygen from water and the reduction of oxygen to water, and has a structure that supports the flow of both water and gases between the catalytically active surface and a flow field or electrode chamber for bulk flow of the fluids. The electrode has an electrocatalyst layer and a diffusion backing layer interspersed with hydrophilic and hydrophobic regions. The diffusion backing layer consists of a metal core having gas diffusion structures bonded to the metal core.

Molecular and macro-scale analysis of enzyme-crosslinked silk hydrogels for rational biomaterial design.

PubMed

McGill, Meghan; Coburn, Jeannine M; Partlow, Benjamin P; Mu, Xuan; Kaplan, David L

2017-11-01

Silk fibroin-based hydrogels have exciting applications in tissue engineering and therapeutic molecule delivery; however, their utility is dependent on their diffusive properties. The present study describes a molecular and macro-scale investigation of enzymatically-crosslinked silk fibroin hydrogels, and demonstrates that these systems have tunable crosslink density and diffusivity. We developed a liquid chromatography tandem mass spectroscopy (LC-MS/MS) method to assess the quantity and order of covalent tyrosine crosslinks in the hydrogels. This analysis revealed between 28 and 56% conversion of tyrosine to dityrosine, which was dependent on the silk concentration and reactant concentration. The crosslink density was then correlated with storage modulus, revealing that both crosslinking and protein concentration influenced the mechanical properties of the hydrogels. The diffusive properties of the bulk material were studied by fluorescence recovery after photobleaching (FRAP), which revealed a non-linear relationship between silk concentration and diffusivity. As a result of this work, a model for synthesizing hydrogels with known crosslink densities and diffusive properties has been established, enabling the rational design of silk hydrogels for biomedical applications. Hydrogels from naturally-derived silk polymers offer versitile opportunities in the biomedical field, however, their design has largely been an empirical process. We present a fundamental study of the crosslink density, storage modulus, and diffusion behavior of enzymatically-crosslinked silk hydrogels to better inform scaffold design. These studies revealed unexpected non-linear trends in the crosslink density and diffusivity of silk hydrogels with respect to protein concentration and crosslink reagent concentration. This work demonstrates the tunable diffusivity and crosslinking in silk fibroin hydrogels, and enables the rational design of biomaterials. Further, the characterization methods presented have applications for other materials with dityrosine crosslinks, which are found in nature as post-translational modificaitons, as well as in engineered matrices such as tyramine-substituted hyaluronic acid and recombinant resilin. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Evaluation of Electroplated Co-P Film as Diffusion Barrier Between In-48Sn Solder and SiC-Dispersed Bi2Te3 Thermoelectric Material

NASA Astrophysics Data System (ADS)

Li, Siyang; Yang, Donghua; Tan, Qing; Li, Liangliang

2015-06-01

The diffusion barrier property of Co-P film as a buffer layer between SiC-dispersed Bi2Te3 bulk material and In-48Sn solder was investigated. A Co-P film with thickness of ~6 µm was electroplated on SiC-dispersed Bi2Te3 substrate, joined with In-48Sn solder by a reflow process, and annealed at 100°C for up to 625 h. The formation and growth kinetics of intermetallic compounds (IMCs) at the interface between the In-48Sn and substrate were studied using transmission electron microscopy and scanning electron microscopy with energy-dispersive x-ray spectroscopy. The results showed that crystalline Co(In,Sn)3 formed as an irregular layer adjacent to the solder side at the solder/Co-P interface due to diffusion of Co towards the solder, and a small amount of amorphous Co45P13In12Sn30 appeared at the Co-P side because of diffusion of In and Sn into Co-P. The growth of Co(In,Sn)3 and Co45P13In12Sn30 during solid-state aging was slow, being controlled by interfacial reaction and diffusion, respectively. For comparison, In-48Sn/Bi2Te3-SiC joints were prepared and the IMCs in the joints analyzed. Without a diffusion barrier, In penetrated rapidly into the substrate, which led to the formation of amorphous In x Bi y phase in crystalline In4Te3 matrix. These IMCs grew quickly with prolongation of the annealing time, and their growth was governed by volume diffusion of elements. The experimental data demonstrate that electroplated Co-P film is an effective diffusion barrier for use in Bi2Te3-based thermoelectric modules.

Determination of In-situ Porosity and Investigation of Diffusion Processes at the Grimsel Test Site, Switzerland.

NASA Astrophysics Data System (ADS)

Biggin, C.; Ota, K.; Siittari-Kauppi, M.; Moeri, A.

2004-12-01

In the context of a repository for radioactive waste, 'matrix diffusion' is used to describe the process by which solute, flowing in distinct flow paths, penetrates the surrounding rock matrix. Diffusion into the matrix occurs in a connected system of pores or microfractures. Matrix diffusion provides a mechanism for greatly enlarging the area of rock surface in contact with advecting radionuclides, from that of the flow path surfaces (and infills), to a much larger portion of the bulk rock and increases the global pore volume which can retard radionuclides. In terms of a repository safety assessment, demonstration of a significant depth of diffusion-accessible pore space may result in a significant delay in the calculated release of any escaping radionuclides to the environment and a dramatic reduction in the resulting concentration released into the biosphere. For the last decade, Nagra has investigated in situ matrix diffusion at the Grimsel Test Site (GTS) in the Swiss Alps. The in situ investigations offer two distinct advantages to those performed in the lab, namely: 1. Lab-based determination of porosity and diffusivity can lead to an overestimation of matrix diffusion due to stress relief when the rock is sampled (which would overestimate the retardation in the geosphere) 2. Lab-based analysis usually examines small (cm scale) samples and cannot therefore account for any matrix heterogeneity over the hundreds or thousands of metres a typical flow path The in situ investigations described began with the Connected Porosity project, wherein a specially developed acrylic resin was injected into the rock matrix to fill the pore space and determine the depth of connected porosity. The resin was polymerised in situ and the entire rock mass removed by overcoring. The results indicated that lab-based porosity measurements may be two to three times higher than those obtained in situ. While the depth of accessible matrix from a water-conducting feature assumed in repository performance assessments is generally 1 to 10 cm, the results from the GTS in situ experiment suggested depths of several metres could be more appropriate. More recently, the Pore Space Geometry (PSG) experiment at the GTS has used a C-14 doped acrylic resin, combined with state-of-the-art digital beta autoradiography and fluorescence detection to examine a larger area of rock for determination of porosity and the degree of connected pore space. Analysis is currently ongoing and the key findings will be reported in this paper. Starting at the GTS in 2005, the Long-term Diffusion (LTD) project will investigate such processes over spatial and temporal scales more relevant to a repository than traditional lab-based experiments. In the framework of this experiment, long-term (10 to 50 years) in situ diffusion experiments and resin injection experiments are planned to verify current models for matrix diffusion as a radionuclide retardation process. This paper will discuss the findings of the first two experiments and their significance to repository safety assessments before discussing the strategy for the future in relation to the LTD project.

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

Nagata, Kohki, E-mail: nagata.koki@iri-tokyo.jp; School of Science and Technology, Meiji University, 1-1-1 Higashimita, Tama-ku, Kawasaki, Kanagawa 214-8571; Ogura, Atsushi

The effects of the fabrication process conditions on the microstructure of silicon dioxide thin films of <10 nm thickness are presented. The microstructure was investigated using grazing-incidence wide and small-angle X-ray scattering methods with synchrotron radiation. The combination of a high brilliance light source and grazing incident configuration enabled the observation of very weak diffuse X-ray scattering from SiO{sub 2} thin films. The results revealed different microstructures, which were dependent on oxidizing species or temperature. The micro-level properties differed from bulk properties reported in the previous literature. It was indicated that these differences originate from inner stress. The detailed structure inmore » an amorphous thin film was not revealed owing to detection difficulties.« less

Hybrid method for numerical modelling of LWR coolant chemistry

NASA Astrophysics Data System (ADS)

Swiatla-Wojcik, Dorota

2016-10-01

A comprehensive approach is proposed to model radiation chemistry of the cooling water under exposure to neutron and gamma radiation at 300 °C. It covers diffusion-kinetic processes in radiation tracks and secondary reactions in the bulk coolant. Steady-state concentrations of the radiolytic products have been assessed based on the simulated time dependent concentration profiles. The principal reactions contributing to the formation of H2, O2 and H2O2 were indicated. Simulation was carried out depending on the amount of extra hydrogen dissolved in the coolant to reduce concentration of corrosive agents. High sensitivity to the rate of reaction H+H2O=OH+H2 is shown and discussed.

