Multi-layer light-weight protective coating and method for application

NASA Technical Reports Server (NTRS)

Wiedemann, Karl E. (Inventor); Clark, Ronald K. (Inventor); Taylor, Patrick J. (Inventor)

1992-01-01

A thin, light-weight, multi-layer coating is provided for protecting metals and their alloys from environmental attack at high temperatures. A reaction barrier is applied to the metal substrate and a diffusion barrier is then applied to the reaction barrier. A sealant layer may also be applied to the diffusion barrier if desired. The reaction barrier is either non-reactive or passivating with respect to the metal substrate and the diffusion barrier. The diffusion barrier is either non-reactive or passivating with respect to the reaction barrier and the sealant layer. The sealant layer is immiscible with the diffusion barrier and has a softening point below the expected use temperature of the metal.

Theory and simulation of ion conduction in the pentameric GLIC channel.

PubMed

Zhu, Fangqiang; Hummer, Gerhard

2012-10-09

GLIC is a bacterial member of the large family of pentameric ligand-gated ion channels. To study ion conduction through GLIC and other membrane channels, we combine the one-dimensional potential of mean force for ion passage with a Smoluchowski diffusion model, making it possible to calculate single-channel conductance in the regime of low ion concentrations from all-atom molecular dynamics (MD) simulations. We then perform MD simulations to examine sodium ion conduction through the GLIC transmembrane pore in two systems with different bulk ion concentrations. The ion potentials of mean force, calculated from umbrella sampling simulations with Hamiltonian replica exchange, reveal a major barrier at the hydrophobic constriction of the pore. The relevance of this barrier for ion transport is confirmed by a committor function that rises sharply in the barrier region. From the free evolution of Na(+) ions starting at the barrier top, we estimate the effective diffusion coefficient in the barrier region, and subsequently calculate the conductance of the pore. The resulting diffusivity compares well with the position-dependent ion diffusion coefficient obtained from restrained simulations. The ion conductance obtained from the diffusion model agrees with the value determined via a reactive-flux rate calculation. Our results show that the conformation in the GLIC crystal structure, with an estimated conductance of ~1 picosiemens at 140 mM ion concentration, is consistent with a physiologically open state of the channel.

Hybrid functional studies of stability and diffusion of hydrogen in Mg-doped GaN

NASA Astrophysics Data System (ADS)

Park, Ji-Sang; Chang, K. J.

2012-02-01

Nitride semiconductors are known to suffer from low p-type doping efficiency due to the high activation energy of Mg acceptors and the compensation of hole carriers. To enhance hole carrier concentration, the hydrogen co-doping method is widely used, in which hydrogen is intentionally doped with Mg dopants and removed by subsequent thermal annealing. In this work, we perform first-principles density functional calculations to study the stability and diffusion of hydrogen in Mg-doped GaN. For the exchange-correlation potential, we employ both the generalized gradient approximation (GGA) proposed by Perdew, Burke, and Ernzerhof and the hybrid density functional of Heyd, Scuseria, and Ernzerhof. We examine the diffusion pathways and dissociation barriers of H from the Mg-H complex using the nudged elastic band and dimer methods. We compare the results of the GGA and hybrid density functional calculations for the stability of various H interstitial configurations and the migration barriers for H diffusion. Finally, using the calculated migration barriers as inputs, we perform kinetic Monte Carlo simulations for the dissociation of the Mg-H complex and find that the Mg acceptors are activated by thermal annealing up to 700-800 ^oC, in good agreement with experiments.

Reactive diffusion in the presence of a diffusion barrier: Experiment and model

NASA Astrophysics Data System (ADS)

Mangelinck, D.; Luo, T.; Girardeaux, C.

2018-05-01

Reactions in thin films and diffusion barriers are important for applications such as protective coatings, electrical contact, and interconnections. In this work, the effect of a barrier on the kinetics of the formation for a single phase by reactive diffusion is investigated from both experimental and modeling point of views. Two types of diffusion barriers are studied: (i) a thin layer of W deposited between a Ni film and Si substrate and (ii) Ni alloy films, Ni(1%W) and Ni(5%Pt), that form a diffusion barrier during the reaction with the Si substrate. The effect of the barriers on the kinetics of δ-Ni2Si formation is determined by in situ X ray diffraction and compared to models that explain the kinetic slowdown induced by both types of barrier. A linear parabolic growth is found for the deposited barrier with an increasing linear contribution for increasing barrier thickness. On the contrary, the growth is mainly parabolic for the barrier formed by the reaction between an alloy film and the substrate. The permeability of the two types of barrier is determined and discussed. The developed models fit well with the dedicated model experiments, leading to a better understanding of the barrier effect on the reactive diffusion and allowing us to predict the barrier behaviour in various applications.

Metal diffusion barriers for GaAs solar cells.

PubMed

van Leest, R H; Mulder, P; Bauhuis, G J; Cheun, H; Lee, H; Yoon, W; van der Heijden, R; Bongers, E; Vlieg, E; Schermer, J J

2017-03-15

In this study accelerated ageing testing (AAT), J-V characterization and TEM imaging in combination with phase diagram data from literature are used to assess the potential of Ti, Ni, Pd and Pt as diffusion barriers for Au/Cu-based metallization of III-V solar cells. Ni barriers show the largest potential as at an AAT temperature of 250 °C both cells with 10 and 100 nm thick Ni barriers show significantly better performance compared to Au/Cu cells, with the cells with 10 nm Ni barriers even showing virtually no degradation after 7.5 days at 250 °C (equivalent to 10 years at 100 °C at an E a of 0.70 eV). Detailed investigation shows that Ni does not act as a barrier in the classical sense, i.e. preventing diffusion of Cu and Au across the barrier. Instead Ni modifies or slows down the interactions taking place during device degradation and thus effectively acts as an 'interaction' barrier. Different interactions occur at temperatures below and above 250 °C and for thin (10 nm) and thick (100 nm) barriers. The results of this study indicate that 10-100 nm thick Ni intermediate layers in the Cu/Au based metallization of III-V solar cells may be beneficial to improve the device stability upon exposure to elevated temperatures.

Physical barrier effect of geopolymeric waste form on diffusivity of cesium and strontium.

PubMed

Jang, J G; Park, S M; Lee, H K

2016-11-15

The present study investigates the physical barrier effect of geopolymeric waste form on leaching behavior of cesium and strontium. Fly ash-based geopolymers and slag-blended geopolymers were used as solidification agents. The leaching behavior of cesium and strontium from geopolymers was evaluated in accordance with ANSI/ANS-16.1. The diffusivity of cesium and strontium in a fly ash-based geopolymer was lower than that in Portland cement by a factor of 10(3) and 10(4), respectively, showing significantly improved immobilization performance. The leaching resistance of fly ash-based geopolymer was relatively constant regardless of the type of fly ash. The diffusivity of water-soluble cesium and strontium ions were highly correlated with the critical pore diameter of the binder. The critical pore diameter of the fly ash-based geopolymer was remarkably smaller than those of Portland cement and slag-blended geopolymer; consequently, its ability physically to retard the diffusion of nuclides (physical barrier effect) was superior. Copyright © 2016 Elsevier B.V. All rights reserved.

Diffusion barriers

NASA Technical Reports Server (NTRS)

Nicolet, M. A.

1983-01-01

The choice of the metallic film for the contact to a semiconductor device is discussed. One way to try to stabilize a contact is by interposing a thin film of a material that has low diffusivity for the atoms in question. This thin film application is known as a diffusion barrier. Three types of barriers can be distinguished. The stuffed barrier derives its low atomic diffusivity to impurities that concentrate along the extended defects of a polycrystalline layer. Sacrificial barriers exploit the fact that some (elemental) thin films react in a laterally uniform and reproducible fashion. Sacrificial barriers have the advantage that the point of their failure is predictable. Passive barriers are those most closely approximating an ideal barrier. The most-studied case is that of sputtered TiN films. Stuffed barriers may be viewed as passive barriers whose low diffusivity material extends along the defects of the polycrystalline host.

Performance of two differently designed permeable reactive barriers with sulfate and zinc solutions.

PubMed

Pérez, Norma; Schwarz, Alex O; Barahona, Esteban; Sanhueza, Pamela; Diaz, Isabel; Urrutia, Homero

2018-06-18

For the first time, this laboratory-scale study evaluates the feasibility of incorporating diffusive exchange in permeable reactive barriers. In order to do this, the performance of two permeable reactive barriers (PRB) with different internal substrate arrangements were compared during the administration of a sulfate solution without metals (for 163 days) and with metals (for 60 days), simulating groundwater contaminated with acid mine drainage (AMD). In order to simulate a traditional PRB, a homogeneous distribution was implemented in the first reactor and the other PRB reactor utilized diffusion-active technology (DAPRB). In the DAPRB, the distribution of the reactive material was interspersed with the conductive material. The measurements in the internal ports showed that transverse gradients of sulfide formed in the DAPRB, causing the diffusion of sulfide from the substrate toward the layer interface, which is where the sulfide reacts by forming complexes with the metal. The DAPRB prevents the microorganisms from direct contact with AMD. This protection caused greater activity (sulfide production). Copyright © 2018 Elsevier B.V. All rights reserved.

Method for improving the performance of oxidizable ceramic materials in oxidizing environments

NASA Technical Reports Server (NTRS)

Nagaraj, Bangalore A. (Inventor)

2002-01-01

Improved adhesion of thermal barrier coatings to nonmetallic substrates using a dense layer of ceramic on an underlying nonmetallic substrate that includes at least one oxidizable component. The improved adhesion occurs because the application of the dense ceramic layer forms a diffusion barrier for oxygen. This diffusion barrier prevents the oxidizable component of the substrate from decomposing. The present invention applies ceramic by a process that deposits a relatively thick and dense ceramic layer on the underlying substrate. The formation of the dense layer of ceramic avoids the problem of void formation associated with ceramic formation by most prior art thermal decomposition processes. The formation of voids has been associated with premature spalling of thermal barrier layers and other protective layers applied to substrates.

Diffusion chamber system for testing of collagen-based cell migration barriers for separation of ligament enthesis zones in tissue-engineered ACL constructs.

PubMed

Hahner, J; Hoyer, M; Hillig, S; Schulze-Tanzil, G; Meyer, M; Schröpfer, M; Lohan, A; Garbe, L-A; Heinrich, G; Breier, A

2015-01-01

A temporary barrier separating scaffold zones seeded with different cell types prevents faster growing cells from overgrowing co-cultured cells within the same construct. This barrier should allow sufficient nutrient diffusion through the scaffold. The aim of this study was to test the effect of two variants of collagen-based barriers on macromolecule diffusion, viability, and the spreading efficiency of primary ligament cells on embroidered scaffolds. Two collagen barriers, a thread consisting of a twisted film tape and a sponge, were integrated into embroidered poly(lactic-co-caprolactone) and polypropylene scaffolds, which had the dimension of lapine anterior cruciate ligaments (ACL). A diffusion chamber system was designed and established to monitor nutrient diffusion using fluorescein isothiocyanate-labeled dextran of different molecular weights (20, 40, 150, 500 kDa). Vitality of primary lapine ACL cells was tested at days 7 and 14 after seeding using fluorescein diacetate and ethidium bromide staining. Cell spreading on the scaffold surface was measured using histomorphometry. Nuclei staining of the cross-sectioned scaffolds revealed the penetration of ligament cells through both barrier types. The diffusion chamber was suitable to characterize the diffusivity of dextran molecules through embroidered scaffolds with or without integrated collagen barriers. The diffusion coefficients were generally significantly lower in scaffolds with barriers compared to those without barriers. No significant differences between diffusion coefficients of both barrier types were detected. Both barriers were cyto-compatible and prevented most of the ACL cells from crossing the barrier, whereby the collagen thread was easier to handle and allowed a higher rate of cell spreading.

Diffusion behavior of Cu/Ta heterogeneous interface under high temperature and high strain: An atomistic investigation

NASA Astrophysics Data System (ADS)

Li, Ganglong; Wu, Houya; Luo, Honglong; Chen, Zhuo; Tay, Andrew A. O.; Zhu, Wenhui

2017-09-01

Three-dimensional (3D) integration technology using Cu interconnections has emerged as a promising solution to improve the performance of silicon microelectronic devices. However, Cu diffuses into SiO2 and requires a barrier layer such as Ta to ensure acceptable reliability. In this paper, the effects of temperature and strain normal to the interface on the inter-diffusion of Cu and Ta at annealing conditions are investigated using a molecular dynamics (MD) technique with embedded atomic method (EAM) potentials. Under thermal annealing conditions without strain, it is found that a Cu-rich diffusion region approximately 2 nm thick is formed at 1000 K after 10 ns of annealing. Ta is capable of diffusing into the interior of Cu but Cu hardly diffuses into the inner lattice of Ta. At the Cu side near the interface an amorphous structure is formed due to the process of diffusion. The diffusion activation energy of Cu and Ta are found to be 0.9769 and 0.586 eV, respectively. However, when a strain is applied, a large number of crystal defects are generated in the sample. As the strain is increased, extrinsic stacking faults (ESFs) and lots of Shockley partial dislocations appear. The density of the dislocations and the diffusion channels increase, promoting the diffusion of Cu atoms into the inner lattice of Ta. The thickness of the diffusion layer increases to 4 times the value when only a temperature load of 700 K is applied. The MD simulations demonstrated that Ta is very effective as a barrier layer under thermal loading only, and its effectiveness is impaired by tensile strain at the Cu/Ta interface. The simulations also clarified the mechanism that caused the impairment. The methodology and approach described in this paper can be followed further to study the effectiveness of barrier layers under various annealing and strain conditions, and to determine the minimum thickness of barrier layers required for a particular application.

Density functional theory study of lithium diffusion at the interface between olivine-type LiFePO4 and LiMnPO4

NASA Astrophysics Data System (ADS)

Shi, Jianjian; Wang, Zhiguo; Qing Fu, Yong

2016-12-01

Coating LiMnPO4 with a thin layer of LiFePO4 shows a better electrochemical performance than the pure LiFePO4 and LiMnPO4, thus it is critical to understand Li diffusion at their interfaces to improve the performance of electrode materials. Li diffusion at the (1 0 0)\\text{LiFeP{{\\text{O}}4}} //(1 0 0)\\text{LiMnP{{\\text{O}}4}} , (0 1 0)\\text{LiFeP{{\\text{O}}4}} //(0 1 0)\\text{LiMnP{{\\text{O}}4}} , and (0 0 1)\\text{LiFeP{{\\text{O}}4}} //(0 0 1)\\text{LiMnP{{\\text{O}}4}} interfaces between LiFePO4 and LiMnPO4 was investigated using density functional theory. The calculated diffusion energy barriers are 0.55 eV for Li to diffuse along the (0 0 1) interface, 0.44 and 0.49 eV for the Li diffusion inside the LiMnPO4 and along the (1 0 0) interface, respectively. When Li diffuses from the LiFePO4 to LiMnPO4 by passing through the (0 1 0) interfaces, the diffusion barriers are 0.45 and 0.60 eV for the Li diffusions in both sides. The diffusion barriers for Li to diffuse in LiMnPO4 near the interfaces decrease compared with those in the pure LiMnPO4. The calculated diffusion coefficient of Li along the (1 0 0) interface is in the range of 3.65  ×  10-11-5.28  ×  10-12 cm2 s-1, which is larger than that in the pure LiMnPO4 with a value of 7.5  ×  10-14 cm2 s-1. Therefore, the charging/discharging rate performance of the LiMnPO4 can be improved by surface coating with the LiFePO4.

Enhancement of tunneling magnetoresistance by inserting a diffusion barrier in L10-FePd perpendicular magnetic tunnel junctions

NASA Astrophysics Data System (ADS)

Zhang, De-Lin; Schliep, Karl B.; Wu, Ryan J.; Quarterman, P.; Reifsnyder Hickey, Danielle; Lv, Yang; Chao, Xiaohui; Li, Hongshi; Chen, Jun-Yang; Zhao, Zhengyang; Jamali, Mahdi; Mkhoyan, K. Andre; Wang, Jian-Ping

2018-04-01

We studied the tunnel magnetoresistance (TMR) of L10-FePd perpendicular magnetic tunnel junctions (p-MTJs) with an FePd free layer and an inserted diffusion barrier. The diffusion barriers studied here (Ta and W) were shown to enhance the TMR ratio of the p-MTJs formed using high-temperature annealing, which are necessary for the formation of high quality L10-FePd films and MgO barriers. The L10-FePd p-MTJ stack was developed with an FePd free layer with a stack of FePd/X/Co20Fe60B20, where X is the diffusion barrier, and patterned into micron-sized MTJ pillars. The addition of the diffusion barrier was found to greatly enhance the magneto-transport behavior of the L10-FePd p-MTJ pillars such that those without a diffusion barrier exhibited negligible TMR ratios (<1.0%), whereas those with a Ta (W) diffusion barrier exhibited TMR ratios of 8.0% (7.0%) at room temperature and 35.0% (46.0%) at 10 K after post-annealing at 350 °C. These results indicate that diffusion barriers could play a crucial role in realizing high TMR ratios in bulk p-MTJs such as those based on FePd and Mn-based perpendicular magnetic anisotropy materials for spintronic applications.

Enhanced oxygen vacancy diffusion in Ta2O5 resistive memory devices due to infinitely adaptive crystal structure

NASA Astrophysics Data System (ADS)

Jiang, Hao; Stewart, Derek A.

2016-04-01

Metal oxide resistive memory devices based on Ta2O5 have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta2O5 is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta2O5. Identified diffusion paths are associated with collective motion of neighboring atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta2O5 is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta2O5 based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.

Understanding the anisotropic strain effects on lithium diffusion in graphite anodes: A first-principles study

NASA Astrophysics Data System (ADS)

Ji, Xiang; Wang, Yang; Zhang, Junqian

2018-06-01

The lithium diffusion in graphite anode, which is the most widely used commercial electrode material today, affects the charge/discharge performance of lithium-ion batteries. In this study, the anisotropic strain effects on lithium diffusion in graphite anodes are systematically investigated using first-principles calculations based on density functional theory (DFT) with van der Waals corrections. It is found that the effects of external applied strains along various directions of LixC6 (i.e., perpendicular or parallel to the basal planes of the graphite host) on lithium diffusivity are different. Along the direction perpendicular to the graphite planes, the tensile strain facilitates in-plane Li diffusion by reducing the energy barrier, and the compressive strain hinders in-plane Li diffusion by raising the energy barrier. In contrast, the in-plane biaxial tensile strain (parallel to the graphite planes) hinders in-plane Li diffusion, and the in-plane biaxial compressive strain facilitates in-plane Li diffusion. Furthermore, both in-plane and transverse shear strains slightly influence Li diffusion in graphite anodes. A discussion is presented to explain the anisotropic strain dependence of lithium diffusion. This research provides data for the continuum modelling of the electrodes in the lithium-ion batteries.

Effect of dual-dielectric hydrogen-diffusion barrier layers on the performance of low-temperature processed transparent InGaZnO thin-film transistors

NASA Astrophysics Data System (ADS)

Tari, Alireza; Wong, William S.

2018-02-01

Dual-dielectric SiOx/SiNx thin-film layers were used as back-channel and gate-dielectric barrier layers for bottom-gate InGaZnO (IGZO) thin-film transistors (TFTs). The concentration profiles of hydrogen, indium, gallium, and zinc oxide were analyzed using secondary-ion mass spectroscopy characterization. By implementing an effective H-diffusion barrier, the hydrogen concentration and the creation of H-induced oxygen deficiency (H-Vo complex) defects during the processing of passivated flexible IGZO TFTs were minimized. A bilayer back-channel passivation layer, consisting of electron-beam deposited SiOx on plasma-enhanced chemical vapor-deposition (PECVD) SiNx films, effectively protected the TFT active region from plasma damage and minimized changes in the chemical composition of the semiconductor layer. A dual-dielectric PECVD SiOx/PECVD SiNx gate-dielectric, using SiOx as a barrier layer, also effectively prevented out-diffusion of hydrogen atoms from the PECVD SiNx-gate dielectric to the IGZO channel layer during the device fabrication.

Nanoscopic compartmentalization of membrane protein motion at the axon initial segment.

PubMed

Albrecht, David; Winterflood, Christian M; Sadeghi, Mohsen; Tschager, Thomas; Noé, Frank; Ewers, Helge

2016-10-10

The axon initial segment (AIS) is enriched in specific adaptor, cytoskeletal, and transmembrane molecules. During AIS establishment, a membrane diffusion barrier is formed between the axonal and somatodendritic domains. Recently, an axonal periodic pattern of actin, spectrin, and ankyrin forming 190-nm-spaced, ring-like structures has been discovered. However, whether this structure is related to the diffusion barrier function is unclear. Here, we performed single-particle tracking time-course experiments on hippocampal neurons during AIS development. We analyzed the mobility of lipid-anchored molecules by high-speed single-particle tracking and correlated positions of membrane molecules with the nanoscopic organization of the AIS cytoskeleton. We observe a strong reduction in mobility early in AIS development. Membrane protein motion in the AIS plasma membrane is confined to a repetitive pattern of ∼190-nm-spaced segments along the AIS axis as early as day in vitro 4, and this pattern alternates with actin rings. Mathematical modeling shows that diffusion barriers between the segments significantly reduce lateral diffusion along the axon. © 2016 Albrecht et al.

Hole Polaron Diffusion in the Final Discharge Product of Lithium–Sulfur Batteries

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

Liu, Zhixiao; Balbuena, Perla B.; Mukherjee, Partha P.

Poor electronic conductivity of bulk lithium sulfide (Li 2S) is a critical challenge for the debilitating performance of the lithium–sulfur battery. In this study we focus on investigating the thermodynamic and kinetic properties of native defects in Li 2S based on a first-principles approach. It is found that the hole polaron p + can form in Li 2S by removing a 3p electron from an S 2– anion. The p + diffusion barrier is only 90 meV, which is much lower than the Li vacancy (V Li –) diffusion barrier. Hence p + has the potential to serve as amore » charge carrier in the discharge product. Once the vacancy–polaron complex (V Li -––2p +) forms, the charge transport will be hindered due to the relatively higher diffusion barrier of the complex. Heteroatom dopants, which can decrease the p + formation energy and increase V Li – formation energy, are expected to be introduced to the discharge product to improve the electronic conductivity.« less

Hole Polaron Diffusion in the Final Discharge Product of Lithium–Sulfur Batteries

DOE PAGES

Liu, Zhixiao; Balbuena, Perla B.; Mukherjee, Partha P.

2017-07-24

Poor electronic conductivity of bulk lithium sulfide (Li 2S) is a critical challenge for the debilitating performance of the lithium–sulfur battery. In this study we focus on investigating the thermodynamic and kinetic properties of native defects in Li 2S based on a first-principles approach. It is found that the hole polaron p + can form in Li 2S by removing a 3p electron from an S 2– anion. The p + diffusion barrier is only 90 meV, which is much lower than the Li vacancy (V Li –) diffusion barrier. Hence p + has the potential to serve as amore » charge carrier in the discharge product. Once the vacancy–polaron complex (V Li -––2p +) forms, the charge transport will be hindered due to the relatively higher diffusion barrier of the complex. Heteroatom dopants, which can decrease the p + formation energy and increase V Li – formation energy, are expected to be introduced to the discharge product to improve the electronic conductivity.« less

Visualizing Molecular Diffusion through Passive Permeability Barriers in Cells: Conventional and Novel Approaches

PubMed Central

Lin, Yu-Chun; Phua, Siew Cheng; Lin, Benjamin; Inoue, Takanari

2013-01-01

Diffusion barriers are universal solutions for cells to achieve distinct organizations, compositions, and activities within a limited space. The influence of diffusion barriers on the spatiotemporal dynamics of signaling molecules often determines cellular physiology and functions. Over the years, the passive permeability barriers in various subcellular locales have been characterized using elaborate analytical techniques. In this review, we will summarize the current state of knowledge on the various passive permeability barriers present in mammalian cells. We will conclude with a description of several conventional techniques and one new approach based on chemically-inducible diffusion trap (C-IDT) for probing permeable barriers. PMID:23731778

Temperature dependence of copper diffusion in different thickness amorphous tungsten/tungsten nitride layer

NASA Astrophysics Data System (ADS)

Asgary, Somayeh; Hantehzadeh, Mohammad Reza; Ghoranneviss, Mahmood

2017-11-01

The amorphous W/WN films with various thickness (10, 30 and 40 nm) and excellent thermal stability were successfully prepared on SiO2/Si substrate with evaporation and reactive evaporation method. The W/WN bilayer has technological importance because of its low resistivity, high melting point, and good diffusion barrier properties between Cu and Si. The thermal stability was evaluated by X-ray diffractometer (XRD) and Scanning Electron Microscope (SEM). In annealing process, the amorphous W/WN barrier crystallized and this phenomenon is supposed to be the start of Cu atoms diffusion through W/WN barrier into Si. With occurrence of the high-resistive Cu3Si phase, the W/WN loses its function as a diffusion barrier. The primary mode of Cu diffusion is the diffusion through grain boundaries that form during heat treatments. The amorphous structure with optimum thickness is the key factor to achieve a superior diffusion barrier characteristic. The results show that the failure temperature increased by increasing the W/WN film thickness from 10 to 30 nm but it did not change by increasing the W/WN film thickness from 30 to 40 nm. It is found that the 10 and 40 nm W/WN films are good diffusion barriers at least up to 800°C while the 30 nm W/WN film shows superior properties as a diffusion barrier, but loses its function as a diffusion barrier at about 900°C (that is 100°C higher than for 10 and 40 nm W/WN films).

[Diffusion and diffusion-osmosis models of the charged macromolecule transfer in barriers of biosystems].

PubMed

Varakin, A I; Mazur, V V; Arkhipova, N V; Serianov, Iu V

2009-01-01

Mathematical models of the transfer of charged macromolecules have been constructed on the basis of the classical equations of electromigration diffusion of Helmholtz-Smolukhovskii, Goldman, and Goldman-Hodgkin-Katz. It was shown that ion transfer in placental (mimicking lipid-protein barriers) and muscle barriers occurs by different mechanisms. In placental barriers, the electromigration diffusion occurs along lipid-protein channels formed due to the conformational deformation of phospholipid and protein molecules with the coefficients of diffusion D = (2.6-3.6) x 10(-8) cm2/s. The transfer in muscle barriers is due to the migration across charged interfibrillar channels with the negative diffusion activation energy, which is explained by changes in the structure of muscle fibers and expenditures of thermal energy for the extrusion of Cl- from channel walls with the diffusion coefficient D = (6.0-10.0) x 10(-6) cm2/s.

Visualizing molecular diffusion through passive permeability barriers in cells: conventional and novel approaches.

PubMed

Lin, Yu-Chun; Phua, Siew Cheng; Lin, Benjamin; Inoue, Takanari

2013-08-01

Diffusion barriers are universal solutions for cells to achieve distinct organizations, compositions, and activities within a limited space. The influence of diffusion barriers on the spatiotemporal dynamics of signaling molecules often determines cellular physiology and functions. Over the years, the passive permeability barriers in various subcellular locales have been characterized using elaborate analytical techniques. In this review, we will summarize the current state of knowledge on the various passive permeability barriers present in mammalian cells. We will conclude with a description of several conventional techniques and one new approach based on chemically inducible diffusion trap (CIDT) for probing permeable barriers. Copyright © 2013 Elsevier Ltd. All rights reserved.

Computational characterization of lightweight multilayer MXene Li-ion battery anodes

NASA Astrophysics Data System (ADS)

Ashton, Michael; Hennig, Richard G.; Sinnott, Susan B.

2016-01-01

MXenes, a class of two-dimensional transition metal carbides and nitrides, have shown promise experimentally and computationally for use in energy storage applications. In particular, the most lightweight members of the monolayer MXene family (M = Sc, Ti, V, or Cr) are predicted to have gravimetric capacities above 400 mAh/g, higher than graphite. Additionally, intercalation of ions into multilayer MXenes can be accomplished at low voltages, and low diffusion barriers exist for Li diffusing across monolayer MXenes. However, large discrepancies have been observed between the calculated and experimental reversible capacities of MXenes. Here, dispersion-corrected density functional theory calculations are employed to predict reversible capacities and other battery-related properties for six of the most promising members of the MXene family (O-functionalized Ti- and V-based carbide MXenes) as bilayer structures. The calculated reversible capacities of the V2CO2 and Ti2CO2 bilayers agree more closely with experiment than do previous calculations for monolayers. Additionally, the minimum energy paths and corresponding energy barriers along the in-plane [1000] and [0100] directions for Li travelling between neighboring MXene layers are determined. V4C3O2 exhibits the lowest diffusion barrier of the compositions considered, at 0.42 eV, but its reversible capacity (148 mAh/g) is dragged down by its heavy formula unit. Conversely, the V2CO2 MXene shows good reversible capacity (276 mAh/g), but a high diffusion barrier (0.82 eV). We show that the diffusion barriers of all bilayer structures are significantly higher than those calculated for the corresponding monolayers, advocating the use of dispersed monolayer MXenes instead of multilayers in high performance anodes.

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

NASA Astrophysics Data System (ADS)

Bedane, T.; Di Maio, L.; Scarfato, P.; Incarnato, L.; Marra, F.

2015-12-01

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values of poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction in the permeability and oxygen transfer rate values. Scavenging capacity of the multilayer film increased linearly with the increase of the reactive layer thickness and the oxygen absorption reaction at short times decreased proportionally with the thickness of the external PET layer.

Modeling and sensitivity analysis of mass transfer in active multilayer polymeric film for food applications

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

Bedane, T.; Di Maio, L.; Scarfato, P.

The barrier performance of multilayer polymeric films for food applications has been significantly improved by incorporating oxygen scavenging materials. The scavenging activity depends on parameters such as diffusion coefficient, solubility, concentration of scavenger loaded and the number of available reactive sites. These parameters influence the barrier performance of the film in different ways. Virtualization of the process is useful to characterize, design and optimize the barrier performance based on physical configuration of the films. Also, the knowledge of values of parameters is important to predict the performances. Inverse modeling and sensitivity analysis are sole way to find reasonable values ofmore » poorly defined, unmeasured parameters and to analyze the most influencing parameters. Thus, the objective of this work was to develop a model to predict barrier properties of multilayer film incorporated with reactive layers and to analyze and characterize their performances. Polymeric film based on three layers of Polyethylene terephthalate (PET), with a core reactive layer, at different thickness configurations was considered in the model. A one dimensional diffusion equation with reaction was solved numerically to predict the concentration of oxygen diffused into the polymer taking into account the reactive ability of the core layer. The model was solved using commercial software for different film layer configurations and sensitivity analysis based on inverse modeling was carried out to understand the effect of physical parameters. The results have shown that the use of sensitivity analysis can provide physical understanding of the parameters which highly affect the gas permeation into the film. Solubility and the number of available reactive sites were the factors mainly influencing the barrier performance of three layered polymeric film. Multilayer films slightly modified the steady transport properties in comparison to net PET, giving a small reduction in the permeability and oxygen transfer rate values. Scavenging capacity of the multilayer film increased linearly with the increase of the reactive layer thickness and the oxygen absorption reaction at short times decreased proportionally with the thickness of the external PET layer.« less

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

Jiang, Hao; Materials Science Program, University of Wisconsin, Madison, Wisconsin 53706; Stewart, Derek A., E-mail: derek.stewart@hgst.com

Metal oxide resistive memory devices based on Ta{sub 2}O{sub 5} have demonstrated high switching speed, long endurance, and low set voltage. However, the physical origin of this improved performance is still unclear. Ta{sub 2}O{sub 5} is an important archetype of a class of materials that possess an adaptive crystal structure that can respond easily to the presence of defects. Using first principles nudged elastic band calculations, we show that this adaptive crystal structure leads to low energy barriers for in-plane diffusion of oxygen vacancies in λ phase Ta{sub 2}O{sub 5}. Identified diffusion paths are associated with collective motion of neighboringmore » atoms. The overall vacancy diffusion is anisotropic with higher diffusion barriers found for oxygen vacancy movement between Ta-O planes. Coupled with the fact that oxygen vacancy formation energy in Ta{sub 2}O{sub 5} is relatively small, our calculated low diffusion barriers can help explain the low set voltage in Ta{sub 2}O{sub 5} based resistive memory devices. Our work shows that other oxides with adaptive crystal structures could serve as potential candidates for resistive random access memory devices. We also discuss some general characteristics for ideal resistive RAM oxides that could be used in future computational material searches.« less

Fast self-diffusion of ions in CH 3 NH 3 PbI 3 : the interstiticaly mechanism versus vacancy-assisted mechanism

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

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

2016-01-01

The stability of organic-inorganic halide perovskites is a major challenge for their applications and has been extensively studied. Among the possible underlying reasons, ion self-diffusion has been inferred to play important roles. While theoretical studies congruously support that iodine is more mobile, experimental studies only observe the direct diffusion of the MA ion and possible diffusion of iodine. The discrepancy may result from the incomplete understanding of ion diffusion mechanisms. With the help of first-principles calculations, we studied ion diffusion in CH3NH3PbI3 (MAPbI3) through not only the vacancy-assisted mechanisms presumed in previous theoretical studies, but also the neglected interstiticaly mechanisms.more » We found that compared to the diffusion through the vacancy-assisted mechanism, MA ion diffusion through the interstiticaly mechanism has a much smaller barrier which could explain experimental observations. For iodine diffusion, both mechanisms can yield relatively small barriers. Depending on the growth conditions, defect densities of vacancies and interstitials can vary and so do the diffusion species as well as diffusion mechanisms. Our work thus supports that both MA and iodine ion diffusion could contribute to the performance instability of MAPbI3. While being congruous with experimental results, our work fills the research gap by providing a full understanding of ion diffusion in halide perovskites.« less

Feasibility study of tungsten as a diffusion barrier between nickel-chromium-aluminum and Gamma/Gamma prime - Delta eutectic alloys

NASA Technical Reports Server (NTRS)

Young, S. G.; Zellars, G. R.

1978-01-01

Coating systems proposed for potential use on eutectic alloy components in high-temperature gas turbine engines were studied with emphasis on deterioration of such systems by diffusion. A 1-mil thick W sheet was placed between eutectic alloys and a NiCrAl layer. Layered test specimens were aged at 1100 C for as long as long as 500 hours. Without the W barrier, the delta phase of the eutectic deteriorated by diffusion of Nb into the NiCrAl. Insertion of the W barrier stopped the diffusion of Nb from delta. Chromium diffusion from the NiCrAl into the gamma/gamma prime phase of the eutectic was greatly reduced by the barrier. However, the barrier thickness decreased with time; and W diffused into both the NiCrAl and the eutectic. When the delta platelets were alined parallel to the NiCrAl layer, rather than perpendicular, diffusion into the eutectic was reduced.

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

Diffusion properties of molecules at the blood-brain interface: potential contributions of astrocyte endfeet to diffusion barrier functions.

PubMed

Nuriya, Mutsuo; Shinotsuka, Takanori; Yasui, Masato

2013-09-01

Molecular diffusion in the extracellular space (ECS) plays a key role in determining tissue physiology and pharmacology. The blood-brain barrier regulates the exchange of substances between the brain and the blood, but the diffusion properties of molecules at this blood-brain interface, particularly around the astrocyte endfeet, are poorly characterized. In this study, we used 2-photon microscopy and acute brain slices of mouse neocortex and directly assessed the diffusion patterns of fluorescent molecules. By observing the diffusion of unconjugated and 10-kDa dextran-conjugated Alexa Fluor 488 from the ECS of the brain parenchyma to the blood vessels, we find various degrees of diffusion barriers at the endfeet: Some allow the invasion of dye inside the endfoot network while others completely block it. Detailed analyses of the time course for dye clearance support the existence of a tight endfoot network capable of acting as a diffusion barrier. Finally, we show that this diffusion pattern collapses under pathological conditions. These data demonstrate the heterogeneous nature of molecular diffusion dynamics around the endfeet and suggest that these structures can serve as the diffusion barrier. Therefore, astrocyte endfeet may add another layer of regulation to the exchange of molecules between blood vessels and brain parenchyma.

Lifetime of Major Histocompatibility Complex Class-I Membrane Clusters Is Controlled by the Actin Cytoskeleton

PubMed Central

Lavi, Yael; Gov, Nir; Edidin, Michael; Gheber, Levi A.

2012-01-01

Lateral heterogeneity of cell membranes has been demonstrated in numerous studies showing anomalous diffusion of membrane proteins; it has been explained by models and experiments suggesting dynamic barriers to free diffusion, that temporarily confine membrane proteins into microscopic patches. This picture, however, comes short of explaining a steady-state patchy distribution of proteins, in face of the transient opening of the barriers. In our previous work we directly imaged persistent clusters of MHC-I, a type I transmembrane protein, and proposed a model of a dynamic equilibrium between proteins newly delivered to the cell surface by vesicle traffic, temporary confinement by dynamic barriers to lateral diffusion, and dispersion of the clusters by diffusion over the dynamic barriers. Our model predicted that the clusters are dynamic, appearing when an exocytic vesicle fuses with the plasma membrane and dispersing with a typical lifetime that depends on lateral diffusion and the dynamics of barriers. In a subsequent work, we showed this to be the case. Here we test another prediction of the model, and show that changing the stability of actin barriers to lateral diffusion changes cluster lifetimes. We also develop a model for the distribution of cluster lifetimes, consistent with the function of barriers to lateral diffusion in maintaining MHC-I clusters. PMID:22500754

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A [Idaho Falls, ID

2008-07-22

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A.

2004-09-07

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Diffusion barrier properties of single- and multilayered quasi-amorphous tantalum nitride thin films against copper penetration

NASA Astrophysics Data System (ADS)

Chen, G. S.; Chen, S. T.

2000-06-01

Tantalum-related thin films containing different amounts of nitrogen are sputter deposited at different argon-to-nitrogen flow rate ratios on (100) silicon substrates. Using x-ray diffractometry, transmission electron microscopy, composition and resistivity analyses, and bending-beam stress measurement technique, this work examines the impact of varying the nitrogen flow rate, particularly on the crystal structure, composition, resistivity, and residual intrinsic stress of the deposited Ta2N thin films. With an adequate amount of controlled, reactive nitrogen in the sputtering gas, thin films of the tantalum nitride of nominal formula Ta2N are predominantly amorphous and can exist over a range of nitrogen concentrations slightly deviated from stoichiometry. The single-layered quasi-amorphous Ta2N (a-Ta2N) thin films yield intrinsic compressive stresses in the range 3-5 GPa. In addition, the use of the 40-nm-thick a-Ta2N thin films with different nitrogen atomic concentrations (33% and 36%) and layering designs as diffusion barriers between silicon and copper are also evaluated. When subjected to high-temperature annealing, the single-layered a-Ta2N barrier layers degrade primarily by an amorphous-to-crystalline transition of the barrier layers. Crystallization of the single-layered stoichiometric a-Ta2N (Ta67N33) diffusion barriers occurs at temperatures as low as 450 °C. Doing so allows copper to preferentially penetrate through the grain boundaries or thermal-induced microcracks of the crystallized barriers and react with silicon, sequentially forming {111}-facetted pyramidal Cu3Si precipitates and TaSi2 Overdoping nitrogen into the amorphous matrix can dramatically increase the crystallization temperature to 600 °C. This temperature increase slows down the inward diffusion of copper and delays the formation of both silicides. The nitrogen overdoped Ta2N (Ta64N36) diffusion barriers can thus be significantly enhanced so as to yield a failure temperature 100 °C greater than that of the Ta67N33 diffusion barriers. Moreover, multilayered films, formed by alternately stacking the Ta67N33 and Ta64N36 layers with an optimized bilayer thickness (λ) of 10 nm, can dramatically reduce the intrinsic compressive stress to only 0.7 GPa and undergo high-temperature annealing without crystallization. Therefore, the Ta67N33/Ta64N36 multilayered films exhibit a much better barrier performance than the highly crystallization-resistant Ta64N36 single-layered films.