Photoluminescence characteristics of ZnTe bulk crystal and ZnTe epilayer grown on GaAs substrate by MOVPE

NASA Astrophysics Data System (ADS)

Lü, Hai-Yan; Mu, Qi; Zhang, Lei; Lü, Yuan-Jie; Ji, Zi-Wu; Feng, Zhi-Hong; Xu, Xian-Gang; Guo, Qi-Xin

2015-12-01

Excitation power and temperature-dependent photoluminescence (PL) spectra of the ZnTe epilayer grown on (100) GaAs substrate and ZnTe bulk crystal are investigated. The measurement results show that both the structures are of good structural quality due to their sharp bound excitonic emissions and absence of the deep level structural defect-related emissions. Furthermore, in contrast to the ZnTe bulk crystal, although excitonic emissions for the ZnTe epilayer are somewhat weak, perhaps due to As atoms diffusing from the GaAs substrate into the ZnTe epilayer and/or because of the strain-induced degradation of the crystalline quality of the ZnTe epilayer, neither the donor-acceptor pair (DAP) nor conduction band-acceptor (e-A) emissions are observed in the ZnTe epilayer. This indicates that by further optimizing the growth process it is possible to obtain a high-crystalline quality ZnTe heteroepitaxial layer that is comparable to the ZnTe bulk crystal. Project supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20120131110006), the Key Science and Technology Program of Shandong Province, China (Grant No. 2013GGX10221), the Key Laboratory of Functional Crystal Materials and Device (Shandong University, Ministry of Education), China (Grant No. JG1401), the National Natural Science Foundation of China (Grant No. 61306113), the Major Research Plan of the National Natural Science Foundation of China (Grant No. 91433112), and the Partnership Project for Fundamental Technology Researches of the Ministry of Education, Culture, Sports, Science and Technology, Japan.

Possibility of H2O2 decomposition in thin liquid films on Mars

NASA Astrophysics Data System (ADS)

Kereszturi, Akos; Gobi, Sandor

2014-11-01

In this work the pathways and possibilities of H2O2 decomposition on Mars in microscopic liquid interfacial water were analyzed by kinetic calculations. Thermal and photochemical driven decomposition, just like processes catalyzed by various metal oxides, is too slow compared to the annual duration while such microscopic liquid layers exist on Mars today, to produce substantial decomposition. The most effective analyzed process is catalyzed by Fe ions, which could decompose H2O2 under pH<4.5 with a half life of 1-2 days. This process might be important during volcanically influenced periods when sulfur release produces acidic pH, and rotational axis tilt change driven climatic changes also influence the volatile circulation and spatial occurrence just like the duration of thin liquid layer. Under current conditions, using the value of 200 K as the temperature in interfacial water (at the southern hemisphere), and applying Phoenix lander's wet chemistry laboratory results, the pH is not favorable for Fe mobility and this kind of decomposition. Despite current conditions (especially pH) being unfavorable for H2O2 decomposition, microscopic scale interfacial liquid water still might support the process. By the reaction called heterogeneous catalysis, without acidic pH and mobile Fe, but with minerals surfaces containing Fe decomposition of H2O2 with half life of 20 days can happen. This duration is still longer but not several orders than the existence of springtime interfacial liquid water on Mars today. This estimation is relevant for activation energy controlled reaction rates. The other main parameter that may influence the reaction rate is the diffusion speed. Although the available tests and theoretical calculations do not provide firm values for the diffusion speed in such a “2-dimensional” environment, using relevant estimations this parameter in the interfacial liquid layer is smaller than in bulk water. But the 20 days' duration mentioned above is still relevant, as the activation energy driven reaction rate is the main limiting factor in the decomposition and not the diffusion speed. The duration of dozen(s) days is still longer but not with orders of magnitude than the expected duration for the existence of springtime interfacial liquid water on Mars today. The results suggest such decomposition may happen today, however, because of our limited knowledge on chemical processes in thin interfacial liquid layers, this possibility waits for confirmation - and also points to the importance of conducting laboratory tests to validate the possible process. Although some tests were already realized for diffusion in an almost 2-dimensional liquid, the same is not true for activation energy, where only the value from the “normal” measurements was applied. Even if H2O2 decomposition is too slow today, the analysis of such a process is important, as under volcanic influence more effective decomposition might take place in thin interfacial liquids close to the climate of today if released sulfur produces pH<4.5. Large quantity and widespread occurrence of bulk liquid phase are not expected in the Amazonian period, but interfacial liquid water probably appeared regularly, and its locations, especially during volcanically active periods, might make certain sites than others more interesting for astrobiology with the lower concentration of oxidizing H2O2.

Helium measurements of pore fluids obtained from the San Andreas Fault Observatory at Depth (SAFOD, USA) drill cores

NASA Astrophysics Data System (ADS)

Ali, S.; Stute, M.; Torgersen, T.; Winckler, G.; Kennedy, B. M.

2011-02-01

4He accumulated in fluids is a well established geochemical tracer used to study crustal fluid dynamics. Direct fluid samples are not always collectable; therefore, a method to extract rare gases from matrix fluids of whole rocks by diffusion has been adapted. Helium was measured on matrix fluids extracted from sandstones and mudstones recovered during the San Andreas Fault Observatory at Depth (SAFOD) drilling in California, USA. Samples were typically collected as subcores or from drillcore fragments. Helium concentration and isotope ratios were measured 4-6 times on each sample, and indicate a bulk 4He diffusion coefficient of 3.5 ± 1.3 × 10-8 cm2 s-1 at 21°C, compared to previously published diffusion coefficients of 1.2 × 10-18 cm2 s-1 (21°C) to 3.0 × 10-15 cm2 s-1 (150°C) in the sands and clays. Correcting the diffusion coefficient of 4Hewater for matrix porosity (˜3%) and tortuosity (˜6-13) produces effective diffusion coefficients of 1 × 10-8 cm2 s-1 (21°C) and 1 × 10-7 (120°C), effectively isolating pore fluid 4He from the 4He contained in the rock matrix. Model calculations indicate that <6% of helium initially dissolved in pore fluids was lost during the sampling process. Complete and quantitative extraction of the pore fluids provide minimum in situ porosity values for sandstones 2.8 ± 0.4% (SD, n = 4) and mudstones 3.1 ± 0.8% (SD, n = 4).

Integration of bulk piezoelectric materials into microsystems

NASA Astrophysics Data System (ADS)

Aktakka, Ethem Erkan

Bulk piezoelectric ceramics, compared to deposited piezoelectric thin-films, provide greater electromechanical coupling and charge capacity, which are highly desirable in many MEMS applications. In this thesis, a technology platform is developed for wafer-level integration of bulk piezoelectric substrates on silicon, with a final film thickness of 5-100microm. The characterized processes include reliable low-temperature (200°C) AuIn diffusion bonding and parylene bonding of bulk-PZT on silicon, wafer-level lapping of bulk-PZT with high-uniformity (+/-0.5microm), and low-damage micro-machining of PZT films via dicing-saw patterning, laser ablation, and wet-etching. Preservation of ferroelectric and piezoelectric properties is confirmed with hysteresis and piezo-response measurements. The introduced technology offers higher material quality and unique advantages in fabrication flexibility over existing piezoelectric film deposition methods. In order to confirm the preserved bulk properties in the final film, diaphragm and cantilever beam actuators operating in the transverse-mode are designed, fabricated and tested. The diaphragm structure and electrode shapes/sizes are optimized for maximum deflection through finite-element simulations. During tests of fabricated devices, greater than 12microm PP displacement is obtained by actuation of a 1mm2 diaphragm at 111kHz with <7mW power consumption. The close match between test data and simulation results suggests that the piezoelectric properties of bulk-PZT5A are mostly preserved without any necessity of repolarization. Three generations of resonant vibration energy harvesters are designed, simulated and fabricated to demonstrate the competitive performance of the new fabrication process over traditional piezoelectric deposition systems. An unpackaged PZT/Si unimorph harvester with 27mm3 active device volume produces up to 205microW at 1.5g/154Hz. The prototypes have achieved the highest figure-of-merits (normalized-power-density x bandwidth) amongst previously reported inertial energy harvesters. The fabricated energy harvester is utilized to create an autonomous energy generation platform in 0.3cm3 by system-level integration of a 50-80% efficient power management IC, which incorporates a supply-independent bias circuitry, an active diode for low-dropout rectification, a bias-flip system for higher efficiency, and a trickle battery charger. The overall system does not require a pre-charged battery, and has power consumption of <1microW in active-mode (measured) and <5pA in sleep-mode (simulated). Under lg vibration at 155Hz, a 70mF ultra-capacitor is charged from OV to 1.85V in 50 minutes.

Mathematical Development of the Spill Assessment Model (SAM) for Hydrazine and Similar Acting Materials in Water Bodies.

DTIC Science & Technology

1980-02-01

migration of the chemical mass in the fluid volume according to two entirely different means, yet governed by the same form of the equation: molecular ...pressure or temperature gradients, gravitational or other body forces, or bulk fluid motion, is observed as molecular diffusion. In general, the...need be made at this stage as to whether the diffusion of a released mass in the fluid is molecular or turbulent in nature. The general form of the one

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

Emin, David, E-mail: emin@unm.edu; Akhtari, Massoud; Ellingson, B. M.

We analyze the transient-dc and frequency-dependent electrical conductivities between blocking electrodes. We extend this analysis to measurements of ions’ transport in freshly excised bulk samples of human brain tissue whose complex cellular structure produces blockages. The associated ionic charge-carrier density and diffusivity are consistent with local values for sodium cations determined non-invasively in brain tissue by MRI (NMR) and diffusion-MRI (spin-echo NMR). The characteristic separation between blockages, about 450 microns, is very much shorter than that found for sodium-doped gel proxies for brain tissue, >1 cm.

Bubble Formation Modeling in IE-911

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

Fondeur, F.F.

2000-09-27

The author used diffusion modeling to determine the hydrogen and oxygen concentration inside IE-911. The study revealed gas bubble nucleation will not occur in the bulk solution inside the pore or on the pore wall. This finding results from the fast oxygen and hydrogen gas molecular diffusion and a very confined pore space. The net steady state concentration of these species inside the pore proves too low to drive bubble nucleation. This study did not investigate other gas bubble nucleating mechanism such as suspended particles in solution.

76 FR 16263 - Revision to Electric Reliability Organization Definition of Bulk Electric System

Federal Register 2010, 2011, 2012, 2013, 2014

2011-03-23

...'s Reliability Standards Development Process, to revise its definition of the term ``bulk electric... definition of ``bulk electric system'' through the NERC Standards Development Process to address the... undertake the process of revising the bulk electric system definition to address the Commission's concerns...

Variability analysis of the bulk resistivity measured using concrete cylinders.

DOT National Transportation Integrated Search

2011-01-01

"Many agencies are interested in using a rapid test method for measuring the electrical properties of concrete (i.e., the : resistivity or conductivity) since the electrical properties can be related to fluid transport (e.g., ion diffusion). The adva...

Anomalous Diffusion of Water in Lamellar Membranes Formed by Pluronic Polymers

NASA Astrophysics Data System (ADS)

Zhang, Zhe; Ohl, Michael; Han, Youngkyu; Smith, Gregory; Do, Changwoo; Biology; Soft-Matter Division, Oak Ridge National Laboratory Team; Julich CenterNeutron Science Team

Water diffusion is playing an important role in polymer systems. We calculated the water diffusion coefficient at different layers along z-direction which is perpendicular to the lamellar membrane formed by Pluronic block copolymers (L62: (EO6-PO34-EO6)) with the molecular dynamics simulation trajectories. Water molecules at bulk layers are following the normal diffusion, while that at hydration layers formed by polyethylene oxide (PEO) and hydrophobic layers formed by polypropylene oxide (PPO) are following anomalous diffusion. We find that although the subdiffusive regimes at PEO layers and PPO layers are the same, which is the fractional Brownian motion, however, the dynamics are different, i.e. diffusion at the PEO layers is much faster than that at the PPO layers, and meanwhile it exhibits a normal diffusive approximation within a short time period which is governed by the localized free self-diffusion, but becomes subdiffusive after t >8 ps, which is governed by the viscoelastic medium. The Scientific User Facilities Division, Office of Basic Energy Sciences, U.S. Department of Energy; and Zhe Zhang gratefully acknowledges financial support from Julich Center for Neutron Science.

Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane-water interface

NASA Astrophysics Data System (ADS)

Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale

2011-12-01

The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol-capped gold nanoparticles at the hexane-water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). A series of gold colloids were made using nanoparticles ranging in size from 1.60 to 2.85 nm dissolved in hexane for the interfacial tension analysis. Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense monolayer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. (Phys Chem Chem Phys 9:6351-6358, 2007). The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol-capped gold nanoparticles at liquid-liquid interfaces.

CdCl2 Passivation of Polycrystalline CdMgTe and CdZnTe Absorbers for Tandem Photovoltaic Cells

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

Metzger, Wyatt K; Swanson, Drew; Reich, Carey

As single-junction silicon solar cells approach their theoretical limits, tandems provide the primary path to higher efficiencies. CdTe alloys can be tuned with magnesium (CdMgTe) or zinc (CdZnTe) for ideal tandem pairing with silicon. A II-VI/Si tandem holds the greatest promise for inexpensive, high-efficiency top cells that can be quickly deployed in the market using existing polycrystalline CdTe manufacturing lines combined with mature silicon production lines. Currently, all high efficiency polycrystalline CdTe cells require a chloride-based passivation process to passivate grain boundaries and bulk defects. This research examines the rich chemistry and physics that has historically limited performance when extendingmore » Cl treatments to polycrystalline 1.7-eV CdMgTe and CdZnTe absorbers. A combination of transmittance, quantum efficiency, photoluminescence, transmission electron microscopy, and energy-dispersive X-ray spectroscopy clearly reveals that during passivation, Mg segregates and out-diffuses, initially at the grain boundaries but eventually throughout the bulk. CdZnTe exhibits similar Zn segregation behavior; however, the onset and progression is localized to the back of the device. After passivation, CdMgTe and CdZnTe can render a layer that is reduced to predominantly CdTe electro-optical behavior. Contact instabilities caused by inter-diffusion between the layers create additional complications. The results outline critical issues and paths for these materials to be successfully implemented in Si-based tandems and other applications.« less

The staging mechanism of AlCl4 intercalation in a graphite electrode for an aluminium-ion battery.

PubMed

Bhauriyal, Preeti; Mahata, Arup; Pathak, Biswarup

2017-03-15

Identifying a suitable electrode material with desirable electrochemical properties remains a primary challenge for rechargeable Al-ion batteries. Recently an ultrafast rechargeable Al-ion battery was reported with high charge/discharge rate, (relatively) high discharge voltage and high capacity that uses a graphite-based cathode. Using calculations from first-principles, we have investigated the staging mechanism of AlCl 4 intercalation into bulk graphite and evaluated the stability, specific capacity and voltage profile of AlCl 4 intercalated compounds. Ab initio molecular dynamics is performed to investigate the thermal stability of AlCl 4 intercalated graphite structures. Our voltage profiles show that the first AlCl 4 intercalation step could be a more sluggish step than the successive intercalation steps. However, the diffusion of AlCl 4 is very fast in the expanded graphite host layers with a diffusion barrier of ∼0.01 eV, which justifies the ultrafast charging rate of a graphite based Al-ion battery. And such an AlCl 4 intercalated battery provides an average voltage of 2.01-2.3 V with a maximum specific capacity of 69.62 mA h g -1 , which is excellent for anion intercalated batteries. Our density of states and Bader charge analysis shows that the AlCl 4 intercalation into the bulk graphite is a charging process. Hence, we believe that our present study will be helpful in understanding the staging mechanism of AlCl 4 intercalation into graphite-like layered electrodes for Al-ion batteries, thus encouraging further experimental work.

Ultra-fast grain boundary diffusion and its contribution to surface segregation on a martensitic steel. Experiments and modeling

NASA Astrophysics Data System (ADS)

Christien, F.; Le Gall, R.

2011-09-01

Phosphorus surface segregation was measured by Auger Electron Spectroscopy on a 17-4 PH martensitic stainless steel at 450, 550 and 600 °C. Surface segregation was shown to be much faster than expected which was attributed to a high contribution of phosphorus diffusion along the former austenitic grain boundaries. A model of surface segregation was developed following the Darken-du Plessis approach and taking account of both bulk and grain boundary solute diffusion. The phosphorus grain boundary diffusion coefficient in 17-4 PH was estimated: DGB< = 6.2 10 4 exp(- 157 kJ mol - 1 /RT)cm 2 s - 1 . It is found to be more than three orders of magnitude higher in 17-4 PH steel than in α-iron.

Molecular dynamics study of rhodamine 6G diffusion at n-decane-water interfaces.

PubMed

Popov, Piotr; Steinkerchner, Leo; Mann, Elizabeth K

2015-05-01

Two-dimensional diffusion of a rhodamine 6G fluorescent tracer molecule at the n-decane-water interface was studied with all-atom molecular dynamics simulations. In agreement with experimental data, we find increased mobility of the tracer at the n-decane-water interfaces in comparison to its mobility in bulk water. Orientational ordering of water and n-decane molecules near the interface is observed, and may change the interfacial viscosity as suggested to explain the experimental data. However, the restricted rotational motion of the rhodamine molecule at the interface suggests that the Saffman-Delbrück model may be a more appropriate approximation of rhodamine diffusion at n-decane-water interfaces, and, without any decrease in interfacial viscosity, suggests faster diffusion consistent with both experimental and simulation values.

Anomalous cation diffusion in salt-doped confined bilayer ice.