Kinetic Monte Carlo Simulation of Oxygen and Cation Diffusion in Yttria-Stabilized Zirconia

NASA Technical Reports Server (NTRS)

Good, Brian

2011-01-01

Yttria-stabilized zirconia (YSZ) is of interest to the aerospace community, notably for its application as a thermal barrier coating for turbine engine components. In such an application, diffusion of both oxygen ions and cations is of concern. Oxygen diffusion can lead to deterioration of a coated part, and often necessitates an environmental barrier coating. Cation diffusion in YSZ is much slower than oxygen diffusion. However, such diffusion is a mechanism by which creep takes place, potentially affecting the mechanical integrity and phase stability of the coating. In other applications, the high oxygen diffusivity of YSZ is useful, and makes the material of interest for use as a solid-state electrolyte in fuel cells. The kinetic Monte Carlo (kMC) method offers a number of advantages compared with the more widely known molecular dynamics simulation method. In particular, kMC is much more efficient for the study of processes, such as diffusion, that involve infrequent events. We describe the results of kinetic Monte Carlo computer simulations of oxygen and cation diffusion in YSZ. Using diffusive energy barriers from ab initio calculations and from the literature, we present results on the temperature dependence of oxygen and cation diffusivity, and on the dependence of the diffusivities on yttria concentration and oxygen sublattice vacancy concentration. We also present results of the effect on diffusivity of oxygen vacancies in the vicinity of the barrier cations that determine the oxygen diffusion energy barriers.

Diffusion mechanisms in chemical vapor-deposited iridium coated on chemical vapor-deposited rhenium

NASA Technical Reports Server (NTRS)

Hamilton, J. C.; Yang, N. Y. C.; Clift, W. M.; Boehme, D. R.; Mccarty, K. F.; Franklin, J. E.

1992-01-01

Radiation-cooled rocket thruster chambers have been developed which use CVD Re coated with CVD Ir on the interior surface that is exposed to hot combustion gases. The Ir serves as an oxidation barrier which protects the structural integrity-maintaining Re at elevated temperatures. The diffusion kinetics of CVD materials at elevated temperatures is presently studied with a view to the prediction and extension of these thrusters' performance limits. Line scans for Ir and Re were fit on the basis of a diffusion model, in order to extract relevant diffusion constants; the fastest diffusion process is grain-boundary diffusion, where Re diffuses down grain boundaries in the Ir overlayer.

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.

Effect of SiN x diffusion barrier thickness on the structural properties and photocatalytic activity of TiO2 films obtained by sol-gel dip coating and reactive magnetron sputtering.

PubMed

Ghazzal, Mohamed Nawfal; Aubry, Eric; Chaoui, Nouari; Robert, Didier

2015-01-01

We investigate the effect of the thickness of the silicon nitride (SiN x ) diffusion barrier on the structural and photocatalytic efficiency of TiO2 films obtained with different processes. We show that the structural and photocatalytic efficiency of TiO2 films produced using soft chemistry (sol-gel) and physical methods (reactive sputtering) are affected differentially by the intercalating SiN x diffusion barrier. Increasing the thickness of the SiN x diffusion barrier induced a gradual decrease of the crystallite size of TiO2 films obtained by the sol-gel process. However, TiO2 obtained using the reactive sputtering method showed no dependence on the thickness of the SiN x barrier diffusion. The SiN x barrier diffusion showed a beneficial effect on the photocatalytic efficiency of TiO2 films regardless of the synthesis method used. The proposed mechanism leading to the improvement in the photocatalytic efficiency of the TiO2 films obtained by each process was discussed.

Cell based metabolic barriers to glucose diffusion: macrophages and continuous glucose monitoring.

PubMed

Klueh, Ulrike; Frailey, Jackman T; Qiao, Yi; Antar, Omar; Kreutzer, Donald L

2014-03-01

It is assumed that MQ are central to glucose sensor bio-fouling and therefore have a major negative impact on continuous glucose monitoring (CGM) performance in vivo. However to our knowledge there is no data in the literature to directly support or refute this assumption. Since glucose and oxygen (O2) are key to glucose sensor function in vivo, understanding and controlling glucose and O2 metabolic activity of MQ is likely key to successful glucose sensor performance. We hypothesized that the accumulation of MQ at the glucose sensor-tissue interface will act as "Cell Based Metabolic Barriers" (CBMB) to glucose diffusing from the interstitial tissue compartment to the implanted glucose sensor and as such creating an artificially low sensor output, thereby compromising sensor function and CGM. Our studies demonstrated that 1) direct injections of MQ at in vivo sensor implantation sites dramatically decreased sensor output (measured in nA), 2) addition of MQ to glucose sensors in vitro resulted in a rapid and dramatic fall in sensor output and 3) lymphocytes did not affect sensor function in vitro or in vivo. These data support our hypothesis that MQ can act as metabolic barriers to glucose and O2 diffusion in vivo and in vitro. Copyright © 2014 Elsevier Ltd. All rights reserved.

Improved performance of In0.83Ga0.17As/InP photodetectors through modifying the position of In0.66Ga0.34As/InAs superlattice electron barrier

NASA Astrophysics Data System (ADS)

Shi, Yan-hui; Zhang, Yong-gang; Ma, Ying-jie; Gu, Yi; Chen, Xing-you; Gong, Qian; Du, Ben; Zhang, Jian; Zhu, Yi

2018-03-01

The performance of wavelength extended In0.83Ga0.17As/InP photodetectors has been improved notably through modifying the position of electron barriers in absorption layer. In order to fully utilize the diffusion component of the photocurrent, the In0.66Ga0.34As/InAs superlattice electron barrier is moved to the edge of the depletion region. Enhanced peak photo responsivity up to 0.84 A/W is realized, which raises 24% compared to that of a reference detector with the superlattice barrier in the middle of the absorber. The dark current slightly increases by 25% at room temperature while decreases by more than an order of magnitude at 150 K, resulting in about 10% or more than twofold improvements for the detectivity, respectively. The results suggest that optimized barrier position is a necessity for barrier-type photodetectors to achieve better performances.

Diffusion Barriers to Increase the Oxidative Life of Overlay Coatings

NASA Technical Reports Server (NTRS)

Nesbitt, James A.; Lei, Jih-Fen

1999-01-01

Currently, most blades and vanes in the hottest section of aero gas turbine engines require some type of coating for oxidation protection. Newly developed single crystal superalloys have the mechanical potential to operate at increasingly higher component temperatures. However, at these elevated temperatures, coating/substrate interdiffusion can shorten the protective life of the coating. Diffusion barriers between overlay coatings and substrates are being examined to extend the protective life of the coating. A previously- developed finite-difference diffusion model has been modified to predict the oxidative life enhancement due to use of a diffusion barrier. The original diffusion model, designated COSIM, simulates Al diffusion in the coating to the growing oxide scale as well as Al diffusion into the substrate. The COSIM model incorporates an oxide growth and spalling model to provide the rate of Al consumption during cyclic oxidation. Coating failure is predicted when the Al concentration at the coating surface drops to a defined critical level. The modified COSIM model predicts the oxidative life of an overlay coating when a diffusion barrier is present eliminating diffusion of Al from the coating into the substrate. Both the original and the modified diffusion models have been used to predict the effectiveness of a diffusion barrier in extending the protective life of a NiCrAl overlay coating undergoing cyclic oxidation at 1100 C.

A sphingolipid-dependent diffusion barrier confines ER stress to the yeast mother cell

PubMed Central

Clay, Lori; Caudron, Fabrice; Denoth-Lippuner, Annina; Boettcher, Barbara; Buvelot Frei, Stéphanie; Snapp, Erik Lee; Barral, Yves

2014-01-01

In many cell types, lateral diffusion barriers compartmentalize the plasma membrane and, at least in budding yeast, the endoplasmic reticulum (ER). However, the molecular nature of these barriers, their mode of action and their cellular functions are unclear. Here, we show that misfolded proteins of the ER remain confined into the mother compartment of budding yeast cells. Confinement required the formation of a lateral diffusion barrier in the form of a distinct domain of the ER-membrane at the bud neck, in a septin-, Bud1 GTPase- and sphingolipid-dependent manner. The sphingolipids, but not Bud1, also contributed to barrier formation in the outer membrane of the dividing nucleus. Barrier-dependent confinement of ER stress into the mother cell promoted aging. Together, our data clarify the physical nature of lateral diffusion barriers in the ER and establish the role of such barriers in the asymmetric segregation of proteotoxic misfolded proteins during cell division and aging. DOI: http://dx.doi.org/10.7554/eLife.01883.001 PMID:24843009

Adsorption and diffusion of lithium in a graphene/blue-phosphorus heterostructure and the effect of an external electric field.

PubMed

Fan, Kaimin; Tang, Jing; Wu, Shiyun; Yang, Chengfu; Hao, Jiabo

2016-12-21

The adsorption and diffusion behaviors of lithium (Li) in a graphene/blue-phosphorus (G/BP) heterostructure have been investigated using a first principles method based on density functional theory (DFT). The effect of an external electric field on the adsorption and diffusion behaviors has also been investigated. The results show that the adsorption energy of Li on the graphene side of the G/BP heterostructure is higher than that on monolayer graphene, and Li adsorption on the BP side of the G/BP/Li system is slightly stronger than that on monolayer BP (BP/Li). The adsorption energy of Li reaches 2.47 eV, however, the energy barriers of Li diffusion decrease in the interlayer of the G/BP heterostructure. The results mentioned above suggest that the rate performance of the G/BP heterostructure is better than that of monolayer graphene. Furthermore, the adsorption energies of Li atoms in the three different most stable sites, i.e., H G , T P and H 1 sites, increase by about 0.49 eV, 0.26 eV, and 0.13 eV, respectively, as the electric field intensity reaches 0.6 V Å -1 . The diffusion energy barrier is significantly decreased by an external electric field. It is demonstrated that the external electric field can not only enhance the adsorption but can also modulate the diffusion barriers of Li atoms in the G/BP heterostructure.

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.

CO Diffusion into Amorphous H2O Ices

NASA Astrophysics Data System (ADS)

Lauck, Trish; Karssemeijer, Leendertjan; Shulenberger, Katherine; Rajappan, Mahesh; Öberg, Karin I.; Cuppen, Herma M.

2015-03-01

The mobility of atoms, molecules, and radicals in icy grain mantles regulates ice restructuring, desorption, and chemistry in astrophysical environments. Interstellar ices are dominated by H2O, and diffusion on external and internal (pore) surfaces of H2O-rich ices is therefore a key process to constrain. This study aims to quantify the diffusion kinetics and barrier of the abundant ice constituent CO into H2O-dominated ices at low temperatures (15-23 K), by measuring the mixing rate of initially layered H2O(:CO2)/CO ices. The mixed fraction of CO as a function of time is determined by monitoring the shape of the infrared CO stretching band. Mixing is observed at all investigated temperatures on minute timescales and can be ascribed to CO diffusion in H2O ice pores. The diffusion coefficient and final mixed fraction depend on ice temperature, porosity, thickness, and composition. The experiments are analyzed by applying Fick’s diffusion equation under the assumption that mixing is due to CO diffusion into an immobile H2O ice. The extracted energy barrier for CO diffusion into amorphous H2O ice is ˜160 K. This is effectively a surface diffusion barrier. The derived barrier is low compared to current surface diffusion barriers in use in astrochemical models. Its adoption may significantly change the expected timescales for different ice processes in interstellar environments.

Molecular dynamics simulations of hydrogen diffusion in aluminum

DOE PAGES

Zhou, X. W.; El Gabaly, F.; Stavila, V.; ...

2016-03-23

In this study, hydrogen diffusion impacts the performance of solid-state hydrogen storage materials and contributes to the embrittlement of structural materials under hydrogen-containing environments. In atomistic simulations, the diffusion energy barriers are usually calculated using molecular statics simulations where a nudged elastic band method is used to constrain a path connecting the two end points of an atomic jump. This approach requires prior knowledge of the “end points”. For alloy and defective systems, the number of possible atomic jumps with respect to local atomic configurations is tremendous. Even when these jumps can be exhaustively studied, it is still unclear howmore » they can be combined to give an overall diffusion behavior seen in experiments. Here we describe the use of molecular dynamics simulations to determine the overall diffusion energy barrier from the Arrhenius equation. This method does not require information about atomic jumps, and it has additional advantages, such as the ability to incorporate finite temperature effects and to determine the pre-exponential factor. As a test case for a generic method, we focus on hydrogen diffusion in bulk aluminum. We find that the challenge of this method is the statistical variation of the results. However, highly converged energy barriers can be achieved by an appropriate set of temperatures, output time intervals (for tracking hydrogen positions), and a long total simulation time. Our results help elucidate the inconsistencies of the experimental diffusion data published in the literature. The robust approach developed here may also open up future molecular dynamics simulations to rapidly study diffusion properties of complex material systems in multidimensional spaces involving composition and defects.« less

Reduction of diffusion barriers in isolated rat islets improves survival, but not insulin secretion or transplantation outcome

PubMed Central

Janette Williams, S; Huang, Han-Hung; Kover, Karen; Moore, Wayne; Berkland, Cory; Singh, Milind; Smirnova, Irina V; MacGregor, Ronal

2010-01-01

For people with type 1 diabetes and severe hypoglycemic unawareness, islet transplants offer hope for improving the quality of life. However, islet cell death occurs quickly during or after transplantation, requiring large quantities of islets per transplant. The purpose of this study was to determine whether poor function demonstrated in large islets was a result of diffusion barriers and if removing those barriers could improve function and transplantation outcomes. Islets were isolated from male DA rats and measured for cell viability, islet survival, glucose diffusion and insulin secretion. Modeling of diffusion barriers was completed using dynamic partial differential equations for a sphere. Core cell death occurred in 100% of the large islets (diameter >150 µm), resulting in poor survival within 7 days after isolation. In contrast, small islets (diameter <100 µm) exhibited good survival rates in culture (91%). Glucose diffusion into islets was tracked with 2-NBDG; 4.2 µm/min in small islets and 2.8 µm/min in large islets. 2-NBDG never permeated to the core cells of islets larger than 150 µm diameter. Reducing the diffusion barrier in large islets improved their immediate and long-term viability in culture. However, reduction of the diffusion barrier in large islets failed to improve their inferior in vitro insulin secretion compared to small islets, and did not return glucose control to diabetic animals following transplantation. Thus, diffusion barriers lead to low viability and poor survival for large islets, but are not solely responsible for the inferior insulin secretion or poor transplantation outcomes of large versus small islets. PMID:20885858

The Long and Viscous Road: Uncovering Nuclear Diffusion Barriers in Closed Mitosis

PubMed Central

Zavala, Eder; Marquez-Lago, Tatiana T.

2014-01-01

Diffusion barriers are effective means for constraining protein lateral exchange in cellular membranes. In Saccharomyces cerevisiae, they have been shown to sustain parental identity through asymmetric segregation of ageing factors during closed mitosis. Even though barriers have been extensively studied in the plasma membrane, their identity and organization within the nucleus remains poorly understood. Based on different lines of experimental evidence, we present a model of the composition and structural organization of a nuclear diffusion barrier during anaphase. By means of spatial stochastic simulations, we propose how specialised lipid domains, protein rings, and morphological changes of the nucleus may coordinate to restrict protein exchange between mother and daughter nuclear lobes. We explore distinct, plausible configurations of these diffusion barriers and offer testable predictions regarding their protein exclusion properties and the diffusion regimes they generate. Our model predicts that, while a specialised lipid domain and an immobile protein ring at the bud neck can compartmentalize the nucleus during early anaphase; a specialised lipid domain spanning the elongated bridge between lobes would be entirely sufficient during late anaphase. Our work shows how complex nuclear diffusion barriers in closed mitosis may arise from simple nanoscale biophysical interactions. PMID:25032937

First-principles study of transition-metal nitrides as diffusion barriers against Al

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

Mei, Zhi-Gang; Yacout, Abdellatif M.; Kim, Yeon Soo

2016-04-01

Using density-functional theory based first-principles calculations we provided a comparative study of the diffusion barrier properties of TiN, ZrN, and HfN against Al for U-Mo dispersion fuel applications. We firstly examined the thermodynamic stability of these transition-metal nitrides with Al. The calculated heats of reaction show that both TiN and ZrN are thermodynamically unstable diffusion barrier materials, which might be decomposed by Al at relatively high temperatures. As a comparison, HfN is a stable diffusion barrier material for Al. To evaluate the kinetic stability of these nitride systems against Al diffusion, we investigated the diffusion mechanisms of Al in TiN,more » ZrN and HfN using atomic scale simulations. The effect of non-stoichiometry on the defect formation and Al migration was systematically studied. (C) 2015 ELSEVIER B.V. All rights reserved« less

Nitrogen diffusion in hafnia and the impact of nitridation on oxygen and hydrogen diffusion: A first-principles study

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

Sathiyanarayanan, Rajesh, E-mail: rajessat@in.ibm.com, E-mail: rajesh.sathiyanarayanan@gmail.com; Pandey, R. K.; Murali, K. V. R. M.

2015-01-21

Using first-principles simulations, we have computed incorporation energies and diffusion barriers of ammonia, the nitrogen molecule and atomic nitrogen in monoclinic hafnia (m-HfO{sub 2}). Our calculations show that ammonia is likely to dissociate into an NH{sub 2} molecular unit, whereas the nitrogen molecule remains as a molecule either in the interstitial space or at an oxygen lattice site. The lowest energy pathway for the diffusion of atomic nitrogen interstitials consists of the hopping of the nitrogen interstitial between neighboring three-coordinated lattice oxygen atoms that share a single Hf atom, and the barrier for such hops is determined by a switchingmore » mechanism. The substitutional nitrogen atom shows a preference for diffusion through the doubly positive oxygen vacancy-mediated mechanism. Furthermore, we have investigated the impact of nitrogen atoms on the diffusion barriers of oxygen and hydrogen interstitials in m-HfO{sub 2}. Our results show that nitrogen incorporation has a significant impact on the barriers for oxygen and hydrogen diffusion: nitrogen atoms attract oxygen and hydrogen interstitials diffusing in the vicinity, thereby slowing down (reducing) their diffusion (diffusion length)« less

Enzyme localization, crowding, and buffers collectively modulate diffusion-influenced signal transduction: Insights from continuum diffusion modeling

PubMed Central

Kekenes-Huskey, Peter M.; Eun, Changsun; McCammon, J. A.

2015-01-01

Biochemical reaction networks consisting of coupled enzymes connect substrate signaling events with biological function. Substrates involved in these reactions can be strongly influenced by diffusion “barriers” arising from impenetrable cellular structures and macromolecules, as well as interactions with biomolecules, especially within crowded environments. For diffusion-influenced reactions, the spatial organization of diffusion barriers arising from intracellular structures, non-specific crowders, and specific-binders (buffers) strongly controls the temporal and spatial reaction kinetics. In this study, we use two prototypical biochemical reactions, a Goodwin oscillator, and a reaction with a periodic source/sink term to examine how a diffusion barrier that partitions substrates controls reaction behavior. Namely, we examine how conditions representative of a densely packed cytosol, including reduced accessible volume fraction, non-specific interactions, and buffers, impede diffusion over nanometer length-scales. We find that diffusion barriers can modulate the frequencies and amplitudes of coupled diffusion-influenced reaction networks, as well as give rise to “compartments” of decoupled reactant populations. These effects appear to be intensified in the presence of buffers localized to the diffusion barrier. These findings have strong implications for the role of the cellular environment in tuning the dynamics of signaling pathways. PMID:26342355

Strain effect on the adsorption, diffusion, and molecular dissociation of hydrogen on Mg (0001) surface

NASA Astrophysics Data System (ADS)

Lei, Huaping; Wang, Caizhuang; Yao, Yongxin; Wang, Yangang; Hupalo, Myron; McDougall, Dan; Tringides, Michael; Ho, Kaiming

2013-12-01

The adsorption, diffusion, and molecular dissociation of hydrogen on the biaxially strained Mg (0001) surface have been systematically investigated by the first principle calculations based on density functional theory. When the strain changes from the compressive to tensile state, the adsorption energy of H atom linearly increases while its diffusion barrier linearly decreases oppositely. The dissociation barrier of H2 molecule linearly reduces in the tensile strain region. Through the chemical bonding analysis including the charge density difference, the projected density of states and the Mulliken population, the mechanism of the strain effect on the adsorption of H atom and the dissociation of H2 molecule has been elucidated by an s-p charge transfer model. With the reduction of the orbital overlap between the surface Mg atoms upon the lattice expansion, the charge transfers from p to s states of Mg atoms, which enhances the hybridization of H s and Mg s orbitals. Therefore, the bonding interaction of H with Mg surface is strengthened and then the atomic diffusion and molecular dissociation barriers of hydrogen decrease accordingly. Our works will be helpful to understand and to estimate the influence of the lattice deformation on the performance of Mg-containing hydrogen storage materials.

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).

Cu diffusion in single-crystal and polycrystalline TiN barrier layers: A high-resolution experimental study supported by first-principles calculations

NASA Astrophysics Data System (ADS)

Mühlbacher, Marlene; Bochkarev, Anton S.; Mendez-Martin, Francisca; Sartory, Bernhard; Chitu, Livia; Popov, Maxim N.; Puschnig, Peter; Spitaler, Jürgen; Ding, Hong; Schalk, Nina; Lu, Jun; Hultman, Lars; Mitterer, Christian

2015-08-01

Dense single-crystal and polycrystalline TiN/Cu stacks were prepared by unbalanced DC magnetron sputter deposition at a substrate temperature of 700 °C and a pulsed bias potential of -100 V. The microstructural variation was achieved by using two different substrate materials, MgO(001) and thermally oxidized Si(001), respectively. Subsequently, the stacks were subjected to isothermal annealing treatments at 900 °C for 1 h in high vacuum to induce the diffusion of Cu into the TiN. The performance of the TiN diffusion barrier layers was evaluated by cross-sectional transmission electron microscopy in combination with energy-dispersive X-ray spectrometry mapping and atom probe tomography. No Cu penetration was evident in the single-crystal stack up to annealing temperatures of 900 °C, due to the low density of line and planar defects in single-crystal TiN. However, at higher annealing temperatures when diffusion becomes more prominent, density-functional theory calculations predict a stoichiometry-dependent atomic diffusion mechanism of Cu in bulk TiN, with Cu diffusing on the N sublattice for the experimental N/Ti ratio. In comparison, localized diffusion of Cu along grain boundaries in the columnar polycrystalline TiN barriers was detected after the annealing treatment. The maximum observed diffusion length was approximately 30 nm, yielding a grain boundary diffusion coefficient of the order of 10-16 cm2 s-1 at 900 °C. This is 10 to 100 times less than for comparable underdense polycrystalline TiN coatings deposited without external substrate heating or bias potential. The combined numerical and experimental approach presented in this paper enables the contrasting juxtaposition of diffusion phenomena and mechanisms in two TiN coatings, which differ from each other only in the presence of grain boundaries.

Diffusion Barrier Selection from Refractory Metals (Zr, Mo and Nb) via Interdiffusion Investigation for U-Mo RERTR Fuel Alloy

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

K. Huang; C. Kammerer; D. D. Keiser, Jr.

2014-04-01

U-Mo alloys are being developed as low enrichment monolithic fuel under the Reduced Enrichment for Research and Test Reactor (RERTR) Program. Diffusional interactions between the U-Mo fuel alloy and Al-alloy cladding within the monolithic fuel plate construct necessitate incorporation of a barrier layer. Fundamentally, a diffusion barrier candidate must have good thermal conductivity, high melting point, minimal metallurgical interaction, and good irradiation performance. Refractory metals, Zr, Mo, and Nb are considered based on their physical properties, and the diffusion behavior must be carefully examined first with U-Mo fuel alloy. Solid-to-solid U-10wt.%Mo vs. Mo, Zr, or Nb diffusion couples were assembledmore » and annealed at 600, 700, 800, 900 and 1000 degrees C for various times. The interdiffusion microstructures and chemical composition were examined via scanning electron microscopy and electron probe microanalysis, respectively. For all three systems, the growth rate of interdiffusion zone were calculated at 1000, 900 and 800 degrees C under the assumption of parabolic growth, and calculated for lower temperature of 700, 600 and 500 degrees C according to Arrhenius relationship. The growth rate was determined to be about 10 3 times slower for Zr, 10 5 times slower for Mo and 10 6 times slower for Nb, than the growth rates reported for the interaction between the U-Mo fuel alloy and pure Al or Al-Si cladding alloys. Zr, however was selected as the barrier metal due to a concern for thermo- mechanical behavior of UMo/Nb interface observed from diffusion couples, and for ductile-to-brittle transition of Mo near room temperature.« less

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

Custer, Jonathan S.; Fleming, James G.; Roherty-Osmun, Elizabeth

Refractory ternary nitride films for diffusion barriers in microelectronics have been grown using chemical vapor deposition. Thin films of titanium-silicon-nitride, tungsten-boron-nitride, and tungsten-silicon-nitride of various compositions have been deposited on 150 mm Si wafers. The microstructure of the films are either fully amorphous for the tungsten based films, or nauocrystalline TiN in an amorphous matrix for titanium-silicon-nitride. All films exhibit step coverages suitable for use in future microelectronics generations. Selected films have been tested as diffusion barriers between copper and silicon, and generally perform extremely weH. These fiIms are promising candidates for advanced diffusion barriers for microelectronics applications. The manufacturingmore » of silicon wafers into integrated circuits uses many different process and materials. The manufacturing process is usually divided into two parts: the front end of line (FEOL) and the back end of line (BEOL). In the FEOL the individual transistors that are the heart of an integrated circuit are made on the silicon wafer. The responsibility of the BEOL is to wire all the transistors together to make a complete circuit. The transistors are fabricated in the silicon itself. The wiring is made out of metal, currently aluminum and tungsten, insulated by silicon dioxide, see Figure 1. Unfortunately, silicon will diffuse into aluminum, causing aluminum spiking of junctions, killing transistors. Similarly, during chemical vapor deposition (CVD) of tungsten from ~fj, the reactivity of the fluorine can cause "worn-holes" in the silicon, also destroying transistors. The solution to these problems is a so-called diffusion barrier, which will allow current to pass from the transistors to the wiring, but will prevent reactions between silicon and the metal.« less

Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

DOE PAGES

Han, Yong; Evans, James W.

2015-10-27

Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C6-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atom inmore » the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ~0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. Furthermore, this in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001).« less

Density Functional Theory Investigation of Proton Diffusion in Tungsten Oxide And Its Hydrates

NASA Astrophysics Data System (ADS)

Lin, Hao

Fast proton conduction mechanism is of key importance for achieving high performance in fuel cell membranes, batteries, supercapacitors, and electrochromic materials. Enhanced proton diffusion is often observed in hydrated materials where it is thought to occur via the famous Grotthuss mechanism through pathways formed by structural water. Using first-principles calculations, we demonstrate that proton diffusion in tungsten oxide dihydrate (WO3·2H 2O), a known good proton conductor, takes place within the layers of corner-sharing WO6 octahedra without direct involvement of structural water. The calculated proton migration barrier in WO3·2H 2O is in good agreement with the experimental value inferred from the temperature dependence of conductivity. The preferred proton diffusion path in WO3·2H2O is essentially the same as in gamma-WO 3. In contrast to the small intercalation voltages calculated for WO 3 and WO3·2H2O, we find that proton absorption in the monohydrate WO3·H2O is energetically highly favorable. However, strong proton-proton repulsion limits the equilibrium H content at zero voltage. We find a fast one-dimensional diffusion channel in WO3·H2O at dilute proton concentrations, but much higher barriers are expected at near-equilibrium concentrations due to strong repulsive interactions with other protons. Our results illustrate that low proton diffusion barriers and low insertion voltages both contribute to fast proton transport in bulk WO3·2H2O and gamma-WO 3.

Adsorption and diffusion of Ru adatoms on Ru(0001)-supported graphene: Large-scale first-principles calculations

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

Han, Yong; Evans, James W.

2015-10-28

Large-scale first-principles density functional theory calculations are performed to investigate the adsorption and diffusion of Ru adatoms on monolayer graphene (G) supported on Ru(0001). The G sheet exhibits a periodic moiré-cell superstructure due to lattice mismatch. Within a moiré cell, there are three distinct regions: fcc, hcp, and mound, in which the C{sub 6}-ring center is above a fcc site, a hcp site, and a surface Ru atom of Ru(0001), respectively. The adsorption energy of a Ru adatom is evaluated at specific sites in these distinct regions. We find the strongest binding at an adsorption site above a C atommore » in the fcc region, next strongest in the hcp region, then the fcc-hcp boundary (ridge) between these regions, and the weakest binding in the mound region. Behavior is similar to that observed from small-unit-cell calculations of Habenicht et al. [Top. Catal. 57, 69 (2014)], which differ from previous large-scale calculations. We determine the minimum-energy path for local diffusion near the center of the fcc region and obtain a local diffusion barrier of ∼0.48 eV. We also estimate a significantly lower local diffusion barrier in the ridge region. These barriers and information on the adsorption energy variation facilitate development of a realistic model for the global potential energy surface for Ru adatoms. This in turn enables simulation studies elucidating diffusion-mediated directed-assembly of Ru nanoclusters during deposition of Ru on G/Ru(0001)« less

Review of Graphene as a Solid State Diffusion Barrier.

PubMed

Morrow, Wayne K; Pearton, Stephen J; Ren, Fan

2016-01-06

Conventional thin-film diffusion barriers consist of 3D bulk films with high chemical and thermal stability. The purpose of the barrier material is to prevent intermixing or penetration from the two materials that encase it. Adhesion to both top and bottom materials is critical to the success of the barrier. Here, the effectiveness of a single atomic layer of graphene as a solid-state diffusion barrier for common metal schemes used in microelectronics is reviewed, and specific examples are discussed. Initial studies of electrical contacts to graphene show a distinct separation in behavior between metallic groups that strongly or weakly bond to it. The two basic classes of metal reactions with graphene are either physisorbed metals, which bond weakly with graphene, or chemisorbed metals, which bond strongly to graphene. For graphene diffusion barrier testing on Si substrates, an effective barrier can be achieved through the formation of a carbide layer with metals that are chemisorbed. For physisorbed metals, the barrier failure mechanism is loss of adhesion at the metal–graphene interface. A graphene layer encased between two metal layers, in certain cases, can increase the binding energy of both films with graphene, however, certain combinations of metal films are detrimental to the bonding with graphene. While the prospects for graphene's future as a solid-state diffusion barrier are positive, there are open questions, and areas for future research are discussed. A better understanding of the mechanisms which influence graphene's ability to be an effective diffusion barrier in microelectronic applications is required, and additional experiments are needed on a broader range of metals, as well as common metal stack contact structures used in microelectronic applications. The role of defects in the graphene is also a key area, since they will probably influence the barrier properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Atomistic Modeling of Cation Diffusion in Transition Metal Perovskites La1-xSrxMnO3+/-δfor Solid Oxide Fuel Cell Cathodes Applications

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin; Duan, Yuhua; Morgan, Dane; Sorescu, Dan; Abernathy, Harry

Cation diffusion in La1-xSrxMnO3+/-δ (LSM) and in related perovskite materials play an important role in controlling long term performance and stability of solid oxide fuel cell (SOFCs) cathodes. Due to sluggish rates of cation diffusion and complex coupling between defect chemistry and cation diffusion pathways, currently there is still lack of quantitative theoretical model predictions on cation diffusivity vs. T and P(O2) to describe experimental cation tracer diffusivities. In this work, based on ab initio modeling of LSM defect chemistry and migration barriers of the possible cation diffusion pathways, we assess the rates of A-site and B-site cation diffusion in a wide range of T and P(O2) at x =0.0 and 0.2 for SOFC applications. We demonstrate the active cation diffusion pathways in LSM involve cation defect clusters as cation transport carriers, where reduction in the cation migration barriers, which are governed by the steric effect associated with the metal-oxygen cage in the perovskite lattice, is much greater than the penalty of repulsive interaction in the A-site and B-site cation vacancy clusters, leading to higher cation diffusion rates as compared to those of single cation vacancy hopping mechanisms. The predicted Mn and La/Sr cation self-diffusion coefficients of LSM at at x =0.0 and 0.2 along with their 1/T and P(O2) dependences, are in good agreement with the experimental tracer diffusion coefficients.

Protective coatings for sensitive materials

DOEpatents

Egert, Charles M.

1997-01-01

An enhanced protective coating to prevent interaction between constituents of the environment and devices that can be damaged by those constituents. This coating is provided by applying a synergistic combination of diffusion barrier and physical barrier materials. These materials can be, for example, in the form of a plurality of layers of a diffusion barrier and a physical barrier, with these barrier layers being alternated. Further protection in certain instances is provided by including at least one layer of a getter material to actually react with one or more of the deleterious constituents. The coating is illustrated by using alternating layers of an organic coating (such as Parylene-C.TM.) as the diffusion barrier, and a metal coating (such as aluminum) as the physical barrier. For best results there needs to be more than one of at least one of the constituent layers.

A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress

NASA Astrophysics Data System (ADS)

Tchitchekova, Deyana S.; Morthomas, Julien; Ribeiro, Fabienne; Ducher, Roland; Perez, Michel

2014-07-01

A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ˜3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress.

A novel method for calculating the energy barriers for carbon diffusion in ferrite under heterogeneous stress.

PubMed

Tchitchekova, Deyana S; Morthomas, Julien; Ribeiro, Fabienne; Ducher, Roland; Perez, Michel

2014-07-21

A novel method for accurate and efficient evaluation of the change in energy barriers for carbon diffusion in ferrite under heterogeneous stress is introduced. This method, called Linear Combination of Stress States, is based on the knowledge of the effects of simple stresses (uniaxial or shear) on these diffusion barriers. Then, it is assumed that the change in energy barriers under a complex stress can be expressed as a linear combination of these already known simple stress effects. The modifications of energy barriers by either uniaxial traction/compression and shear stress are determined by means of atomistic simulations with the Climbing Image-Nudge Elastic Band method and are stored as a set of functions. The results of this method are compared to the predictions of anisotropic elasticity theory. It is shown that, linear anisotropic elasticity fails to predict the correct energy barrier variation with stress (especially with shear stress) whereas the proposed method provides correct energy barrier variation for stresses up to ∼3 GPa. This study provides a basis for the development of multiscale models of diffusion under non-uniform stress.

Origins and implications of the ordering of oxygen vacancies and localized electrons on partially reduced CeO 2(111)

DOE PAGES

Sutton, Jonathan E.; Beste, Ariana; Steven H. Overbury

2015-10-12

In this study, we use density functional theory to explain the preferred structure of partially reduced CeO 2(111). Low-energy ordered structures are formed when the vacancies are isolated (maximized intervacancy separation) and the size of the Ce 3+ ions is minimized. Both conditions help minimize disruptions to the lattice around the vacancy. The stability of the ordered structures suggests that isolated vacancies are adequate for modeling more complex (e.g., catalytic) systems. Oxygen diffusion barriers are predicted to be low enough that O diffusion between vacancies is thermodynamically controlled at room temperature. The O-diffusion-reaction energies and barriers are decreased when onemore » Ce f electron hops from a nearest-neighbor Ce cation to a next-nearest-neighbor Ce cation, with a barrier that has been estimated to be slightly less than the barrier to O diffusion in the absence of polaron hopping. In conculsion, this indicates that polaron hopping plays a key role in facilitating the overall O diffusion process, and depending on the relative magnitudes of the polaron hopping and O diffusion barriers, polaron hopping may be the kinetically limiting process.« less

Axial diffusion barriers in near-infrared nanopillar LEDs.

PubMed

Scofield, Adam C; Lin, Andrew; Haddad, Michael; Huffaker, Diana L

2014-11-12

The growth of GaAs/GaAsP axial heterostructures is demonstrated and implemented as diffusion current barriers in nanopillar light-emitting diodes at near-infrared wavelengths. The nanopillar light-emitting diodes utilize an n-GaAs/i-InGaAs/p-GaAs axial heterostructure for current injection. Axial GaAsP segments are inserted into the n- and p-GaAs portions of the nanopillars surrounding the InGaAs emitter region, acting as diffusion barriers to provide enhanced carrier confinement. Detailed characterization of growth of the GaAsP inserts and electronic band-offset measurements are used to effectively implement the GaAsP inserts as diffusion barriers. The implementation of these barriers in nanopillar light-emitting diodes provides a 5-fold increase in output intensity, making this a promising approach to high-efficiency pillar-based emitters in the near-infrared wavelength range.

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

NASA Technical Reports Server (NTRS)

Good, Brian S.

2017-01-01

Ceramic Matrix Composite (CMC) materials are of interest for use in next-generation turbine engine components, offering a number of significant advantages, including reduced weight and high operating temperatures. However, in the hot environment in which such components operate, the presence of water vapor can lead to corrosion and recession, limiting the useful life of the components. Such degradation can be reduced through the use of Environmental Barrier Coatings (EBCs) that limit the amount of oxygen and water vapor reaching the component. Candidate EBC materials include Yttrium and Ytterbium silicates. In this work we present results of kinetic Monte Carlo (kMC) simulations of oxygen diffusion, via the vacancy mechanism, in Yttrium and Ytterbium disilicates, along with a brief discussion of interstitial diffusion. An EBC system typically includes a bond coat located between the EBC and the component surface. Bond coat materials are generally chosen for properties other than low oxygen diffusivity, but low oxygen diffusivity is nevertheless a desirable characteristic, as the bond coat could provide some additional component protection, particularly in the case where cracks in the coating system provide a direct path from the environment to the bond coat interface. We have therefore performed similar kMC simulations of oxygen diffusion in this material.

Kinetic Monte Carlo Simulation of Oxygen Diffusion in Ytterbium Disilicate

NASA Technical Reports Server (NTRS)

Good, Brian S.

2015-01-01

Silicon-based ceramic components for next-generation jet turbine engines offer potential weight savings, as well as higher operating temperatures, both of which lead to increased efficiency and lower fuel costs. Silicon carbide (SiC), in particular, offers low density, good strength at high temperatures, and good oxidation resistance in dry air. However, reaction of SiC with high-temperature water vapor, as found in the hot section of jet turbine engines in operation, can cause rapid surface recession, which limits the lifetime of such components. Environmental Barrier Coatings (EBCs) are therefore needed if long component lifetime is to be achieved. Rare earth silicates such as Yb2Si2O7 and Yb2SiO5 have been proposed for such applications; in an effort to better understand diffusion in such materials, we have performed kinetic Monte Carlo (kMC) simulations of oxygen diffusion in Ytterbium disilicate, Yb2- Si2O7. The diffusive process is assumed to take place via the thermally activated hopping of oxygen atoms among oxygen vacancy sites or among interstitial sites. Migration barrier energies are computed using density functional theory (DFT).

Protective coatings for sensitive materials

DOEpatents

Egert, C.M.