PubMed

Qiu, Hu; Xue, Minmin; Shen, Chun; Guo, Wanlin

2018-05-17

The diffusive dynamics of aqueous electrolyte solutions in nanoconfined spaces has attracted considerable attention due to their potential applications in desalination, biosensors and supercapacitors. Here we show by molecular dynamics simulations that lithium and sodium ions diffuse at a rate at least an order of magnitude higher than that of water molecules when the ions are trapped in an ice bilayer confined between two parallel plates. This novel picture is in sharp contrast to the prevailing view that the diffusion rate of ions is comparable to or even lower than that of water in both bulk and confined solutions. The predicted high ion mobility stems from frequent lateral hopping of ions along the coordination sites inside the hydrogen-bonding network connecting the two water layers of the ice bilayer. This anomalous diffusion should provide new insights into the physics of confined aqueous electrolytes.

Diffusion lengths of silicon solar cells from luminescence images

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

Wuerfel, P.; Trupke, T.; Puzzer, T.

A method for spatially resolved measurement of the minority carrier diffusion length in silicon wafers and in silicon solar cells is introduced. The method, which is based on measuring the ratio of two luminescence images taken with two different spectral filters, is applicable, in principle, to both photoluminescence and electroluminescence measurements and is demonstrated experimentally by electroluminescence measurements on a multicrystalline silicon solar cell. Good agreement is observed with the diffusion length distribution obtained from a spectrally resolved light beam induced current map. In contrast to the determination of diffusion lengths from one single luminescence image, the method proposed heremore » gives absolute values of the diffusion length and, in comparison, it is much less sensitive to lateral voltage variations across the cell area as caused by local variations of the series resistance. It is also shown that measuring the ratio of two luminescence images allows distinguishing shunts or surface defects from bulk defects.« less

Proton transfer and the diffusion of H+ and OH- ions along water wires.

PubMed

Lee, Song Hi; Rasaiah, Jayendran C

2013-09-28

Hydrogen and hydroxide ion transport in narrow carbon nanotubes (CNTs) of diameter 8.1 Å and lengths up to 582 Å are investigated by molecular dynamics simulations using a dissociating water model. The diffusion coefficients of the free ions in an open chain are significantly larger than in periodically replicated wires that necessarily contain D or L end defects, and both are higher than they are in bulk water. The free hydroxide ion diffuses faster than the free hydronium ion in short CNTs, unlike diffusion in liquid water, and both coefficients increase and converge to nearly the same value with increasing tube length. The diffusion coefficients of the two ions increase further when the tubes are immersed in a water reservoir and they move easily out of the tube, suggesting an additional pathway for proton transport via OH(-) ions in biological channels.

Theoretical models for supercritical fluid extraction.

PubMed

Huang, Zhen; Shi, Xiao-Han; Jiang, Wei-Juan

2012-08-10

For the proper design of supercritical fluid extraction processes, it is essential to have a sound knowledge of the mass transfer mechanism of the extraction process and the appropriate mathematical representation. In this paper, the advances and applications of kinetic models for describing supercritical fluid extraction from various solid matrices have been presented. The theoretical models overviewed here include the hot ball diffusion, broken and intact cell, shrinking core and some relatively simple models. Mathematical representations of these models have been in detail interpreted as well as their assumptions, parameter identifications and application examples. Extraction process of the analyte solute from the solid matrix by means of supercritical fluid includes the dissolution of the analyte from the solid, the analyte diffusion in the matrix and its transport to the bulk supercritical fluid. Mechanisms involved in a mass transfer model are discussed in terms of external mass transfer resistance, internal mass transfer resistance, solute-solid interactions and axial dispersion. The correlations of the external mass transfer coefficient and axial dispersion coefficient with certain dimensionless numbers are also discussed. Among these models, the broken and intact cell model seems to be the most relevant mathematical model as it is able to provide realistic description of the plant material structure for better understanding the mass-transfer kinetics and thus it has been widely employed for modeling supercritical fluid extraction of natural matters. Copyright © 2012 Elsevier B.V. All rights reserved.

Solubility and Diffusivity: Important Metrics in the Search for the Root Cause of Light- and Elevated Temperature-Induced Degradation

DOE PAGES

Jensen, Mallory A.; Morishige, Ashley E.; Chakraborty, Sagnik; ...

2018-02-02

Light- and elevated temperature-induced degradation (LeTID) is a detrimental effect observed under operating conditions in p-type multicrystalline silicon (mc-Si) solar cells. In this paper, we employ synchrotron-based techniques to study the dissolution of precipitates due to different firing processes at grain boundaries in LeTID-affected mc-Si. The synchrotron measurements show clear dissolution of collocated metal precipitates during firing. We compare our observations with degradation behavior in the same wafers. The experimental results are complemented with process simulations to provide insight into the change in bulk point defect concentration due to firing. Several studies have proposed that LeTID is caused by metal-richmore » precipitate dissolution during contact firing, and we find that the solubility and diffusivity are promising screening metrics to identify metals that are compatible with this hypothesis. While slower and less soluble elements (e.g., Fe and Cr) are not compatible according to our simulations, the point defect concentrations of faster and more soluble elements (e.g., Cu and Ni) increase after a high-temperature firing process, primarily due to emitter segregation rather than precipitate dissolution. Finally, these results are a useful complement to lifetime spectroscopy techniques, and can be used to evaluate additional candidates in the search for the root cause of LeTID.« less

Solubility and Diffusivity: Important Metrics in the Search for the Root Cause of Light- and Elevated Temperature-Induced Degradation

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

Jensen, Mallory A.; Morishige, Ashley E.; Chakraborty, Sagnik

Light- and elevated temperature-induced degradation (LeTID) is a detrimental effect observed under operating conditions in p-type multicrystalline silicon (mc-Si) solar cells. In this paper, we employ synchrotron-based techniques to study the dissolution of precipitates due to different firing processes at grain boundaries in LeTID-affected mc-Si. The synchrotron measurements show clear dissolution of collocated metal precipitates during firing. We compare our observations with degradation behavior in the same wafers. The experimental results are complemented with process simulations to provide insight into the change in bulk point defect concentration due to firing. Several studies have proposed that LeTID is caused by metal-richmore » precipitate dissolution during contact firing, and we find that the solubility and diffusivity are promising screening metrics to identify metals that are compatible with this hypothesis. While slower and less soluble elements (e.g., Fe and Cr) are not compatible according to our simulations, the point defect concentrations of faster and more soluble elements (e.g., Cu and Ni) increase after a high-temperature firing process, primarily due to emitter segregation rather than precipitate dissolution. Finally, these results are a useful complement to lifetime spectroscopy techniques, and can be used to evaluate additional candidates in the search for the root cause of LeTID.« less

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

Transport of gases between the environment and alveoli – theoretical foundations

PubMed Central

Butler, James P.; Tsuda, Akira

2015-01-01

The transport of oxygen and carbon dioxide in the gas phase from the ambient environment to and from the alveolar gas/blood interface is accomplished through the tracheobronchial tree, and involves mechanisms of bulk or convective transport and diffusive net transport. The geometry of the airway tree and the fluid dynamics of these two transport processes combine in such a way that promotes a classical fractionation of ventilation into dead space and alveolar ventilation respectively. This simple picture continues to capture much of the essence of gas phase transport. On the other hand, a more detailed look at the interaction of convection and diffusion leads to significant new issues, many of which remain open questions. These are associated with parallel and serial inhomogeneities especially within the distal acinar units, velocity profiles in distal airways and terminal spaces subject to moving boundary conditions, and the serial transport of respiratory gases within the complex acinar architecture. This chapter focuses specifically on the theoretical foundations of gas transport, addressing two broad areas. The first deals with the reasons why the classical picture of alveolar and dead space ventilation is so successful; the second examines the underlying assumptions within current approximations to convective and diffusive transport, and how they interact to effect net gas exchange. PMID:23733643

Growth kinetics and island evolution during double-pulsed molecular beam epitaxy of InN

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

Kraus, A.; Hein, C.; Bremers, H.

The kinetic processes of InN growth using alternating source fluxes with sub-monolayer In pulses in plasma-assisted molecular beam epitaxy have been investigated. Growth at various temperatures reveals the existence of two growth regimes. While growth at low temperatures is solely governed by surface diffusion, a combination of decomposition, desorption, and diffusion becomes decisive at growth temperatures of 470 °C and above. At this critical temperature, the surface morphology changes from a grainy structure to a structure made of huge islands. The formation of those islands is attributed to the development of an indium adlayer, which can be observed via reflection highmore » energy electron diffraction monitoring. Based on the growth experiments conducted at temperatures below T{sub Growth} = 470 °C, an activation energy for diffusion of 0.54 ± 0.02 eV has been determined from the decreasing InN island density. A comparison between growth on metalorganic vapor phase epitaxy GaN templates and pseudo bulk GaN indicates that step edges and dislocations are favorable nucleation sites. Based on the results, we developed a growth model, which describes the main mechanisms of the growth.« less

Real Time Quantification of Ultrafast Photoinduced Bimolecular Electron Transfer Rate: Direct Probing of the Transient Intermediate.

PubMed

Mukherjee, Puspal; Biswas, Somnath; Sen, Pratik

2015-08-27

Fluorescence quenching studies through steady-state and time-resolved measurements are inadequate to quantify the bimolecular electron transfer rate in bulk homogeneous solution due to constraints from diffusion. To nullify the effect of diffusion, direct evaluation of the rate of formation of a transient intermediate produced upon the electron transfer is essential. Methyl viologen, a well-known electron acceptor, produces a radical cation after accepting an electron, which has a characteristic strong and broad absorption band centered at 600 nm. Hence it is a good choice to evaluate the rate of photoinduced electron transfer reaction employing femtosecond broadband transient absorption spectroscopy. The time constant of the aforementioned process between pyrene and methyl viologen in methanol has been estimated to be 2.5 ± 0.4 ps using the same technique. The time constant for the backward reaction was found to be 14 ± 1 ps. These values did not change with variation of concentration of quencher, i.e., methyl viologen. Hence, we can infer that diffusion has no contribution in the estimation of rate constants. However, on changing the solvent from methanol to ethanol, the time constant of the electron transfer reaction has been found to increase and has accounted for the change in solvent reorganization energy.

Extended dynamic model for ion diffusion in all-vanadium redox flow battery including the effects of temperature and bulk electrolyte transfer

NASA Astrophysics Data System (ADS)

Badrinarayanan, Rajagopalan; Zhao, Jiyun; Tseng, K. J.; Skyllas-Kazacos, Maria

2014-12-01

As with all redox flow batteries, the Vanadium Redox flow Battery (VRB) can suffer from capacity loss as the vanadium ions diffuse at different rates leading to a build-up on one half-cell and dilution on the other. In this paper an extended dynamic model of the vanadium ion transfer is developed including the effect of temperature and bulk electrolyte transfer. The model is used to simulate capacity decay for a range of different ion exchange membranes that are being used in the VRB. The simulations show that Selemion CMV and Nafion 115 membranes have similar behavior where the impact of temperature on capacity loss is highest within the first 100 cycles. The results for Selemion AMV membrane however are seen to be very different where the capacity loss at different temperatures observed to increase linearly with increasing charging/discharging cycles. The model is made more comprehensive by including the effect of bulk electrolyte transfer. A volume change of 19% is observed in each half-cell for Nafion 115 membrane based on the simulation parameters. The effect of this change in volume directly affects concentration, and the characteristics are analyzed for each vanadium species as well as the overall concentration in the half-cells.

Evaluating the hydraulic and transport properties of peat soil using pore network modeling and X-ray micro computed tomography

NASA Astrophysics Data System (ADS)

Gharedaghloo, Behrad; Price, Jonathan S.; Rezanezhad, Fereidoun; Quinton, William L.

2018-06-01

Micro-scale properties of peat pore space and their influence on hydraulic and transport properties of peat soils have been given little attention so far. Characterizing the variation of these properties in a peat profile can increase our knowledge on the processes controlling contaminant transport through peatlands. As opposed to the common macro-scale (or bulk) representation of groundwater flow and transport processes, a pore network model (PNM) simulates flow and transport processes within individual pores. Here, a pore network modeling code capable of simulating advective and diffusive transport processes through a 3D unstructured pore network was developed; its predictive performance was evaluated by comparing its results to empirical values and to the results of computational fluid dynamics (CFD) simulations. This is the first time that peat pore networks have been extracted from X-ray micro-computed tomography (μCT) images of peat deposits and peat pore characteristics evaluated in a 3D approach. Water flow and solute transport were modeled in the unstructured pore networks mapped directly from μCT images. The modeling results were processed to determine the bulk properties of peat deposits. Results portray the commonly observed decrease in hydraulic conductivity with depth, which was attributed to the reduction of pore radius and increase in pore tortuosity. The increase in pore tortuosity with depth was associated with more decomposed peat soil and decreasing pore coordination number with depth, which extended the flow path of fluid particles. Results also revealed that hydraulic conductivity is isotropic locally, but becomes anisotropic after upscaling to core-scale; this suggests the anisotropy of peat hydraulic conductivity observed in core-scale and field-scale is due to the strong heterogeneity in the vertical dimension that is imposed by the layered structure of peat soils. Transport simulations revealed that for a given solute, the effective diffusion coefficient decreases with depth due to the corresponding increase of diffusional tortuosity. Longitudinal dispersivity of peat also was computed by analyzing advective-dominant transport simulations that showed peat dispersivity is similar to the empirical values reported in the same peat soil; it is not sensitive to soil depth and does not vary much along the soil profile.

Diffusion of 99-technetium in compacted bentonite under aerobic and anaerobic conditions

NASA Astrophysics Data System (ADS)

Večerník, P.; Jedináková-Křížová, V.

2006-01-01

The main aim of this study was to investigate diffusion of technetium 99Tc under different conditions. Because technetium represents one of the most dangerous fission products due to its very long halftime and high mobility in aerobic conditions diffusion experiments of technetium (as 99TcO 4 - anion) in Czech bentonite from Rokle locality have been carried out. For performance and evaluation of experiments the through-diffusion method was chosen and apparent (Da) and effective (De) diffusion coefficients were evaluated. The effects of particle mesh-size, dry bulk density and aerobic or anaerobic conditions on diffusion were studied. In the presence of oxygen, technetium occurs in oxidation state VII, as an anion, soluble and mobile in the environment. However, under reducing conditions it occurs in a lower oxidation states, mainly as insoluble oxides or hydroxides. Aerobic experiments were carried out under laboratory conditions and anaerobic experiments were performed in a nitrogen atmosphere in a glove box, to simulate the real underground conditions.

Web interface for Brownian dynamics simulation of ion transport and its applications to beta-barrel pores.

PubMed

Lee, Kyu Il; Jo, Sunhwan; Rui, Huan; Egwolf, Bernhard; Roux, Benoît; Pastor, Richard W; Im, Wonpil

2012-01-30

Brownian dynamics (BD) based on accurate potential of mean force is an efficient and accurate method for simulating ion transport through wide ion channels. Here, a web-based graphical user interface (GUI) is presented for carrying out grand canonical Monte Carlo (GCMC) BD simulations of channel proteins: http://www.charmm-gui.org/input/gcmcbd. The webserver is designed to help users avoid most of the technical difficulties and issues encountered in setting up and simulating complex pore systems. GCMC/BD simulation results for three proteins, the voltage dependent anion channel (VDAC), α-Hemolysin (α-HL), and the protective antigen pore of the anthrax toxin (PA), are presented to illustrate the system setup, input preparation, and typical output (conductance, ion density profile, ion selectivity, and ion asymmetry). Two models for the input diffusion constants for potassium and chloride ions in the pore are compared: scaling of the bulk diffusion constants by 0.5, as deduced from previous all-atom molecular dynamics simulations of VDAC, and a hydrodynamics based model (HD) of diffusion through a tube. The HD model yields excellent agreement with experimental conductances for VDAC and α-HL, while scaling bulk diffusion constants by 0.5 leads to underestimates of 10-20%. For PA, simulated ion conduction values overestimate experimental values by a factor of 1.5-7 (depending on His protonation state and the transmembrane potential), implying that the currently available computational model of this protein requires further structural refinement. Copyright © 2011 Wiley Periodicals, Inc.

Web Interface for Brownian Dynamics Simulation of Ion Transport and Its Applications to Beta-Barrel Pores

PubMed Central

Lee, Kyu Il; Jo, Sunhwan; Rui, Huan; Egwolf, Bernhard; Roux, Benoît; Pastor, Richard W.; Im, Wonpil

2011-01-01

Brownian dynamics (BD) in a suitably constructed potential of mean force is an efficient and accurate method for simulating ion transport through wide ion channels. Here, a web-based graphical user interface (GUI) is presented for grand canonical Monte Carlo (GCMC) BD simulations of channel proteins: http://www.charmm-gui.org/input/gcmcbd. The webserver is designed to help users avoid most of the technical difficulties and issues encountered in setting up and simulating complex pore systems. GCMC/BD simulation results for three proteins, the voltage dependent anion channel (VDAC), α-Hemolysin, and the protective antigen pore of the anthrax toxin (PA), are presented to illustrate system setup, input preparation, and typical output (conductance, ion density profile, ion selectivity, and ion asymmetry). Two models for the input diffusion constants for potassium and chloride ions in the pore are compared: scaling of the bulk diffusion constants by 0.5, as deduced from previous all-atom molecular dynamics simulations of VDAC; and a hydrodynamics based model (HD) of diffusion through a tube. The HD model yields excellent agreement with experimental conductances for VDAC and α-Hemolysin, while scaling bulk diffusion constants by 0.5 leads to underestimates of 10–20%. For PA, simulated ion conduction values overestimate experimental values by a factor of 1.5 to 7 (depending on His protonation state and the transmembrane potential), implying that the currently available computational model of this protein requires further structural refinement. PMID:22102176

Analysis of single quantum-dot mobility inside 1D nanochannel devices

NASA Astrophysics Data System (ADS)

Hoang, H. T.; Segers-Nolten, I. M.; Tas, N. R.; van Honschoten, J. W.; Subramaniam, V.; Elwenspoek, M. C.