1997-08-05

An enhanced protective coating is disclosed to prevent interaction between constituents of the environment and devices that can be damaged by those constituents. This coating is provided by applying a synergistic combination of diffusion barrier and physical barrier materials. These materials can be, for example, in the form of a plurality of layers of a diffusion barrier and a physical barrier, with these barrier layers being alternated. Further protection in certain instances is provided by including at least one layer of a getter material to actually react with one or more of the deleterious constituents. The coating is illustrated by using alternating layers of an organic coating (such as Parylene-C{trademark}) as the diffusion barrier, and a metal coating (such as aluminum) as the physical barrier. For best results there needs to be more than one of at least one of the constituent layers. 4 figs.

First-principles investigation of point defect and atomic diffusion in Al2Ca

NASA Astrophysics Data System (ADS)

Tian, Xiao; Wang, Jia-Ning; Wang, Ya-Ping; Shi, Xue-Feng; Tang, Bi-Yu

2017-04-01

Point defects and atomic diffusion in Al2Ca have been studied from first-principles calculations within density functional framework. After formation energy and relative stability of point defects are investigated, several predominant diffusion processes in Al2Ca are studied, including sublattice one-step mechanism, 3-jump vacancy cycles and antistructure sublattice mechanism. The associated energy profiles are calculated with climbing image nudged elastic band (CI-NEB) method, then the saddle points and activation barriers during atomic diffusion are further determined. The resulted activation barriers show that both Al and Ca can diffuse mainly mediated by neighbor vacancy on their own sublattice. 3-jump cycle mechanism mediated by VCa may make some contribution to the overall Al diffusion. And antistructure (AS) sublattice mechanism can also play an important role in Ca atomic diffusion owing to the moderate activation barrier.

Investigation to develop a method to apply diffusion barrier to high strength fibers

NASA Technical Reports Server (NTRS)

Veltri, R. D.; Paradis, R. D.; Douglas, F. C.

1975-01-01

A radio frequency powered ion plating process was used to apply the diffusion barriers of aluminum oxide, yttrium oxide, hafnium oxide and titanium carbide to a substrate tungsten fiber. Each of the coatings was examined as to its effect on both room temperature strength and tensile strength of the base tungsten fiber. The coated fibers were then overcoated with a nickel alloy to become single cell diffusion couples. These diffusion couples were exposed to 1093 C for 24 hours, cycled between room temperature and 1093 C, and given a thermal anneal for 100 hours at 1200 C. Tensile testing and metallographic examinations determined that the hafnium oxide coating produced the best high temperature diffusion barrier for tungsten of the four coatings.

Very-high thermal and electrical conductivity in overpressure-processed Bi2Sr2CaCu2O8+x wires

NASA Astrophysics Data System (ADS)

Bonura, M.; Avitabile, F.; Barth, C.; Jiang, J.; Larbalestier, D.; Fête, A.; Leo, A.; Bottura, L.; Senatore, C.

2018-05-01

The residual-resistivity ratio (RRR) of the normal-metal matrix is a key parameter for the electrical and thermal stability of technical superconductors. In Bi2Sr2CaCu2 {{{O}}}8+x (Bi-2212) round wires, the precursor powders are embedded in a Ag matrix without any diffusion barrier, and elemental diffusion from the superconducting filaments into the Ag might be expected to contaminate the matrix during the melt processing required for high critical current density development. This work shows that the overpressure processing, which is adopted to enhance the critical current performance, improves the thermal and electrical conductivities of the conductor, too. In the case of wires reacted with a standard processing performed in 1 bar O2, the RRR of the Ag matrix is about 90, in spite of the simple conductor design that does not include diffusion barriers. Increasing the total reaction pressure to 100 bar improves the RRR to about 200. The differences in RRR reflect on the thermal conductivity of the whole conductor, which has been investigated in magnetic fields up to 19 T.

Oxygen self-diffusion mechanisms in monoclinic Zr O2 revealed and quantified by density functional theory, random walk analysis, and kinetic Monte Carlo calculations

NASA Astrophysics Data System (ADS)

Yang, Jing; Youssef, Mostafa; Yildiz, Bilge

2018-01-01

In this work, we quantify oxygen self-diffusion in monoclinic-phase zirconium oxide as a function of temperature and oxygen partial pressure. A migration barrier of each type of oxygen defect was obtained by first-principles calculations. Random walk theory was used to quantify the diffusivities of oxygen interstitials by using the calculated migration barriers. Kinetic Monte Carlo simulations were used to calculate diffusivities of oxygen vacancies by distinguishing the threefold- and fourfold-coordinated lattice oxygen. By combining the equilibrium defect concentrations obtained in our previous work together with the herein calculated diffusivity of each defect species, we present the resulting oxygen self-diffusion coefficients and the corresponding atomistically resolved transport mechanisms. The predicted effective migration barriers and diffusion prefactors are in reasonable agreement with the experimentally reported values. This work provides insights into oxygen diffusion engineering in Zr O2 -related devices and parametrization for continuum transport modeling.

Alloyed coatings for dispersion strengthened alloys

NASA Technical Reports Server (NTRS)

Wermuth, F. R.; Stetson, A. R.

1971-01-01

Processing techniques were developed for applying several diffusion barriers to TD-Ni and TD-NiCr. Barrier coated specimens of both substrates were clad with Ni-Cr-Al and Fe-Cr-Al alloys and diffusion annealed in argon. Measurement of the aluminum distribution after annealing showed that, of the readily applicable diffusion barriers, a slurry applied tungsten barrier most effectively inhibited the diffusion of aluminum from the Ni-Cr-Al clad into the TD-alloy substrates. No barrier effectively limited interdiffusion of the Fe-Cr-Al clad with the substrates. A duplex process was then developed for applying Ni-Cr-Al coating compositions to the tungsten barrier coated substrates. A Ni-(16 to 32)Cr-3Si modifier was applied by slurry spraying and firing in vacuum, and was then aluminized by a fusion slurry process. Cyclic oxidation tests at 2300 F resulted in early coating failure due to inadequate edge coverage and areas of coating porosity. EMP analysis showed that oxidation had consumed 70 to 80 percent of the aluminum in the coating in less than 50 hours.

Analysis and experimental study on formation conditions of large-scale barrier-free diffuse atmospheric pressure air plasmas in repetitive pulse mode

NASA Astrophysics Data System (ADS)

Li, Lee; Liu, Lun; Liu, Yun-Long; Bin, Yu; Ge, Ya-Feng; Lin, Fo-Chang

2014-01-01

Atmospheric air diffuse plasmas have enormous application potential in various fields of science and technology. Without dielectric barrier, generating large-scale air diffuse plasmas is always a challenging issue. This paper discusses and analyses the formation mechanism of cold homogenous plasma. It is proposed that generating stable diffuse atmospheric plasmas in open air should meet the three conditions: high transient power with low average power, excitation in low average E-field with locally high E-field region, and multiple overlapping electron avalanches. Accordingly, an experimental configuration of generating large-scale barrier-free diffuse air plasmas is designed. Based on runaway electron theory, a low duty-ratio, high voltage repetitive nanosecond pulse generator is chosen as a discharge excitation source. Using the wire-electrodes with small curvature radius, the gaps with highly non-uniform E-field are structured. Experimental results show that the volume-scaleable, barrier-free, homogeneous air non-thermal plasmas have been obtained between the gap spacing with the copper-wire electrodes. The area of air cold plasmas has been up to hundreds of square centimeters. The proposed formation conditions of large-scale barrier-free diffuse air plasmas are proved to be reasonable and feasible.

Local Versus Long-Range Diffusion Effects of Photoexcited States on Radiative Recombination in Organic-Inorganic Lead Halide Perovskites.

PubMed

Vrućinić, Milan; Matthiesen, Clemens; Sadhanala, Aditya; Divitini, Giorgio; Cacovich, Stefania; Dutton, Sian E; Ducati, Caterina; Atatüre, Mete; Snaith, Henry; Friend, Richard H; Sirringhaus, Henning; Deschler, Felix

2015-09-01

Radiative recombination in thin films of the archetypical, high-performing perovskites CH 3 NH 3 PbBr 3 and CH 3 NH 3 PbI 3 shows localized regions of increased emission with dimensions ≈500 nm. Maps of the spectral emission line shape show narrower emission lines in high emission regions, which can be attributed to increased order. Excited states do not diffuse out of high emission regions before they decay, but are decoupled from nearby regions, either by slow diffusion rates or energetic barriers.

Suppression of Lateral Diffusion and Surface Leakage Currents in nBn Photodetectors Using an Inverted Design

NASA Astrophysics Data System (ADS)

Du, X.; Savich, G. R.; Marozas, B. T.; Wicks, G. W.

2018-02-01

Surface leakage and lateral diffusion currents in InAs-based nBn photodetectors have been investigated. Devices fabricated using a shallow etch processing scheme that etches through the top contact and stops at the barrier exhibited large lateral diffusion current but undetectably low surface leakage. Such large lateral diffusion current significantly increased the dark current, especially in small devices, and causes pixel-to-pixel crosstalk in detector arrays. To eliminate the lateral diffusion current, two different approaches were examined. The conventional solution utilized a deep etch process, which etches through the top contact, barrier, and absorber. This deep etch processing scheme eliminated lateral diffusion, but introduced high surface current along the device mesa sidewalls, increasing the dark current. High device failure rate was also observed in deep-etched nBn structures. An alternative approach to limit lateral diffusion used an inverted nBn structure that has its absorber grown above the barrier. Like the shallow etch process on conventional nBn structures, the inverted nBn devices were fabricated with a processing scheme that only etches the top layer (the absorber, in this case) but avoids etching through the barrier. The results show that inverted nBn devices have the advantage of eliminating the lateral diffusion current without introducing elevated surface current.

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.

The effects of interfacial recombination and injection barrier on the electrical characteristics of perovskite solar cells

NASA Astrophysics Data System (ADS)

Shi, Lin Xing; Wang, Zi Shuai; Huang, Zengguang; Sha, Wei E. I.; Wang, Haoran; Zhou, Zhen

2018-02-01

Charge carrier recombination in the perovskite solar cells (PSCs) has a deep influence on the electrical performance, such as open circuit voltage, short circuit current, fill factor and ultimately power conversion efficiency. The impacts of injection barrier, recombination channels, doping properties of carrier transport layers and light intensity on the performance of PSCs are theoretically investigated by drift-diffusion model in this work. The results indicate that due to the injection barrier at the interfaces of perovskite and carrier transport layer, the accumulated carriers modify the electric field distribution throughout the PSCs. Thus, a zero electric field is generated at a specific applied voltage, with greatly increases the interfacial recombination, resulting in a local kink of current density-voltage (J-V) curve. This work provides an effective strategy to improve the efficiency of PSCs by pertinently reducing both the injection barrier and interfacial recombination.

Migration mechanisms and diffusion barriers of vacancies in Ga2O3

NASA Astrophysics Data System (ADS)

Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico

2017-06-01

We employ the nudged elastic band and the dimer methods within the standard density functional theory (DFT) formalism to study the migration of the oxygen and gallium vacancies in the monoclinic structure of β -Ga2O3 . We identify all the first nearest neighbor paths and calculate the migration barriers for the diffusion of the oxygen and gallium vacancies. We also identify the metastable sites of the gallium vacancies which are critical for the diffusion of the gallium atoms. The migration barriers for the diffusion of the gallium vacancies are lower than the migration barriers for oxygen vacancies by 1 eV on average, suggesting that the gallium vacancies are mobile at lower temperatures. Using the calculated migration barriers we estimate the annealing temperature of these defects within the harmonic transition state theory formalism, finding excellent agreement with the observed experimental annealing temperatures. Finally, we suggest the existence of percolation paths which enable the migration of the species without utilizing all the migration paths of the crystal.

Effect of polyethyleneimine modified graphene on the mechanical and water vapor barrier properties of methyl cellulose composite films.

PubMed

Liu, Hongyu; Liu, Cuiyun; Peng, Shuge; Pan, Bingli; Lu, Chang

2018-02-15

A series of novel methyl cellulose (MC) composite films were prepared using polyethyleneimine reduced graphene oxide (PEI-RGO) as an effective filler for water vapor barrier application. The as-prepared PEI-RGO/MC composites were characterized by Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, tensile test and scanning electron microscopy. The experimental and theoretical results exhibited that PEI-RGO was uniformly dispersed in the MC matrix without aggregation and formed an aligned dispersion. The addition of PEI-RGO resulted in an enhanced surface hydrophobicity and a tortuous diffusion pathway for water molecules. Water vapor permeability of PEI-RGO/MC with loading of 3.0% of surface modified graphene was as low as 5.98×10 -11 gmm -2 s -1 Pa -1 . The synergistic effects of enhanced surface hydrophobicity and tortuous diffusion pathway were accounted for the improved water vapor barrier performance of the PEI-RGO/MC composite films. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of Nanoporosity in Moisture Permeation Barrier Layers by Electrochemical Impedance Spectroscopy.

PubMed

Perrotta, Alberto; García, Santiago J; Michels, Jasper J; Andringa, Anne-Marije; Creatore, Mariadriana

2015-07-29

Water permeation in inorganic moisture permeation barriers occurs through macroscale defects/pinholes and nanopores, the latter with size approaching the water kinetic diameter (0.27 nm). Both permeation paths can be identified by the calcium test, i.e., a time-consuming and expensive optical method for determining the water vapor transmission rate (WVTR) through barrier layers. Recently, we have shown that ellipsometric porosimetry (i.e., a combination of spectroscopic ellipsometry and isothermal adsorption studies) is a valid method to classify and quantify the nanoporosity and correlate it with the WVTR values. Nevertheless, no information is obtained about the macroscale defects or the kinetics of water permeation through the barrier, both essential in assessing the quality of the barrier layer. In this study, electrochemical impedance spectroscopy (EIS) is shown as a sensitive and versatile method to obtain information on nanoporosity and macroscale defects, water permeation, and diffusivity of moisture barrier layers, complementing the barrier property characterization obtained by means of EP and calcium test. EIS is performed on thin SiO2 barrier layers deposited by plasma enhanced-CVD. It allows the determination of the relative water uptake in the SiO2 layers, found to be in agreement with the nanoporosity content inferred by EP. Furthermore, the kinetics of water permeation is followed by EIS, and the diffusivity (D) is determined and found to be in accordance with literature values. Moreover, differently from EP, EIS data are shown to be sensitive to the presence of local macrodefects, correlated with the barrier failure during the calcium test.

Technical and Economical Aspects of Current Thermal Barrier Coating Systems for Gas Turbine Engines by Thermal Spray and EBPVD: A Review

NASA Astrophysics Data System (ADS)

Feuerstein, Albert; Knapp, James; Taylor, Thomas; Ashary, Adil; Bolcavage, Ann; Hitchman, Neil

2008-06-01

The most advanced thermal barrier coating (TBC) systems for aircraft engine and power generation hot section components consist of electron beam physical vapor deposition (EBPVD) applied yttria-stabilized zirconia and platinum modified diffusion aluminide bond coating. Thermally sprayed ceramic and MCrAlY bond coatings, however, are still used extensively for combustors and power generation blades and vanes. This article highlights the key features of plasma spray and HVOF, diffusion aluminizing, and EBPVD coating processes. The coating characteristics of thermally sprayed MCrAlY bond coat as well as low density and dense vertically cracked (DVC) Zircoat TBC are described. Essential features of a typical EBPVD TBC coating system, consisting of a diffusion aluminide and a columnar TBC, are also presented. The major coating cost elements such as material, equipment and processing are explained for the different technologies, with a performance and cost comparison given for selected examples.

The role of the Ti and Mo barrier layer in Ti/Al metallization to AlGaN/GaN heterostructures at identical process conditions: a structural and chemical characterization

NASA Astrophysics Data System (ADS)

Chandran, Narendraraj; Kolakieva, Lilyana; Kakanakov, Roumen; Polychroniadis, E. K.

2015-11-01

The composition and structure of TiAl-based metallizations have been investigated depending on the Ti and Mo barriers. The lowest contact resistivity of 4 × 10-6 Ω.cm2 for a Ti barrier and 7 × 10-6 Ω.cm2 for a Mo barrier is obtained at a Ti/Al ratio of 0.43 after annealing at 800 °C. The scanning transmission electron microscope (STEM) and energy dispersive spectroscopy (EDS) analyses reveal that Mo is not an effective barrier for the Au in-diffusion and Al out of diffusion during annealing. The intensive diffusion processes lead to the formation of the semimetal TiN compound at the interface and intermetallic phases of Au, Al, and Ti, the structure and composition of which depend on the barrier metal.

Performance of WCN diffusion barrier for Cu multilevel interconnects

NASA Astrophysics Data System (ADS)

Lee, Seung Yeon; Ju, Byeong-Kwon; Kim, Yong Tae

2018-04-01

The electrical and thermal properties of a WCN diffusion barrier have been studied for Cu multilevel interconnects. The WCN has been prepared using an atomic layer deposition system with WF6-CH4-NH3-H2 gases and has a very low resistivity of 100 µΩ cm and 96.9% step coverage on the high-aspect-ratio vias. The thermally stable WCN maintains an amorphous state at 800 °C and Cu/WCN contact resistance remains within a 10% deviation from the initial value after 700 °C. The mean time to failure suggests that the Cu/WCN interconnects have a longer lifetime than Cu/TaN and Cu/WN interconnects because WCN prevents Cu migration owing to the stress evolution from tensile to compressive.

Novel Fabrication of Biodegradable Superabsorbent Microspheres with Diffusion Barrier through Thermo-Chemical Modification and Their Potential Agriculture Applications for Water Holding and Sustained Release of Fertilizer.

PubMed

Feng, Diejing; Bai, Bo; Wang, Honglun; Suo, Yourui

2017-07-26

Synergistic utilization of water and fertilizer has vital contribution to the modern production of agriculture. This work reports on a simple and facile strategy to prepare biodegradable yeast/sodium alginate/poly(vinyl alcohol) superabsorbent microspheres with a diffusion barrier merit by thermo-chemical modification route. The integrated performances, including water absorbency, water retention, water evaporation ratio, leaching loss control, sustained-release behaviors, and degradation in soil, were systematically investigated. The results revealed that the modified microspheres were a triumphant water and fertilizer manager to effectively hold water and control the unexpected leakage of fertilizer for sustained release. Therefore, this work provides a promising approach to ameliorate the utilization efficiency of water and fertilizer in potential agriculture applications.

Material Barriers to Diffusive Mixing

NASA Astrophysics Data System (ADS)

Haller, George; Karrasch, Daniel

2017-11-01

Transport barriers, as zero-flux surfaces, are ill-defined in purely advective mixing in which the flux of any passive scalar is zero through all material surfaces. For this reason, Lagrangian Coherent Structures (LCSs) have been argued to play the role of mixing barriers as most repelling, attracting or shearing material lines. These three kinematic concepts, however, can also be defined in different ways, both within rigorous mathematical treatments and within the realm of heuristic diagnostics. This has lead to a an ever-growing number of different LCS methods, each generally identifying different objects as transport barriers. In this talk, we examine which of these methods have actual relevance for diffusive transport barriers. The latter barriers are arguably the practically relevant inhibitors in the mixing of physically relevant tracers, such as temperature, salinity, vorticity or potential vorticity. We demonstrate the role of the most effective diffusion barriers in analytical examples and observational data. Supported in part by the DFG Priority Program on Turbulent Superstructures.

Oxidation Resistant Ti-Al-Fe Diffusion Barrier for FeCrAlY Coatings on Titanium Aluminides

NASA Technical Reports Server (NTRS)

Brady, Michael P. (Inventor); Smialke, James L. (Inventor); Brindley, William J. (Inventor)

1996-01-01

A diffusion barrier to help protect titanium aluminide alloys, including the coated alloys of the TiAl gamma + Ti3Al (alpha2) class, from oxidative attack and interstitial embrittlement at temperatures up to at least 1000 C is disclosed. The coating may comprise FeCrAlX alloys. The diffusion barrier comprises titanium, aluminum, and iron in the following approximate atomic percent: Ti-(50-55)Al-(9-20)Fe. This alloy is also suitable as an oxidative or structural coating for such substrates.

Three-Dimensional Structure Analysis and Percolation Properties of a Barrier Marine Coating

PubMed Central

Chen, Bo; Guizar-Sicairos, Manuel; Xiong, Gang; Shemilt, Laura; Diaz, Ana; Nutter, John; Burdet, Nicolas; Huo, Suguo; Mancuso, Joel; Monteith, Alexander; Vergeer, Frank; Burgess, Andrew; Robinson, Ian

2013-01-01

Artificially structured coatings are widely employed to minimize materials deterioration and corrosion, the annual direct cost of which is over 3% of the gross domestic product (GDP) for industrial countries. Manufacturing higher performance anticorrosive coatings is one of the most efficient approaches to reduce this loss. However, three-dimensional (3D) structure of coatings, which determines their performance, has not been investigated in detail. Here we present a quantitative nano-scale analysis of the 3D spatial structure of an anticorrosive aluminium epoxy barrier marine coating obtained by serial block-face scanning electron microscopy (SBFSEM) and ptychographic X-ray computed tomography (PXCT). We then use finite element simulations to demonstrate how percolation through this actual 3D structure impedes ion diffusion in the composite materials. We found the aluminium flakes align within 15° of the coating surface in the material, causing the perpendicular diffusion resistance of the coating to be substantially higher than the pure epoxy. PMID:23378910

Moisture barrier properties of single-layer graphene deposited on Cu films for Cu metallization

NASA Astrophysics Data System (ADS)

Gomasang, Ploybussara; Abe, Takumi; Kawahara, Kenji; Wasai, Yoko; Nabatova-Gabain, Nataliya; Thanh Cuong, Nguyen; Ago, Hiroki; Okada, Susumu; Ueno, Kazuyoshi

2018-04-01

The moisture barrier properties of large-grain single-layer graphene (SLG) deposited on a Cu(111)/sapphire substrate are demonstrated by comparing with the bare Cu(111) surface under an accelerated degradation test (ADT) at 85 °C and 85% relative humidity (RH) for various durations. The change in surface color and the formation of Cu oxide are investigated by optical microscopy (OM) and X-ray photoelectron spectroscopy (XPS), respectively. First-principle simulation is performed to understand the mechanisms underlying the barrier properties of SLG against O diffusion. The correlation between Cu oxide thickness and SLG quality are also analyzed by spectroscopic ellipsometry (SE) measured on a non-uniform SLG film. SLG with large grains shows high performance in preventing the Cu oxidation due to moisture during ADT.

Rotation and diffusion of naphthalene on Pt(111)

NASA Astrophysics Data System (ADS)

Kolsbjerg, E. L.; Goubert, G.; McBreen, P. H.; Hammer, B.

2018-03-01

The behavior of naphthalene on Pt(111) surfaces is studied by combining insight from scanning tunneling microscopy (STM) and van der Waals enabled density functional theory. Adsorption, diffusion, and rotation are investigated by a series of variable temperature STM experiments revealing naphthalene ability to rotate on-site with ease with a rotational barrier of 0.69 eV. Diffusion to neighbouring sites is found to be more difficult. The experimental results are in good agreement with the theoretical investigations which confirm that the barrier for diffusion is slightly higher than the one for rotation. The theoretical barriers for rotation and translation are found to be 0.75 and 0.78 eV, respectively. An automatic mapping of the possible diffusion pathways reveals very detailed diffusion paths with many small local minima that would have been practically impossible to find manually. This automated procedure provides detailed insight into the preferred diffusion pathways that are important for our understanding of molecule-substrate interactions.

Migration of inorganic ions from the leachate of the Rio das Ostras landfill: a comparison of three different configurations of protective barriers.

PubMed

Lacerda, Cláudia Virgínia; Ritter, Elisabeth; Pires, João Antônio da Costa; de Castro, José Adilson

2014-11-01

Batch tests and diffusion tests were performed to analyze the efficiency of a protective barrier in a landfill consisting of compacted soil with 10% bentonite compared to the results obtained for only compacted soil and for compacted soil covered with a 1-mm-thick HDPE geomembrane; the soil and leachate were collected from the Rio das Ostras Landfill in Rio de Janeiro, Brazil. The diffusion tests were performed for periods of 3, 10 and 60 days. After the test period, the soil pore water was analyzed and the profiles for chloride, potassium and ammonium were determined along a 6-cm soil depth. The results of the batch tests performed to define sorption parameters were used to adjust the profiles obtained in the diffusion cell experiment by applying an ion transfer model between the interstitial solution and the soil particles. The MPHMTP model (Multi Phase Heat and Mass Transfer Program), which is based upon the solution of the transport equations of the ionic contaminants, was used to solve the inverse problem of simultaneously determining the effective diffusion coefficients. The results of the experimental tests and of the model simulation confirmed that the compacted soil with 10% bentonite was moderately efficient in the retention of chloride, potassium and ammonium ions compared to the configurations of compacted soil with a geomembrane and compacted soil alone, representing a solution that is technically feasible and requires potentially lower costs for implementation in landfills. Copyright © 2014 Elsevier Ltd. All rights reserved.

The Drosophila blood-brain barrier: development and function of a glial endothelium.

PubMed

Limmer, Stefanie; Weiler, Astrid; Volkenhoff, Anne; Babatz, Felix; Klämbt, Christian

2014-01-01

The efficacy of neuronal function requires a well-balanced extracellular ion homeostasis and a steady supply with nutrients and metabolites. Therefore, all organisms equipped with a complex nervous system developed a so-called blood-brain barrier, protecting it from an uncontrolled entry of solutes, metabolites or pathogens. In higher vertebrates, this diffusion barrier is established by polarized endothelial cells that form extensive tight junctions, whereas in lower vertebrates and invertebrates the blood-brain barrier is exclusively formed by glial cells. Here, we review the development and function of the glial blood-brain barrier of Drosophila melanogaster. In the Drosophila nervous system, at least seven morphologically distinct glial cell classes can be distinguished. Two of these glial classes form the blood-brain barrier. Perineurial glial cells participate in nutrient uptake and establish a first diffusion barrier. The subperineurial glial (SPG) cells form septate junctions, which block paracellular diffusion and thus seal the nervous system from the hemolymph. We summarize the molecular basis of septate junction formation and address the different transport systems expressed by the blood-brain barrier forming glial cells.

Stable metallization for diamond and other materials

NASA Technical Reports Server (NTRS)

Bachli, Andreas (Inventor); Kolawa, Elzbieta (Inventor); Nicolet, Marc-Aurele (Inventor); Vandersande, Jan W. (Inventor)

2000-01-01

An adherent and metallurgically stable metallization system for diamond is presented. The big improvement in metallurgical stability is attributed to the use of a ternary, amorphous Ti--Si--N diffusion barrier. No diffusion between the layers and no delamination of the metallization was observed after annealing the schemes at 400.degree. C. for 100 hours and at 900.degree. C. for 30 minutes. Thermal cycling experiments in air from -65 to 155.degree. C. and adhesion tests were performed. Various embodiments are disclosed.

Oxygen vacancy diffusion in bulk SrTiO3 from density functional theory calculations

DOE PAGES

Zhang, Lipeng; Liu, Bin; Zhuang, Houlong; ...

2016-04-01

Point defects and point defect diffusion contribute significantly to the properties of perovskite materials. However, even for the prototypical case of oxygen vacancies in SrTiO 3 (STO), predictions vary widely. Here we present a comprehensive and systematic study of the diffusion barriers for this material. We use density functional theory (DFT) and assess the role of different cell sizes, density functionals, and charge states. Our results show that vacancy-induced octahedral rotations, which are limited by the boundary conditions of the supercell, can significantly affect the computed oxygen vacancy diffusion energy barrier. The diffusion energy barrier of a charged oxygen vacancymore » is lower than that of a neutral one. Unexpectedly, we find that with increasing supercell size, the effects of the oxygen vacancy charge state, the type of DFT exchange and correlation functional on the energy barrier diminish, and the different DFT predictions asymptote to a value in the range of 0.39-0.49 eV. This work provides important insight and guidance that should be considered for investigations of point defect diffusion in other perovskite materials and in oxide superlattices.« less

Copper diffusion in Ti Si N layers formed by inductively coupled plasma implantation

NASA Astrophysics Data System (ADS)

Ee, Y. C.; Chen, Z.; Law, S. B.; Xu, S.; Yakovlev, N. L.; Lai, M. Y.

2006-11-01

Ternary Ti-Si-N refractory barrier films of 15 nm thick was prepared by low frequency, high density, inductively coupled plasma implantation of N into TixSiy substrate. This leads to the formation of Ti-N and Si-N compounds in the ternary film. Diffusion of copper in the barrier layer after annealing treatment at various temperatures was investigated using time-of-flight secondary ion mass spectrometer (ToF-SIMS) depth profiling, X-ray diffractometer (XRD), field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) and sheet resistance measurement. The current study found that barrier failure did not occur until 650 °C annealing for 30 min. The failure occurs by the diffusion of copper into the Ti-Si-N film to form Cu-Ti and Cu-N compounds. FESEM surface morphology and EDX show that copper compounds were formed on the ridge areas of the Ti-Si-N film. The sheet resistance verifies the diffusion of Cu into the Ti-Si-N film; there is a sudden drop in the resistance with Cu compound formation. This finding provides a simple and effective method of monitoring Cu diffusion in TiN-based diffusion barriers.

Microstructural characterization of a thin film ZrN diffusion barrier in an As-fabricated U-7Mo/Al matrix dispersion fuel plate

NASA Astrophysics Data System (ADS)

Keiser, Dennis D.; Perez, Emmanuel; Wiencek, Tom; Leenaers, Ann; Van den Berghe, Sven

2015-03-01

The United States High Performance Research Reactor Fuel Development program is developing low enriched uranium fuels for application in research and test reactors. One concept utilizes U-7 wt.% Mo (U-7Mo) fuel particles dispersed in Al matrix, where the fuel particles are coated with a 1 μm-thick ZrN coating. The ZrN serves as a diffusion barrier to eliminate a deleterious reaction that can occur between U-7Mo and Al when a dispersion fuel is irradiated under aggressive reactor conditions. To investigate the final microstructure of a physically-vapor-deposited ZrN coating in a dispersion fuel plate after it was fabricated using a rolling process, characterization samples were taken from a fuel plate that was fabricated at 500 °C using ZrN-coated U-7Mo particles, Al matrix and AA6061 cladding. Scanning electron and transmission electron microscopy analysis were performed. Data from these analyses will be used to support future microstructural examinations of irradiated fuel plates, in terms of understanding the effects of irradiation on the ZrN microstructure, and to determine the role of diffusion barrier microstructure in eliminating fuel/matrix interactions during irradiation. The as-fabricated coating was determined to be cubic-ZrN (cF8) phase. It exhibited a columnar microstructure comprised of nanometer-sized grains and a region of relatively high porosity, mainly near the Al matrix. Small impurity-containing phases were observed at the U-7Mo/ZrN interface, and no interaction zone was observed at the ZrN/Al interface. The bonding between the U-7Mo and ZrN appeared to be mechanical in nature. A relatively high level of oxygen was observed in the ZrN coating, extending from the Al matrix in the ZrN coating in decreasing concentration. The above microstructural characteristics are discussed in terms of what may be most optimal for a diffusion barrier in a dispersion fuel plate application.

Improving the light output power of DUV-LED by introducing an intrinsic last quantum barrier interlayer on the high-quality AlN template

NASA Astrophysics Data System (ADS)

Tsai, Chia-Lung; Liu, Hsueh-Hsing; Chen, Jun-Wei; Lu, Chien-Pin; Ikenaga, Kazutada; Tabuchi, Toshiya; Matsumoto, Koh; Fu, Yi-Keng

2017-12-01

We demonstrate that the light output power of deep ultraviolet light-emitting diodes (DUV-LEDs) can be improved by introducing an intrinsic last quantum barrier interlayer to a high quality AlN template. The light output power of the DUV-LEDs can be doubled by substituting the last quantum barrier with an intrinsic last quantum barrier (u-LQB)/Mg-doped LQB for only pure u-LQB in the same thickness with a 35 A/cm2 injection current. It is believed that the improved performance of the DUV LED could be attributed to the decreased diffusion of Mg tunneling into MQW and the reduction of sub-band parasitic emissions.

Pyridine adsorption and diffusion on Pt(111) investigated with density functional theory

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

Kolsbjerg, Esben L.; Groves, Michael N.; Hammer, Bjørk, E-mail: hammer@phys.au.dk

2016-04-28

The adsorption, diffusion, and dissociation of pyridine, C{sub 5}H{sub 5}N, on Pt(111) are investigated with van der Waals-corrected density functional theory. An elaborate search for local minima in the adsorption potential energy landscape reveals that the intact pyridine adsorbs with the aromatic ring parallel to the surface. Piecewise interconnections of the local minima in the energy landscape reveal that the most favourable diffusion path for pyridine has a barrier of 0.53 eV. In the preferred path, the pyridine remains parallel to the surface while performing small single rotational steps with a carbon-carbon double bond hinged above a single Pt atom.more » The origin of the diffusion pathway is discussed in terms of the C{sub 2}–Pt π-bond being stronger than the corresponding CN–Pt π-bond. The energy barrier and reaction enthalpy for dehydrogenation of adsorbed pyridine into an adsorbed, upright bound α-pyridyl species are calculated to 0.71 eV and 0.18 eV, respectively (both zero-point energy corrected). The calculations are used to rationalize previous experimental observations from the literature for pyridine on Pt(111).« less

Ion-barrier for memristors/ReRAM and methods thereof

DOEpatents

Haase, Gad S.

2017-11-28

The present invention relates to memristive devices including a resistance-switching element and a barrier element. In particular examples, the barrier element is a monolayer of a transition metal chalcogenide that sufficiently inhibits diffusion of oxygen atoms or ions out of the switching element. As the location of these atoms and ions determine the state of the device, inhibiting diffusion would provide enhanced state retention and device reliability. Other types of barrier elements, as well as methods for forming such elements, are described herein.

Enhanced Atom Mobility on the Surface of a Metastable Film

NASA Astrophysics Data System (ADS)

Picone, A.; Riva, M.; Fratesi, G.; Brambilla, A.; Bussetti, G.; Finazzi, M.; Duò, L.; Ciccacci, F.

2014-07-01

A remarkable enhancement of atomic diffusion is highlighted by scanning tunneling microscopy performed on ultrathin metastable body-centered tetragonal Co films grown on Fe(001). The films follow a nearly perfect layer-by-layer growth mode with a saturation island density strongly dependent on the layer on which the nucleation occurs, indicating a lowering of the diffusion barrier. Density functional theory calculations reveal that this phenomenon is driven by the increasing capability of the film to accommodate large deformations as the thickness approaches the limit at which a structural transition occurs. These results disclose the possibility of tuning surface diffusion dynamics and controlling cluster nucleation and self-organization.

Enhanced atom mobility on the surface of a metastable film.

PubMed

Picone, A; Riva, M; Fratesi, G; Brambilla, A; Bussetti, G; Finazzi, M; Duò, L; Ciccacci, F

2014-07-25

A remarkable enhancement of atomic diffusion is highlighted by scanning tunneling microscopy performed on ultrathin metastable body-centered tetragonal Co films grown on Fe(001). The films follow a nearly perfect layer-by-layer growth mode with a saturation island density strongly dependent on the layer on which the nucleation occurs, indicating a lowering of the diffusion barrier. Density functional theory calculations reveal that this phenomenon is driven by the increasing capability of the film to accommodate large deformations as the thickness approaches the limit at which a structural transition occurs. These results disclose the possibility of tuning surface diffusion dynamics and controlling cluster nucleation and self-organization.

Self-learning kinetic Monte Carlo simulations of diffusion in ferromagnetic α -Fe–Si alloys

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

Nandipati, Giridhar; Jiang, Xiujuan; Vemuri, Rama S.

Diffusion in α-Fe-Si alloys is studied using AKSOME, an on-lattice self-learning KMC code, in the ferromagnetic state. Si diffusivity in the α-Fe matrix were obtained with and without the magnetic disorder in various temperature ranges. In addition we studied vacancy diffusivity in ferromagnetic α-Fe at various Si concentrations up to 12.5at.% in the temperature range of 350–550 K. The results were compared with available experimental and theoretical values in the literature. Local Si-atom dependent activation energies for vacancy hops were calculated using a broken-model and were stored in a database. The migration barrier and prefactors for Si-diffusivity were found tomore » be in reasonable agreement with available modeling results in the literature. Magnetic disorder has a larger effect on the prefactor than on the migration barrier. Prefactor was approximately an order of magnitude and the migration barrier a tenth of an electron-volt higher with magnetic disorder when compared to a fully ferromagnetic ordered state. In addition, the correlation between various have a larger effect on the Si-diffusivity extracted in various temperature range than the magnetic disorder. In the case of vacancy diffusivity, the migration barrier more or less remained constant while the prefactor decreased with increasing Si concentration in the disordered or A2-phase of Fe-Si alloy. Important vacancy-Si/Fe atom exchange processes and their activation barriers were also identified and discuss the effect of energetics on the formation of ordered phases in Fe-Si alloys.« less

Computational study of graphene-based vertical field effect transistor

NASA Astrophysics Data System (ADS)

Chen, Wenchao; Rinzler, Andrew; Guo, Jing

2013-03-01

Poisson and drift-diffusion equations are solved in a three-dimensional device structure to simulate graphene-based vertical field effect transistors (GVFETs). Operation mechanisms of the GVFET with and without punched holes in the graphene source contact are presented and compared. The graphene-channel Schottky barrier can be modulated by gate electric field due to graphene's low density of states. For the graphene contact with punched holes, the contact barrier thinning and lowering around punched hole edge allow orders of magnitude higher tunneling current compared to the region away from the punched hole edge, which is responsible for significant performance improvement as already verified by experiments. Small hole size is preferred due to less electrostatic screening from channel inversion layer, which gives large electric field around the punched hole edge, thus, leading to a thinner and lower barrier. Bilayer and trilayer graphenes as the source contact degrade the performance improvement because stronger electrostatic screening leads to smaller contact barrier lowering and thinning. High punched hole area percentage improves current performance by allowing more gate electric field to modulate the graphene-channel barrier. Low effective mass channel material gives better on-off current ratio.

Cell Based Metabolic Barriers to Glucose Diffusion: Macrophages and Continuous Glucose Monitoring

PubMed Central

Klueh, Ulrike; Frailey, Jackman; Qiao, Yi; Antar, Omar; Kreutzer, Donald L.

2014-01-01

It is assumed that MQ are central to glucose sensor bio-fouling and therefore have a major negative impact on continuous glucose monitoring (CGM) performance in vivo. However to our knowledge there is no data in the literature to directly support or refute this assumption. Since glucose and oxygen (O2) are key to glucose sensor function in vivo, understanding and controlling glucose and O2 metabolic activity of MQ is likely key to successful glucose sensor performance. We hypothesized that the accumulation of MQ at the glucose sensor-tissue interface will act as “Cell Based Metabolic Barriers” (CBMB) to glucose diffusing from the interstitial tissue compartment to the implanted glucose sensor and as such creating an artificially low sensor output, thereby compromising sensor function and CGM. Our studies demonstrated that 1) direct injections of MQ at in vivo sensor implantation sites dramatically decreased sensor output (measured in nA), 2) addition of MQ to glucose sensors in vitro resulted in a rapid and dramatic fall in sensor output and 3) lymphocytes did not affect sensor function in vitro or in vivo. These data support our hypothesis that MQ can act as metabolic barriers to glucose and O2 diffusion in vivo and in vitro. PMID:24461328

Investigation of heavy-ion fusion with deformed surface diffuseness: Actinide and lanthanide targets

NASA Astrophysics Data System (ADS)

Alavi, S. A.; Dehghani, V.

2017-05-01

By using a deformed Broglia-Winther nuclear interaction potential in the framework of the WKB method, the near- and above-barrier heavy-ion-fusion cross sections of 16O with some lanthanides and actinides have been calculated. The effect of deformed surface diffuseness on the nuclear interaction potential, the effective interaction potential at distinct angle, barrier position, barrier height, cross section at each angles, and fusion cross sections of 16O+147Sm,150Nd,154Sm , and 166Er and 16O+232Th,238U,237Np , and 248Cm have been studied. The differences between the results obtained by using deformed surface diffuseness and those obtained by using constant surface diffuseness were noticeable. Good agreement between experimental data and theoretical calculation with deformed surface diffuseness were observed for 16O+147Sm,154Sm,166Er,238U,237Np , and 248Cm reactions. It has been observed that deformed surface diffuseness plays a significant role in heavy-ion-fusion studies.

In Situ Ramp Anneal X-ray Diffraction Study of Atomic Layer Deposited Ultrathin TaN and Ta 1-x Al x N y Films for Cu Diffusion Barrier Applications

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

Consiglio, S.; Dey, S.; Yu, K.

2016-01-01

Ultrathin TaN and Ta 1-xAl xN y films with x = 0.21 to 0.88 were deposited by atomic layer deposition (ALD) and evaluated for Cu diffusion barrier effectiveness compared to physical vapor deposition (PVD) grown TaN. Cu diffusion barrier effectiveness was investigated using in-situ ramp anneal synchrotron X-ray diffraction (XRD) on Cu/1.8 nm barrier/Si stacks. A Kissinger-like analysis was used to assess the kinetics of Cu 3Si formation and determine the effective activation energy (E a) for Cu silicidation. Compared to the stack with a PVD TaN barrier, the stacks with the ALD films exhibited a higher crystallization temperature (Tmore » c) for Cu silicidation. The Ea values of Cu 3Si formation for stacks with the ALD films were close to the reported value for grain boundary diffusion of Cu whereas the Ea of Cu 3Si formation for the stack with PVD TaN is closer to the reported value for lattice diffusion. For 3 nm films, grazing incidence in-plane XRD showed evidence of nanocrystallites in an amorphous matrix with broad peaks corresponding to high density cubic phase for the ALD grown films and lower density hexagonal phase for the PVD grown film further elucidating the difference in initial failure mechanisms due to differences in barrier crystallinity and associated phase.« less

SC lipid model membranes designed for studying impact of ceramide species on drug diffusion and permeation--part II: diffusion and permeation of model drugs.

PubMed

Ochalek, M; Podhaisky, H; Ruettinger, H-H; Wohlrab, J; Neubert, R H H

2012-10-01

The barrier function of two quaternary stratum corneum (SC) lipid model membranes, which were previously characterized with regard to the lipid organization, was investigated based on diffusion studies of model drugs with varying lipophilicities. Diffusion experiments of a hydrophilic drug, urea, and more lipophilic drugs than urea (i.e. caffeine, diclofenac sodium) were conducted using Franz-type diffusion cells. The amount of permeated drug was analyzed using either HPLC or CE technique. The subjects of interest in the present study were the investigation of the influence of physicochemical properties of model drugs on their diffusion and permeation through SC lipid model membranes, as well as the study of the impact of the constituents of these artificial systems (particularly ceramide species) on their barrier properties. The diffusion through both SC lipid model membranes and the human SC of the most hydrophilic model drug, urea, was faster than the permeation of the more lipophilic drugs. The slowest rate of permeation through SC lipid systems occurred in the case of caffeine. The composition of SC lipid model membranes has a significant impact on their barrier function. Model drugs diffused and permeated faster through Membrane II (presence of Cer [EOS]). In terms of the barrier properties, Membrane II is much more similar to the human SC than Membrane I. Copyright © 2012 Elsevier B.V. All rights reserved.

Modeling the Impenetrable Barrier to Inward Transport of Ultra-relativistic Radiation Belt Electrons

NASA Astrophysics Data System (ADS)

Tu, W.; Cunningham, G.; Chen, Y.; Baker, D. N.; Henderson, M. G.; Reeves, G. D.

2014-12-01

It has long been considered that the inner edge of the Earth's outer radiation belt is closely correlated with the minimum plasmapause location. However, recent discoveries by Baker et al. [1] show that it is not the case for ultra-relativistic electrons (2-10 MeV) in the radiation belt. Based on almost two years of Van Allen Probes/REPT data, they find that the inner edge of highly relativistic electrons is rarely collocated with the plasmapause; and more interestingly, there is a clear, persistent, and nearly impenetrable barrier to inward transport of high energy electrons, observed to locate at L~2.8. The presence of such an impenetrable barrier at this very specific location poses a significant puzzle. Using our DREAM3D diffusion model, which includes radial, pitch angle, and momentum diffusion, we are able to simulate the observed impenetrable barrier of ultra-relativistic electrons. The simulation demonstrates that during strong geomagnetic storms the plasmapause can be compressed to very low L region (sometimes as low as L~3), then strong chorus waves just outside the plasmapause can locally accelerate electrons up to multiple-MeV; when storm recovers, plasmapause moves back to large L, while the highly-relativistic electrons generated at low L continue to diffuse inward and slow decay by pitch angle diffusion from plasmaspheric hiss. The delicate balance between slow inward radial diffusion and weak pitch angle scattering creates a fixed inner boundary or barrier for ultra-relativistic electrons. The barrier is found to locate at a fixed L location, independent of the initial penetration depth of electrons that is correlated with the plasmapause location. Our simulation results quantitatively reproduce the evolution of the flux versus L profile, the L location of the barrier, and the decay rate of highly energetic electrons right outside the barrier. 1Baker, D. N., et al. (2014), Nearly Impenetrable Barrier to Inward Ultra-relativistic Magnetospheric Electron Transport, submitted to Nature.

Self-learning kinetic Monte Carlo simulations of diffusion in ferromagnetic α-Fe-Si alloys

NASA Astrophysics Data System (ADS)

Nandipati, Giridhar; Jiang, Xiujuan; Vemuri, Rama S.; Mathaudhu, Suveen; Rohatgi, Aashish

2018-01-01

Diffusion of Si atom and vacancy in the A2-phase of α-Fe-Si alloys in the ferromagnetic state, with and without magnetic order and in various temperature ranges, are studied using AKSOME, an on-lattice self-learning KMC code. Diffusion of the Si atom and the vacancy are studied in the dilute limit and up to 12 at.% Si, respectively, in the temperature range 350-700 K. Local Si neighborhood dependent activation energies for vacancy hops were calculated on-the-fly using a broken-bond model based on pairwise interaction. The migration barrier and prefactor for the Si diffusion in the dilute limit were obtained and found to agree with published data within the limits of uncertainty. Simulations results show that the prefactor and the migration barrier for the Si diffusion are approximately an order of magnitude higher, and a tenth of an electron-volt higher, respectively, in the magnetic disordered state than in the fully ordered state. However, the net result is that magnetic disorder does not have a significant effect on Si diffusivity within the range of parameters studied in this work. Nevertheless, with increasing temperature, the magnetic disorder increases and its effect on the Si diffusivity also increases. In the case of vacancy diffusion, with increasing Si concentration, its diffusion prefactor decreases while the migration barrier more or less remained constant and the effect of magnetic disorder increases with Si concentration. Important vacancy-Si/Fe atom exchange processes and their activation barriers were identified, and the effect of energetics on ordered phase formation in Fe-Si alloys are discussed.

Reactive Membrane Barriers for Containment of Subsurface Contamination

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

William A. Arnold; Edward L. Cussler

2007-02-26

The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe{sup 0}) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents andmore » cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe{sup 0} and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu{sup 2+}) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe{sup 0} barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a factor of three when groundwater was used in place of deionized water. The performance of high density polyethylene (HDPE) membranes containing Fe{sup 0} was then evaluating using carbon tetrachloride as the target contaminant. Only with a hydrophilic additive (glycerol), was the iron able to extend lag times. Lag times were increased by a factor of 15, but only 2-3% of the iron was used, likely due to formation of oxide precipitates on the iron surface, which slowed the reaction. With thicker membranes and lower carbon tetrachloride concentrations, it is expected that performance will improve. Previous models for reactive membranes were also extended. The lag time is a measurement of when the barrier is breached, but contaminants do slowly leak through prior to the lag time. Thus, two parameters, the leakage and the kill time, were developed to determine when a certain amount of pollutant has escaped (the kill time) or when a given exposure (concentration x time) occurs (the leakage). Finally, a model was developed to explain the behavior of mobile reaction products in reactive barrier membranes. Although the goal of the technology is to avoid such products, it is important to be able to predict how these products will behave. Interestingly, calculations show that for any mobile reaction products, one half of the mass will diffuse into the containment area and one half will escape, assuming that the volumes of the containment area and the surrounding environment are much larger than the barrier membrane. These parameters/models will aid in the effective design of barrier membranes.« less

Production of atmospheric pressure diffuse nanosecond pulsed dielectric barrier discharge using the array needles-plate electrode in air

NASA Astrophysics Data System (ADS)

Yang, De-zheng; Wang, Wen-chun; Jia, Li; Nie, Dong-xia; Shi, Heng-chao

2011-04-01

In this paper, a bidirectional high pulse voltage with 20 ns rising time is employed to generate an atmospheric pressure diffuse dielectric barrier discharge using the array needles-plate electrode configuration. Both double needle and multiple needle electrode configurations nanosecond pulsed dielectric barrier discharges are investigated. It is found that a diffuse discharge plasma with low gas temperature can be obtained, and the plasma volume increases with the increase of the pulse peak voltage, but remains almost constant with the increase of the pulse repetition rate. In addition to showing the potential application on a topographically nonuniform surface treatment of the discharge, the multiple needle-plate electrode configuration with different needle-plate electrode gaps are also employed to generate diffuse discharge plasma.

Anomalous diffusion of brain metabolites evidenced by diffusion-weighted magnetic resonance spectroscopy in vivo

PubMed Central

Marchadour, Charlotte; Brouillet, Emmanuel; Hantraye, Philippe; Lebon, Vincent; Valette, Julien

2012-01-01

Translational displacement of molecules within cells is a key process in cellular biology. Molecular motion potentially depends on many factors, including active transport, cytosol viscosity and molecular crowding, tortuosity resulting from cytoskeleton and organelles, and restriction barriers. However, the relative contribution of these factors to molecular motion in the cytoplasm remains poorly understood. In this work, we designed an original diffusion-weighted magnetic resonance spectroscopy strategy to probe molecular motion at subcellular scales in vivo. This led to the first observation of anomalous diffusion, that is, dependence of the apparent diffusion coefficient (ADC) on the diffusion time, for endogenous intracellular metabolites in the brain. The observed increase of the ADC at short diffusion time yields evidence that metabolite motion is characteristic of hindered random diffusion rather than active transport, for time scales up to the dozen milliseconds. Armed with this knowledge, data modeling based on geometrically constrained diffusion was performed. Results suggest that metabolite diffusion occurs in a low-viscosity cytosol hindered by ∼2-μm structures, which is consistent with known intracellular organization. PMID:22929443

Method and apparatus for operating an improved thermocline storage unit

DOEpatents

Copeland, R.J.

1982-09-30

A method and apparatus for operating a thermocline storage unit in which an insulated barrier member is provided substantially at the interface region between the hot and cold liquids in the storage tank. The barrier member physically and thermally separates the hot and cold liquids substantially preventing any diffusing or mixing between them and substantially preventing any heat transfer there between. The barrier member follows the rise and fall of the interface region between the liquids as the tank is charged and discharged. Two methods of maintaining it in the interface region are disclosed. With the structure and operation of the present invention and in particular the significant reduction in diffusing or mixing between the hot and cold liquids as well as the significant reduction in the thermal heat transfer between them, the performance of the storage tank is improved. More specifically, the stability of the interface region or thermocline is enhanced and the thickness of the thermocline is reduced producing a corresponding increase in the steepness of the temperature gradient across the thermocline and a more efficiently operating thermocline storage unit.

Method and apparatus for operating an improved thermocline storage unit

DOEpatents

Copeland, Robert J.

1985-01-01

A method and apparatus for operating a thermocline storage unit in which an insulated barrier member is provided substantially at the interface region between the hot and cold liquids in the storage tank. The barrier member physically and thermally separates the hot and cold liquids substantially preventing any diffusing or mixing between them and substantially preventing any heat transfer therebetween. The barrier member follows the rise and fall of the interface region between the liquids as the tank is charged and discharged. Two methods of maintaining it in the interface region are disclosed. With the structure and operation of the present invention and in particular the significant reduction in diffusing or mixing between the hot and cold liquids as well as the significant reduction in the thermal heat transfer between them, the performance of the storage tank is improved. More specifically, the stability of the interface region or thermocline is enhanced and the thickness of the thermocline is reduced producing a corresponding increase in the steepness of the temperature gradient across the thermocline and a more efficiently operating thermocline storage unit.

Diffusion of multiwall carbon nanotubes (MWCNTs) through a high density polyethylene (HDPE) geomembrane.

PubMed

Saheli, P T; Rowe, R K; Petersen, E J; O'Carroll, D M

2017-05-01

The new applications for carbon nanotubes (CNTs) in various fields and consequently their greater production volume have increased their potential release to the environment. Landfills are one of the major locations where carbon nanotubes are expected to be disposed and it is important to ensure that they can limit the release of CNTs. Diffusion of multiwall carbon nanotubes (MWCNTs) dispersed in an aqueous media through a high-density polyethylene (HDPE) geomembrane (as a part of the landfill barrier system) was examined. Based on the laboratory tests, the permeation coefficient was estimated to be less than 5.1×10 -15 m 2 /s. The potential performance of a HDPE geomembrane and geosynthetic clay liner (GCL) as parts of a composite liner in containing MWCNTs was modelled for six different scenarios. The results suggest that the low value of permeation coefficient of an HDPE geomembrane makes it an effective diffusive barrier for MWCNTs and by keeping the geomembrane defects to minimum during the construction (e.g., number of holes and length of wrinkles) a composite liner commonly used in municipal solid waste landfills will effectively contain MWCNTs.

Graphene-Based Environmental Barriers

PubMed Central

Guo, Fei; Silverberg, Gregory; Bowers, Shin; Kim, Sang-Pil; Datta, Dibakar; Shenoy, Vivek; Hurt, Robert H.

2012-01-01

Many environmental technologies rely on containment by engineered barriers that inhibit the release or transport of toxicants. Graphene is a new, atomically thin, two-dimensional sheet material, whose aspect ratio, chemical resistance, flexibility, and impermeability make it a promising candidate for inclusion in a next generation of engineered barriers. Here we show that ultrathin graphene oxide (GO) films can serve as effective barriers for both liquid and vapor permeants. First, GO deposition on porous substrates is shown to block convective flow at much lower mass loadings than other carbon nanomaterials, and can achieve hydraulic conductivities of 5×10−12 cm/s or lower. Second we show that ultrathin GO films of only 20 nm thickness coated on polyethylene films reduce their vapor permeability by 90% using elemental mercury as a model vapor toxicant. The barrier performance of GO in this thin-film configuration is much better than the Nielsen model limit, which describes ideal behavior of flake-like fillers uniformly imbedded in a polymer. The Hg barrier performance of GO films is found to be sensitive to residual water in the films, which is consistent with molecular dynamics (MD) simulations that show lateral diffusion of Hg atoms in graphene interlayer spaces that have been expanded by hydration. PMID:22717015

Kinetic Monte Carlo Simulations of Diffusion in Environmental Barrier Coating Materials

NASA Technical Reports Server (NTRS)

Good, Brian

2017-01-01

Ceramic Matrix Components (CMC) components for use in turbine engines offer a number of advantages compared with current practice. However, such components are subject to degradation through a variety of mechanisms. In particular, in the hot environment inside a turbine in operation a considerable amount of water vapor is present, and this can lead to corrosion and recession. Environmental Barrier Coating (EBC) systems that limit the amount of oxygen and water reaching the component are required to reduce this degradation and extend component life. A number of silicate-based materials are under consideration for use in such coating systems, including Yttterbium and Yttrium di- and monosilicates. In this work, we present results of kinetic Monte Carlo computer simulations of oxygen diffusion in Yttrium disilicate, and compare with previous work on Yttterbium disilicate. Coatings may also exhibit cracking, and the cracks can provide a direct path for oxygen to reach the component. There is typically a bond coat between the coating and component surface, but the bond coat material is generally chosen for properties other than low oxygen diffusivity. Nevertheless, the degree to which the bond coat can inhibit oxygen diffusion is of interest, as it may form the final defense against oxygen impingement on the component. We have therefore performed similar simulations of oxygen diffusion through HfSiO4, a proposed bond coat material.

The Diffusion Process of Patient Education in Dutch Community Pharmacy: An Exploration.

ERIC Educational Resources Information Center

Pronk, M. C. M.; Blom, A. Th. G.; Van Burg, A.; Jonkers, R.

2001-01-01

Identifies barriers and facilitators to the implementation of patient education in community pharmacies and classifies these barriers and facilitators into the diffusion stages of Rogers'"Innovations in Organizations" model. Discusses the implementation of patient education activities that require individual and organizational change in…

High Efficiency Centrifugal Compressor for Rotorcraft Applications

NASA Technical Reports Server (NTRS)

Medic, Gorazd; Sharma, Om P.; Jongwook, Joo; Hardin, Larry W.; McCormick, Duane C.; Cousins, William T.; Lurie, Elizabeth A.; Shabbir, Aamir; Holley, Brian M.; Van Slooten, Paul R.

2017-01-01

A centrifugal compressor research effort conducted by United Technologies Research Center under NASA Research Announcement NNC08CB03C is documented. The objectives were to identify key technical barriers to advancing the aerodynamic performance of high-efficiency, high work factor, compact centrifugal compressor aft-stages for turboshaft engines; to acquire measurements needed to overcome the technical barriers and inform future designs; to design, fabricate, and test a new research compressor in which to acquire the requisite flow field data. A new High-Efficiency Centrifugal Compressor stage -- splittered impeller, splittered diffuser, 90 degree bend, and exit guide vanes -- with aerodynamically aggressive performance and configuration (compactness) goals were designed, fabricated, and subquently tested at the NASA Glenn Research Center.

Multi-scale simulation of lithium diffusion in the presence of a 30° partial dislocation and stacking fault in Si

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

Wang, Chao-Ying; Li, Chen-liang; Wu, Guo-Xun

The multi-scale simulation method is employed to investigate how defects affect the performances of Li-ion batteries (LIBs). The stable positions, binding energies and dynamics properties of Li impurity in Si with a 30° partial dislocation and stacking fault (SF) have been studied in comparison with the ideal crystal. It is found that the most table position is the tetrahedral (T{sub d}) site and the diffusion barrier is 0.63 eV in bulk Si. In the 30° partial dislocation core and SF region, the most stable positions are at the centers of the octagons (Oct-A and Oct-B) and pentahedron (site S), respectively. Inmore » addition, Li dopant may tend to congregate in these defects. The motion of Li along the dislocation core are carried out by the transport among the Oct-A (Oct-B) sites with the barrier of 1.93 eV (1.12 eV). In the SF region, the diffusion barrier of Li is 0.91 eV. These two types of defects may retard the fast migration of Li dopant that is finally trapped by them. Thus, the presence of the 30° partial dislocation and SF may deactivate the Li impurity and lead to low rate capability of LIB.« less

Amorphous-Metal-Film Diffusion Barriers

NASA Technical Reports Server (NTRS)

Nicolet, M. A.

1987-01-01

Incorporation of N into Ni/W films reduces reactivity with Si substrate. Paper describes reactions between Si substrates and deposited amorphous Ni/W or Ni/N/W films. Thermal stability of amorphous Ni/W films as diffusion barriers in Si markedly improved by introduction of N into Ni/W films during deposition.

Thermal stability, adhesion and electrical studies on (Ti,Zr)N x thin films as low resistive diffusion barriers between Cu and Si

NASA Astrophysics Data System (ADS)

Huang, Cheng-Lin; Lai, Chih-Huang; Tsai, Po-Hao; Kuo, Yu-Lin; Lin, Jing-Cheng; Lee, Chiapyng

2014-05-01

In this study, we investigated the thermal stability, wettability, adhesion and reliability of (Ti,Zr)N x films used as the diffusion barrier between Cu and Si. (Ti,Zr)N x films were prepared by DC reactive magnetron sputtering from a Ti-5 at. % Zr alloy target in N2/Ar gas mixtures. A minimum film resistivity of 59.3 µω cm was obtained at an N2/Ar flow ratio of 2.75, which corresponds to the near stoichiometric composition (N/(Ti,Zr) ratio ˜0.95). The sheet resistance of Cu/(Ti,Zr)N0.95/Si was not significantly increased until annealing above 750°C, indicating good thermal stability. On the other hand, the adhesion energy between Cu and the (Ti,Zr)Nx film was reduced as the N/Ti ratio was increased. To obtain reliable performance on stress-induced-voiding (SIV) and electromigration (EM) tests, we proposed to use (Ti,Zr)/(Ti,Zr)N x /(Ti,Zr) tri-layers. We suggest that the interfacial adhesion between barrier and Cu plays an important role in reliability. The proposed tri-layer structure may be a promising candidate for a barrier, as it exhibits excellent reliability without increasing resistance.

Effect of stratum corneum heterogeneity, anisotropy, asymmetry and follicular pathway on transdermal penetration.

PubMed

Barbero, Ana M; Frasch, H Frederick

2017-08-28

The impact of the complex structure of the stratum corneum on transdermal penetration is not yet fully described by existing models. A quantitative and thorough study of skin permeation is essential for chemical exposure assessment and transdermal delivery of drugs. The objective of this study is to analyze the effects of heterogeneity, anisotropy, asymmetry, follicular diffusion, and location of the main barrier of diffusion on percutaneous permeation. In the current study, the solution of the transient diffusion through a two-dimensional-anisotropic brick-and-mortar geometry of the stratum corneum is obtained using the commercial finite element program COMSOL Multiphysics. First, analytical solutions of an equivalent multilayer geometry are used to determine whether the lipids or corneocytes constitute the main permeation barrier. Also these analytical solutions are applied for validations of the finite element solutions. Three illustrative compounds are analyzed in these sections: diethyl phthalate, caffeine and nicotine. Then, asymmetry with depth and follicular diffusion are studied using caffeine as an illustrative compound. The following findings are drawn from this study: the main permeation barrier is located in the lipid layers; the flux and lag time of diffusion through a brick-and-mortar geometry are almost identical to the values corresponding to a multilayer geometry; the flux and lag time are affected when the lipid transbilayer diffusivity or the partition coefficients vary with depth, but are not affected by depth-dependent corneocyte diffusivity; and the follicular contribution has significance for low transbilayer lipid diffusivity, especially when flux between the follicle and the surrounding stratum corneum is involved. This study demonstrates that the diffusion is primarily transcellular and the main barrier is located in the lipid layers. Published by Elsevier B.V.

Transport of Organic Compounds Through Porous Systems Containing Humic Acids.

PubMed

Smilek, Jiri; Sedlacek, Petr; Lastuvkova, Marcela; Kalina, Michal; Klucakova, Martina

2017-03-01

Soil pollution by the presence of different contaminants (e.g. heavy metal ions or pesticides) is one of the biggest problems worldwide. The positive affinity of natural humic acids towards these contaminants might contribute to the soil and ground water protection; therefore it is necessary to study the reactivity and barrier properties of humic acids. An original reactivity-mapping tool based on diffusion techniques designed to study the reactivity and barrier properties of polyelectrolytes was developed and tested on humic acids. The results of diffusion experiments demonstrate that the electrostatic interactions between humic acids functioning as a polyelectrolyte interpenetrated in a supporting hydrogel matrix (agarose) and cationic dye (methylene blue) as a model solute have a crucial impact on the rate of diffusion processes and on the barrier properties of hydrogels. The intensity of interactions was evaluated by fundamental diffusion parameters (effective diffusion coefficients and breakthrough time). The impact of modification of humic acids was also studied by means of diffusion experiments conducted on two types of standard humic acids (Leonardite 1S104H) and humic acids with selectively methylated carboxylic groups.

Microstructural characteristics of HIP-bonded monolithic nuclear fuels with a diffusion barrier

NASA Astrophysics Data System (ADS)

Jue, Jan-Fong; Keiser, Dennis D.; Breckenridge, Cynthia R.; Moore, Glenn A.; Meyer, Mitchell K.

2014-05-01

Due to the limitation of maximum uranium load achievable by dispersion fuel type, the Global Threat Reduction Initiative is developing an advanced monolithic fuel to convert US high-performance research reactors to low-enriched uranium. Hot-isostatic-press (HIP) bonding was the single process down-selected to bond monolithic U-Mo fuel meat to aluminum alloy cladding. A diffusion barrier was applied to the U-Mo fuel meat by roll-bonding process to prevent extensive interaction between fuel meat and aluminum-alloy cladding. Microstructural characterization was performed on fresh fuel plates fabricated at Idaho National Laboratory. Interfaces between the fuel meat, the cladding, and the diffusion barrier, as well as between the U-10Mo fuel meat and the Al-6061 cladding, were characterized by scanning electron microscopy. Preliminary results indicate that the interfaces contain many different phases while decomposition, second phases, and chemical banding were also observed in the fuel meat. The important attributes of the HIP-bonded monolithic fuel are:

Microstructural Characteristics of HIP-bonded Monolithic Nuclear Fuels with a Diffusion Barrier

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

Jan-Fong Jue; Dennis D. Keiser, Jr.; Cynthia R. Breckenridge

Due to the limitation of maximum uranium load achievable by dispersion fuel type, the Global Threat Reduction Initiative (GTRI) is developing an advanced monolithic fuel to convert US high performance research reactors to low-enriched uranium. Hot-isostatic-press bonding was the single process down-selected to bond monolithic U-Mo fuel meat to aluminum alloy cladding. A diffusion barrier was applied to the U–Mo fuel meat by roll-bonding process to prevent extensive interaction between fuel meat and aluminum-alloy cladding. Microstructural characterization was performed on fresh fuel plates fabricated at Idaho National Laboratory. Interfaces between fuel meat, cladding, and diffusion barrier, as well as U–10Momore » fuel meat and Al–6061 cladding were characterized by scanning electron microscopy. Preliminary results indicate that the interfaces contain many different phases while decomposition, second phases, and chemical banding were also observed in the fuel meat. The important attributes of the HIP-bonded monolithic fuel are • A typical Zr diffusion barrier of thickness 25 µm • Transverse cross section that exhibits relatively equiaxed grains with an average grain diameter of 10 µm • Chemical banding, in some areas more than 100 µm in length, that is very pronounced in longitudinal (i.e., rolling) direction with Mo concentration varying from 7–13 wt% • Decomposed areas containing plate-shaped low-Mo phase • A typical Zr/cladding interaction layer of thickness 1-2 µm • A visible UZr2 bearing layer of thickness 1-2 µm • Mo-rich precipitates (mainly Mo2Zr, forming a layer in some areas) followed by a Mo-depleted sub-layer between the visible UZr2-bearing layer and the U–Mo matrix • No excessive interaction between cladding and the uncoated fuel edge • Cladding-to-cladding bonding that exhibits no cracks or porosity with second phases high in Mg, Si, and O decorating the bond line. • Some of these attributes might be critical to the irradiation performance of monolithic U-10Mo nuclear fuel. There are several issues or concerns that warrant more detailed study, such as precipitation along cladding-to-cladding bond line, chemical banding, uncovered fuel-zone edge, and interaction layer between U–Mo fuel meat and zirconium. Future post-irradiation examination results will focus, among other things, on identifying in-reactor failure mechanisms and, eventually, directing further fresh fuel characterization efforts.« 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.

Structural and Thermodynamic Factors of Suppressed Interdiffusion Kinetics in Multi-component High-entropy Materials

PubMed Central

Chang, Shou-Yi; Li, Chen-En; Huang, Yi-Chung; Hsu, Hsun-Feng; Yeh, Jien-Wei; Lin, Su-Jien

2014-01-01

We report multi-component high-entropy materials as extraordinarily robust diffusion barriers and clarify the highly suppressed interdiffusion kinetics in the multi-component materials from structural and thermodynamic perspectives. The failures of six alloy barriers with different numbers of elements, from unitary Ti to senary TiTaCrZrAlRu, against the interdiffusion of Cu and Si were characterized, and experimental results indicated that, with more elements incorporated, the failure temperature of the barriers increased from 550 to 900°C. The activation energy of Cu diffusion through the alloy barriers was determined to increase from 110 to 163 kJ/mole. Mechanistic analyses suggest that, structurally, severe lattice distortion strains and a high packing density caused by different atom sizes, and, thermodynamically, a strengthened cohesion provide a total increase of 55 kJ/mole in the activation energy of substitutional Cu diffusion, and are believed to be the dominant factors of suppressed interdiffusion kinetics through the multi-component barrier materials. PMID:24561911

Excess oxygen limited diffusion and precipitation of iron in amorphous silicon dioxide

NASA Astrophysics Data System (ADS)

Leveneur, J.; Langlois, M.; Kennedy, J.; Metson, James B.

2017-10-01

In micro- and nano- electronic device fabrication, and particularly 3D designs, the diffusion of a metal into sublayers during annealing needs to be minimized as it is usually detrimental to device performance. Diffusion also causes the formation and growth of nanoprecipitates in solid matrices. In this paper, the diffusion behavior of low energy, low fluence, ion implanted iron into a thermally grown silicon oxide layer on silicon is investigated. Different ion beam analysis and imaging techniques were used. Magnetization measurements were also undertaken to provide evidence of nanocrystalline ordering. While standard vacuum furnace annealing and electron beam annealing lead to fast diffusion of the implanted species towards the Si/SiO2 interface, we show that furnace annealing in an oxygen rich atmosphere prevents the diffusion of iron that, in turn, limits the growth of the nanoparticles. The diffusion and particle growth is also greatly reduced when oxygen atoms are implanted in the SiO2 prior to Fe implantation, effectively acting as a diffusion barrier. The excess oxygen is hypothesized to trap Fe atoms and reduce their mean free path during the diffusion. Monte-Carlo simulations of the diffusion process which consider the random walk of Fe, Fick's diffusion of O atoms, Fe precipitation, and desorption of the SiO2 layer under the electron beam annealing were performed. Simulation results for the three preparation conditions are found in good agreement with the experimental data.

Different approach to the modeling of nonfree particle diffusion

NASA Astrophysics Data System (ADS)

Buhl, Niels

2018-03-01

A new approach to the modeling of nonfree particle diffusion is presented. The approach uses a general setup based on geometric graphs (networks of curves), which means that particle diffusion in anything from arrays of barriers and pore networks to general geometric domains can be considered and that the (free random walk) central limit theorem can be generalized to cover also the nonfree case. The latter gives rise to a continuum-limit description of the diffusive motion where the effect of partially absorbing barriers is accounted for in a natural and non-Markovian way that, in contrast to the traditional approach, quantifies the absorptivity of a barrier in terms of a dimensionless parameter in the range 0 to 1. The generalized theorem gives two general analytic expressions for the continuum-limit propagator: an infinite sum of Gaussians and an infinite sum of plane waves. These expressions entail the known method-of-images and Laplace eigenfunction expansions as special cases and show how the presence of partially absorbing barriers can lead to phenomena such as line splitting and band gap formation in the plane wave wave-number spectrum.

Multiple Diffusion Mechanisms Due to Nanostructuring in Crowded Environments

PubMed Central

Sanabria, Hugo; Kubota, Yoshihisa; Waxham, M. Neal

2007-01-01

One of the key questions regarding intracellular diffusion is how the environment affects molecular mobility. Mostly, intracellular diffusion has been described as hindered, and the physical reasons for this behavior are: immobile barriers, molecular crowding, and binding interactions with immobile or mobile molecules. Using results from multi-photon fluorescence correlation spectroscopy, we describe how immobile barriers and crowding agents affect translational mobility. To study the hindrance produced by immobile barriers, we used sol-gels (silica nanostructures) that consist of a continuous solid phase and aqueous phase in which fluorescently tagged molecules diffuse. In the case of molecular crowding, translational mobility was assessed in increasing concentrations of 500 kDa dextran solutions. Diffusion of fluorescent tracers in both sol-gels and dextran solutions shows clear evidence of anomalous subdiffusion. In addition, data from the autocorrelation function were analyzed using the maximum entropy method as adapted to fluorescence correlation spectroscopy data and compared with the standard model that incorporates anomalous diffusion. The maximum entropy method revealed evidence of different diffusion mechanisms that had not been revealed using the anomalous diffusion model. These mechanisms likely correspond to nanostructuring in crowded environments and to the relative dimensions of the crowding agent with respect to the tracer molecule. Analysis with the maximum entropy method also revealed information about the degree of heterogeneity in the environment as reported by the behavior of diffusive molecules. PMID:17040979

General Protein Diffusion Barriers create Compartments within Bacterial Cells

PubMed Central

Schlimpert, Susan; Klein, Eric A.; Briegel, Ariane; Hughes, Velocity; Kahnt, Jörg; Bolte, Kathrin; Maier, Uwe G.; Brun, Yves V.; Jensen, Grant J.; Gitai, Zemer; Thanbichler, Martin

2013-01-01

SUMMARY In eukaryotes, the differentiation of cellular extensions such as cilia or neuronal axons depends on the partitioning of proteins to distinct plasma membrane domains by specialized diffusion barriers. However, examples of this compartmentalization strategy are still missing for prokaryotes, although complex cellular architectures are widespread among this group of organisms. This study reveals the existence of a protein-mediated membrane diffusion barrier in the stalked bacterium Caulobacter crescentus. We show that the Caulobacter cell envelope is compartmentalized by macromolecular complexes that prevent the exchange of both membrane and soluble proteins between the polar stalk extension and the cell body. The barrier structures span the cross-sectional area of the stalk and comprise at least four proteins that assemble in a cell cycle-dependent manner. Their presence is critical for cellular fitness, as they minimize the effective cell volume, allowing faster adaptation to environmental changes that require de novo synthesis of envelope proteins. PMID:23201141

Theoretical analysis of nBn infrared photodetectors

NASA Astrophysics Data System (ADS)

Ting, David Z.; Soibel, Alexander; Khoshakhlagh, Arezou; Gunapala, Sarath D.

2017-09-01

The depletion and surface leakage dark current suppression properties of unipolar barrier device architectures such as the nBn have been highly beneficial for III-V semiconductor-based infrared detectors. Using a one-dimensional drift-diffusion model, we theoretically examine the effects of contact doping, minority carrier lifetime, and absorber doping on the dark current characteristics of nBn detectors to explore some basic aspects of their operation. We found that in a properly designed nBn detector with highly doped excluding contacts the minority carriers are extracted to nonequilibrium levels under reverse bias in the same manner as the high operating temperature (HOT) detector structure. Longer absorber Shockley-Read-Hall (SRH) lifetimes result in lower diffusion and depletion dark currents. Higher absorber doping can also lead to lower diffusion and depletion dark currents, but the benefit should be weighted against the possibility of reduced diffusion length due to shortened SRH lifetime. We also briefly examined nBn structures with unintended minority carrier blocking barriers due to excessive n-doping in the unipolar electron barrier, or due to a positive valence band offset between the barrier and the absorber. Both types of hole blocking structures lead to higher turn-on bias, although barrier n-doping could help suppress depletion dark current.

Large size self-assembled quantum rings: quantum size effect and modulation on the surface diffusion.

PubMed

Tong, Cunzhu; Yoon, Soon Fatt; Wang, Lijun

2012-09-24

We demonstrate experimentally the submicron size self-assembled (SA) GaAs quantum rings (QRs) by quantum size effect (QSE). An ultrathin In0.1 Ga0.9As layer with different thickness is deposited on the GaAs to modulate the surface nucleus diffusion barrier, and then the SA QRs are grown. It is found that the density of QRs is affected significantly by the thickness of inserted In0.1 Ga0.9As, and the diffusion barrier modulation reflects mainly on the first five monolayer . The physical mechanism behind is discussed. The further analysis shows that about 160 meV decrease in diffusion barrier can be achieved, which allows the SA QRs with density of as low as one QR per 6 μm2. Finally, the QRs with diameters of 438 nm and outer diameters of 736 nm are fabricated using QSE.

Solid state oxygen sensor

DOEpatents

Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

1996-01-01

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

Influence of La/W ratio on electrical conductivity of lanthanum tungstate with high La/W ratio

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

Kojo, Gen; Shono, Yohei; Ushiyama, Hiroshi

The proton-conducting properties of lanthanum tungstates (LWOs) with high La/W ratios were investigated using electrochemical measurements and quantum chemical calculations. Single phases of LWOs with high La/W ratios (6.3≤La/W≤6.7) were synthesized by high-temperature sintering at around 1700 °C. The electrical conductivity of LWO increased with increasing La/W ratio in the single-phase region. The LWO synthesized at the optimum sintering temperature and time, and with the optimum La/W ratio gave the maximum conductivity, i.e., 2.7×10{sup −3} S cm{sup −1} with La/W=6.7 at 500 °C. Density functional theory calculations, using the nudged elastic band method, were performed to investigate the proton diffusionmore » barrier. The results suggest that the proton diffusion paths around La sites have the lowest proton diffusion barrier. These findings improve our understanding of LWO synthesis and the proton-conducting mechanism and provide a strategy for improving proton conduction in LWOs. - Graphical abstract: The LWOs with high La/W ratios were synthesized for the first time. The optimum La/W ratio gave the maximum conductivity with La/W=6.7 at 500 °C. The proton diffusion paths were also considered with density functional theory calculations. - Highlights: • The proton-conducting properties of lanthanum tungstates (LWOs) were investigated. • Single phase LWOs with high La/W ratios (6.3≤La/W≤6.7) were synthesized successfully. • LWOs with the high La/W ratios showed high proton conductivity. • The DFT calculation suggested the lowest proton diffusion barrier in the path around La sites.« less

Crowding-facilitated macromolecular transport in attractive micropost arrays.

PubMed

Chien, Fan-Tso; Lin, Po-Keng; Chien, Wei; Hung, Cheng-Hsiang; Yu, Ming-Hung; Chou, Chia-Fu; Chen, Yeng-Long

2017-05-02

Our study of DNA dynamics in weakly attractive nanofabricated post arrays revealed crowding enhances polymer transport, contrary to hindered transport in repulsive medium. The coupling of DNA diffusion and adsorption to the microposts results in more frequent cross-post hopping and increased long-term diffusivity with increased crowding density. We performed Langevin dynamics simulations and found maximum long-term diffusivity in post arrays with gap sizes comparable to the polymer radius of gyration. We found that macromolecular transport in weakly attractive post arrays is faster than in non-attractive dense medium. Furthermore, we employed hidden Markov analysis to determine the transition of macromolecular adsorption-desorption on posts and hopping between posts. The apparent free energy barriers are comparable to theoretical estimates determined from polymer conformational fluctuations.

Molecular dynamics simulation of the evolution of hydrophobic defects in one monolayer of a phosphatidylcholine bilayer: relevance for membrane fusion mechanisms.