2011-07-01

We visualized individual quantum dots using a combination of a confining nanochannel and an ultra-sensitive microscope system, equipped with a high numerical aperture lens and a highly sensitive camera. The diffusion coefficients of the confined quantum dots were determined from the experimentally recorded trajectories according to the classical diffusion theory for Brownian motion in two dimensions. The calculated diffusion coefficients were three times smaller than those in bulk solution. These observations confirm and extend the results of Eichmann et al (2008 Langmuir 24 714-21) to smaller particle diameters and more narrow confinement. A detailed analysis shows that the observed reduction in mobility cannot be explained by conventional hydrodynamic theory.

The Weakly Nonlinear Magnetorotational Instability in a Local Geometry

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

Clark, S. E.; Oishi, Jeffrey S., E-mail: seclark@astro.columbia.edu

2017-05-20

The magnetorotational instability (MRI) is a fundamental process of accretion disk physics, but its saturation mechanism remains poorly understood despite considerable theoretical and computational effort. We present a multiple-scales analysis of the non-ideal MRI in the weakly nonlinear regime—that is, when the most unstable MRI mode has a growth rate asymptotically approaching zero from above. Here, we develop our theory in a local, Cartesian channel. Our results confirm the finding by Umurhan et al. that the perturbation amplitude follows a Ginzburg–Landau equation. We further find that the Ginzburg–Landau equation will arise for the local MRI system with shear-periodic boundary conditions,more » when the effects of ambipolar diffusion are considered. A detailed force balance for the saturated azimuthal velocity and vertical magnetic field demonstrates that, even when diffusive effects are important, the bulk flow saturates via the combined processes of reducing the background shear and rearranging and strengthening the background vertical magnetic field. We directly simulate the Ginzburg–Landau amplitude evolution for our system, and demonstrate the pattern formation our model predicts on long scales of length- and timescales. We compare the weakly nonlinear theory results to a direct numerical simulation of the MRI in a thin-gap Taylor Couette flow.« less

Numerical analysis of breakdown dynamics dependence on pulse width in laser-induced damage in fused silica: Role of optical system

NASA Astrophysics Data System (ADS)

Hamam, Kholoud A.; Gamal, Yosr E. E.-D.

2018-06-01

We report a numerical investigation of the breakdown and damage in fused silica caused by ultra-short laser pulses. The study based on a modified model (Gaabour et al., 2012) that solves the rate equation numerically for the electron density evolution during the laser pulse, under the combined effect of both multiphoton and electron impact ionization processes. Besides, electron loss processes due to diffusion out of the focal volume and recombination are also considered in this analysis. The model is applied to investigate the threshold intensity dependence on laser pulse width in the experimental measurements that are given by Liu et al. (2005). In this experiment, a Ti-sapphire laser source operating at 800 nm with pulse duration varies between 240 fs and 2.5 ps is used to irradiate a bulk of fused silica with dimensions 10 × 5 × 3 mm. The laser beam was focused into the bulk using two optical systems with effective numerical apertures (NA) 0.126 and 0.255 to give beam spot radius at the focus of the order 2.0 μm and 0.95 μm respectively. Reasonable agreement between the calculated thresholds and the measured ones is attained. Moreover, a study is performed to examine the respective role of the physical processes of the breakdown of fused silica in relation to the pulse width and focusing optical system. The analysis revealed a real picture of the location and size of the generated plasma.

Quantitative Characterization of the Microstructure and Transport Properties of Biopolymer Networks

PubMed Central

Jiao, Yang; Torquato, Salvatore

2012-01-01

Biopolymer networks are of fundamental importance to many biological processes in normal and tumorous tissues. In this paper, we employ the panoply of theoretical and simulation techniques developed for characterizing heterogeneous materials to quantify the microstructure and effective diffusive transport properties (diffusion coefficient De and mean survival time τ) of collagen type I networks at various collagen concentrations. In particular, we compute the pore-size probability density function P(δ) for the networks and present a variety of analytical estimates of the effective diffusion coefficient De for finite-sized diffusing particles, including the low-density approximation, the Ogston approximation, and the Torquato approximation. The Hashin-Strikman upper bound on the effective diffusion coefficient De and the pore-size lower bound on the mean survival time τ are used as benchmarks to test our analytical approximations and numerical results. Moreover, we generalize the efficient first-passage-time techniques for Brownian-motion simulations in suspensions of spheres to the case of fiber networks and compute the associated effective diffusion coefficient De as well as the mean survival time τ, which is related to nuclear magnetic resonance (NMR) relaxation times. Our numerical results for De are in excellent agreement with analytical results for simple network microstructures, such as periodic arrays of parallel cylinders. Specifically, the Torquato approximation provides the most accurate estimates of De for all collagen concentrations among all of the analytical approximations we consider. We formulate a universal curve for τ for the networks at different collagen concentrations, extending the work of Yeong and Torquato [J. Chem. Phys. 106, 8814 (1997)]. We apply rigorous cross-property relations to estimate the effective bulk modulus of collagen networks from a knowledge of the effective diffusion coefficient computed here. The use of cross-property relations to link other physical properties to the transport properties of collagen networks is also discussed. PMID:22683739

Detection of Extraplanar Diffuse Ionized Gas in M83

NASA Astrophysics Data System (ADS)

Boettcher, Erin; Gallagher, J. S., III; Zweibel, Ellen G.

2017-08-01

We present the first kinematic study of extraplanar diffuse ionized gas (eDIG) in the nearby, face-on disk galaxy M83 using optical emission-line spectroscopy from the Robert Stobie Spectrograph on the Southern African Large Telescope. We use a Markov Chain Monte Carlo method to decompose the [N II]λ λ 6548, 6583, Hα, and [S II]λ λ 6717, 6731 emission lines into H II region and diffuse ionized gas emission. Extraplanar, diffuse gas is distinguished by its emission-line ratios ([N II]λ6583/Hα ≳ 1.0) and its rotational velocity lag with respect to the disk ({{Δ }}v=-24 km s-1 in projection). With interesting implications for isotropy, the velocity dispersion of the diffuse gas, σ =96 km s-1, is a factor of a few higher in M83 than in the Milky Way and nearby, edge-on disk galaxies. The turbulent pressure gradient is sufficient to support the eDIG layer in dynamical equilibrium at an electron scale height of {h}z=1 kpc. However, this dynamical equilibrium model must be finely tuned to reproduce the rotational velocity lag. There is evidence of local bulk flows near star-forming regions in the disk, suggesting that the dynamical state of the gas may be intermediate between a dynamical equilibrium and a galactic fountain flow. As one of the first efforts to study eDIG kinematics in a face-on galaxy, this study demonstrates the feasibility of characterizing the radial distribution, bulk velocities, and vertical velocity dispersions in low-inclination systems. Based on observations made with the Southern African Large Telescope (SALT) under program 2015-2-SCI-004 (PI: E. Boettcher).

Computational investigation of longitudinal diffusion, eddy dispersion, and trans-particle mass transfer in bulk, random packings of core-shell particles with varied shell thickness and shell diffusion coefficient.

PubMed

Daneyko, Anton; Hlushkou, Dzmitry; Baranau, Vasili; Khirevich, Siarhei; Seidel-Morgenstern, Andreas; Tallarek, Ulrich

2015-08-14

In recent years, chromatographic columns packed with core-shell particles have been widely used for efficient and fast separations at comparatively low operating pressure. However, the influence of the porous shell properties on the mass transfer kinetics in core-shell packings is still not fully understood. We report on results obtained with a modeling approach to simulate three-dimensional advective-diffusive transport in bulk random packings of monosized core-shell particles, covering a range of reduced mobile phase flow velocities from 0.5 up to 1000. The impact of the effective diffusivity of analyte molecules in the porous shell and the shell thickness on the resulting plate height was investigated. An extension of Giddings' theory of coupled eddy dispersion to account for retention of analyte molecules due to stagnant regions in porous shells with zero mobile phase flow velocity is presented. The plate height equation involving a modified eddy dispersion term excellently describes simulated data obtained for particle-packings with varied shell thickness and shell diffusion coefficient. It is confirmed that the model of trans-particle mass transfer resistance of core-shell particles by Kaczmarski and Guiochon [42] is applicable up to a constant factor. We analyze individual contributions to the plate height from different mass transfer mechanisms in dependence of the shell parameters. The simulations demonstrate that a reduction of plate height in packings of core-shell relative to fully porous particles arises mainly due to reduced trans-particle mass transfer resistance and transchannel eddy dispersion. Copyright © 2015 Elsevier B.V. All rights reserved.