PubMed Central

Tieleman, D Peter; Bentz, Joe

2002-01-01

The spontaneous formation of the phospholipid bilayer underlies the permeability barrier function of the biological membrane. Tears or defects that expose water to the acyl chains are spontaneously healed by lipid lateral diffusion. However, mechanical barriers, e.g., protein aggregates held in place, could sustain hydrophobic defects. Such defects have been postulated to occur in processes such as membrane fusion. This gives rise to a new question in bilayer structure: What do the lipids do in the absence of lipid lateral diffusion to minimize the free energy of a hydrophobic defect? As a first step to understand this rather fundamental question about bilayer structure, we performed molecular dynamic simulations of up to 10 ns of a planar bilayer from which lipids have been deleted randomly from one monolayer. In one set of simulations, approximately one-half of the lipids in the defect monolayer were restrained to form a mechanical barrier. In the second set, lipids were free to diffuse around. The question was simply whether the defects caused by removing a lipid would aggregate together, forming a large hydrophobic cavity, or whether the membrane would adjust in another way. When there are no mechanical barriers, the lipids in the defect monolayer simply spread out and thin with little effect on the other intact monolayer. In the presence of a mechanical barrier, the behavior of the lipids depends on the size of the defect. When 3 of 64 lipids are removed, the remaining lipids adjust the lower one-half of their chains, but the headgroup structure changes little and the intact monolayer is unaffected. When 6 to 12 lipids are removed, the defect monolayer thins, lipid disorder increases, and lipids from the intact monolayer move toward the defect monolayer. Whereas this is a highly simplified model of a fusion site, this engagement of the intact monolayer into the fusion defect is strikingly consistent with recent results for influenza hemagglutinin mediated fusion. PMID:12202375

Experimental investigation of defect-assisted and intrinsic water vapor permeation through ultrabarrier films

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

Kim, Hyungchul; Singh, Ankit Kumar; Wang, Cheng-Yin

In the development of ultrabarrier films for packaging electronics, the effective water vapor transmission rate is a combination of permeation through pinhole defects and the intrinsic permeation through the actual barrier film. While it is possible to measure the effective permeation rate through barriers, it is important to develop a better understanding of the contribution from defects to the overall effective barrier performance. Here, we demonstrate a method to investigate independently defect-assisted permeation and intrinsic permeation rates by observing the degradation of a calcium layer encapsulated with a hybrid barrier film, that is, prepared using atomic layer deposition (ALD) andmore » plasma enhanced deposition (PECVD). The results are rationalized using an analytical diffusion model to calculate the permeation rate as a function of spatial position within the barrier. It was observed that a barrier film consisting of a PECVD SiN{sub x} layer combined with an ALD Al{sub 2}O{sub 3}/HfO{sub x} nanolaminate resulted in a defect-assisted water vapor transmission rate (WVTR) of 4.84 × 10{sup −5} g/m{sup 2} day and intrinsic WVTR of 1.41 × 10{sup −4} g/m{sup 2} day at 50 °C/85% RH. Due to the low defect density of the tested barrier film, the defect-assisted WVTR was found to be three times lower than the intrinsic WVTR, and an effective (or total) WVTR value was 1.89 × 10{sup −4} g/m{sup 2} day. Thus, improvements of the barrier performance should focus on reducing the number of defects while also improving the intrinsic barrier performance of the hybrid layer.« less

Diffusion barriers in modified air brazes

DOEpatents

Weil, Kenneth Scott; Hardy, John S; Kim, Jin Yong; Choi, Jung-Pyung

2013-04-23

A method for joining two ceramic parts, or a ceramic part and a metal part, and the joint formed thereby. The method provides two or more parts, a braze consisting of a mixture of copper oxide and silver, a diffusion barrier, and then heats the braze for a time and at a temperature sufficient to form the braze into a bond holding the two or more parts together. The diffusion barrier is an oxidizable metal that forms either a homogeneous component of the braze, a heterogeneous component of the braze, a separate layer bordering the braze, or combinations thereof. The oxidizable metal is selected from the group Al, Mg, Cr, Si, Ni, Co, Mn, Ti, Zr, Hf, Pt, Pd, Au, lanthanides, and combinations thereof.

Diffusion barriers in modified air brazes

DOEpatents

Weil, Kenneth Scott [Richland, WA; Hardy, John S [Richland, WA; Kim, Jin Yong [Richland, WA; Choi, Jung-Pyung [Richland, WA

2010-04-06

A method for joining two ceramic parts, or a ceramic part and a metal part, and the joint formed thereby. The method provides two or more parts, a braze consisting of a mixture of copper oxide and silver, a diffusion barrier, and then heats the braze for a time and at a temperature sufficient to form the braze into a bond holding the two or more parts together. The diffusion barrier is an oxidizable metal that forms either a homogeneous component of the braze, a heterogeneous component of the braze, a separate layer bordering the braze, or combinations thereof. The oxidizable metal is selected from the group Al, Mg, Cr, Si, Ni, Co, Mn, Ti, Zr, Hf, Pt, Pd, Au, lanthanides, and combinations thereof.

The Ponseti method in Latin America: initial impact and barriers to its diffusion and implementation.

PubMed

Boardman, Allison; Jayawardena, Asitha; Oprescu, Florin; Cook, Thomas; Morcuende, Jose A

2011-01-01

The Ponseti method for correcting clubfoot is a safe, effective, and minimally invasive treatment that has recently been implemented in Latin America. This study evaluates the initial impact and unique barriers to the diffusion of the Ponseti method throughout this region. Structured interviews were conducted with 30 physicians practicing the Ponseti method in three socioeconomically diverse countries: Chile, Peru and Guatemala. Since learning the Ponseti method, these physicians have treated approximately 1,740 clubfoot patients, with an estimated 1,705 (98%) patients treated using the Ponseti method, and 35 (2%) patients treated using surgical techniques. The barriers were classified into the following themes: physician education, health care system of the country, culture and beliefs of patients, physical distance and transport, financial barriers for patients, and parental compliance with the method. The results yielded several common barriers throughout Latin America including lack of physician education, physical distance to the treatment centers, and financial barriers for patients. Information from this study can be used to inform, and to implement and evaluate specific strategies to improve the diffusion of the Ponseti method for treating clubfoot throughout Latin America.

Interfacial strain effects on lithium diffusion pathways in the spinel solid electrolyte Li-doped MgAl2O4

NASA Astrophysics Data System (ADS)

O'Rourke, Conn; Morgan, Benjamin J.

2018-04-01

The (Li,Al)-codoped magnesium spinel (LixMg1 -2 xAl2 +xO4 ) is a solid lithium-ion electrolyte with potential use in all-solid-state lithium-ion batteries. The spinel structure means that interfaces with spinel electrodes, such as LiyMn2O4 and Li4 +3 zTi5O12 , may be lattice matched, with potentially low interfacial resistances. Small lattice parameter differences across a lattice-matched interface are unavoidable, causing residual epitaxial strain. This strain potentially modifies lithium diffusion near the electrolyte-electrode interface, contributing to interfacial resistance. Here, we report a density functional theory study of strain effects on lithium diffusion pathways for (Li,Al)-codoped magnesium spinel, for xLi=0.25 and xLi=0.5 . We have calculated diffusion profiles for the unstrained materials, and for isotropic and biaxial tensile strains of up to 6 % , corresponding to {100 } epitaxial interfaces with LiyMn2O4 and Li4 +3 zTi5O12 . We find that isotropic tensile strain reduces lithium diffusion barriers by as much as 0.32 eV , with typical barriers reduced by ˜0.1 eV. This effect is associated with increased volumes of transitional octahedral sites, and broadly follows qualitative changes in local electrostatic potentials. For biaxial (epitaxial) strain, which more closely approximates strain at a lattice-matched electrolyte-electrode interface, changes in octahedral site volumes and in lithium diffusion barriers are much smaller than under isotropic strain. Typical barriers are reduced by only ˜0.05 eV. Individual effects, however, depend on the pathway considered and the relative strain orientation. These results predict that isotropic strain strongly affects ionic conductivities in (Li,Al)-codoped magnesium spinel electrolytes, and that tensile strain is a potential route to enhanced lithium transport. For a lattice-matched interface with candidate spinel-structured electrodes, however, epitaxial strain has a small, but complex, effect on lithium diffusion barriers.

Molecular dynamics simulations of substitutional diffusion

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

Zhou, Xiaowang; Jones, Reese E.; Gruber, Jacob

2016-12-18

In atomistic simulations, diffusion energy barriers are usually calculated for each atomic jump path using a nudged elastic band method. Practical materials often involve thousands of distinct atomic jump paths that are not known a priori. Hence, it is often preferred to determine an overall diffusion energy barrier and an overall pre-exponential factor from the Arrhenius equation constructed through molecular dynamics simulations of mean square displacement of the diffusion species at different temperatures. This approach has been well established for interstitial diffusion, but not for substitutional diffusion at the same confidence. Using In 0.1 Ga 0.9 N as an example,more » we have identified conditions where molecular dynamics simulations can be used to calculate highly converged Arrhenius plots for substitutional alloys. As a result, this may enable many complex diffusion problems to be easily and reliably studied in the future using molecular dynamics, provided that moderate computing resources are available.« less

Diffusion quantum Monte Carlo calculations of SrFeO 3 and LaFeO 3

DOE PAGES

Santana, Juan A.; Krogel, Jaron T.; Kent, Paul R. C.; ...

2017-07-18

The equations of state, formation energy, and migration energy barrier of the oxygen vacancy in SrFeO 3 and LaFeO 3 were calculated in this paper with the diffusion quantum Monte Carlo (DMC) method. Calculations were also performed with various Density Functional Theory (DFT) approximations for comparison. DMC reproduces the measured cohesive energies of these materials with errors below 0.23(5) eV and the structural properties within 1% of the experimental values. The DMC formation energies of the oxygen vacancy in SrFeO 3 and LaFeO 3 under oxygen-rich conditions are 1.3(1) and 6.24(7) eV, respectively. Similar calculations with semi-local DFT approximations formore » LaFeO 3 yielded vacancy formation energies 1.5 eV lower. Comparison of charge density evaluated with DMC and DFT approximations shows that DFT tends to overdelocalize the electrons in defected SrFeO 3 and LaFeO 3. Finally, calculations with DMC and local density approximation yield similar vacancy migration energy barriers, indicating that steric/electrostatic effects mainly determine migration barriers in these materials.« less

Investigation of amorphous RuMoC alloy films as a seedless diffusion barrier for Cu/ p-SiOC:H ultralow- k dielectric integration

NASA Astrophysics Data System (ADS)

Jiao, Guohua; Liu, Bo; Li, Qiran

2015-08-01

Ultrathin RuMoC amorphous films prepared by magnetron co-sputtering with Ru and MoC targets in a sandwiched scheme Si/ p-SiOC:H/RuMoC/Cu were investigated as barrier in copper metallization. The evolution of final microstructure of RuMoC alloy films show sensitive correlation with the content of doped Mo and C elements and can be easily controlled by adjusting the sputtering power of the MoC target. There was no signal of interdiffusion between the Cu and SiOC:H layer in the sample of Cu/RuMoC/ p-SiOC:H/Si, even annealing up to 500 °C. Very weak signal of oxygen have been confirmed in the RuMoC barrier layer both as-deposited and after being annealed, and a good performance on preventing oxygen diffusion has been proved. Leakage current and resistivity evaluations also reveal the excellent thermal reliability of this Si/ p-SiOC:H/RuMoC/Cu film stack at the temperatures up to 500 °C, indicating its potential application in the advanced barrierless Cu metallization.

Designing solid-liquid interphases for sodium batteries.

PubMed

Choudhury, Snehashis; Wei, Shuya; Ozhabes, Yalcin; Gunceler, Deniz; Zachman, Michael J; Tu, Zhengyuan; Shin, Jung Hwan; Nath, Pooja; Agrawal, Akanksha; Kourkoutis, Lena F; Arias, Tomas A; Archer, Lynden A

2017-10-12

Secondary batteries based on earth-abundant sodium metal anodes are desirable for both stationary and portable electrical energy storage. Room-temperature sodium metal batteries are impractical today because morphological instability during recharge drives rough, dendritic electrodeposition. Chemical instability of liquid electrolytes also leads to premature cell failure as a result of parasitic reactions with the anode. Here we use joint density-functional theoretical analysis to show that the surface diffusion barrier for sodium ion transport is a sensitive function of the chemistry of solid-electrolyte interphase. In particular, we find that a sodium bromide interphase presents an exceptionally low energy barrier to ion transport, comparable to that of metallic magnesium. We evaluate this prediction by means of electrochemical measurements and direct visualization studies. These experiments reveal an approximately three-fold reduction in activation energy for ion transport at a sodium bromide interphase. Direct visualization of sodium electrodeposition confirms large improvements in stability of sodium deposition at sodium bromide-rich interphases.The chemistry at the interface between electrolyte and electrode plays a critical role in determining battery performance. Here, the authors show that a NaBr enriched solid-electrolyte interphase can lower the surface diffusion barrier for sodium ions, enabling stable electrodeposition.

Regulatory Promotion of Emergent CCS Technology

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

Davies, Lincoln; Uchitel, Kirsten; Johnson, David

2014-01-01

Despite the growing inevitability of climate change and the attendant need for mitigation strategies, carbon capture and sequestration (CCS) has yet to gain much traction in the United States. Recent regulatory proposals by the U.S. Environmental Protection Agency (EPA), limited in scope to new-build power plants, represent the only significant policy initiative intended to mandate diffusion of CCS technology. Phase I of this Project assessed barriers to CCS deployment as prioritized by the CCS community. That research concluded that there were four primary barriers: (1) cost, (2) lack of a carbon price, (3) liability, and (4) lack of a comprehensivemore » regulatory regime. Phase II of this Project, as presented in this Report, assesses potential regulatory models for CCS and examines where those models address the hurdles to diffusing CCS technology identified in Phase I. It concludes (1) that a CCS-specific but flexible standard, such as a technology performance standard or a very particular type of market-based regulation, likely will promote CCS diffusion, and (2) that these policies cannot work alone, but rather, should be combined with other measures, such as liability limits and a comprehensive CCS regulatory regime.« less

Diffusion of multiwall carbon nanotubes (MWCNTs) through a high density polyethylene (HDPE) geomembrane

PubMed Central

Saheli, P. T.; Rowe, R. K.; Petersen, E. J.; O’Carroll, D. M.

2017-01-01

The new applications for carbon nanotubes (CNTs) in various fields and consequently their greater production volume have increased their potential release to the environment. Landfills are one of the major locations where carbon nanotubes are expected to be disposed and it is important to ensure that they can limit the release of CNTs. Diffusion of multiwall carbon nanotubes (MWCNTs) dispersed in an aqueous media through a high-density polyethylene (HDPE) geomembrane (as a part of the landfill barrier system) was examined. Based on the laboratory tests, the permeation coefficient was estimated to be less than 5.1×10−15 m2/s. The potential performance of a HDPE geomembrane and geosynthetic clay liner (GCL) as parts of a composite liner in containing MWCNTs was modelled for six different scenarios. The results suggest that the low value of permeation coefficient of an HDPE geomembrane makes it an effective diffusive barrier for MWCNTs and by keeping the geomembrane defects to minimum during the construction (e.g., number of holes and length of wrinkles) a composite liner commonly used in municipal solid waste landfills will effectively contain MWCNTs. PMID:28740357

Chromium oxide as a metal diffusion barrier layer: An x-ray absorption fine structure spectroscopy study

NASA Astrophysics Data System (ADS)

Ahamad Mohiddon, Md.; Lakshun Naidu, K.; Ghanashyam Krishna, M.; Dalba, G.; Ahmed, S. I.; Rocca, F.

2014-01-01

The interaction at the interface between chromium and amorphous Silicon (a-Si) films in the presence of a sandwich layer of chromium oxide is investigated using X-ray absorption fine structure (XAFS) spectroscopy. The oxidized interface was created, in situ, prior to the deposition of a 400 nm tick a-Si layer over a 50 nm tick Cr layer. The entire stack of substrate/metallic Cr/Cr2O3/a-Si was then annealed at temperatures from 300 up to 700 °C. Analysis of the near edge and extended regions of each XAFS spectrum shows that only a small fraction of Cr is able to diffuse through the oxide layer up to 500 °C, while the remaining fraction is buried under the oxide layer in the form of metallic Cr. At higher temperatures, diffusion through the oxide layer is enhanced and the diffused metallic Cr reacts with a-Si to form CrSi2. At 700 °C, the film contains Cr2O3 and CrSi2 without evidence of unreacted metallic Cr. The activation energy and diffusion coefficient of Cr are quantitatively determined in the two temperature regions, one where the oxide acts as diffusion barrier and another where it is transparent to Cr diffusion. It is thus demonstrated that chromium oxide can be used as a diffusion barrier to prevent metal diffusion into a-Si.

Characteristics of WN{sub x}C{sub y} films deposited using remote plasma atomic layer deposition with ({sup Me}Cp)W(CO){sub 2}(NO) for Cu diffusion barrier

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

Kim, Hyunjung; Park, Jingyu; Jeon, Heeyoung

Diffusion barrier characteristics of tungsten–nitride–carbide (WN{sub x}C{sub y}) thin films interposed between Cu and SiO{sub 2} layers were studied. The WN{sub x}C{sub y} films were deposited by remote plasma atomic layer deposition (RPALD) using a metal organic source, ({sup Me}Cp)W(CO){sub 2}(NO), and ammonia. Auger electron spectroscopy analysis indicated the WN{sub x}C{sub y} films consisted of tungsten, nitrogen, carbon, and oxygen. X-ray diffraction (XRD) analysis showed that the film deposited at 350 °C was nanocrystalline. The resistivity of WN{sub x}C{sub y} film deposited by RPALD was very low compared to that in previous research because of the lower nitrogen content and differentmore » crystal structures of the WN{sub x}C{sub y}. To verify the diffusion barrier characteristics of the WN{sub x}C{sub y} film, Cu films were deposited by physical vapor deposition after WN{sub x}C{sub y} film was formed by RPALD on Si substrate. The Cu/WN{sub x}C{sub y}/Si film stack was annealed in a vacuum by rapid thermal annealing at 500 °C. Cu diffusion through the barrier layer was verified by XRD. Stable film properties were observed up to 500 °C, confirming that WN{sub x}C{sub y} film is suitable as a Cu diffusion barrier in microelectronic circuits.« less

Diffusion Dominant Solute Transport Modelling In Deep Repository Under The Effect of Emplacement Media Degradation - 13285

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

Kwong, S.; Jivkov, A.P.

2013-07-01

Deep geologic disposal of high activity and long-lived radioactive waste is being actively considered and pursued in many countries, where low permeability geological formations are used to provide long term waste contaminant with minimum impact to the environment and risk to the biosphere. A multi-barrier approach that makes use of both engineered and natural barriers (i.e. geological formations) is often used to further enhance the containment performance of the repository. As the deep repository system subjects to a variety of thermo-hydro-chemo-mechanical (THCM) effects over its long 'operational' lifespan (e.g. 0.1 to 1.0 million years, the integrity of the barrier systemmore » will decrease over time (e.g. fracturing in rock or clay)). This is broadly referred as media degradation in the present study. This modelling study examines the effects of media degradation on diffusion dominant solute transport in fractured media that are typical of deep geological environment. In particular, reactive solute transport through fractured media is studied using a 2-D model, that considers advection and diffusion, to explore the coupled effects of kinetic and equilibrium chemical processes, while the effects of degradation is studied using a pore network model that considers the media diffusivity and network changes. Model results are presented to demonstrate the use of a 3D pore-network model, using a novel architecture, to calculate macroscopic properties of the medium such as diffusivity, subject to pore space changes as the media degrade. Results from a reactive transport model of a representative geological waste disposal package are also presented to demonstrate the effect of media property change on the solute migration behaviour, illustrating the complex interplay between kinetic biogeochemical processes and diffusion dominant transport. The initial modelling results demonstrate the feasibility of a coupled modelling approach (using pore-network model and reactive transport model) to examine the long term behaviour of deep geological repositories with media property change under complex geochemical conditions. (authors)« less

Solid state oxygen sensor

DOEpatents

Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

1996-08-06

Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

Characterization of cesium diffusion behavior into granite matrix using Rutherford backscattering spectrometry

NASA Astrophysics Data System (ADS)

Tsai, Shih-Chin; Lee, Chuan-Pin; Tsai, Tsuey-Lin; Yu, Yueh-Chung

2017-10-01

The characterization of radionuclide diffusion behavior is necessary for performance assessment of granite as a geological barrier for high-level radioactive waste disposal. Rutherford backscattering spectrometry (RBS), a novel nuclear ion-beam technique, was selected in this study because it is suitable for analyzing the concentration gradients of heavy elements in a well-defined matrix and allows measuring diffusion coefficients on a micrometer scale. In this study Cs was selected to represent Cs-135 (a key radionuclide in high-level waste) diffusion in granite. The Cs energy spectrum and concentration deep profile were analyzed and the diffusion coefficient of Cs in granite for three different locations were determined, which were 2.06 × 10-19m2 s-1, 3.58 × 10-19m2 s-1, and 7.19 × 10-19m2 s-1-19m2 s-19m2 s-1, respectively, which were of a similiar order of magnitude. Results from other studies are also compared and discussed in this paper.

On trans-parenchymal transport after blood brain barrier opening: pump-diffuse-pump hypothesis

NASA Astrophysics Data System (ADS)

Postnov, D. E.; Postnikov, E. B.; Karavaev, A. S.; Glushkovskaya-Semyachkina, O. V.

2018-04-01

Transparenchymal transport attracted the attention of many research groups after the discovery of glymphatic mechanism for the brain drainage in 2012. While the main facts of rapid transport of substances across the parenchyma are well established experimentally, specific mechanisms that drive this drainage are just hypothezised but not proved yed. Moreover, the number of modeling studies show that the pulse wave powered mechanism is unlikely able to perform pumping as suggested. Thus, the problem is still open. In addition, new data obtained under the conditions of intensionally opened blood brain barrier shows the presence of equally fast transport in opposite durection. In our study we investigate the possible physical mechanisms for rapid transport of substances after the opening of blood-brain barrier under the conditions of zero net flow.

Comparative performance of short-term diffusion barrier charcoal canisters and long-term alpha-track monitors for indoor 222Rn measurements.

PubMed

Martz, D E; George, J L; Langner, G H

1991-04-01

The accuracy and precision of indoor 222Rn measurements obtained with the use of diffusion barrier charcoal canisters (DBCC) under actual field conditions were determined by comparing the integrated average of 26 successive 7-d exposures of DBCC in each of 16 occupied residences over a 6-mo period with simultaneous measurements using four types of commercially available alpha-track monitors (ATM) and one type of scintillation chamber continuous 222Rn monitor. The results suggest that properly calibrated DBCCs provide very good estimates of the integrated 222Rn concentrations in residential structures over the standard 1-wk exposure period despite the occurrence of large diurnal variations in the actual 222Rn concentrations. The results also suggest that a relatively small number of 1-wk DBCC measurements at selected times throughout the calendar year would provide estimates of the annual average indoor 222Rn concentrations that compare favorably with single long-term ATM measurements.

High-temperature properties of joint interface of VPS-tungsten coated CFC

NASA Astrophysics Data System (ADS)

Tamura, S.; Liu, X.; Tokunaga, K.; Tsunekawa, Y.; Okumiya, M.; Noda, N.; Yoshida, N.

2004-08-01

Tungsten coated carbon fiber composite (CFC) is a candidate material for the high heat flux components in fusion reactors. In order to investigate the high-temperature properties at the joint interface of coating, heat load experiments by using electron beam were performed on VPS-tungsten coated CX-2002U samples. After the heat load test for 3.6 ks at 1400 °C, tungsten-rhenium multilayer (diffusion barrier for carbon) at the joint interface of coating was observed clearly. But, at the temperatures above 1600 °C, the multilayer was disappeared and a tungsten carbide layer was formed in the VPS-tungsten coating. At the temperatures below 1800 °C, the thickness of this layer logarithmically increased with increasing its loading time. At 2000 °C, the growth of the tungsten carbide layer was proportional to the square root of loading time. These results indicate that the diffusion barrier for carbon is not expected to suppress the carbide formation at the joint interface of the VPS-tungsten coating above 1600 °C.

A first-principles and experimental study of helium diffusion in periclase MgO

NASA Astrophysics Data System (ADS)

Song, Zhewen; Wu, Henry; Shu, Shipeng; Krawczynski, Mike; Van Orman, James; Cherniak, Daniele J.; Bruce Watson, E.; Mukhopadhyay, Sujoy; Morgan, Dane

2018-02-01

The distribution of He isotopes is used to trace heterogeneities in the Earth's mantle, and is particularly useful for constraining the length scale of heterogeneity due to the generally rapid diffusivity of helium. However, such an analysis is challenging because He diffusivities are largely unknown in lower mantle phases, which can influence the He profiles in regions that cycle through the lower mantle. With this motivation, we have used first-principles simulations based on density functional theory to study He diffusion in MgO, an important lower mantle phase. We first studied the case of interstitial helium diffusion in perfect MgO and found a migration barrier of 0.73 eV at zero pressure. Then we used the kinetic Monte Carlo method to study the case of substitutional He diffusion in MgO, where we assumed that He diffuses on the cation sublattice through cation vacancies. We also performed experiments on He diffusion at atmospheric pressure using ion implantation and nuclear reaction analysis in both as-received and Ga-doped samples. A comparison between the experimental and simulation results are shown. This work provides a foundation for further studies at high-pressure.

Diffusion and interactions of interstitials in hard-sphere interstitial solid solutions

NASA Astrophysics Data System (ADS)

van der Meer, Berend; Lathouwers, Emma; Smallenburg, Frank; Filion, Laura

2017-12-01

Using computer simulations, we study the dynamics and interactions of interstitial particles in hard-sphere interstitial solid solutions. We calculate the free-energy barriers associated with their diffusion for a range of size ratios and densities. By applying classical transition state theory to these free-energy barriers, we predict the diffusion coefficients, which we find to be in good agreement with diffusion coefficients as measured using event-driven molecular dynamics simulations. These results highlight that transition state theory can capture the interstitial dynamics in the hard-sphere model system. Additionally, we quantify the interactions between the interstitials. We find that, apart from excluded volume interactions, the interstitial-interstitial interactions are almost ideal in our system. Lastly, we show that the interstitial diffusivity can be inferred from the large-particle fluctuations alone, thus providing an empirical relationship between the large-particle fluctuations and the interstitial diffusivity.

Influence of cell shape, inhomogeneities and diffusion barriers in cell polarization models

NASA Astrophysics Data System (ADS)

Giese, Wolfgang; Eigel, Martin; Westerheide, Sebastian; Engwer, Christian; Klipp, Edda

2015-12-01

In silico experiments bear the potential for further understanding of biological transport processes by allowing a systematic modification of any spatial property and providing immediate simulation results. Cell polarization and spatial reorganization of membrane proteins are fundamental for cell division, chemotaxis and morphogenesis. We chose the yeast Saccharomyces cerevisiae as an exemplary model system which entails the shuttling of small Rho GTPases such as Cdc42 and Rho, between an active membrane-bound form and an inactive cytosolic form. We used partial differential equations to describe the membrane-cytosol shuttling of proteins. In this study, a consistent extension of a class of 1D reaction-diffusion systems into higher space dimensions is suggested. The membrane is modeled as a thin layer to allow for lateral diffusion and the cytosol is modeled as an enclosed volume. Two well-known polarization mechanisms were considered. One shows the classical Turing-instability patterns, the other exhibits wave-pinning dynamics. For both models, we investigated how cell shape and diffusion barriers like septin structures or bud scars influence the formation of signaling molecule clusters and subsequent polarization. An extensive set of in silico experiments with different modeling hypotheses illustrated the dependence of cell polarization models on local membrane curvature, cell size and inhomogeneities on the membrane and in the cytosol. In particular, the results of our computer simulations suggested that for both mechanisms, local diffusion barriers on the membrane facilitate Rho GTPase aggregation, while diffusion barriers in the cytosol and cell protrusions limit spontaneous molecule aggregations of active Rho GTPase locally.

Silica-sol-based spin-coating barrier layer against phosphorous diffusion for crystalline silicon solar cells

PubMed Central

2014-01-01

The phosphorus barrier layers at the doping procedure of silicon wafers were fabricated using a spin-coating method with a mixture of silica-sol and tetramethylammonium hydroxide, which can be formed at the rear surface prior to the front phosphorus spin-on-demand (SOD) diffusion and directly annealed simultaneously with the front phosphorus layer. The optimization of coating thickness was obtained by changing the applied spin-coating speed; from 2,000 to 8,000 rpm. The CZ-Si p-type silicon solar cells were fabricated with/without using the rear silica-sol layer after taking the sheet resistance measurements, SIMS analysis, and SEM measurements of the silica-sol material evaluations into consideration. For the fabrication of solar cells, a spin-coating phosphorus source was used to form the n+ emitter and was then diffused at 930°C for 35 min. The out-gas diffusion of phosphorus could be completely prevented by spin-coated silica-sol film placed on the rear side of the wafers coated prior to the diffusion process. A roughly 2% improvement in the conversion efficiency was observed when silica-sol was utilized during the phosphorus diffusion step. These results can suggest that the silica-sol material can be an attractive candidate for low-cost and easily applicable spin-coating barrier for any masking purpose involving phosphorus diffusion. PMID:25520602

Silica-sol-based spin-coating barrier layer against phosphorous diffusion for crystalline silicon solar cells.

PubMed

Uzum, Abdullah; Fukatsu, Ken; Kanda, Hiroyuki; Kimura, Yutaka; Tanimoto, Kenji; Yoshinaga, Seiya; Jiang, Yunjian; Ishikawa, Yasuaki; Uraoka, Yukiharu; Ito, Seigo

2014-01-01

The phosphorus barrier layers at the doping procedure of silicon wafers were fabricated using a spin-coating method with a mixture of silica-sol and tetramethylammonium hydroxide, which can be formed at the rear surface prior to the front phosphorus spin-on-demand (SOD) diffusion and directly annealed simultaneously with the front phosphorus layer. The optimization of coating thickness was obtained by changing the applied spin-coating speed; from 2,000 to 8,000 rpm. The CZ-Si p-type silicon solar cells were fabricated with/without using the rear silica-sol layer after taking the sheet resistance measurements, SIMS analysis, and SEM measurements of the silica-sol material evaluations into consideration. For the fabrication of solar cells, a spin-coating phosphorus source was used to form the n(+) emitter and was then diffused at 930°C for 35 min. The out-gas diffusion of phosphorus could be completely prevented by spin-coated silica-sol film placed on the rear side of the wafers coated prior to the diffusion process. A roughly 2% improvement in the conversion efficiency was observed when silica-sol was utilized during the phosphorus diffusion step. These results can suggest that the silica-sol material can be an attractive candidate for low-cost and easily applicable spin-coating barrier for any masking purpose involving phosphorus diffusion.

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.

Diffusion of One-Dimensional Crystals in Channels of Single-Walled Carbon Nanotubes

NASA Astrophysics Data System (ADS)

Zhigalina, V. G.; Kumskov, A. S.; Falaleev, N. S.; Vasiliev, A. L.; Kiselev, N. A.

2018-05-01

The transport of one-dimensional CuI crystals in channels of single-walled carbon nanotubes (SWCNTs) has been studied by high resolution electron microscopy. The diffusion kinetics has been investigated by counting the number of CuI atoms escaping from the nanotube channel. The diffusivity is calculated to be 6.8 × 10-21 m2/s, which corresponds to an activation-barrier height of 1 eV/atom. A comparison with the theoretically estimated height of the energy barrier for molecular transport through a graphene layer is indicative of mass transfer through vacancy defects in graphene.

Self-learning kinetic Monte Carlo simulations of Al diffusion in Mg

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

Nandipati, Giridhar; Govind, Niranjan; Andersen, Amity

2016-03-16

Atomistic on-lattice self-learning kinetic Monte Carlo (SLKMC) method was used to examine the vacancy-mediated diffusion of an Al atom in pure hcp Mg. Local atomic environment dependent activation barriers for vacancy-atom exchange processes were calculated on-the-fly using climbing image nudged-elastic band method (CI-NEB) and using a Mg-Al binary modified embedded-atom method (MEAM) interatomic potential. Diffusivities of vacancy and Al atom in pure Mg were obtained from SLKMC simulations and are compared with values available in the literature that are obtained from experiments and first-principle calculations. Al Diffusivities obtained from SLKMC simulations are lower, due to larger activation barriers and lowermore » diffusivity prefactors, than those available in the literature but have same order of magnitude. We present all vacancy-Mg and vacancy-Al atom exchange processes and their activation barriers that were identified in SLKMC simulations. We will describe a simple mapping scheme to map a hcp lattice on to a simple cubic lattice that would enable hcp lattices to be simulated in an on-lattice KMC framework. We also present the pattern recognition scheme used in SLKMC simulations.« less

Multiscale modeling of transdermal drug delivery

NASA Astrophysics Data System (ADS)

Rim, Jee Eun

2006-04-01

This study addresses the modeling of transdermal diffusion of drugs, to better understand the permeation of molecules through the skin, and especially the stratum corneum, which forms the main permeation barrier of the skin. In transdermal delivery of systemic drugs, the drugs diffuse from a patch placed on the skin through the epidermis to the underlying blood vessels. The epidermis is the outermost layer of the skin and can be further divided into the stratum corneum (SC) and the viable epidermis layers. The SC consists of keratinous cells (corneocytes) embedded in the lipid multi-bilayers of the intercellular space. It is widely accepted that the barrier properties of the skin mostly arises from the ordered structure of the lipid bilayers. The diffusion path, at least for lipophilic molecules, seems to be mainly through the lipid bilayers. Despite the advantages of transdermal drug delivery compared to other drug delivery routes such as oral dosing and injections, the low percutaneous permeability of most compounds is a major difficulty in the wide application of transdermal drug delivery. In fact, many transdermal drug formulations include one or more permeation enhancers that increase the permeation of the drug significantly. During the last two decades, many researchers have studied percutaneous absorption of drugs both experimentally and theoretically. However, many are based on pharmacokinetic compartmental models, in which steady or pseudo-steady state conditions are assumed, with constant diffusivity and partitioning for single component systems. This study presents a framework for studying the multi-component diffusion of drugs coupled with enhancers through the skin by considering the microstructure of the stratum corneum (SC). A multiscale framework of modeling the transdermal diffusion of molecules is presented, by first calculating the microscopic diffusion coefficient in the lipid bilayers of the SC using molecular dynamics (MD). Then a homogenization procedure is performed over a model unit cell of the heterogeneous SC, resulting in effective diffusion parameters. These effective parameters are the macroscopic diffusion coefficients for the homogeneous medium that is "equivalent" to the heterogeneous SC, and thus can be used in finite element simulations of the macroscopic diffusion process.

Electronic Devices With Diffusion Barrier and Process for Making Same

DTIC Science & Technology

2000-05-03

components. Diffusion is also a problem with other high 10 conductivity metallization materials such as gold , silver, and platinum. As can be...those of subgroup IB of the Periodic Table (i.e., copper, silver, gold ), as well as platinum. These metals are highly attractive 10 for...the metal halide molecules of the desired thickness, is formed upon the monolayer portion of the barrier -7- material. The monolayer ( monoatomic

Principles of diffusion kurtosis imaging and its role in early diagnosis of neurodegenerative disorders.

PubMed

Arab, Anas; Wojna-Pelczar, Anna; Khairnar, Amit; Szabó, Nikoletta; Ruda-Kucerova, Jana

2018-05-01

Pathology of neurodegenerative diseases can be correlated with intra-neuronal as well as extracellular changes which lead to neuronal degeneration. The central nervous system (CNS) is a complex structure comprising of many biological barriers. These microstructural barriers might be affected by a variety of pathological processes. Specifically, changes in the brain tissue's microstructure affect the diffusion of water which can be assessed non-invasively by diffusion weighted (DW) magnetic resonance imaging (MRI) techniques. Diffusion tensor imaging (DTI) is a diffusion MRI technique that considers diffusivity as a Gaussian process, i.e. does not account for any diffusion hindrance. However, environment of the brain tissues is characterized by a non-Gaussian diffusion. Therefore, diffusion kurtosis imaging (DKI) was developed as an extension of DTI method in order to quantify the non-Gaussian distribution of water diffusion. This technique represents a promising approach for early diagnosis of neurodegenerative diseases when the neurodegenerative process starts. Hence, the purpose of this article is to summarize the ongoing clinical and preclinical research on Parkinson's, Alzheimer's and Huntington diseases, using DKI and to discuss the role of this technique as an early stage biomarker of neurodegenerative conditions. Copyright © 2018 Elsevier Inc. All rights reserved.

Giant Acceleration of Diffusion Observed in a Single-Molecule Experiment on F(1)-ATPase.

PubMed

Hayashi, Ryunosuke; Sasaki, Kazuo; Nakamura, Shuichi; Kudo, Seishi; Inoue, Yuichi; Noji, Hiroyuki; Hayashi, Kumiko

2015-06-19

The giant acceleration (GA) of diffusion is a universal phenomenon predicted by the theoretical analysis given by Reimann et al. [Phys. Rev. Lett. 87, 010602 (2001)]. Here we apply the theory of the GA of diffusion to a single-molecule experiment on a rotary motor protein, F(1), which is a component of F(o)F(1) adenosine triphosphate synthase. We discuss the energetic properties of F(1) and identify a high energy barrier of the rotary potential to be 20k(B)T, with the condition that the adenosine diphosphates are tightly bound to the F(1) catalytic sites. To conclude, the GA of diffusion is useful for measuring energy barriers in nonequilibrium and single-molecule experiments.

Giant Acceleration of Diffusion Observed in a Single-Molecule Experiment on F1-ATPase

NASA Astrophysics Data System (ADS)

Hayashi, Ryunosuke; Sasaki, Kazuo; Nakamura, Shuichi; Kudo, Seishi; Inoue, Yuichi; Noji, Hiroyuki; Hayashi, Kumiko

2015-06-01

The giant acceleration (GA) of diffusion is a universal phenomenon predicted by the theoretical analysis given by Reimann et al. [Phys. Rev. Lett. 87, 010602 (2001)]. Here we apply the theory of the GA of diffusion to a single-molecule experiment on a rotary motor protein, F1 , which is a component of Fo F1 adenosine triphosphate synthase. We discuss the energetic properties of F1 and identify a high energy barrier of the rotary potential to be 20 kBT , with the condition that the adenosine diphosphates are tightly bound to the F1 catalytic sites. To conclude, the GA of diffusion is useful for measuring energy barriers in nonequilibrium and single-molecule experiments.

Analysis of Molecular Movement Reveals Latticelike Obstructions to Diffusion in Heart Muscle Cells

PubMed Central

Illaste, Ardo; Laasmaa, Martin; Peterson, Pearu; Vendelin, Marko

2012-01-01

Intracellular diffusion in muscle cells is known to be restricted. Although characteristics and localization of these restrictions is yet to be elucidated, it has been established that ischemia-reperfusion injury reduces the overall diffusion restriction. Here we apply an extended version of raster image correlation spectroscopy to determine directional anisotropy and coefficients of diffusion in rat cardiomyocytes. Our experimental results indicate that diffusion of a smaller molecule (1127 MW fluorescently labeled ATTO633-ATP) is restricted more than that of a larger one (10,000 MW Alexa647-dextran), when comparing diffusion in cardiomyocytes to that in solution. We attempt to provide a resolution to this counterintuitive result by applying a quantitative stochastic model of diffusion. Modeling results suggest the presence of periodic intracellular barriers situated ∼1 μm apart having very low permeabilities and a small effect of molecular crowding in volumes between the barriers. Such intracellular structuring could restrict diffusion of molecules of energy metabolism, reactive oxygen species, and apoptotic signals, enacting a significant role in normally functioning cardiomyocytes as well as in pathological conditions of the heart. PMID:22385844

Fast diffusion of native defects and impurities in perovskite solar cell material CH 3NH 3PbI 3

DOE PAGES

Yang, Dongwen; Ming, Wenmei; Shi, Hongliang; ...

2016-06-01

CH 3NH 3PbI 3-based solar cells have shown remarkable progress in recent years but have also suffered from structural, electrical, and chemical instabilities related to the soft lattices and the chemistry of these halides. One of the instabilities is ion migration, which may cause current–voltage hysteresis in CH 3NH 3PbI 3 solar cells. Significant ion diffusion and ionic conductivity in CH 3NH 3PbI 3 have been reported; their nature, however, remain controversial. In the literature, the use of different experimental techniques leads to the observation of different diffusing ions (either iodine or CH 3NH 3 ion); the calculated diffusion barriersmore » for native defects scatter in a wide range; the calculated defect formation energies also differ qualitatively. These controversies hinder the understanding and the control of the ion migration in CH 3NH 3PbI 3. In this paper, we show density functional theory calculations of both the diffusion barriers and the formation energies for native defects (V I +, MA i +, V MA –, and I i –) and the Au impurity in CH 3NH 3PbI 3. V I + is found to be the dominant diffusing defect due to its low formation energy and the low diffusion barrier. I i – and MA i + also have low diffusion barriers but their formation energies are relatively high. The hopping rate of V I + is further calculated taking into account the contribution of the vibrational entropy, confirming V I + as a fast diffuser. We discuss approaches for managing defect population and migration and suggest that chemically modifying surfaces, interfaces, and grain boundaries may be effective in controlling the population of the iodine vacancy and the device polarization. We further show that the formation energy and the diffusion barrier of Au interstitial in CH 3NH 3PbI 3 are both low. As a result, it is thus possible that Au can diffuse into CH3NH3PbI3 under bias in devices (e.g., solar cell, photodetector) with Au/CH 3NH 3PbI 3 interfaces and modify the electronic properties of CH 3NH 3PbI 3.« less

Fast diffusion of native defects and impurities in perovskite solar cell material CH 3NH 3PbI 3

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

Yang, Dongwen; Ming, Wenmei; Shi, Hongliang

CH 3NH 3PbI 3-based solar cells have shown remarkable progress in recent years but have also suffered from structural, electrical, and chemical instabilities related to the soft lattices and the chemistry of these halides. One of the instabilities is ion migration, which may cause current–voltage hysteresis in CH 3NH 3PbI 3 solar cells. Significant ion diffusion and ionic conductivity in CH 3NH 3PbI 3 have been reported; their nature, however, remain controversial. In the literature, the use of different experimental techniques leads to the observation of different diffusing ions (either iodine or CH 3NH 3 ion); the calculated diffusion barriersmore » for native defects scatter in a wide range; the calculated defect formation energies also differ qualitatively. These controversies hinder the understanding and the control of the ion migration in CH 3NH 3PbI 3. In this paper, we show density functional theory calculations of both the diffusion barriers and the formation energies for native defects (V I +, MA i +, V MA –, and I i –) and the Au impurity in CH 3NH 3PbI 3. V I + is found to be the dominant diffusing defect due to its low formation energy and the low diffusion barrier. I i – and MA i + also have low diffusion barriers but their formation energies are relatively high. The hopping rate of V I + is further calculated taking into account the contribution of the vibrational entropy, confirming V I + as a fast diffuser. We discuss approaches for managing defect population and migration and suggest that chemically modifying surfaces, interfaces, and grain boundaries may be effective in controlling the population of the iodine vacancy and the device polarization. We further show that the formation energy and the diffusion barrier of Au interstitial in CH 3NH 3PbI 3 are both low. As a result, it is thus possible that Au can diffuse into CH3NH3PbI3 under bias in devices (e.g., solar cell, photodetector) with Au/CH 3NH 3PbI 3 interfaces and modify the electronic properties of CH 3NH 3PbI 3.« less

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon

PubMed Central

2015-01-01

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO2 and CH4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO2 and CH4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2–3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH4 in the nanostructure of SiC-DC. PMID:24932319

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon.

PubMed

Farmahini, Amir H; Shahtalebi, Ali; Jobic, Hervé; Bhatia, Suresh K

2014-06-05

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO 2 and CH 4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO 2 and CH 4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2-3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH 4 in the nanostructure of SiC-DC.

Thin film encapsulation for flexible AM-OLED: a review

NASA Astrophysics Data System (ADS)

Park, Jin-Seong; Chae, Heeyeop; Chung, Ho Kyoon; In Lee, Sang

2011-03-01

Flexible organic light emitting diode (OLED) will be the ultimate display technology to customers and industries in the near future but the challenges are still being unveiled one by one. Thin-film encapsulation (TFE) technology is the most demanding requirement to prevent water and oxygen permeation into flexible OLED devices. As a polymer substrate does not offer the same barrier performance as glass, the TFE should be developed on both the bottom and top side of the device layers for sufficient lifetimes. This work provides a review of promising thin-film barrier technologies as well as the basic gas diffusion background. Topics include the significance of the device structure, permeation rate measurement, proposed permeation mechanism, and thin-film deposition technologies (Vitex system and atomic layer deposition (ALD)/molecular layer deposition (MLD)) for effective barrier films.

Y0.08Sr0.88TiO3-CeO2 composite as a diffusion barrier layer for stainless-steel supported solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kim, Kun Joong; Kim, Sun Jae; Choi, Gyeong Man

2016-03-01

A new diffusion barrier layer (DBL) is proposed for solid oxide fuel cells (SOFCs) supported on stainless-steel where DBL prevents inter-diffusion of atoms between anode and stainless steel (STS) support during fabrication and operation of STS-supported SOFCs. Half cells consisting of dense yttria-stabilized zirconia (YSZ) electrolyte, porous Ni-YSZ anode layer, and ferritic STS support, with or without Y0.08Sr0.88TiO3-CeO2 (YST-CeO2) composite DBL, are prepared by tape casting and co-firing at 1250 and 1350 °C, respectively, in reducing (H2) atmosphere. The porous YST-CeO2 layer (t ∼ 60 μm) blocks inter-diffusion of Fe and Ni, and captures the evaporated Cr during cell fabrication (1350 °C). The cell with DBL and La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode achieved a maximum power density of ∼220 mW cm-2 which is stable at 700 °C. In order to further improve the power performance, Ni coarsening in anode during co-firing must be prevented or alternative anode which is resistive to coarsening is suggested. This study demonstrates that the new YST-CeO2 layer is a promising as a DBL for stainless-steel-supported SOFCs fabricated with co-firing process.

Efficacy of Tantalum Tungsten Alloys for Diffusion Barrier Applications

NASA Astrophysics Data System (ADS)

Smathers, D. B.; Aimone, P. R.

2017-12-01

Traditionally either Niobium, Tantalum or a combination of both have been used as diffusion barriers in Nb3Sn Multi-filament wire. Vanadium has also been used successfully but the ultimate RRR of the copper is limited unless an external shell of Niobium is included. Niobium is preferred over Tantalum when alternating current losses are not an issue as the Niobium will react to form Nb3Sn. Pure Tantalum tends to deform irregularly requiring extra starting thickness to ensure good barrier qualities. Our evaluations showed Tantalum lightly alloyed with 3 wt% Tungsten is compatible with the wire drawing process while deforming as well as or better than pure Niobium. Ta3wt%W has been processed as a single barrier and as a distributed barrier to fine dimensions. In addition, the higher modulus and strength of the Tantalum Tungsten alloy improves the overall tensile properties of the wire.

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.

Superconducting MgB2 wires with vanadium diffusion barrier

NASA Astrophysics Data System (ADS)

Hušek, I.; Kováč, P.; Melišek, T.; Kulich, M.; Rosová, A.; Kopera, L.; Szundiová, B.

2017-10-01

Single-core MgB2 wires with a vanadium barrier and Cu stabilization have been made by the in situ powder-in-tube (PIT) and internal magnesium diffusion (IMD) into boron processes. Heat treatment of PIT wires was done at the temperature range of 650 °C-850 °C/30 min. Critical currents of differently treated MgB2/V/Cu wires have been measured and related with the structure of MgB2. It was found that critical current density of MgB2/V wire annealed above 700 °C decreases rapidly. The obtained results clearly show that vanadium is a well formable metal and can be applied as an effective diffusion barrier for MgB2 wires heat-treated at temperatures ≤700 °C. This temperature limit is well applicable for MgB2 wires with high current densities made by PIT and also by the IMD process.

Diffusion of pain management research into nursing practice.

PubMed

Dooks, P

2001-04-01

The promotion of evidence based practice is a challenge within nursing. Pain management is a prime example of this practice research gap. There is solid evidence for 20 years to promote positive change in our methods of pain management, yet outdated approaches are still amazingly evident. Even among oncology nurses, who place a high value on promoting patient comfort, there is a lack of evidence-based pain management. Rogers' Diffusion of Innovation Theory provides an interesting framework for examining the issues and possible solutions to this complex problem. Rogers' theory examines how changes diffuse through a social system over time and also exposes some of the barriers and facilitators to this process. The theory looks at adopters, the nature of the innovation, the social system, and communication patterns. Identifying the barriers of the past will help nursing to overcome these same barriers and increase the adoption of evidence-based pain management approaches in the future.

Application of diffusion barriers to the refractory fibers of tungsten, columbium, carbon and aluminum oxide

NASA Technical Reports Server (NTRS)

Douglas, F. C.; Paradis, E. L.; Veltri, R. D.

1973-01-01

A radio frequency powered ion-plating system was used to plate protective layers of refractory oxides and carbide onto high strength fiber substrates. Subsequent overplating of these combinations with nickel and titanium was made to determine the effectiveness of such barrier layers in preventing diffusion of the overcoat metal into the fibers with consequent loss of fiber strength. Four substrates, five coatings, and two metal matrix materials were employed for a total of forty material combinations. The substrates were tungsten, niobium, NASA-Hough carbon, and Tyco sapphire. The diffusion-barrier coatings were aluminum oxide, yttrium oxide, titanium carbide, tungsten carbide with 14% cobalt addition, and zirconium carbide. The metal matrix materials were IN 600 nickel and Ti 6/4 titanium. Adhesion of the coatings to all substrates was good except for the NASA-Hough carbon, where flaking off of the oxide coatings in particular was observed.

Hydrogenated amorphous carbon coatings on implants drastically reduce biofilm formation and water permeation

NASA Astrophysics Data System (ADS)

Bernsmann, Falk; Laube, Norbert; Baldsiefen, Gerhard; Castellucci, Mattia

2014-11-01

Inflammations and crystalline bacterial biofilms (encrustations) remain a major complication in long-term artificial urinary tract drainage. To solve this problem we present urological implants with coatings made of amorphous hydrogenated carbon (a-C:H) that show excellent protection from encrustation in-vitro as well as in-vivo. Part of the success of a-C:H coatings is attributed to their ability to act as a diffusion barrier between an implant and the body, which prevents leaching of solvents from polymeric implants. To further enhance their barrier properties a-C:H coatings are combined with parylene coatings to develop diffusion-barrier multilayer coatings with a total thickness between 0.2 μm and 0.8 μm. The combination of the two types of coatings leads to a reduction of water diffusion by a factor of up to ten with respect to uncoated 25 μm thick polyimide sub-strates. The diffusion of water vapour from a controlled atmospheric pressure chamber through coated foils to a vacuum chamber is measured in a custom-built device.

Blocking germanium diffusion inside silicon dioxide using a co-implanted silicon barrier

NASA Astrophysics Data System (ADS)

Barba, D.; Wang, C.; Nélis, A.; Terwagne, G.; Rosei, F.

2018-04-01

We investigate the effect of co-implanting a silicon sublayer on the thermal diffusion of germanium ions implanted into SiO2 and the growth of Ge nanocrystals (Ge-ncs). High-resolution imaging obtained by transmission electron microscopy and energy dispersive spectroscopy measurements supported by Monte-Carlo calculations shows that the Si-enriched region acts as a diffusion barrier for Ge atoms. This barrier prevents Ge outgassing during thermal annealing at 1100 °C. Both the localization and the reduced size of Ge-ncs formed within the sample region co-implanted with Si are observed, as well as the nucleation of mixed Ge/Si nanocrystals containing structural point defects and stacking faults. Although it was found that the Si co-implantation affects the crystallinity of the formed Ge-ncs, this technique can be implemented to produce size-selective and depth-ordered nanostructured systems by controlling the spatial distribution of diffusing Ge. We illustrate this feature for Ge-ncs embedded within a single SiO2 monolayer, whose diameters were gradually increased from 1 nm to 5 nm over a depth of 100 nm.

Global diffusive fluxes of methane in marine sediments

NASA Astrophysics Data System (ADS)

Egger, Matthias; Riedinger, Natascha; Mogollón, José M.; Jørgensen, Bo Barker

2018-06-01

Anaerobic oxidation of methane provides a globally important, yet poorly constrained barrier for the vast amounts of methane produced in the subseafloor. Here we provide a global map and budget of the methane flux and degradation in diffusion-controlled marine sediments in relation to the depth of the methane oxidation barrier. Our new budget suggests that 45-61 Tg of methane are oxidized with sulfate annually, with approximately 80% of this oxidation occurring in continental shelf sediments (<200 m water depth). Using anaerobic oxidation as a nearly quantitative sink for methane in steady-state diffusive sediments, we calculate that 3-4% of the global organic carbon flux to the seafloor is converted to methane. We further report a global imbalance of diffusive methane and sulfate fluxes into the sulfate-methane transition with no clear trend with respect to the corresponding depth of the methane oxidation barrier. The observed global mean net flux ratio between sulfate and methane of 1.4:1 indicates that, on average, the methane flux to the sulfate-methane transition accounts for only 70% of the sulfate consumption in the sulfate-methane transition zone of marine sediments.

Ultrathin Cr added Ru film as a seedless Cu diffusion barrier for advanced Cu interconnects

NASA Astrophysics Data System (ADS)

Hsu, Kuo-Chung; Perng, Dung-Ching; Yeh, Jia-Bin; Wang, Yi-Chun

2012-07-01

A 5 nm thick Cr added Ru film has been extensively investigated as a seedless Cu diffusion barrier. High-resolution transmission electron microscopy micrograph, X-ray diffraction (XRD) pattern and Fourier transform-electron diffraction pattern reveal that a Cr contained Ru (RuCr) film has a glassy microstructure and is an amorphous-like film. XRD patterns and sheet resistance data show that the RuCr film is stable up to 650 °C, which is approximately a 200 °C improvement in thermal stability as compared to that of the pure Ru film. X-ray photoelectron spectroscopy depth profiles show that the RuCr film can successfully block Cu diffusion, even after a 30-min 650 °C annealing. The leakage current of the Cu/5 nm RuCr/porous SiOCH/Si stacked structure is about two orders of magnitude lower than that of a pristine Ru sample for electric field below 1 MV/cm. The RuCr film can be a promising Cu diffusion barrier for advanced Cu metallization.

Diffusion of gas mixtures in the sI hydrate structure

NASA Astrophysics Data System (ADS)

Waage, Magnus H.; Trinh, Thuat T.; van Erp, Titus S.

2018-06-01

Replacing methane with carbon dioxide in gas hydrates has been suggested as a way of harvesting methane, while at the same time storing carbon dioxide. Experimental evidence suggests that this process is facilitated if gas mixtures are used instead of pure carbon dioxide. We studied the free energy barriers for diffusion of methane, carbon dioxide, nitrogen, and hydrogen in the sI hydrate structure using molecular simulation techniques. Cage hops between neighboring cages were considered with and without a water vacancy and with a potential inclusion of an additional gas molecule in either the initial or final cage. Our results give little evidence for enhanced methane and carbon dioxide diffusion if nitrogen is present as well. However, the inclusion of hydrogen seems to have a substantial effect as it diffuses rapidly and can easily enter occupied cages, which reduces the barriers of diffusion for the gas molecules that co-occupy a cage with hydrogen.

Tin Oxide Crystals Exposed by Low-Energy {110} Facets for Enhanced Electrochemical Heavy Metal Ions Sensing: X-ray Absorption Fine Structure Experimental Combined with Density-Functional Theory Evidence.

PubMed

Jin, Zhen; Yang, Meng; Chen, Shao-Hua; Liu, Jin-Huai; Li, Qun-Xiang; Huang, Xing-Jiu

2017-02-21

Herein, we revealed that the electrochemical behaviors on the detection of heavy metal ions (HMIs) would largely rely on the exposed facets of SnO 2 nanoparticles. Compared to the high-energy {221} facet, the low-energy {110} facet of SnO 2 possessed better electrochemical performance. The adsorption/desorption tests, density-functional theory (DFT) calculations, and X-ray absorption fine structure (XAFS) studies showed that the lower barrier energy of surface diffusion on {110} facet was critical for the superior electrochemical property, which was favorable for the ions diffusion on the electrode, and further leading the enhanced electrochemical performance. Through the combination of experiments and theoretical calculations, a reliable interpretation of the mechanism for electroanalysis of HMIs with nanomaterials exposed by different crystal facets has been provided. Furthermore, it provides a deep insight into understanding the key factor to improve the electrochemical performance for HMIs detection, so as to design high-performance electrochemical sensors.

Stability diagrams for the surface patterns of GaN(0001bar) as a function of Schwoebel barrier height

NASA Astrophysics Data System (ADS)

Krzyżewski, Filip; Załuska-Kotur, Magdalena A.

2017-01-01

Height and type of Schwoebel barriers (direct or inverse) decides about the character of the surface instability. Different surface morphologies are presented. Step bunches, double steps, meanders, mounds and irregular patterns emerge at the surface as a result of step (Schwoebel) barriers at some temperature or miscut values. The study was carried out on the two-component kinetic Monte Carlo (kMC) model of GaN(0001bar) surface grown in nitrogen rich conditions. Diffusion of gallium adatoms over N-polar surface is slow and nitrogen adatoms are almost immobile. We show that in such conditions surfaces remain smooth when gallium adatoms diffuse in the presence of low inverse Schwoebel barrier. It is illustrated by adequate stability diagrams for surface morphologies.

Barriers to the free diffusion of proteins and lipids in the plasma membrane

PubMed Central

Trimble, William S.

2015-01-01

Biological membranes segregate into specialized functional domains of distinct composition, which can persist for the entire life of the cell. How separation of their lipid and (glyco)protein components is generated and maintained is not well understood, but the existence of diffusional barriers has been proposed. Remarkably, the physical nature of such barriers and the manner whereby they impede the free diffusion of molecules in the plane of the membrane has rarely been studied in depth. Moreover, alternative mechanisms capable of generating membrane inhomogeneity are often disregarded. Here we describe prototypical biological systems where membrane segregation has been amply documented and discuss the role of diffusional barriers and other processes in the generation and maintenance of their structural and functional compartmentalization. PMID:25646084

Barriers to the free diffusion of proteins and lipids in the plasma membrane.

PubMed

Trimble, William S; Grinstein, Sergio

2015-02-02

Biological membranes segregate into specialized functional domains of distinct composition, which can persist for the entire life of the cell. How separation of their lipid and (glyco)protein components is generated and maintained is not well understood, but the existence of diffusional barriers has been proposed. Remarkably, the physical nature of such barriers and the manner whereby they impede the free diffusion of molecules in the plane of the membrane has rarely been studied in depth. Moreover, alternative mechanisms capable of generating membrane inhomogeneity are often disregarded. Here we describe prototypical biological systems where membrane segregation has been amply documented and discuss the role of diffusional barriers and other processes in the generation and maintenance of their structural and functional compartmentalization. © 2015 Trimble and Grinstein.

HCO3(-) formation from CO2 at high pH: ab initio molecular dynamics study.

PubMed

Stirling, András

2011-12-15

Ab initio molecular dynamics simulations have been performed to study the dissolution of CO2 in water at high pH. The CO2 + OH(-) --> HCO3(-) forward and the HCO3(-) --> CO2 + OH(-) reverse paths have been simulated by employing the metadynamics technics. We have found that the free energy barrier along the forward direction is predominantly hydration related and significantly entropic in origin, whereas the backward barrier is primarily enthalpic. The main motifs in the forward mechanism are the structural diffusion of the hydroxyl ion to the first hydration sphere of CO2, its desolvation, and the C-O bond formation in concert with the CO2 bending within the hydrate cavity. In the reverse reaction, the origin of the barrier is the rupture of the strong C-O(H) bond. The present findings support the notion that the free energy barrier of the bicarbonate formation is strongly solvation related but provide also additional mechanistic details at the molecular level.

Pulsed laser diffusion of thin hole-barrier contacts in high purity germanium for gamma radiation detectors

NASA Astrophysics Data System (ADS)

Maggioni, G.; Carturan, S.; Raniero, W.; Riccetto, S.; Sgarbossa, F.; Boldrini, V.; Milazzo, R.; Napoli, D. R.; Scarpa, D.; Andrighetto, A.; Napolitani, E.; De Salvador, D.

2018-03-01

A new method for the formation of hole-barrier contacts in high purity germanium (HPGe) is described, which consists in the sputter deposition of a Sb film on HPGe, followed by Sb diffusion produced through laser annealing of the Ge surface in the melting regime. This process gives rise to a very thin ( ≤ 100 nm) n-doped layer, as determined by SIMS measurement, while preserving the defect-free morphology of HPGe surface. A small prototype of gamma ray detector with a Sb laser-diffused contact was produced and characterized, showing low leakage currents and good spectroscopy data with different gamma ray sources.

Proton and hydrogen transport through two-dimensional monolayers

NASA Astrophysics Data System (ADS)

Seel, Max; Pandey, Ravindra

2016-06-01

Diffusion of protons and hydrogen atoms in representative two-dimensional materials is investigated. Specifically, density functional calculations were performed on graphene, hexagonal boron nitride (h-BN), phosphorene, silicene, and molybdenum disulfide (MoS2) monolayers to study the surface interaction and penetration barriers for protons and hydrogen atoms employing finite cluster models. The calculated barrier heights correlate approximately with the size of the opening formed by the three-fold open sites in the monolayers considered. They range from 1.56 eV (proton) and 4.61 eV (H) for graphene to 0.12 eV (proton) and 0.20 eV (H) for silicene. The results indicate that only graphene and h-BN monolayers have the potential for membranes with high selective permeability. The MoS2 monolayer behaves differently: protons and H atoms become trapped between the outer S layers in the Mo plane in a well with a depth of 1.56 eV (proton) and 1.5 eV (H atom), possibly explaining why no proton transport was detected, suggesting MoS2 as a hydrogen storage material instead. For graphene and h-BN, off-center proton penetration reduces the barrier to 1.38 eV for graphene and 0.11 eV for h-BN. Furthermore, Pt acting as a substrate was found to have a negligible effect on the barrier height. In defective graphene, the smallest barrier for proton diffusion (1.05 eV) is found for an oxygen-terminated defect. Therefore, it seems more likely that thermal protons can penetrate a monolayer of h-BN but not graphene and defects are necessary to facilitate the proton transport in graphene.

Effect of Defects on III-V MWIR nBn Detector Performance

DTIC Science & Technology

2014-08-01

SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS (ES) U.S. Army Research Office P.O. Box 12211 Research Triangle Park, NC 27709-2211 infrared detectors ...rather than diffusion based processes. Keywords: infrared detectors , MWIR, nBn, photodiode, defects, irradiation, lattice mismatch, dark current...currents will increase noise in the detector , it is important to understand the impact elevated defect concentrations will have on barrier architecture

Electronic Devices with Strontium Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

structure of the barrier film on an atomic level where the barrier film is comprised of a plurality of contiguous monolayers, while FIG. 7B shows another...another embodiment where the barrier film is comprised of a plurality of contiguous monolayers in which different monolayers thereof are formed of...High Energy Electron 10 Diffraction (RHEED) diagnostic system directed toward the substrate 26. A diffusion barrier precursor compound effusion

Electronic Devices with Composite Atomic Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

structure of the barrier film on an atomic level where the barrier film is comprised of a plurality of contiguous monolayers, while FIG. 7B shows...another embodiment where the barrier film is comprised of a plurality of contiguous monolayers in which different monolayers thereof are formed of...High Energy Electron 10 Diffraction (RHEED) diagnostic system directed toward the substrate 26. A diffusion barrier precursor compound effusion

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

DOE PAGES

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

2016-04-08

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

Permeability and kinetic coefficients for mesoscale BCF surface step dynamics: Discrete two-dimensional deposition-diffusion equation analysis

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

Zhao, Renjie; Evans, James W.; Oliveira, Tiago J.

Here, a discrete version of deposition-diffusion equations appropriate for description of step flow on a vicinal surface is analyzed for a two-dimensional grid of adsorption sites representing the stepped surface and explicitly incorporating kinks along the step edges. Model energetics and kinetics appropriately account for binding of adatoms at steps and kinks, distinct terrace and edge diffusion rates, and possible additional barriers for attachment to steps. Analysis of adatom attachment fluxes as well as limiting values of adatom densities at step edges for nonuniform deposition scenarios allows determination of both permeability and kinetic coefficients. Behavior of these quantities is assessedmore » as a function of key system parameters including kink density, step attachment barriers, and the step edge diffusion rate.« less

Diffusion of Radionuclides in Concrete and Soil

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

Mattigod, Shas V.; Wellman, Dawn M.; Bovaird, Chase C.

2012-04-25

One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Such concrete encasement would contain and isolate the waste packages from the hydrologic environment and would act as an intrusion barrier. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion and move into the surrounding subsurface environment. Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability ofmore » the surrounding soil to retard radionuclide migration. The objective of our study was to measure the diffusivity of Re, Tc and I in concrete containment and the surrounding vadose zone soil. Effects of carbonation, presence of metallic iron, and fracturing of concrete and the varying moisture contents in soil on the diffusivities of Tc and I were evaluated.« less

Formation of Cr2O3 Diffusion Barrier Between Cr-Contained Stainless Steel and Cold-Sprayed Ni Coatings at High Temperature

NASA Astrophysics Data System (ADS)

Xu, Ya-Xin; Luo, Xiao-Tao; Li, Cheng-Xin; Yang, Guan-Jun; Li, Chang-Jiu

2016-02-01

A novel approach to prepare a coating system containing an in situ grown Cr2O3 diffusion barrier between a nickel top layer and 310SS was reported. Cold spraying was employed to deposit Ni(O) interlayer and top nickel coating on the Cr-contained stainless steel substrate. Ni(O) feedstock was prepared by mechanical alloying of pure nickel powders in ambient atmosphere, acting as an oxygen provider. The post-spray annealing was adopted to grow in situ Cr2O3 layer between the substrate and nickel coating. The results revealed that the diffusible oxygen can be introduced into nickel powders by mechanical alloying. The oxygen content increases to 3.25 wt.% with the increase of the ball milling duration to 8 h, while Ni(O) powders maintain a single phase of Ni. By annealing the sample in Ar atmosphere at 900 °C, a continuous Cr2O3 layer of 1-2 μm thick at the interface between 310SS and cold-sprayed Ni coating is formed. The diffusion barrier effect evaluation by thermal exposure at 750 °C shows that the Cr2O3 oxide layer effectively suppresses the outward diffusion of Fe and Cr in the substrate effectively.

Reactivity and oxygen diffusion property of resistive barriers for Bi-2223/Ag tapes

NASA Astrophysics Data System (ADS)

Kováč, P.; Hušek, I.

2002-12-01

Reactivity of several oxide materials (OM) with BSCCO powder and oxygen diffusion through OM layer has been tested at temperature ≈840 °C in air. The OM (e.g.: BaZrO 3, SrCO 3, MgO and ZrO 2) showing the low or no reactivity with BSCCO have been mixed (10 wt.%) with precursor powder and used for single-core tapes. Bi-2223/Ag/OM/Ag single-core tapes with oxide barriers made of BaZrO 3, SrCO 3, ZrO 2 and Al 2O 3 have been also prepared by a standard powder-in-tube technique. The used OM in the direct contact with BSCCO influences the electrical properties of Bi-2223 phase differently. These is because the oxides react with BSCCO during the heat treatment and simultaneously affect the 2212→2223 phase transformation, the Bi-2223 grain growth and so also grain connectivity. SrCO 3 powder has been evaluated as the best material from the point of no destructive effect on 2223 phase transport current property. The oxide barrier controls the oxygen diffusion during the tape heat treatment and simultaneously the HTS phase formation kinetics, its purity and content within the superconducting core. For single-core Bi-2223/Ag/OM/Ag tapes, the highest current density was measured for Al 2O 3 due to only slightly reduced oxygen diffusion through the barrier.

Materials science and integration bases for fabrication of (BaxSr1-x)TiO3 thin film capacitors with layered Cu-based electrodes

NASA Astrophysics Data System (ADS)

Fan, W.; Kabius, B.; Hiller, J. M.; Saha, S.; Carlisle, J. A.; Auciello, O.; Chang, R. P. H.; Ramesh, R.

2003-11-01

The synthesis and fundamental material properties of layered TiAl/Cu/Ta electrodes were investigated to achieve the integration of Cu electrodes with high-dielectric constant (κ) oxide thin films for application to the fabrication of high-frequency devices. The Ta layer is an excellent diffusion barrier to inhibit deleterious Cu diffusion into the Si substrate, while the TiAl layer provides an excellent barrier against oxygen diffusion into the Cu layer to inhibit Cu oxidation during the growth of the high-κ layer in an oxygen atmosphere. Polycrystalline (BaxSr1-x)TiO3 (BST) thin films were grown on the Cu-based bottom electrode by rf magnetron sputtering at temperatures in the range 400-600 °C in oxygen, to investigate the performance of BST/Cu-based capacitors. Characterization of the Cu-based layered structure using surface analytical methods showed that two amorphous oxide layers were formed on both sides of the TiAl barrier, such that the oxide layer on the free surface of the TiAl layer correlates with TiAlOx, while the oxide layer at the TiAl/Cu interface is an Al2O3-rich layer. This double amorphous barrier layer structure effectively prevents oxygen penetration towards the underlying Cu and Ta layers. The TiAlOx interfacial layer, which has a relatively low dielectric constant compared with BST, reduced the total capacitance of the BST thin film capacitors. In addition, the layered electrode-oxide interface roughening observed during the growth of BST films at high temperature, due to copper grain growth, resulted in large dielectric loss on the fabricated BST capacitors. These problems were solved by growing the BST layer at 450 °C followed by a rapid thermal annealing at 700 °C. This process significantly reduced the thickness of the TiAlOx layer and interface roughness resulting in BST capacitors exhibiting properties suitable for the fabrication of high-performance high-frequency devices. In summary, relatively high dielectric constant (280), low dielectric loss (0.007), and low leakage current (<2×10-8 A/cm2 at 100 kV/cm) were achieved for BST thin film capacitors with Cu-based electrodes.

Analysis of molecular movement reveals latticelike obstructions to diffusion in heart muscle cells.

PubMed

Illaste, Ardo; Laasmaa, Martin; Peterson, Pearu; Vendelin, Marko

2012-02-22

Intracellular diffusion in muscle cells is known to be restricted. Although characteristics and localization of these restrictions is yet to be elucidated, it has been established that ischemia-reperfusion injury reduces the overall diffusion restriction. Here we apply an extended version of raster image correlation spectroscopy to determine directional anisotropy and coefficients of diffusion in rat cardiomyocytes. Our experimental results indicate that diffusion of a smaller molecule (1127 MW fluorescently labeled ATTO633-ATP) is restricted more than that of a larger one (10,000 MW Alexa647-dextran), when comparing diffusion in cardiomyocytes to that in solution. We attempt to provide a resolution to this counterintuitive result by applying a quantitative stochastic model of diffusion. Modeling results suggest the presence of periodic intracellular barriers situated ∼1 μm apart having very low permeabilities and a small effect of molecular crowding in volumes between the barriers. Such intracellular structuring could restrict diffusion of molecules of energy metabolism, reactive oxygen species, and apoptotic signals, enacting a significant role in normally functioning cardiomyocytes as well as in pathological conditions of the heart. Copyright © 2012 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Method of manufacturing lightweight thermo-barrier material

NASA Technical Reports Server (NTRS)

Blair, Winford (Inventor)

1987-01-01

A method of manufacturing thermal barrier structures comprising at least three dimpled cores separated by flat plate material with the outer surface of the flat plate material joined together by diffusion bonding.

Changes of composition and microstructure of joint interface of tungsten coated carbon by high heat flux

NASA Astrophysics Data System (ADS)

Tokunaga, K.; Matsubara, T.; Miyamoto, Y.; Takao, Y.; Yoshida, N.; Noda, N.; Kubota, Y.; Sogabe, T.; Kato, T.; Plöchl, L.

2000-12-01

Tungsten coatings of 0.5 and 1 mm thickness were successfully deposited by the vacuum plasma spraying (VPS) technique on carbon/carbon fiber composite (CFC), CX-2002U and isotropic fine grained graphite, IG-430U. High heat flux experiments by irradiation of electron beam with uniform profile were performed on the coated samples in order to prove the suitability and load limit of such coating materials. The cross-sectional composition and structure of the interface of VPS-W and carbon material samples were investigated. Compositional analyses showed that the Re/W multi-layer acts as diffusion barrier for carbon and suppresses tungsten carbide formation in the VPS-W layer at high temperature about 1300°C. Microstructure of the joint interface of the sample changed in the case of a peak temperature of about 2800°C. The multi-layer structure completely disappeared and compositional distribution was almost uniform in the interface of the sample after melting and resolidification. The diffusion barrier for carbon is not expected to act in this stage.

Analysis of Al diffusion processes in TiN barrier layers for the application in silicon solar cell metallization

NASA Astrophysics Data System (ADS)

Kumm, J.; Samadi, H.; Chacko, R. V.; Hartmann, P.; Wolf, A.

2016-07-01

An evaporated Al layer is known as an excellent rear metallization for highly efficient solar cells, but suffers from incompatibility with a common solder process. To enable solar cell-interconnection and module integration, in this work the Al layer is complemented with a solder stack of TiN/Ti/Ag or TiN/NiV/Ag, in which the TiN layer acts as an Al diffusion barrier. X-ray photoelectron spectroscopy measurements prove that diffusion of Al through the stack and the formation of an Al2O3 layer on the stack's surface are responsible for a loss of solderability after a strong post-metallization anneal, which is often mandatory to improve contact resistance and passivation quality. An optimization of the reactive TiN sputter process results in a densification of the TiN layer, which improves its barrier quality against Al diffusion. However, measurements with X-ray diffraction and scanning electron microscopy show that small grains with vertical grain boundaries persist, which still offer fast diffusion paths. Therefore, the concept of stuffing is introduced. By incorporating oxygen into the grain boundaries of the sputtered TiN layer, Al diffusion is strongly reduced as confirmed by secondary ion mass spectroscopy profiles. A quantitative analysis reveals a one order of magnitude lower Al diffusion coefficient for stuffed TiN layers. This metallization system maintains its solderability even after strong post-metallization annealing at 425 °C for 15 min. This paper thus presents an industrially feasible, conventionally solderable, and long-term stable metallization scheme for highly efficient silicon solar cells.

Acrosome reaction inducers impose alterations in repulsive strain and hydration barrier in human sperm membranes.

PubMed

Purohit, S B; Laloraya, M; Kumar, G P

1998-06-01

Spin labeling studies of the lipophilic domains of human spermatozoa during capacitation and during acrosome reaction (AR) under the influence of selected AR-inducers were performed. Significantly enhanced rotational function of molecules was obvious during capacitation, with no significant changes in membrane packaging or the lateral diffusion of molecules. The AR inducers appeared to restrict the rotational freedom of molecules, dramatically enhancing the lateral diffusion and ordering coefficients. A significant decrease in superoxide anion generation was observed in the acrosome reacted groups when compared to the non-acrosome reacted groups. A high level of superoxide anion radical (O2.-) level maintained in capacitated spermatozoa would add to the Van der Waal's repulsive forces at the polar head of phospholipids, holding the membrane in strain where the molecular enjoy little freedom for lateral motion. A sudden drop in the levels of O2.- in spermatozoa upon addition of AR inducers could abruptly release the local hydrophobic repulsive strain within the membrane. This loss of hydration barrier explains the observed enhancement in lateral diffusion profiles of lipids and the packaging of molecules. It is reasonable to assume that these phenomena could be amplified further by interplay of Ca2+ by modifying the local charge aggregation. Thus, we would conclude that AR inducers release the oxyradical load in capacitated spermatozoa, which would modify the repulsive strain and hydration barrier forces in the lipophilic domains permitting vesiculation of the membranes. It appears that various acrosome reaction inducers act as effectors of grossly similar physical alterations in sperm membranes and that the resulting signal cascades proceed through intercalating biochemical sequences.

Integrity of normal-appearing white matter: Influence of age, visible lesion burden and hypertension in patients with small-vessel disease.

PubMed

Muñoz Maniega, Susana; Chappell, Francesca M; Valdés Hernández, Maria C; Armitage, Paul A; Makin, Stephen D; Heye, Anna K; Thrippleton, Michael J; Sakka, Eleni; Shuler, Kirsten; Dennis, Martin S; Wardlaw, Joanna M

2017-02-01

White matter hyperintensities accumulate with age and occur in patients with stroke, but their pathogenesis is poorly understood. We measured multiple magnetic resonance imaging biomarkers of tissue integrity in normal-appearing white matter and white matter hyperintensities in patients with mild stroke, to improve understanding of white matter hyperintensities origins. We classified white matter into white matter hyperintensities and normal-appearing white matter and measured fractional anisotropy, mean diffusivity, water content (T1-relaxation time) and blood-brain barrier leakage (signal enhancement slope from dynamic contrast-enhanced magnetic resonance imaging). We studied the effects of age, white matter hyperintensities burden (Fazekas score) and vascular risk factors on each biomarker, in normal-appearing white matter and white matter hyperintensities, and performed receiver-operator characteristic curve analysis. Amongst 204 patients (34.3-90.9 years), all biomarkers differed between normal-appearing white matter and white matter hyperintensities ( P < 0.001). In normal-appearing white matter and white matter hyperintensities, mean diffusivity and T1 increased with age ( P < 0.001), all biomarkers varied with white matter hyperintensities burden ( P < 0.001; P = 0.02 signal enhancement slope), but only signal enhancement slope increased with hypertension ( P = 0.028). Fractional anisotropy showed complex age-white matter hyperintensities-tissue interactions; enhancement slope showed white matter hyperintensities-tissue interactions. Mean diffusivity distinguished white matter hyperintensities from normal-appearing white matter best at all ages. Blood-brain barrier leakage increases with hypertension and white matter hyperintensities burden at all ages in normal-appearing white matter and white matter hyperintensities, whereas water mobility and content increase as tissue damage accrues, suggesting that blood-brain barrier leakage mediates small vessel disease-related brain damage.

Effect of channelling on water balance, oxygen diffusion and oxidation rate in mine waste rock with an inclined multilayer soil cover

NASA Astrophysics Data System (ADS)

Song, Qing; Yanful, Ernest K.