Connecting localized DNA strand displacement reactions

NASA Astrophysics Data System (ADS)

Mullor Ruiz, Ismael; Arbona, Jean-Michel; Lad, Amitkumar; Mendoza, Oscar; Aimé, Jean-Pierre; Elezgaray, Juan

2015-07-01

Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions.Logic circuits based on DNA strand displacement reactions have been shown to be versatile enough to compute the square root of four-bit numbers. The implementation of these circuits as a set of bulk reactions faces difficulties which include leaky reactions and intrinsically slow, diffusion-limited reaction rates. In this paper, we consider simple examples of these circuits when they are attached to platforms (DNA origamis). As expected, constraining distances between DNA strands leads to faster reaction rates. However, it also induces side-effects that are not detectable in the solution-phase version of this circuitry. Appropriate design of the system, including protection and asymmetry between input and fuel strands, leads to a reproducible behaviour, at least one order of magnitude faster than the one observed under bulk conditions. Electronic supplementary information (ESI) available. See DOI: 10.1039/C5NR02434J

Gallium diffusion in zinc oxide via the paired dopant-vacancy mechanism

NASA Astrophysics Data System (ADS)

Sky, T. N.; Johansen, K. M.; Riise, H. N.; Svensson, B. G.; Vines, L.

2018-02-01

Isochronal and isothermal diffusion experiments of gallium (Ga) in zinc oxide (ZnO) have been performed in the temperature range of 900-1050 °C. The samples used consisted of a sputter-deposited and highly Ga-doped ZnO film at the surface of a single-crystal bulk material. We use a novel reaction diffusion (RD) approach to demonstrate that the diffusion behavior of Ga in ZnO is consistent with zinc vacancy (VZn) mediation via the formation and dissociation of GaZnVZn complexes. In the RD modeling, experimental diffusion data are fitted utilizing recent density-functional-theory estimates of the VZn formation energy and the binding energy of GaZnVZn. From the RD modeling, a migration energy of 2.3 eV is deduced for GaZnVZn, and a total/effective activation energy of 3.0 eV is obtained for the Ga diffusion. Furthermore, and for comparison, employing the so-called Fair model, a total/effective activation energy of 2.7 eV is obtained for the Ga diffusion, reasonably close to the total value extracted from the RD-modeling.

Self-diffusion of magnesium in spinel and in equilibrium melts - Constraints on flash heating of silicates

NASA Technical Reports Server (NTRS)

Sheng, Y. J.; Wasserburg, G. J.; Hutcheon, I. D.

1992-01-01

An isotopic tracer is used to measure Mg self-diffusion in spinel and coexisting melt at bulk chemical equilibrium. The diffusion coefficients were calculated from the measured isotope profiles using a model that includes the complementary diffusion of Mg-24, Mg-25, and Mg-26 in both phases with the constraint that the Mg content of each phase is constant. The activation energy and preexponential factor for Mg self-diffusion in spinel are, respectively, 384 +/- 7 kJ and 74.6 +/- 1.1 sq cm/s. These data indicate Mg diffusion in spinel is much slower than previous estimates. The activation energy for Mg self-diffusion in coexisting melt is 343 +/- 25 kJ and the preexponential factor is 7791.9 +/- 1.3 sq cm/s. These results are used to evaluate cooling rates of plagioclase-olivine inclusions (POIs) in the Allende meteorite. Given a maximum melting temperature for POIs of about 1500 C, these results show that a 1-micron radius spinel would equilibrate isotopically with a melt within about 60 min.

A Mass Diffusion Model for Dry Snow Utilizing a Fabric Tensor to Characterize Anisotropy

NASA Astrophysics Data System (ADS)

Shertzer, Richard H.; Adams, Edward E.

2018-03-01

A homogenization algorithm for randomly distributed microstructures is applied to develop a mass diffusion model for dry snow. Homogenization is a multiscale approach linking constituent behavior at the microscopic level—among ice and air—to the macroscopic material—snow. Principles of continuum mechanics at the microscopic scale describe water vapor diffusion across an ice grain's surface to the air-filled pore space. Volume averaging and a localization assumption scale up and down, respectively, between microscopic and macroscopic scales. The model yields a mass diffusivity expression at the macroscopic scale that is, in general, a second-order tensor parameterized by both bulk and microstructural variables. The model predicts a mass diffusivity of water vapor through snow that is less than that through air. Mass diffusivity is expected to decrease linearly with ice volume fraction. Potential anisotropy in snow's mass diffusivity is captured due to the tensor representation. The tensor is built from directional data assigned to specific, idealized microstructural features. Such anisotropy has been observed in the field and laboratories in snow morphologies of interest such as weak layers of depth hoar and near-surface facets.

Geometrically nonlinear continuum thermomechanics with surface energies coupled to diffusion

NASA Astrophysics Data System (ADS)

McBride, A. T.; Javili, A.; Steinmann, P.; Bargmann, S.

2011-10-01

Surfaces can have a significant influence on the overall response of a continuum body but are often neglected or accounted for in an ad hoc manner. This work is concerned with a nonlinear continuum thermomechanics formulation which accounts for surface structures and includes the effects of diffusion and viscoelasticity. The formulation is presented within a thermodynamically consistent framework and elucidates the nature of the coupling between the various fields, and the surface and the bulk. Conservation principles are used to determine the form of the constitutive relations and the evolution equations. Restrictions on the jump in the temperature and the chemical potential between the surface and the bulk are not a priori assumptions, rather they arise from the reduced dissipation inequality on the surface and are shown to be satisfiable without imposing the standard assumptions of thermal and chemical slavery. The nature of the constitutive relations is made clear via an example wherein the form of the Helmholtz energy is explicitly given.

Heat transfer to and from vegetated surfaces - An analytical method for the bulk exchange coefficients

NASA Technical Reports Server (NTRS)

Massman, William J.

1987-01-01

The semianalytical model outlined in a previous study (Massman, 1987) to describe momentum exchange between the atmosphere and vegetated surfaces is extended to include the exchange of heat. The methods employed are based on one-dimensional turbulent diffusivities, and use analytical solutions to the steady-state diffusion equation. The model is used to assess the influence that the canopy foliage structure and density, the wind profile structure within the canopy, and the shelter factor can have upon the inverse surface Stanton number (kB exp -1), as well as to explore the consequences of introducing a scalar displacement height which can be different from the momentum displacement height. In general, the triangular foliage area density function gives results which agree more closely with observations than that for constant foliage area density. The intended application of this work is for parameterizing the bulk aerodynamic resistances for heat and momentum exchange for use within large-scale models of plant-atmosphere exchanges.

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

Moorhouse, Saul J.; Wu, Yue; O’Hare, Dermot, E-mail: dermot.ohare@chem.ox.ac.uk

A newly developed in situ monochromatic high-energy X-ray diffraction setup was used to investigate the synthesis of MOFs using cation-impregnated polymer resin beads as a ion source. The Co–NDC–DMF (NDC=2,6-naphthalenedicarboxylate; DMF=dimethylformamide) system was investigated, a system which is known to produce at least three distinct frameworks. It was found that the resin-assisted synthesis results in the preferential formation of a topology previously impossible to synthesise in bulk, while the comparable nitrate-salt synthesis appeared to form an alternative phases. It was also found that the resin-assisted synthesis is highly diffusion-controlled. - Graphical abstract: In situ monochromatic high-energy X-ray diffraction study ofmore » a MOF synthesis. - Highlights: • Resin-assisted solvothermal MOF synthesis was studied using in situ diffraction. • Full kinetics of reaction can be obtained from in situ data. • Kinetics show that this resin-assisted synthesis is diffusion controlled. • Resin-assisted synthesis enables the production of an alternative bulk phase.« less

Anisotropic reflectance from turbid media. I. Theory.

PubMed

Neuman, Magnus; Edström, Per

2010-05-01

It is shown that the intensity of light reflected from plane-parallel turbid media is anisotropic in all situations encountered in practice. The anisotropy, in the form of higher intensity at large polar angles, increases when the amount of near-surface bulk scattering is increased, which dominates in optically thin and highly absorbing media. The only situation with isotropic intensity is when a non-absorbing infinitely thick medium is illuminated diffusely. This is the only case where the Kubelka-Munk model gives exact results and there exists an exact translation between Kubelka-Munk and general radiative transfer. This also means that a bulk scattering perfect diffusor does not exist. Angle-resolved models are thus crucial for a correct understanding of light scattering in turbid media. The results are derived using simulations and analytical calculations. It is also shown that there exists an optimal angle for directional detection that minimizes the error introduced when using the Kubelka-Munk model to interpret reflectance measurements with diffuse illumination.