2010-05-01

Engineered soil covers provide an option to mitigate acid rock drainage through reduced water flow and gaseous oxygen influx to underlying mine waste. Channels such as fissures, cracks or fractures developed in the barrier may influence the long-term performance of the soil cover. However, limited published information is available on the extent to which soil cover performance is impacted by these fissures and cracks. This study was conducted to investigate the effect of channelling in a barrier layer on water flow and oxygen transport in a soil cover. Two inclined (a slope of 20%) multilayer soil covers were examined under laboratory conditions. One cover had a 10-cm wide sand-filled channel in a compacted barrier layer (silty clay) at the upslope section, while the other cover was a normal one without the channel pathway. The soil covers were installed in plastic boxes measuring 120 cm × 120 cm × 25 cm (width × height × thickness). The sand-filled channel was designed to represent the aggregate of fissures and cracks that may be present in the compacted barrier. The soil covers were subjected to controlled drying and wetting periods selected to simulate field situation at the Whistle mine site near Capreol, Ontario, Canada. The measured results indicated that interflow decreased from 72.8% of the total precipitation in the soil cover without channel flow to 35.3% in the cover with channel flow, and percolation increased from zero in the normal soil cover to 43.0% of the total precipitation in the cover with channel flow. Gaseous oxygen transfer into the waste rock below the cover soils was 1091 times greater in the cover with channel than in the soil cover without channel. The channel pathway present in the barrier layer acted as a major passage for water movement and gaseous oxygen diffusion into the waste rock layer, thus decreasing the performance of the soil cover. The spacing of the channel with respect to the length of the test box is similar to those found in other published fracture networks. The distribution and partitioning of the water balance components would be expected to be similar to other situations with the same cover slope. This, of course, would depend on rainfall intensity.

Anti-collimation of ballistic electrons by a potential barrier

NASA Astrophysics Data System (ADS)

Coleridge, P. T.; Taylor, R. P.; Sachrajda, A. S.; Adams, J. A.

1994-03-01

A pair of Quantum Point Contacts separated by a continuous barrier have been fabricated using the surface gate technique. Transport measurements for each component of this system and for various combinations have shown both additive and non-additive behaviour. The results are explained by a combination of reflection by the barrier of electrons collimated by the Quantum Point Contacts and transport by diffusion across the barrier.

Interaction of the dopants Mg and Si in Al xGa 1- x As/GaAs heterolayers (MOVPE): application to DQW laser structures

NASA Astrophysics Data System (ADS)

Korte, L.; Treichler, R.; Schreiber, M.; Tanner, Ch.; Kristen, G.; Hanke, C.; Weimann, G.

1991-01-01

The interaction of Mg and Si has been studied in GaAs/Al xGa 1- xAs DQW laser structures with a 50 nm Si diffusion barrier. The samples have been exposed to capless heat treatments at 860°C and under Si/SiO 2 and Si 3N 4 cap layers, and were analysed by SIMS. The Mg diffusion is highly dependent on the surface conditions during heating. A Si barrier is effective for temperature treatments under H 2/AsH 3 and Si/SiO 2. It is not effective under a Si 3N 4 cap where we detected very fast Mg diffusion. The Mg diffusion behaviour is discussed in terms of Si-Mg interaction and the influence of crystal defects.

Lithium-ion diffusion mechanisms in the battery anode material Li(1+x)V(1-x)O₂.

PubMed

Panchmatia, Pooja M; Armstrong, A Robert; Bruce, Peter G; Islam, M Saiful

2014-10-21

Layered Li(1+x)V(1-x)O2 has attracted recent interest as a potential low voltage and high energy density anode material for lithium-ion batteries. A greater understanding of the lithium-ion transport mechanisms is important in optimising such oxide anodes. Here, stoichiometric LiVO2 and Li-rich Li1.07V0.93O2 are investigated using atomistic modelling techniques. Lithium-ion migration is not found in LiVO2, which has also previously shown to be resistant to lithium intercalation. Molecular dynamics simulations of lithiated non-stoichiometric Li(1.07+y)V0.93O2 suggest cooperative interstitial Li(+) diffusion with favourable migration barriers and diffusion coefficients (D(Li)), which are facilitated by the presence of lithium in the transition metal layers; such transport behaviour is important for high rate performance as a battery anode.

High Speed, Low Cost Fabrication of Gas Diffusion Electrodes for Membrane Electrode Assemblies

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

DeCastro, Emory S.; Tsou, Yu-Min; Liu, Zhenyu

Fabrication of membrane electrode assemblies (MEAs) depends on creating inks or pastes of catalyst and binder, and applying this suspension to either the membrane (catalyst coated membrane) or gas diffusion media (gas diffusion electrode) and respectively laminating either gas diffusion media or gas diffusion electrodes (GDEs) to the membrane. One barrier to cost effective fabrication for either of these approaches is the development of stable and consistent suspensions. This program investigated the fundamental forces that destabilize the suspensions and developed innovative approaches to create new, highly stable formulations. These more concentrated formulations needed fewer application passes, could be coated overmore » longer and wider substrates, and resulted in significantly lower coating defects. In March of 2012 BASF Fuel Cell released a new high temperature product based on these advances, whereby our customers received higher performing, more uniform MEAs resulting in higher stack build yields. Furthermore, these new materials resulted in an “instant” increase in capacity due to higher product yields and material throughput. Although not part of the original scope of this program, these new formulations have also led us to materials that demonstrate equivalent performance with 30% less precious metal in the anode. This program has achieved two key milestones in DOE’s Manufacturing R&D program: demonstration of processes for direct coating of electrodes and continuous in-line measurement for component fabrication.« less

3-D Observation of dopant distribution at NAND flash memory floating gate using Atom probe tomography

NASA Astrophysics Data System (ADS)

Lee, Ji-hyun; Chae, Byeong-Kyu; Kim, Joong-Jeong; Lee, Sun Young; Park, Chan Gyung

2015-01-01

Dopant control becomes more difficult and critical as silicon devices become smaller. We observed the dopant distribution in a thermally annealed polysilicon gate using Transmission Electron Microscopy (TEM) and Atom probe tomography (APT). Phosphorus was doped at the silicon-nitride-diffusion-barrier-layer-covered polycrystalline silicon gate. Carbon also incorporated at the gate for the enhancement of operation uniformity. The impurity distribution was observed using atom probe tomography. The carbon atoms had segregated at grain boundaries and suppressed silicon grain growth. Phosphorus atoms, on the other hand, tended to pile-up at the interface. A 1-nm-thick diffusion barrier effectively blocked P atom out-diffusion. [Figure not available: see fulltext.

Modeling the migration of platinum nanoparticles on surfaces using a kinetic Monte Carlo approach

DOE PAGES

Li, Lin; Plessow, Philipp N.; Rieger, Michael; ...

2017-02-15

We propose a kinetic Monte Carlo (kMC) model for simulating the movement of platinum particles on supports, based on atom-by-atom diffusion on the surface of the particle. The proposed model was able to reproduce equilibrium cluster shapes predicted using Wulff-construction. The diffusivity of platinum particles was simulated both purely based on random motion and assisted using an external field that causes a drift velocity. The overall particle diffusivity increases with temperature; however, the extracted activation barrier appears to be temperature independent. Additionally, this barrier was found to increase with particle size, as well as, with the adhesion between the particlemore » and the support.« less

An Ab Initio and Kinetic Monte Carlo Simulation Study of Lithium Ion Diffusion on Graphene

PubMed Central

Zhong, Kehua; Yang, Yanmin; Xu, Guigui; Zhang, Jian-Min; Huang, Zhigao

2017-01-01

The Li+ diffusion coefficients in Li+-adsorbed graphene systems were determined by combining first-principle calculations based on density functional theory with Kinetic Monte Carlo simulations. The calculated results indicate that the interactions between Li ions have a very important influence on lithium diffusion. Based on energy barriers directly obtained from first-principle calculations for single-Li+ and two-Li+ adsorbed systems, a new equation predicting energy barriers with more than two Li ions was deduced. Furthermore, it is found that the temperature dependence of Li+ diffusion coefficients fits well to the Arrhenius equation, rather than meeting the equation from electrochemical impedance spectroscopy applied to estimate experimental diffusion coefficients. Moreover, the calculated results also reveal that Li+ concentration dependence of diffusion coefficients roughly fits to the equation from electrochemical impedance spectroscopy in a low concentration region; however, it seriously deviates from the equation in a high concentration region. So, the equation from electrochemical impedance spectroscopy technique could not be simply used to estimate the Li+ diffusion coefficient for all Li+-adsorbed graphene systems with various Li+ concentrations. Our work suggests that interactions between Li ions, and among Li ion and host atoms will influence the Li+ diffusion, which determines that the Li+ intercalation dependence of Li+ diffusion coefficient should be changed and complex. PMID:28773122

Diffusion and decay chain of radioisotopes in stagnant water in saturated porous media.

PubMed

Guzmán, Juan; Alvarez-Ramirez, Jose; Escarela-Pérez, Rafael; Vargas, Raúl Alejandro

2014-09-01

The analysis of the diffusion of radioisotopes in stagnant water in saturated porous media is important to validate the performance of barrier systems used in radioactive repositories. In this work a methodology is developed to determine the radioisotope concentration in a two-reservoir configuration: a saturated porous medium with stagnant water is surrounded by two reservoirs. The concentrations are obtained for all the radioisotopes of the decay chain using the concept of overvalued concentration. A methodology, based on the variable separation method, is proposed for the solution of the transport equation. The novelty of the proposed methodology involves the factorization of the overvalued concentration in two factors: one that describes the diffusion without decay and another one that describes the decay without diffusion. It is possible with the proposed methodology to determine the required time to obtain equal injective and diffusive concentrations in reservoirs. In fact, this time is inversely proportional to the diffusion coefficient. In addition, the proposed methodology allows finding the required time to get a linear and constant space distribution of the concentration in porous mediums. This time is inversely proportional to the diffusion coefficient. In order to validate the proposed methodology, the distributions in the radioisotope concentrations are compared with other experimental and numerical works. Copyright © 2014 Elsevier Ltd. All rights reserved.

Thermal decay of a metastable state: Influence of rescattering on the quasistationary dynamical rate

NASA Astrophysics Data System (ADS)

Chushnyakova, M. V.; Gontchar, I. I.

2018-03-01

We study the effect of backscattering of the Brownian particles as they escape out of a metastable state overcoming the potential barrier. For this aim, we model this process numerically using the Langevin equations. This modeling is performed for the wide range of the friction constant covering both the energy and spatial diffusion regimes. It is shown how the influence of the descent stage on the quasistationary decay rate gradually disappears as the friction constant decreases. It is found that, in the energy diffusion regime, the rescattering absents and the descent stage does not influence the decay rate. As the value of friction increases, the descent alters the value of the rate by more than 50% for different values of thermal energy and different shapes of the potential. To study the influence of the backscattering on the decay rate, four potentials have been considered which coincide near the potential well and the barrier but differ beyond the barrier. It is shown that the potential for which the well and the barrier are described by two smoothly joined parabolas ("the parabolic potential") plays a role of a dividing range for the mutual layout of the quasistationary dynamical rate and the widely used in the literature Kramers rate. Namely, for the potentials with steeper tails, the Kramers rate RKM underestimates the true quasistationary dynamical rate RD, whereas for the less steep tails the opposite holds (inversion of RD/RKM ). It is demonstrated that the mutual layout of the values of RD for different potentials is explained by the rescattering of the particles from the potential tail.

A charge-based model of Junction Barrier Schottky rectifiers

NASA Astrophysics Data System (ADS)

Latorre-Rey, Alvaro D.; Mudholkar, Mihir; Quddus, Mohammed T.; Salih, Ali

2018-06-01

A new charge-based model of the electric field distribution for Junction Barrier Schottky (JBS) diodes is presented, based on the description of the charge-sharing effect between the vertical Schottky junction and the lateral pn-junctions that constitute the active cell of the device. In our model, the inherently 2-D problem is transformed into a simple but accurate 1-D problem which has a closed analytical solution that captures the reshaping and reduction of the electric field profile responsible for the improved electrical performance of these devices, while preserving physically meaningful expressions that depend on relevant device parameters. The validation of the model is performed by comparing calculated electric field profiles with drift-diffusion simulations of a JBS device showing good agreement. Even though other fully 2-D models already available provide higher accuracy, they lack physical insight making the proposed model an useful tool for device design.

A reaction-diffusion model of the Darien Gap Sterile Insect Release Method

NASA Astrophysics Data System (ADS)

Alford, John G.

2015-05-01

The Sterile Insect Release Method (SIRM) is used as a biological control for invasive insect species. SIRM involves introducing large quantities of sterilized male insects into a wild population of invading insects. A fertile/sterile mating produces offspring that are not viable and the wild insect population will eventually be eradicated. A U.S. government program maintains a permanent sterile fly barrier zone in the Darien Gap between Panama and Columbia to control the screwworm fly (Cochliomyia Hominivorax), an insect that feeds off of living tissue in mammals and has devastating effects on livestock. This barrier zone is maintained by regular releases of massive quantities of sterilized male screwworm flies from aircraft. We analyze a reaction-diffusion model of the Darien Gap barrier zone. Simulations of the model equations yield two types of spatially inhomogeneous steady-state solutions representing a sterile fly barrier that does not prevent invasion and a barrier that does prevent invasion. We investigate steady-state solutions using both phase plane methods and monotone iteration methods and describe how barrier width and the sterile fly release rate affects steady-state behavior.

Morphometric partitioning of the respiratory surface area and diffusion capacity of the gills and swim bladder in juvenile Amazonian air-breathing fish, Arapaima gigas.

PubMed

Fernandes, Marisa Narciso; da Cruz, André Luis; da Costa, Oscar Tadeu Ferreira; Perry, Steven Franklin

2012-09-01

The gills and the respiratory swim bladders of juvenile specimens (mean body mass 100g) of the basal teleost Arapaima gigas (Cuvier 1829) were evaluated using stereological methods in vertical sections. The surface areas, harmonic mean barrier thicknesses and morphometric diffusing capacities for oxygen and carbon dioxide were estimated. The average respiratory surface area of the swim bladder (2173 cm² kg⁻¹) exceeded that of the gills (780 cm² kg⁻¹) by a factor of 2.79. Due to the extremely thin air-blood barrier in the swim bladder (harmonic mean 0.22 μm) and the much thicker water-blood barrier of the gills (9.61 μm), the morphometric diffusing capacity for oxygen and carbon dioxide was 88 times greater in the swim bladder than in the gills. These data clearly indicate the importance of the swim bladder, even in juvenile A. gigas that still engage in aquatic respiration. Because of the much greater diffusion constant of CO₂ than O₂ in water, the gills also remain important for CO₂ release. Copyright © 2012 Elsevier Ltd. All rights reserved.

Transparent, Ultrahigh-Gas-Barrier Films with a Brick-Mortar-Sand Structure.

PubMed

Dou, Yibo; Pan, Ting; Xu, Simin; Yan, Hong; Han, Jingbin; Wei, Min; Evans, David G; Duan, Xue

2015-08-10

Transparent and flexible gas-barrier materials have shown broad applications in electronics, food, and pharmaceutical preservation. Herein, we report ultrahigh-gas-barrier films with a brick-mortar-sand structure fabricated by layer-by-layer (LBL) assembly of XAl-layered double hydroxide (LDH, X=Mg, Ni, Zn, Co) nanoplatelets and polyacrylic acid (PAA) followed by CO2 infilling, denoted as (XAl-LDH/PAA)n-CO2. The near-perfectly parallel orientation of the LDH "brick" creates a long diffusion length to hinder the transmission of gas molecules in the PAA "mortar". Most significantly, both the experimental studies and theoretical simulations reveal that the chemically adsorbed CO2 acts like "sand" to fill the free volume at the organic-inorganic interface, which further depresses the diffusion of permeating gas. The strategy presented here provides a new insight into the perception of barrier mechanism, and the (XAl-LDH/PAA)n-CO2 film is among the best gas barrier films ever reported. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Submersed sensing electrode used in fuel-cell type hydrogen detector

NASA Technical Reports Server (NTRS)

Niedrach, L. W.; Rudek, F. P.; Rutkoneski, M. D.

1971-01-01

Electrode has silicone rubber diffusion barrier with fixed permeation constant for hydrogen. Barrier controls flow of hydrogen to anode and Faraday relationship establishes upper limit for current through cell. Electrode fabrication is described.

10 CFR Appendix C to Part 110 - Illustrative List of Gaseous Diffusion Enrichment Plant Assemblies and Components Under NRC...

Code of Federal Regulations, 2011 CFR

2011-01-01

... welds with substantial amounts of repetition of layout. The equipment, components and piping systems are... fully fluorinated hydrocarbon polymers. 1. Assemblies and components especially designed or prepared for use in gaseous diffusion enrichment. 1.1 Gaseous Diffusion Barriers Especially designed or prepared...

10 CFR Appendix C to Part 110 - Illustrative List of Gaseous Diffusion Enrichment Plant Assemblies and Components Under NRC...

Code of Federal Regulations, 2012 CFR

2012-01-01

... welds with substantial amounts of repetition of layout. The equipment, components and piping systems are... fully fluorinated hydrocarbon polymers. 1. Assemblies and components especially designed or prepared for use in gaseous diffusion enrichment. 1.1 Gaseous Diffusion Barriers Especially designed or prepared...

10 CFR Appendix C to Part 110 - Illustrative List of Gaseous Diffusion Enrichment Plant Assemblies and Components Under NRC...

Code of Federal Regulations, 2014 CFR

2014-01-01

... welds with substantial amounts of repetition of layout. The equipment, components and piping systems are... fully fluorinated hydrocarbon polymers. 1. Assemblies and components especially designed or prepared for use in gaseous diffusion enrichment. 1.1 Gaseous Diffusion Barriers Especially designed or prepared...

10 CFR Appendix C to Part 110 - Illustrative List of Gaseous Diffusion Enrichment Plant Assemblies and Components Under NRC...

Code of Federal Regulations, 2013 CFR

2013-01-01

... welds with substantial amounts of repetition of layout. The equipment, components and piping systems are... fully fluorinated hydrocarbon polymers. 1. Assemblies and components especially designed or prepared for use in gaseous diffusion enrichment. 1.1 Gaseous Diffusion Barriers Especially designed or prepared...

Structural Stability of Diffusion Barriers in Cu/Ru/MgO/Ta/Si

PubMed Central

Hsieh, Shu-Huei; Chen, Wen Jauh; Chien, Chu-Mo

2015-01-01

Various structures of Cu (50 nm)/Ru (2 nm)/MgO (0.5–3 nm)/Ta (2 nm)/Si were prepared by sputtering and electroplating techniques, in which the ultra-thin trilayer of Ru (2 nm)/MgO (0.5–3 nm)/Ta (2 nm) is used as the diffusion barrier against the interdiffusion between Cu film and Si substrate. The various structures of Cu/Ru/MgO/Ta/Si were characterized by four-point probes for their sheet resistances, by X-ray diffractometers for their crystal structures, by scanning electron microscopes for their surface morphologies, and by transmission electron microscopes for their cross-section and high resolution views. The results showed that the ultra-thin tri-layer of Ru (2 nm)/MgO (0.5–3 nm)/Ta (2 nm) is an effective diffusion barrier against the interdiffusion between Cu film and Si substrate. The MgO, and Ta layers as deposited are amorphous. The mechanism for the failure of the diffusion barrier is that the Ru layer first became discontinuous at a high temperature and the Ta layer sequentially become discontinuous at a higher temperature, the Cu atoms then diffuse through the MgO layer and to the substrate at the discontinuities, and the Cu3Si phases finally form. The maximum temperature at which the structures of Cu (50 nm)/Ru (2 nm)/MgO (0.5–3 nm)/Ta (2 nm)/Si are annealed and still have low sheet resistance is from 550 to 750 °C for the annealing time of 5 min and from 500 to 700 °C for the annealing time of 30 min. PMID:28347099

Barrier mechanism of multilayers graphene coated copper against atomic oxygen irradiation

NASA Astrophysics Data System (ADS)

Zhang, Haijing; Ren, Siming; Pu, Jibin; Xue, Qunji

2018-06-01

Graphene has been demonstrated as a protective coating for Cu under ambient condition because of its high impermeability and light-weight oxidation barrier. However, it lacks the research of graphene as a protective coating in space environment. Here, we experimentally and theoretically study the oxidation behavior of graphene-coated Cu in vacuum atomic oxygen (AO) condition. After AO irradiation, the experimental results show multilayer graphene has better anti-oxidation than monolayer graphene. Meanwhile, the calculation results show the oxidation appeared on the graphene's grain boundaries or the film's vacancy defects for the monolayer graphene coated Cu foil. Moreover, the calculation results show the oxidation process proceeds slowly in multilayers because of the matched defects overlaps each other to form a steric hindrance to suppress the O atom diffusion in the vertical direction, and the mismatched defects generates potential energy barriers for interlayer to suppress the O atom diffusion in the horizontal direction. Hence, multilayer graphene films could serve as protection coatings to prevent diffusion of O atom.

Study of Diffusion Barrier for Solder/ n-Type Bi2Te3 and Bonding Strength for p- and n-Type Thermoelectric Modules

NASA Astrophysics Data System (ADS)

Lin, Wen-Chih; Li, Ying-Sih; Wu, Albert T.

2018-01-01

This paper investigates the interfacial reaction between Sn and Sn3Ag0.5Cu (SAC305) solder on n-type Bi2Te3 thermoelectric material. An electroless Ni-P layer successfully suppressed the formation of porous SnTe intermetallic compound at the interface. The formation of the layers between Bi2Te3 and Ni-P indicates that Te is the dominant diffusing species. Shear tests were conducted on both Sn and SAC305 solder on n- and p-type Bi2Te3 with and without a Ni-P barrier layer. Without a Ni-P layer, porous SnTe would result in a more brittle fracture. A comparison of joint strength for n- and p-type thermoelectric modules is evaluated by the shear test. Adding a diffusion barrier increases the mechanical strength by 19.4% in n-type and 74.0% in p-type thermoelectric modules.

Preparation and Bond Properties of Thermal Barrier Coatings on Mg Alloy with Sprayed Al or Diffused Mg-Al Intermetallic Interlayer

NASA Astrophysics Data System (ADS)

Fan, Xizhi; Wang, Ying; Zou, Binglin; Gu, Lijian; Huang, Wenzhi; Cao, Xueqiang

2014-02-01

Sprayed Al or diffused Mg-Al layer was designed as interlayer between the thermal barrier coatings (TBCs) and Mg alloy substrate. The effects of the interlayer on the bond properties of the coats were investigated. Al layers were prepared by arc spraying and atmospheric plasma spraying (APS), respectively. Mg-Al diffused layer was obtained after the heat treatment of the sprayed sample (Mg alloy with APS Al coat) at 400 °C. The results show that sprayed Al interlayer does not improve the bond stability of TBCs. The failure of the TBCs on Mg alloy with Al interlayer occurs mainly due to the low strength of Al layer. Mg-Al diffused layer improves corrosion resistance of substrate and the bond interface. The TBCs on Mg alloy with Mg-Al diffused interlayer shows better bond stability than the sample of which the TBCs is directly sprayed on Mg alloy substrate by APS.

Vacancy–Vacancy Interaction Induced Oxygen Diffusivity Enhancement in Undoped Nonstoichiometric Ceria

DOE PAGES

Yuan, Fenglin; Zhang, Yanwen; Weber, William J.

2015-05-19

In this paper, molecular dynamics simulations and molecular static calculations have been used to systematically study oxygen vacancy transport in undoped nonstoichiometric ceria. A strong oxygen diffusivity enhancement appears in the vacancy concentration range of 2–4% over the temperature range from 1000 to 2000 K. An Arrhenius ion diffusion mechanism by vacancy hopping along the (100) direction is unambiguously identified, and an increasing trend of both the oxygen migration barrier and the prefactor with increasing vacancy concentration is observed. Within the framework of classical diffusion theory, a weak concentration dependence of the prefactor in oxygen vacancy migration is shown tomore » be crucial for explaining the unusual fast oxygen ion migration in the low concentration range and consequently the appearance of a maximum in oxygen diffusivity. Finally, a representative (100) direction interaction model is constructed to identify long-range vacancy–vacancy interaction as the structural origin of the positive correlation between oxygen migration barrier and vacancy concentration.« less

Chemically-inducible diffusion trap at cilia (C-IDTc) reveals molecular sieve-like barrier

PubMed Central

Lin, Yu-Chun; Phua, Siew Cheng; Jiao, John; Levchenko, Andre; Inoue, Takafumi; Rohatgi, Rajat; Inoue, Takanari

2013-01-01

Primary cilia function as specialized compartments for signal transduction. The stereotyped structure and signaling function of cilia inextricably depend on the selective segregation of molecules in cilia. However, the fundamental principles governing the access of soluble proteins to primary cilia remain unresolved. We developed a methodology termed Chemically-Inducible Diffusion Trap at Cilia (C-IDTc) to visualize the diffusion process of a series of fluorescent proteins ranging in size from 3.2 to 7.9 nm into primary cilia. We found that the interior of the cilium was accessible to proteins as large as 7.9 nm. The kinetics of ciliary accumulation of this panel of proteins was exponentially limited by their Stokes radii. Quantitative modeling suggests that the diffusion barrier operates as a molecular sieve at the base of cilia. Our study presents a set of powerful, generally applicable tools for the quantitative monitoring of ciliary protein diffusion under both physiological and pathological conditions. PMID:23666116

First-principles study of fission gas incorporation and migration in zirconium nitride

DOE PAGES

Mei, Zhi-Gang; Liang, Linyun; Yacout, Abdellatif M.

2017-03-24

To evaluate the effectiveness of ZrN as a diffusion barrier against fission gases, we investigate in this paper the incorporation and migration of fission gas atoms, with a focus on Xe, in ZrN by first-principles calculations. The formations of point defects in ZrN, including vacancies, interstitials, divacancies, Frenkel pairs, and Schottky defects, are first studied. Among all the defects, the Schottky defect with two vacancies as first nearest neighbor is predicted to be the most favorable incorporation site for fission gas Xe in ZrN. The migration of Xe gas atom in ZrN is investigated through two diffusion mechanisms, i.e., interstitialmore » and vacancy-assisted diffusions. The migration barrier of Xe gas atom through the intrinsic interstitials in ZrN is considerably lower than that through vacancies. Finally, therefore, at low temperatures fission gas Xe atoms diffuse mainly through interstitials in single crystal ZrN, whereas at high temperatures Xe may diffuse in ZrN assisted by vacancies.« less

Diffusion of point defects in crystalline silicon using the kinetic activation-relaxation technique method

DOE PAGES

Trochet, Mickaël; Béland, Laurent Karim; Joly, Jean -François; ...

2015-06-16

We study point-defect diffusion in crystalline silicon using the kinetic activation-relaxation technique (k-ART), an off-lattice kinetic Monte Carlo method with on-the-fly catalog building capabilities based on the activation-relaxation technique (ART nouveau), coupled to the standard Stillinger-Weber potential. We focus more particularly on the evolution of crystalline cells with one to four vacancies and one to four interstitials in order to provide a detailed picture of both the atomistic diffusion mechanisms and overall kinetics. We show formation energies, activation barriers for the ground state of all eight systems, and migration barriers for those systems that diffuse. Additionally, we characterize diffusion pathsmore » and special configurations such as dumbbell complex, di-interstitial (IV-pair+2I) superdiffuser, tetrahedral vacancy complex, and more. In conclusion, this study points to an unsuspected dynamical richness even for this apparently simple system that can only be uncovered by exhaustive and systematic approaches such as the kinetic activation-relaxation technique.« less

Simple rules for passive diffusion through the nuclear pore complex

PubMed Central

Mironska, Roxana; Kim, Seung Joong

2016-01-01

Passive macromolecular diffusion through nuclear pore complexes (NPCs) is thought to decrease dramatically beyond a 30–60-kD size threshold. Using thousands of independent time-resolved fluorescence microscopy measurements in vivo, we show that the NPC lacks such a firm size threshold; instead, it forms a soft barrier to passive diffusion that intensifies gradually with increasing molecular mass in both the wild-type and mutant strains with various subsets of phenylalanine-glycine (FG) domains and different levels of baseline passive permeability. Brownian dynamics simulations replicate these findings and indicate that the soft barrier results from the highly dynamic FG repeat domains and the diffusing macromolecules mutually constraining and competing for available volume in the interior of the NPC, setting up entropic repulsion forces. We found that FG domains with exceptionally high net charge and low hydropathy near the cytoplasmic end of the central channel contribute more strongly to obstruction of passive diffusion than to facilitated transport, revealing a compartmentalized functional arrangement within the NPC. PMID:27697925

High-velocity DC-VPS for diffusion and protecting barrier layers in solid oxide fuel cells (SOFCs)

NASA Astrophysics Data System (ADS)

Henne, R. H.; Franco, T.; Ruckdäschel, R.

2006-12-01

High-temperature fuel cells of the solid oxide fuel cell (SOFC) type as direct converter of chemical into electrical energy show a high potential for reducing considerably the specific energy consumption in different application fields. Of particular interest are advanced lightweight planar cells for electricity supply units in cars and other mobile systems. Such cells, in one new design, consist mainly of metallic parts, for example, of ferrite steels. These cells shall operate in the temperature range of 700 to 800 °C where oxidation and diffusion processes can be of detrimental effect on cell performance for long-term operation. Problems arise in particular by diffusion of chromium species from the interconnect or the cell containment into the electrolyte/cathode interface forming insulating phases and by the mutual diffusion of substrate and anode material, for example, iron and chromium from the ferrite into the anode and nickel from the anode into the ferrite, which in both cases reduces performance and system lifetime. Additional intermediate layers of perovskite-type material, (e.g., doped LaCrO3) applied with high-velocity direct-current vacuum plasma spraying (DC-VPS) can reduce such effects considerably if they are stable and of high electronic conductivity.

Modelisation de la diffusion sur les surfaces metalliques: De l'adatome aux processus de croissance

NASA Astrophysics Data System (ADS)

Boisvert, Ghyslain

Cette these est consacree a l'etude des processus de diffusion en surface dans le but ultime de comprendre, et de modeliser, la croissance d'une couche mince. L'importance de bien mai triser la croissance est primordiale compte tenu de son role dans la miniaturisation des circuits electroniques. Nous etudions ici les surface des metaux nobles et de ceux de la fin de la serie de transition. Dans un premier temps, nous nous interessons a la diffusion d'un simple adatome sur une surface metallique. Nous avons, entre autres, mis en evidence l'apparition d'une correlation entre evenements successifs lorsque la temperature est comparable a la barriere de diffusion, i.e., la diffusion ne peut pas etre associee a une marche aleatoire. Nous proposons un modele phenomenologique simple qui reproduit bien les resultats des simulations. Ces calculs nous ont aussi permis de montrer que la diffusion obeit a la loi de Meyer-Neldel. Cette loi stipule que, pour un processus active, le prefacteur augmente exponentiellement avec la barriere. En plus, ce travail permet de clarifier l'origine physique de cette loi. En comparant les resultats dynamiques aux resultats statiques, on se rend compte que la barriere extraite des calculs dynamiques est essentiellement la meme que celle obtenue par une approche statique, beaucoup plus simple. On peut donc obtenir cette barriere a l'aide de methodes plus precises, i.e., ab initio, comme la theorie de la fonctionnelle de la densite, qui sont aussi malheureusement beaucoup plus lourdes. C'est ce que nous avons fait pour plusieurs systemes metalliques. Nos resultats avec cette derniere approche se comparent tres bien aux resultats experimentaux. Nous nous sommes attardes plus longuement a la surface (111) du platine. Cette surface regorge de particularites interessantes, comme la forme d'equilibre non-hexagonale des i lots et deux sites d'adsorption differents pour l'adatome. De plus, des calculs ab initio precedents n'ont pas reussi a confirmer la forme d'equilibre et surestiment grandement la barriere. Nos calculs, plus complets et dans un formalisme mieux adapte a ce genre de probleme, predisent correctement la forme d'equilibre, qui est en fait due a un relachement different du stress de surface aux deux types de marches qui forment les cotes des i lots. Notre valeur pour la barriere est aussi fortement diminuee lorsqu'on relaxe les forces sur les atomes de la surface, amenant le resultat theorique beaucoup plus pres de la valeur experimentale. Nos calculs pour le cuivre demontre en effet que la diffusion de petits i lots pendant la croissance ne peut pas etre negligee dans ce cas, mettant en doute la valeur des interpretations des mesures experimentales. (Abstract shortened by UMI.)

Oxygen diffusion barrier coating

NASA Technical Reports Server (NTRS)

Unnam, Jalaiah (Inventor); Clark, Ronald K. (Inventor)

1987-01-01

A method for coating a titanium panel or foil with aluminum and amorphous silicon to provide an oxygen barrier abrogating oxidation of the substrate metal is developed. The process is accomplished with known inexpensive procedures common in materials research laboratories, i.e., electron beam deposition and sputtering. The procedures are conductive to treating foil gage titanium and result in submicron layers which virtually add no weight to the titanium. There are no costly heating steps. The coatings blend with the substrate titanium until separate mechanical properties are subsumed by those of the substrate without cracking or spallation. This method appreciably increases the ability of titanium to mechanically perform in high thermal environments such as those witnessed on structures of space vehicles during re-entry

Analysis of Al diffusion processes in TiN barrier layers for the application in silicon solar cell metallization

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

Kumm, J.; Samadi, H.; Chacko, R. V.

An evaporated Al layer is known as an excellent rear metallization for highly efficient solar cells, but suffers from incompatibility with a common solder process. To enable solar cell-interconnection and module integration, in this work the Al layer is complemented with a solder stack of TiN/Ti/Ag or TiN/NiV/Ag, in which the TiN layer acts as an Al diffusion barrier. X-ray photoelectron spectroscopy measurements prove that diffusion of Al through the stack and the formation of an Al{sub 2}O{sub 3} layer on the stack's surface are responsible for a loss of solderability after a strong post-metallization anneal, which is often mandatorymore » to improve contact resistance and passivation quality. An optimization of the reactive TiN sputter process results in a densification of the TiN layer, which improves its barrier quality against Al diffusion. However, measurements with X-ray diffraction and scanning electron microscopy show that small grains with vertical grain boundaries persist, which still offer fast diffusion paths. Therefore, the concept of stuffing is introduced. By incorporating oxygen into the grain boundaries of the sputtered TiN layer, Al diffusion is strongly reduced as confirmed by secondary ion mass spectroscopy profiles. A quantitative analysis reveals a one order of magnitude lower Al diffusion coefficient for stuffed TiN layers. This metallization system maintains its solderability even after strong post-metallization annealing at 425 °C for 15 min. This paper thus presents an industrially feasible, conventionally solderable, and long-term stable metallization scheme for highly efficient silicon solar cells.« less

Gauge calibration by diffusion

NASA Technical Reports Server (NTRS)

Brock, F. J.; Feakes, F. (Inventor)

1968-01-01

Vacuum gage calibration by diffusing a known quantity of gas through a heated barrier into a gauge is examined. The gas flow raises the pressure in the gauge to known level and is then compared with the gauge's pressure reading.

Field Testing of an Unvented Roof with Fibrous Insulation, Tiles, and Vapor Diffusion Venting

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

Ueno, K.; Lstiburek, J. W.

This research is a test implementation of an unvented tile roof assembly in a hot-humid climate (Orlando, FL; Zone 2A), insulated with air permeable insulation (netted and blown fiberglass). Given the localized moisture accumulation and failures seen in previous unvented roof field work, it was theorized that a 'diffusion vent' (water vapor open, but air barrier 'closed') at the highest points in the roof assembly might allow for the wintertime release of moisture, to safe levels. The 'diffusion vent' is an open slot at the ridge and hips, covered with a water-resistant but vapor open (500+ perm) air barrier membrane.more » As a control comparison, one portion of the roof was constructed as a typical unvented roof (self-adhered membrane at ridge). The data collected to date indicate that the diffusion vent roof shows greater moisture safety than the conventional, unvented roof design.« less

First principles calculations of ceramics surfaces and interfaces: Examples from beta-silicon nitride and alpha-alumina

NASA Astrophysics Data System (ADS)

Dunn, Jennifer Synowczynski

The goal of this thesis was to use first principles calculations to provide a fundamental understanding at the atomistic level of the mechanisms (e.g. structural relaxations of ceramic surfaces/interfaces, charge transfer reactions, adsorption and dissociation phenomena, localized debonding) behind macroscopic behavior in ceramics (e.g. fracture toughness, corrosion, catalysis). This thesis includes the results from three independent Density Functional Theory (DFT) studies of beta-Si3N4 and alpha-Al2O 3. Due to the computational complexity of first principles calculations, the models in this thesis do not consider temperature or pressure effects and are limited to describing the behavior of systems containing less than 200 atoms. In future studies, these calculations can be used to train a reactive molecular dynamics force field (REAXFF) so that larger scale phenomena including temperature effects can be explicitly simulated. In the first study, the effect of over 30 dopants on the stability of the interface between beta-Si3N4 grains and the intergranular glassy SiON film (IGF) was investigated. The dopants chosen not only represented commonly known glass modifiers and sintering aides but also enabled us to search for dependencies based on atomic size and electronic orbital configuration. To ensure that the approximations used in our model captured the key physical phenomena occurring on the beta-Si3N4 (100) surface and at the Si3N4/ IGF interface, we compared to experimental data (i.e. High Angle Annual Dark Field-Scanning Transmission Electron Microscopy atomic positions and fracture toughness values (Mikijelj B., 2009)). We identified a computational metric (the interfacial stability factor S) which correlates with experimentally measured fracture toughness values. The interfacial stability factor S is defined as the binding energy of the doped system minus the binding energy of the undoped system, where the binding energy is the total energy of the system minus the sum of the energies of the constituent atoms. In the second study, we performed constrained geometry barrier calculations of the interaction of CO with the (001) beta-Si3N4 surface to answer the following questions: (1) Does the CO combustion product interact with the Si3N4 surface and if so, what is the mechanism? (2) Once adsorbed, can CO further dissociate into isolated surface active C and O species? (3) Is it more energetically favorable for C to diffuse into the bulk beta-Si3N4 or along its surface? and (4) What is the barrier to C diffusing into an amorphous SiO2 intergranular film? Our calculations indicated that CO spontaneously adsorbs to the (001) beta-Si 3N4 surface. However, at ambient temperatures, further dissociation into isolated surface adsorbed C and O species was not thermodynamically or kinetically feasible. The barrier to C diffusing interstitially 1A and 5A into the bulk crystalline lattice is 2.12 and 4.42 eV respectively for a defect free, clean surface. However, the barrier for C surface diffusion is much smaller, ˜ 0.87 eV. Therefore, we concluded that surface is rich in C which can diffuse to the Si3N4/SiO2 interface and contribute to chemical erosion near the grain boundary interface. In the final study, we created a DFT model to investigate the 'inverse spillover effect' that occurs during hydrogen combustion on catalytically active Pt clusters supported by alpha-Al2O3. Our results indicated that the dissociation of O2 was not thermodynamically favored on the alpha-Al2O3 surface. However, both H2 and H2O dissociated, forming hydroxyls with oxygen atoms in the second atomic layer. Once dissociated, the oxygen species could diffuse locally but encountered a large barrier to long-range surface diffusion in the absence of defects or other species. In contrast, the barrier to the long-range surface diffusion of hydrogen was modest under ideal conditions. We also identified several adsorption and dissociation products for Pt, Pt-O [ads] Pt3, O, H, O2, H2, and H 2O on the alpha-Al2O3 (0001) surface and described how these structures changed the surface reconstruction. Specifically, we concluded that the adsorption of molecular H2O, atomic Pt, and Pt trimers changed the termination for the alpha-Al2O3 (0001) surface from aluminum to oxygen terminated in the vicinity of the adsorption products. This should have a dramatic affect on catalytic activity and surface diffusion. We confirmed this for O surface diffusion near surface Al where the presence of atomic Pt decreased the diffusion barrier from 1.17 to 0.22 eV.