Momentum and charge transport in non-relativistic holographic fluids from Hořava gravity

NASA Astrophysics Data System (ADS)

Davison, Richard A.; Grozdanov, Sašo; Janiszewski, Stefan; Kaminski, Matthias

2016-11-01

We study the linearized transport of transverse momentum and charge in a conjectured field theory dual to a black brane solution of Hořava gravity with Lifshitz exponent z = 1. As expected from general hydrodynamic reasoning, we find that both of these quantities are diffusive over distance and time scales larger than the inverse temperature. We compute the diffusion constants and conductivities of transverse momentum and charge, as well the ratio of shear viscosity to entropy density, and find that they differ from their relativistic counterparts. To derive these results, we propose how the holographic dictionary should be modified to deal with the multiple horizons and differing propagation speeds of bulk excitations in Hořava gravity. When possible, as a check on our methods and results, we use the covariant Einstein-Aether formulation of Hořava gravity, along with field redefinitions, to re-derive our results from a relativistic bulk theory.

Large-scale ordering of nanoparticles using viscoelastic shear processing.

PubMed

Zhao, Qibin; Finlayson, Chris E; Snoswell, David R E; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P; Petukhov, Andrei V; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J

2016-06-03

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles.

Spreading of mercury droplets on thin silver films at room temperature.

PubMed

Be'er, Avraham; Lereah, Yossi; Frydman, Aviad; Taitelbaum, Haim

2007-05-01

We study the spreading characteristics of a reactive-wetting system of mercury (Hg) droplets on silver (Ag) films in room temperature. This is done using our recently developed method for reconstructing the dynamical three-dimensional shape of spreading droplets from two-dimensional microscope images [A. Be'er and Y. Lereah, J. Microsc. 208, 148 (2002)]. We study the time evolution of the droplet radius and its contact angle, and find that the spreading process consists of two stages: (i) the "bulk propagation" regime, controlled by chemical reaction on the surface, and (ii) the "fast-flow" regime, which occurs within the metal film as well as on the surface and consists of both reactive and diffusive propagation. We show that the transition time between the two main time regimes depends solely on the thickness of the Ag film. We also discuss the chemical structure of the intermetallic compound formed in this process.

A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

NASA Technical Reports Server (NTRS)

Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

1998-01-01

Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

Large-scale ordering of nanoparticles using viscoelastic shear processing

PubMed Central

Zhao, Qibin; Finlayson, Chris E.; Snoswell, David R. E.; Haines, Andrew; Schäfer, Christian; Spahn, Peter; Hellmann, Goetz P.; Petukhov, Andrei V.; Herrmann, Lars; Burdet, Pierre; Midgley, Paul A.; Butler, Simon; Mackley, Malcolm; Guo, Qixin; Baumberg, Jeremy J.

2016-01-01

Despite the availability of elaborate varieties of nanoparticles, their assembly into regular superstructures and photonic materials remains challenging. Here we show how flexible films of stacked polymer nanoparticles can be directly assembled in a roll-to-roll process using a bending-induced oscillatory shear technique. For sub-micron spherical nanoparticles, this gives elastomeric photonic crystals termed polymer opals showing extremely strong tunable structural colour. With oscillatory strain amplitudes of 300%, crystallization initiates at the wall and develops quickly across the bulk within only five oscillations. The resulting structure of random hexagonal close-packed layers is improved by shearing bidirectionally, alternating between two in-plane directions. Our theoretical framework indicates how the reduction in shear viscosity with increasing order of each layer accounts for these results, even when diffusion is totally absent. This general principle of shear ordering in viscoelastic media opens the way to manufacturable photonic materials, and forms a generic tool for ordering nanoparticles. PMID:27255808

Bulk Growth of Wide Band Gap II-VI Compound Semiconductors by Physical Vapor Transport

NASA Technical Reports Server (NTRS)

Su, Ching-Hua

1997-01-01

The mechanism of physical vapor transport of II-VI semiconducting compounds was studied both theoretically, using a one-dimensional diffusion model, as well as experimentally. It was found that the vapor phase stoichiometry is critical in determining the vapor transport rate. The experimental heat treatment methods to control the vapor composition over the starting materials were investigated and the effectiveness of the heat treatments was confirmed by partial pressure measurements using an optical absorption technique. The effect of residual (foreign) gas on the transport rate was also studies theoretically by the diffusion model and confirmed experimentally by the measurements of total pressure and compositions of the residual gas. An in-situ dynamic technique for the transport rate measurements and a further extension of the technique that simultaneously measured the partial pressures and transport rates were performed and, for the first time, the experimentally determined mass fluxes were compared with those calculated, without any adjustable parameters, from the diffusion model. Using the information obtained from the experimental transport rate measurements as guideline high quality bulk crystal of wide band gap II-VI semiconductor were grown from the source materials which undergone the same heat treatment methods. The grown crystals were then extensively characterized with emphasis on the analysis of the crystalline structural defects.

Non-traditional stable isotope behaviors in immiscible silica-melts in a mafic magma chamber.

PubMed

Zhu, Dan; Bao, Huiming; Liu, Yun

2015-12-01

Non-traditional stable isotopes have increasingly been applied to studies of igneous processes including planetary differentiation. Equilibrium isotope fractionation of these elements in silicates is expected to be negligible at magmatic temperatures (δ(57)Fe difference often less than 0.2 per mil). However, an increasing number of data has revealed a puzzling observation, e.g., the δ(57)Fe for silicic magmas ranges from 0‰ up to 0.6‰, with the most positive δ(57)Fe almost exclusively found in A-type granitoids. Several interpretations have been proposed by different research groups, but these have so far failed to explain some aspects of the observations. Here we propose a dynamic, diffusion-induced isotope fractionation model that assumes Si-melts are growing and ascending immiscibly in a Fe-rich bulk magma chamber. Our model offers predictions on the behavior of non-traditional stable isotope such as Fe, Mg, Si, and Li that are consistent with observations from many A-type granitoids, especially those associated with layered intrusions. Diffusion-induced isotope fractionation may be more commonly preserved in magmatic rocks than was originally predicted.

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

NASA Technical Reports Server (NTRS)

Heinemann, K.; Rao, D. B.; Douglass, D. L.

1975-01-01

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

DOE PAGES

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.; ...

2017-09-06

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less

Growth and Interaction of Colloid Nuclei

NASA Astrophysics Data System (ADS)

Lam, Michael-Angelo; Khusid, Boris; Meyer, William; Kondic, Lou

2017-11-01

We study evolution of colloid systems under zero-gravity conditions. In particular, we focus on the regime where there is a coexistence between a liquid and a solid state. Under zero gravity, the dominating process in the bulk of the fluid phase and the solid phase is diffusion. At the moving solid/liquid interface, osmotic pressure is balanced by surface tension, as well as balancing fluxes (conservation of mass) with the kinematics of nuclei growth (Wilson-Frenkel law). Due to the highly nonlinear boundary condition at the moving boundary, care has to be taken when performing numerical simulations. In this work, we present a nonlinear model for colloid nuclei growth. Numerical simulations using a finite volume method are compared with asymptotic analysis of the governing equation and experimental results for nuclei growth. Novel component in our numerical simulations is the inclusion of nonlinear (collective) diffusion terms that depend on the chemical potentials of the colloid in the solid and fluid phase. The results include growth and dissolution of a single colloidal nucleus, as well as evolution of multiple interacting nuclei. Supported by NASA Grant No. NNX16AQ79G.

Influence of Osmotic Drying with an Aqueous Poly(ethylene Glycol) Liquid Desiccant on Alumina Objects Gelcast with Gelatin

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

Hammel, E. C.; Campa, J. A.; Armbrister, C. E.

Gelcasting and liquid desiccant drying are novel forming and drying methods used to mitigate common issues associated with the fabrication of complex advanced ceramic objects. Here, the molecular weight and osmotic pressure of aqueous poly(ethylene glycol) (PEG) desiccant solutions were simultaneously varied to understand their influence on the net mass loss rates of gelcast alumina samples prepared using gelatin as a gelling agent. Additionally, the amount of PEG diffusion and water diffusion to and from the ceramic samples after 150 min of immersion in the liquid desiccant was correlated to the solution properties as was the final bulk density ofmore » the sintered samples. Furthermore, solutions with high molecular weight and low osmotic pressure resulted in low PEG gain and low water loss, while solutions with low molecular weight and high osmotic pressure resulted in high PEG gain and high water loss. In some cases, more than 40 wt% of the total water per sample was removed through the liquid desiccant drying process.« less