Kinetic Monte Carlo Simulations of Oxygen Diffusion in Environmental Barrier Coating Materials

NASA Technical Reports Server (NTRS)

Good, Brian S.

2017-01-01

Ceramic Matrix Composite (CMC) materials are of interest for use in next-generation turbine engine components, offering a number of significant advantages, including reduced weight and high operating temperatures. However, in the hot environment in which such components operate, the presence of water vapor can lead to corrosion and recession, limiting the useful life of the components. Such degradation can be reduced through the use of Environmental Barrier Coatings (EBCs) that limit the amount of oxygen and water vapor reaching the component. Candidate EBC materials include Yttrium and Ytterbium silicates. In this work we present results of kinetic Monte Carlo (kMC) simulations of oxygen diffusion, via the vacancy mechanism, in Yttrium and Ytterbium disilicates, along with a brief discussion of interstitial diffusion.

High Temperature Characteristics of Pt/TaSi2/Pt/W and Pt/Ti/W Diffusion Barrier Systems for Ohmic Contacts to 4H-SiC

NASA Technical Reports Server (NTRS)

Okojie, Robert S.; Lukco, Dorothy

2017-01-01

The degradation of ohmic contacts to 4H-SiC pressure sensors over time at high temperature is primarily due to two failure mechanisms: migrating bond pad Au and atmospheric O toward the ohmic contact SiC interface and the inter-metallic mixing between diffusion barrier systems (DBS) and the underlying ohmic contact metallization. We investigated the effectiveness of Pt/TaSi2/Pt/W (DBS-A) and Pt/Ti/W (DBS-B) in preventing Au and O diffusion through the underlying binary Ti/W or alloyed W50:Ni50 ohmic contacts to 4H-SiC and the DBS ohmic contact intermixing at temperature up to 700 C.

Bacterial lipopolysaccharide-induced systemic inflammation alters perfusion of white matter-rich regions without altering flow in brain-irrigating arteries: Relationship to blood-brain barrier breakdown?

PubMed

Dhaya, Ibtihel; Griton, Marion; Raffard, Gérard; Amri, Mohamed; Hiba, Bassem; Konsman, Jan Pieter

2018-01-15

To better understand brain dysfunction during sepsis, cerebral arterial blood flow was assessed with Phase Contrast Magnetic Resonance Imaging, perfusion with Arterial Spin Labeling and structure with diffusion-weighted Magnetic Resonance Imaging in rats after intraperitoneal administration of bacterial lipopolysaccharides. Although cerebral arterial flow was not altered, perfusion of the corpus callosum region and diffusion parallel to its fibers were higher after lipopolysaccharide administration as compared to saline injection. In parallel, lipopolysaccharide induced perivascular immunoglobulin-immunoreactivity in white matter. These findings indicate that systemic inflammation can result in increased perfusion, blood-brain barrier breakdown and altered water diffusion in white matter. Copyright © 2017 Elsevier B.V. All rights reserved.

Influence of dislocation strain fields on the diffusion of interstitial iron impurities in silicon

NASA Astrophysics Data System (ADS)

Ziebarth, Benedikt; Mrovec, Matous; Elsässer, Christian; Gumbsch, Peter

2015-09-01

The efficiency of silicon (Si)-based solar cells is strongly affected by crystal defects and impurities. Metallic impurities, in particular interstitial iron (Fe) atoms, cause large electric losses because they act as recombination centers for photogenerated charge carriers. Here, we present a systematic first-principles density functional theory (DFT) study focusing on the influence of hydrostatic, uniaxial, and shear strains on the thermodynamic stability and the diffusivity of Fe impurities in crystalline Si. Our calculations show that the formation energy of neutral Fe interstitials in tetrahedral interstitial sites is almost unaffected by uniform deformations of the Si crystal up to strains of 5%. In contrast, the migration barrier varies significantly with strain, especially for hydrostatic deformation. In order to determine effective diffusion coefficients for different strain states, a kinetic Monte Carlo (kMC) model was set up based on the activation energy barriers and frequency factors obtained from the DFT simulations. By using the strain dependence of the migration barrier, we examined the migration of Fe interstitials in the vicinity of perfect 1 /2 <110 > screw and 60∘ mixed dislocations, and 1 /6 <112 > 90∘ and 30∘ partial dislocations. While the strain field of the perfect screw dislocation always enhances the local Fe diffusion, the existence of tensile and compressive regions around the 60∘ mixed dislocation results in a strong anisotropic diffusion profile with significantly faster and slower diffusivities on its tensile and compressive sides. The influences of the partial dislocations are qualitatively similar to that of the 60∘ mixed dislocation.

Electronic Devices with Rubidium Barrier Film and Process for Making Same

DTIC Science & Technology

1998-08-20

barrier film is comprised of a plurality of contiguous monolayers, while FIG. 7B shows another embodiment of the 20 invention where the barrier film is... plurality of contiguous monolayers in which different monolayers thereof are formed of different types of metal atoms. -10- FIG. 8 is a schematic...system directed toward the substrate 26. A diffusion barrier precursor compound effusion cell, for example a barium fluoride, strontium fluoride or the

[100]-Oriented LiFePO4 Nanoflakes toward High Rate Li-Ion Battery Cathode.

PubMed

Li, Zhaojin; Peng, Zhenzhen; Zhang, Hui; Hu, Tao; Hu, Minmin; Zhu, Kongjun; Wang, Xiaohui

2016-01-13

[100] is believed to be a tough diffusion direction for Li(+) in LiFePO4, leading to the belief that the rate performance of [100]-oriented LiFePO4 is poor. Here we report the fabrication of 12 nm-thick [100]-oriented LiFePO4 nanoflakes by a simple one-pot solvothermal method. The nanoflakes exhibit unexpectedly excellent electrochemical performance, in stark contrast to what was previously believed. Such an exceptional result is attributed to a decreased thermodynamic transformation barrier height (Δμb) associated with increased active population.

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.

Encapsulation of organic light emitting diodes

NASA Astrophysics Data System (ADS)

Visweswaran, Bhadri

Organic Light Emitting Diodes (OLEDs) are extremely attractive candidates for flexible display and lighting panels due to their high contrast ratio, light weight and flexible nature. However, the materials in an OLED get oxidized by extremely small quantities of atmospheric moisture and oxygen. To obtain a flexible OLED device, a flexible thin-film barrier encapsulation with low permeability for water is necessary. Water permeates through a thin-film barrier by 4 modes: microcracks, contaminant particles, along interfaces, and through the bulk of the material. We have developed a flexible barrier film made by Plasma Enhanced Chemical Vapor Deposition (PECVD) that is devoid of any microcracks. In this work we have systematically reduced the permeation from the other three modes to come up with a barrier film design for an operating lifetime of over 10 years. To provide quantitative feedback during barrier material development, techniques for measuring low diffusion coefficient and solubility of water in a barrier material have been developed. The mechanism of water diffusion in the barrier has been identified. From the measurements, we have created a model for predicting the operating lifetime from accelerated tests when the lifetime is limited by bulk diffusion. To prevent the particle induced water permeation, we have encapsulated artificial particles and have studied their cross section. A three layer thin-film that can coat a particle at thicknesses smaller than the particle diameter is identified. It is demonstrated to protect a bottom emission OLED device that was contaminated with standard sized glass beads. The photoresist and the organic layers below the barrier film causes sideways permeation that can reduce the lifetime set by permeation through the bulk of the barrier. To prevent the sideways permeation, an impermeable inorganic grid made of the same barrier material is designed. The reduction in sideways permeation due to the impermeable inorganic grid is demonstrated in an encapsulated OLED. In this work, we have dealt with three permeation mechanisms and shown solution to each of them. These steps give us reliable flexible encapsulation that has a lifetime of greater than 10 years.

High-throughput ab-initio dilute solute diffusion database.

PubMed

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-07-19

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world.

Markov-state model for CO2 binding with carbonic anhydrase under confinement

NASA Astrophysics Data System (ADS)

Chen, Gong; Xu, Weina; Lu, Diannan; Wu, Jianzhong; Liu, Zheng

2018-01-01

Enzyme immobilization with a nanostructure material can enhance its stability and facilitate reusability. However, the apparent activity is often compromised due to additional diffusion barriers and complex interactions with the substrates and solvent molecules. The present study elucidates the effects of the surface hydrophobicity of nano-confinement on CO2 diffusion to the active site of human carbonic anhydrase II (CA), an enzyme that is able to catalyze CO2 hydration at extremely high turnover rates. Using the Markov-state model in combination with coarse-grained molecular dynamics simulations, we demonstrate that a hydrophobic cage increases CO2 local density but hinders its diffusion towards the active site of CA under confinement. By contrast, a hydrophilic cage hinders CO2 adsorption but promotes its binding with CA. An optimal surface hydrophobicity can be identified to maximize both the CO2 occupation probability and the diffusion rate. The simulation results offer insight into understanding enzyme performance under nano-confinement and help us to advance broader applications of CA for CO2 absorption and recovery.

Simultaneous cell death and desquamation of the embryonic diffusion barrier during epidermal development.

PubMed

Saathoff, Manuela; Blum, Barbara; Quast, Thomas; Kirfel, Gregor; Herzog, Volker

2004-10-01

The periderm is an epithelial layer covering the emerging epidermis in early embryogenesis of vertebrates. In the chicken embryo, an additional cellular layer, the subperiderm, occurs at later embryonic stages underneath the periderm. The questions arose what is the function of both epithelial layers and, as they are transitory structures, by which mechanism are they removed. By immunocytochemistry, the tight junction (TJ) proteins occludin and claudin-1 were localized in the periderm and in the subperiderm, and sites of close contact between adjacent cells were detected by electron microscopy. Using horseradish peroxidase (HRP) as tracer, these contacts were identified as tight junctions involved in the formation of the embryonic diffusion barrier. This barrier was lost by desquamation at the end of the embryonic period, when the cornified envelope of the emerging epidermis was formed. By TUNEL and DNA ladder assays, we detected simultaneous cell death in the periderm and the subperiderm shortly before hatching. The absence of caspases-3, -6, and -7 activity, key enzymes of apoptosis, and the lack of typical morphological criteria of apoptosis such as cell fragmentation or membrane blebbing point to a special form of programmed cell death (PCD) leading to the desquamation of the embryonic diffusion barrier. Copyright 2004 Elsevier Inc.

Correlative study of functional and structural regeneration of urothelium after chitosan-induced injury.

PubMed

Erman, Andreja; Kerec Kos, Mojca; Žakelj, Simon; Resnik, Nataša; Romih, Rok; Veranič, Peter

2013-11-01

High transepithelial electrical resistance (TEER) demonstrates a functional permeability barrier of the normal urothelium, which is maintained by a layer of highly differentiated superficial cells. When the barrier is challenged, a quick regeneration is induced. We used side-by-side diffusion chambers as an ex vivo system to determine the time course of functional and structural urothelial regeneration after chitosan-induced injury. The exposure of the urothelium to chitosan caused a 60 % decrease in TEER, the exposure of undifferentiated urothelial cells to the luminal surface and leaky tight junctions. During the regeneration period (350 min), TEER recovered to control values after approximately 200 min, while structural regeneration continued until 350 min after injury. The tight junctions are the earliest and predominant component of the barrier to appear, while complete barrier regeneration is achieved by delayed superficial cell terminal differentiation. The barrier function and the structure of untreated urothelium were unaffected in side-by-side diffusion chambers for at least 6 h. The urinary bladder tissue excised from an animal thus retains the ability to maintain and restore the transepithelial barrier and cellular ultrastructure for a sufficient period to allow for studies of regeneration in ex vivo conditions.

Tin-phthalocyanine adsorption and diffusion on Cu and Au (111) surfaces: A density functional theory study

NASA Astrophysics Data System (ADS)

Qin, Dan; Ge, Xu-Jin; Lü, Jing-Tao

2018-05-01

Through density functional theory based calculations, we study the adsorption and diffusion of tin phthalocyanine (SnPc) molecule on Au(111) and Cu(111) surfaces. SnPc has two conformers with Sn pointing to the vacuum (Sn-up) and substrate (Sn-down), respectively. The binding energies of the two conformers with different adsorption sites on the two surfaces, including top, bridge, fcc, hcp, are calculated and compared. It is found that the SnPc molecule binds stronger on Cu(111) surface, with binding energy about 1 eV larger than that on Au(111). Only the bridge and top adsorption sites are stable on Cu(111), while all the four adsorption sites are stable on Au(111), with small diffusion barriers between them. Moreover, the flipping barrier from Sn-up to Sn-down conformer is of the same magnitude on the two metal surfaces. These results are consistent with a recent experiment [Zhang, et al., Angew. Chem., 56, 11769 (2017)], which shows that conformation change from Sn-up to Sn-down on Cu(111) surface can be induced by a C60-functionalized STM tip, while similar change is difficult to realize on Au(111), due to smaller diffusion barrier on Au(111).

Bio-based coatings as potential barriers to chemical contaminants from recycled paper and board for food packaging.

PubMed

Guazzotti, V; Marti, A; Piergiovanni, L; Limbo, S

2014-01-01

Partition and diffusion experiments were carried out with paper and board samples coated with different biopolymers. The aim was to evaluate the physicochemical behaviour and barrier properties of bio-coatings against migration of typical contaminants from recycled paper packaging. Focus was directed towards water-based, renewable biopolymers, such as modified starches (cationic starch and cationic waxy starch), plant and animal proteins (gluten and gelatine), poured onto paper with an automatic applicator. Additionally, a comparison with polyethylene-laminated paper was performed. Microstructural observations of the bio-coated paper allowed the characterisation of samples. From the partitioning studies, considerable differences in the adsorption behaviour of the selected contaminants between bio-coated or uncoated paper and air were highlighted. For both the polar and non-polar compounds considered (benzophenone and diisobutyl phthalate, respectively), the lowest values of partition coefficients were found when paper was bio-coated, making it evident that biopolymers acted as chemical/physical barriers towards these contaminants. These findings are discussed considering the characteristics of the tested biopolymers. Diffusion studies into the solid food simulant poly 2,6-diphenyl-p-phenylene oxide, also known as Tenax(®), confirmed that all the tested biopolymers slowed down migration. The Weibull kinetic model was fitted to the experimental data to compare migration from paper and bio-coated paper. Values found for β, an index determining the pattern of curvature, ranged from 1.1 to 1.7 for uncoated and polyethylene paper, whereas for bio-coated papers they ranged from 2.2 to 4.9, corresponding to the presence of an evident lag phase due to barrier properties of the tested bio-coatings.

Corneal critical barrier against the penetration of dexamethasone and lomefloxacin hydrochloride: evaluation by the activation energy for drug partition and diffusion in cornea.

PubMed

Yasueda, Shin-ichi; Higashiyama, Masayo; Yamaguchi, Masazumi; Isowaki, Akiharu; Ohtori, Akira

2007-08-01

The cornea is a solid barrier against drug permeation. We searched the critical barrier of corneal drug permeation using a hydrophobic drug, dexamethasone (DM), and a hydrophilic drug, lomefloxacin hydrochloride (LFLX). The activation energies for permeability of DM and LFLX across the intact cornea were 88.0 and 42.1 kJ/mol, respectively. Their activation energies for permeability across the cornea without epithelium decreased to 33.1 and 16.6 kJ/mol, respectively. The results show that epithelium is the critical barrier on the cornea against the permeation of a hydrophobic drug of DM as well as a hydrophilic drug of LFLX. The activation energy of partition for DM (66.8 kJ/mol) was approximately 3-fold larger than that of diffusion (21.2 kJ/mol). The results indicate that the partition for the hydrophobic drug of DM to the corneal epithelium is the primary barrier. Thermodynamic evaluation of activation energy for the drug permeation parameters is a good approach to investigate the mechanism of drug permeability.

Predicting First Traversal Times for Virions and Nanoparticles in Mucus with Slowed Diffusion

PubMed Central

Erickson, Austen M.; Henry, Bruce I.; Murray, John M.; Klasse, Per Johan; Angstmann, Christopher N.

2015-01-01

Particle-tracking experiments focusing on virions or nanoparticles in mucus have measured mean-square displacements and reported diffusion coefficients that are orders of magnitude smaller than the diffusion coefficients of such particles in water. Accurate description of this subdiffusion is important to properly estimate the likelihood of virions traversing the mucus boundary layer and infecting cells in the epithelium. However, there are several candidate models for diffusion that can fit experimental measurements of mean-square displacements. We show that these models yield very different estimates for the time taken for subdiffusive virions to traverse through a mucus layer. We explain why fits of subdiffusive mean-square displacements to standard diffusion models may be misleading. Relevant to human immunodeficiency virus infection, using computational methods for fractional subdiffusion, we show that subdiffusion in normal acidic mucus provides a more effective barrier against infection than previously thought. By contrast, the neutralization of the mucus by alkaline semen, after sexual intercourse, allows virions to cross the mucus layer and reach the epithelium in a short timeframe. The computed barrier protection from fractional subdiffusion is some orders of magnitude greater than that derived by fitting standard models of diffusion to subdiffusive data. PMID:26153713

Bicarbonate diffusion through mucus.

PubMed

Livingston, E H; Miller, J; Engel, E

1995-09-01

The mucus layer overlying duodenal epithelium maintains a pH gradient against high luminal acid concentrations. Despite these adverse conditions, epithelial surface pH remains close to neutrality. The exact nature of the gradient-forming barrier remains unknown. The barrier consists of mucus into which HCO3- is secreted. Quantification of the ability of HCO3- to establish and maintain the gradient depends on accurate measurement of this ion's diffusion coefficient through mucus. We describe new experimental and mathematical methods for diffusion measurement and report diffusion coefficients for HCO3- diffusion through saline, 5% mucin solutions, and rat duodenal mucus. The diffusion coefficients were 20.2 +/- 0.10, 3.02 +/- 0.31, and 1.81 +/- 0.12 x 10(-6) cm2/s, respectively. Modeling of the mucobicarbonate layer with this latter value suggests that for conditions of high luminal acid strength the neutralization of acid by HCO3- occurs just above the epithelial surface. Under these conditions the model predicts that fluid convection toward the lumen could be important in maintaining the pH gradient. In support of this hypothesis we were able to demonstrate a net luminal fluid flux of 5 microliters.min-1.cm-2 after perfusion of 0.15 N HCl in the rat duodenum.

Quantitative SIMS depth profiling of diffusion barrier gate-oxynitride structures in TFT-LCDs.

PubMed

Dreer, Sabine; Wilhartitz, Peter; Piplits, Kurt; Mayerhofer, Karl; Foisner, Johann; Hutter, Herbert

2004-06-01

Gate oxynitride structures of TFT-LCDs were investigated by SIMS, and successful solutions are demonstrated to overcome difficulties arising due to the charging effects of the multilayer systems, the matrix effect of the method, and the small pattern sizes of the samples. Because of the excellent reproducibility achieved by applying exponential relative sensitivity functions for quantitative analysis, minor differences in the barrier gate-oxynitride composition deposited on molybdenum capped aluminium-neodymium metallisation electrodes were determined between the centre and the edge of the TFT-LCD substrates. No differences were found for molybdenum-tungsten metallisations. Furthermore, at the edge of the glass substrates, aluminium, neodymium, and molybdenum SIMS depth profiles show an exponential trend. With TEM micrographs an inhomogeneous thickness of the molybdenum capping is revealed as the source of this effect, which influences the electrical behaviour of the device. The production process was improved after these results and the aging behaviour of TFT-LCDs was investigated in order to explain the change in control voltage occurring during the lifetime of the displays. SIMS and TEM show an enrichment of neodymium at the interface to the molybdenum layer, confirming good diffusion protection of the molybdenum barrier during accelerated aging. The reason for the shift of the control voltage was finally located by semi-quantitative depth profiling of the sodium diffusion originating from the glass substrate. Molybdenum-tungsten was a much better buffer for the highly-mobile charge carriers than aluminium-neodymium. Best results were achieved with PVD silicon oxynitride as diffusion barrier and gate insulator deposited on aluminium-neodymium metallisation layers.

Methane oxidation and formation of EPS in compost: effect of oxygen concentration.

PubMed

Wilshusen, J H; Hettiaratchi, J P A; De Visscher, A; Saint-Fort, R

2004-05-01

Oxygen concentration plays an important role in the regulation of methane oxidation and the microbial ecology of methanotrophs. However, this effect is still poorly quantified in soil and compost ecosystems. The effect of oxygen on the formation of exopolymeric substances (EPS) is as yet unknown. We studied the effect of oxygen on the evolution of methanotrophic activity. At both high and low oxygen concentrations, peak activity was observed twice within a period of 6 months. Phospholipid fatty acid analysis showed that there was a shift from type I to type II methanotrophs during this period. At high oxygen concentration, EPS production was about 250% of the amount at low oxygen concentration. It is hypothesized that EPS serves as a carbon cycling mechanism for type I methanotrophs when inorganic nitrogen is limiting. Simultaneously, EPS stimulates nitrogenase activity in type II methanotrophs by creating oxygen-depleted zones. The kinetic results were incorporated in a simulation model for gas transport and methane oxidation in a passively aerated biofilter. Comparison between the model and experimental data showed that, besides acting as a micro-scale diffusion barrier, EPS can act as a barrier to macro-scale diffusion, reducing the performance of such biofilters.

Superior ionic and electronic properties of ReN2 monolayers for Na-ion battery electrodes.

PubMed

Zhang, Shi-Hao; Liu, Bang-Gui

2018-08-10

Excellent monolayer electrode materials can be used to design high-performance alkali-metal-ion batteries. Here, we propose two-dimensional ReN 2 monolayers as superior sodium-ion battery materials. Our total energy optimization results in a buckled tetragonal structure for the ReN 2 monolayer, and our phonon spectrum and elastic moduli prove that it is dynamically and mechanically stable. Further investigations show that it is metallic and still keeps its metallic feature after the adsorption of Na or K atoms, and the adsorption of Na (or K) atoms changes the lattice parameters by 3.2% (or 3.8%) at most. Its maximum capacity reaches 751 mA h g -1 for Na-ion batteries or 250 mA h g -1 for K-ion batteries, and the diffusion barrier is only 0.027 eV for the Na atom or 0.127 eV for the K atom. The small lattice changes, high storage capacity, metallic feature, and extremely low ion diffusion barriers make the ReN 2 monolayers a superior electrode material for Na-ion rechargeable batteries with ultrafast charging/discharging processes.

A Study to Analyze the Permeation of High Density Gases and Propellant Vapors Through Single Layer Teflon or Teflon Structure Materials and Laminations. Volume 1

NASA Technical Reports Server (NTRS)

Johnson, R. L.; Young, Donald L. (Technical Monitor)

1967-01-01

This report contains the results of a fifteen month analytical and experimental study of the leakage rate of the pressurant gases (N2, He) and the propellant vapors (N2O4,N2H4) through bladder structures consisting of two layers of Teflon separated by a metallic foil diffusion barrier containing microscopic or larger holes. Results were obtained for the steady state leakage rate through circular holes and long rectangular openings in the barrier for arbitrary thicknesses of the two Teflon layers. The effect of hole shape and relative hole position on the leakage rate were studied. The transient problem was analyzed and it was shown that steady state calculations are adequate for estimating the leakage rate. A computer program entitled "Diffusion Analyzer Program" was developed to calculate the leakage rate, both transient and steady state. Finally, the analytical results were compared to experimentally determined values of the leakage rate through a model laminated bladder structure. The results of the analysis are in good agreement with experiment. The experimental effort (Part II of the Bladder Permeation Program) measured the solubility, diffusion coefficient and permeability of helium, nitrogen and nitrogen tetroxide vapor through Teflon TFE and FEP membranes. Data were obtained in the temperature range of 25 to 100 C at pressures ranging from near vacuum to about 20 atmospheres. Results of the experimental effort were compared with the limited data previously reported. As a verification to the applicability of results to actual bladder systems, counter diffusion tests were performed with a laminated sample containing aluminum foil with a selected group of holes.

Barriers to front propagation in laminar, three-dimensional fluid flows

NASA Astrophysics Data System (ADS)

Doan, Minh; Simons, J. J.; Lilienthal, Katherine; Solomon, Tom; Mitchell, Kevin A.

2018-03-01

We present experiments on one-way barriers that block reaction fronts in a fully three-dimensional (3D) fluid flow. Fluorescent Belousov-Zhabotinsky reaction fronts are imaged with laser-scanning in a laminar, overlapping vortex flow. The barriers are analyzed with a 3D extension to burning invariant manifold (BIM) theory that was previously applied to two-dimensional advection-reaction-diffusion processes. We discover tube and sheet barriers that guide the front evolution. The experimentally determined barriers are explained by BIMs calculated from a model of the flow.

Stuffed MO layer as a diffusion barrier in metallizations for high temperature electronics

NASA Technical Reports Server (NTRS)

Boah, J. K.; Russell, V.; Smith, D. P.

1981-01-01

Auger electron spectroscopy was employed to characterize the diffusion barrier properties of molybdenum in the CrSi2/Mo/Au metallization system. The barrier action of Mo was demonstrated to persist even after 2000 hours annealing time at 300 C in a nitrogen ambient. At 340 C annealing temperature, however, rapid interdiffusion was observed to have occurred between the various metal layers after only 261 hours. The presence of controlled amounts of oxygen in the Mo layer is believed to be responsible for suppressing the short circuit interdiffusion between the thin film layers. Above 340 C, its is believed that the increase in the oxygen mobility led to deterioration of its stuffing action, resulting in the rapid interdiffusion of the thin film layers along grain boundaries.

Measuring the continuity of diffusion barriers on porous films using γ-ray energy spectra of escaping positronium

NASA Astrophysics Data System (ADS)

Xu, Jun; Mills, Allen P.; Case, Carlye

2005-08-01

Diffusion barriers for capping porous low dielectric constant films are important for preventing metal migration into a semiconductor circuit. Using the fact that positrons implanted into a porous dielectric form ortho-positronium (o-Ps) copiously, Gidley et al. [D. W. Gidley, W. F. Frieze, T. L. Dull, J. Sun, A. F. Yee, C. V. Nguyen, and D. Y. Yoon, Appl. Phys. Lett. 76, 1282 (2000)], have been able to measure open area fractions as low as 10-5 in porous dielectric film barrier layers from the increase in the ortho-positronium lifetime and intensity associated with positronium escape into vacuum. We demonstrate that it is possible to obtain comparable sensitivities by measuring the gamma-ray energy spectrum of the escaping positronium.

Fractional Brownian motion with a reflecting wall

NASA Astrophysics Data System (ADS)

Wada, Alexander H. O.; Vojta, Thomas

2018-02-01

Fractional Brownian motion, a stochastic process with long-time correlations between its increments, is a prototypical model for anomalous diffusion. We analyze fractional Brownian motion in the presence of a reflecting wall by means of Monte Carlo simulations. Whereas the mean-square displacement of the particle shows the expected anomalous diffusion behavior ˜tα , the interplay between the geometric confinement and the long-time memory leads to a highly non-Gaussian probability density function with a power-law singularity at the barrier. In the superdiffusive case α >1 , the particles accumulate at the barrier leading to a divergence of the probability density. For subdiffusion α <1 , in contrast, the probability density is depleted close to the barrier. We discuss implications of these findings, in particular, for applications that are dominated by rare events.

Electrostatic Estimation of Intercalant Jump-Diffusion Barriers Using Finite-Size Ion Models.

PubMed

Zimmermann, Nils E R; Hannah, Daniel C; Rong, Ziqin; Liu, Miao; Ceder, Gerbrand; Haranczyk, Maciej; Persson, Kristin A

2018-02-01

We report on a scheme for estimating intercalant jump-diffusion barriers that are typically obtained from demanding density functional theory-nudged elastic band calculations. The key idea is to relax a chain of states in the field of the electrostatic potential that is averaged over a spherical volume using different finite-size ion models. For magnesium migrating in typical intercalation materials such as transition-metal oxides, we find that the optimal model is a relatively large shell. This data-driven result parallels typical assumptions made in models based on Onsager's reaction field theory to quantitatively estimate electrostatic solvent effects. Because of its efficiency, our potential of electrostatics-finite ion size (PfEFIS) barrier estimation scheme will enable rapid identification of materials with good ionic mobility.

Development of an ultrahigh-performance infrared detector platform for advanced spectroscopic sensing systems

NASA Astrophysics Data System (ADS)

Jain, Manish; Wicks, Gary; Marshall, Andrew; Craig, Adam; Golding, Terry; Hossain, Khalid; McEwan, Ken; Howle, Chris

2014-05-01

Laser-based stand-off sensing of threat agents (e.g. explosives, toxic industrial chemicals or chemical warfare agents), by detection of distinct infrared spectral absorption signature of these materials, has made significant advances recently. This is due in part to the availability of infrared and terahertz laser sources with significantly improved power and tunability. However, there is a pressing need for a versatile, high performance infrared sensor that can complement and enhance the recent advances achieved in laser technology. This work presents new, high performance infrared detectors based on III-V barrier diodes. Unipolar barrier diodes, such as the nBn, have been very successful in the MWIR using InAs(Sb)-based materials, and in the MWIR and LWIR using type-II InAsSb/InAs superlattice-based materials. This work addresses the extension of the barrier diode architecture into the SWIR region, using GaSb-based and InAs-based materials. The program has resulted in detectors with unmatched performance in the 2-3 μm spectral range. Temperature dependent characterization has shown dark currents to be diffusion limited and equal to, or within a factor of 5, of the Rule 07 expression for Auger-limited HgCdTe detectors. Furthermore, D* values are superior to those of existing detectors in the 2-3 μm band. Of particular significance to spectroscopic sensing systems is the ability to have near-background limited performance at operation temperatures compatible with robust and reliable solid state thermoelectric coolers.

Nonlocal transport in the presence of transport barriers

NASA Astrophysics Data System (ADS)

Del-Castillo-Negrete, D.

2013-10-01

There is experimental, numerical, and theoretical evidence that transport in plasmas can, under certain circumstances, depart from the standard local, diffusive description. Examples include fast pulse propagation phenomena in perturbative experiments, non-diffusive scaling in L-mode plasmas, and non-Gaussian statistics of fluctuations. From the theoretical perspective, non-diffusive transport descriptions follow from the relaxation of the restrictive assumptions (locality, scale separation, and Gaussian/Markovian statistics) at the foundation of diffusive models. We discuss an alternative class of models able to capture some of the observed non-diffusive transport phenomenology. The models are based on a class of nonlocal, integro-differential operators that provide a unifying framework to describe non- Fickian scale-free transport, and non-Markovian (memory) effects. We study the interplay between nonlocality and internal transport barriers (ITBs) in perturbative transport including cold edge pulses and power modulation. Of particular interest in the nonlocal ``tunnelling'' of perturbations through ITBs. Also, flux-gradient diagrams are discussed as diagnostics to detect nonlocal transport processes in numerical simulations and experiments. Work supported by the US Department of Energy.

Kinetic Monte Carlo Investigation of the Effects of Vacancy Pairing on Oxygen Diffusivity in Yttria-Stabilized Zirconia

NASA Technical Reports Server (NTRS)

Good, Brian S.

2011-01-01

Yttria-stabilized zirconia s high oxygen diffusivity and corresponding high ionic conductivity, and its structural stability over a broad range of temperatures, have made the material of interest for use in a number of applications, for example, as solid electrolytes in fuel cells. At low concentrations, the stabilizing yttria also serves to increase the oxygen diffusivity through the presence of corresponding oxygen vacancies, needed to maintain charge neutrality. At higher yttria concentration, however, diffusivity is impeded by the larger number of relatively high energy migration barriers associated with yttrium cations. In addition, there is evidence that oxygen vacancies preferentially occupy nearest-neighbor sites around either dopant or Zr cations, further affecting vacancy diffusion. We present the results of ab initio calculations that indicate that it is energetically favorable for oxygen vacancies to occupy nearest-neighbor sites adjacent to Y ions, and that the presence of vacancies near either species of cation lowers the migration barriers. Kinetic Monte Carlo results from simulations incorporating this effect are presented and compared with results from simulations in which the effect is not present.

Hydrogen-permeable composite metal membrane and uses thereof

DOEpatents

Edlund, D.J.; Friesen, D.T.

1993-06-08

Various hydrogen production and hydrogen sulfide decomposition processes are disclosed that utilize composite metal membranes that contain an intermetallic diffusion barrier separating a hydrogen-permeable base metal and a hydrogen-permeable coating metal. The barrier is a thermally stable inorganic proton conductor.

Submonolayer Ag films on Fe(100): A first-principles analysis of energetics controlling adlayer thermodynamics and kinetics

DOE PAGES

Li, Wei; Huang, Li; Evans, James W.; ...

2016-04-11

Epitaxial growth of Ag on Fe(100) and postdeposition relaxation have been studied in several experiments. We provide a first-principles density functional theory analysis of key adatom interaction energies and diffusion barriers controlling growth and relaxation kinetics for the submonolayer regime, as these have not been assessed previously. A cluster expansion approach is used to obtain an extensive set of conventional lateral interactions between adatoms on fourfold hollow adsorption sites. We find robust oscillatory decay of pair interactions with increasing separation, and of trio interactions with increasing perimeter length. First- and second-nearest-neighbor pair interactions, as well as compact linear and bentmore » trio interactions, dominate. The adatom terrace diffusion barrier is estimated to be E d ≈ 0.39 eV. We also provide a limited analysis of unconventional interactions for which one adatom is at the bridge-site transition state for hopping and one or more others are at fourfold hollow sites. Furthermore, energy barriers for diffusion along island edges can be determined with the aid of both conventional and unconventional interactions.« less

Fabrication of fine-grain tantalum diffusion barrier tube for Nb3Sn conductors

NASA Astrophysics Data System (ADS)

Hartwig, K. T.; Balachandran, S.; Mezyenski, R.; Seymour, N.; Robinson, J.; Barber, R. E.

2014-01-01

Diffusion barriers used in Nb3Sn wire are often fabricated by wrapping Ta sheet into a tube with an overlap seam. A common result of such practice is non-uniform deformation in the Ta sheet as it thins by wire drawing because of non-uniform grain size and texture in the original Ta sheet. Seamless Ta tube with a fine-grain and uniform microstructure would be much better for the diffusion barrier application, but such material is expensive and difficult to manufacture. This report presents results on a new fabrication strategy for Ta tube that shows promise for manufacture of less costly tube with an improved microstructure. The fabrication method begins with seam-welded tube but gives a fine-grain uniform microstructure with little difference between the longitudinal seam weld region and the parent metal after post-weld processing. Severe plastic deformation processing (SPD) applied by area reduction extrusion and tube equal channel angular extrusion (tECAE) are used to refine and homogenize the microstructure. Microstructure and mechanical property results are presented for Ta tubes fabricated by this new processing strategy.

Micro-CT X-ray imaging exposes structured diffusion barriers within biofilms.

PubMed

Keren-Paz, Alona; Brumfeld, Vlad; Oppenheimer-Shaanan, Yaara; Kolodkin-Gal, Ilana

2018-01-01

In nature, bacteria predominantly exist as highly structured biofilms, which are held together by extracellular polymeric substance and protect their residents from environmental insults, such as antibiotics. The mechanisms supporting this phenotypic resistance are poorly understood. Recently, we identified a new mechanism maintaining biofilms - an active production of calcite minerals. In this work, a high-resolution and robust µCT technique is used to study the mineralized areas within intact bacterial biofilms. µCT is a vital tool for visualizing bacterial communities that can provide insights into the relationship between bacterial biofilm structure and function. Our results imply that dense and structured calcium carbonate lamina forms a diffusion barrier sheltering the inner cell mass of the biofilm colony. Therefore, µCT can be employed in clinical settings to predict the permeability of the biofilms. It is demonstrated that chemical interference with urease, a key enzyme in biomineralization, inhibits the assembly of complex bacterial structures, prevents the formation of mineral diffusion barriers and increases biofilm permeability. Therefore, biomineralization enzymes emerge as novel therapeutic targets for highly resistant infections.

Integration of perovskite oxide dielectrics into complementary metal-oxide-semiconductor capacitor structures using amorphous TaSiN as oxygen diffusion barrier

NASA Astrophysics Data System (ADS)

Mešić, Biljana; Schroeder, Herbert

2011-09-01

The high permittivity perovskite oxides have been intensively investigated for their possible application as dielectric materials for stacked capacitors in dynamic random access memory circuits. For the integration of such oxide materials into the CMOS world, a conductive diffusion barrier is indispensable. An optimized stack p++-Si/Pt/Ta21Si57N21/Ir was developed and used as the bottom electrode for the oxide dielectric. The amorphous TaSiN film as oxygen diffusion barrier showed excellent conductive properties and a good thermal stability up to 700 °C in oxygen ambient. The additional protective iridium layer improved the surface roughness after annealing. A 100-nm-thick (Ba,Sr)TiO3 film was deposited using pulsed laser deposition at 550 °C, showing very promising properties for application; the maximum relative dielectric constant at zero field is κ ≈ 470, and the leakage current density is below 10-6 A/cm2 for fields lower then ± 200 kV/cm, corresponding to an applied voltage of ± 2 V.

Ab initio calculation of diffusion barriers for Cu adatom hopping on Cu(1 0 0) surface and evolution of atomic configurations

NASA Astrophysics Data System (ADS)

Zhang, Wei; Gan, Jie; Li, Qian; Gao, Kun; Sun, Jian; Xu, Ning; Ying, Zhifeng; Wu, Jiada

2011-06-01

The self-diffusion dynamics of Cu adatoms on Cu(1 0 0) surface has been studied based on the calculation of the energy barriers for various hopping events using lattice-gas based approach and a modified model. To simplify the description of the interactions and the calculation of the energy barrier, a three-tier hierarchy of description of atomic configurations was conceived in which the active adatom and its nearest atoms were chosen to constitute basic configuration and taken as a whole to study many-body interactions of the atoms in various atomic configurations, whereas the impacts of the next nearest atoms on the diffusion of the active adatom were considered as multi-site interactions. Besides the simple hopping of single adatoms, the movements of dimers and trimers as the results of multiple hopping events have also been examined. Taking into account the hopping events of all adatoms, the stability of atomic configurations has been examined and the evolution of atomic configurations has also been analyzed.

Position-Dependent Diffusion Tensors in Anisotropic Media from Simulation: Oxygen Transport in and through Membranes.

PubMed

Ghysels, An; Venable, Richard M; Pastor, Richard W; Hummer, Gerhard

2017-06-13

A Bayesian-based methodology is developed to estimate diffusion tensors from molecular dynamics simulations of permeants in anisotropic media, and is applied to oxygen in lipid bilayers. By a separation of variables in the Smoluchowski diffusion equation, the multidimensional diffusion is reduced to coupled one-dimensional diffusion problems that are treated by discretization. The resulting diffusivity profiles characterize the membrane transport dynamics as a function of the position across the membrane, discriminating between diffusion normal and parallel to the membrane. The methodology is first validated with neat water, neat hexadecane, and a hexadecane slab surrounded by water, the latter being a simple model for a lipid membrane. Next, a bilayer consisting of pure 1-palmitoyl 2-oleoylphosphatidylcholine (POPC), and a bilayer mimicking the lipid composition of the inner mitochondrial membrane, including cardiolipin, are investigated. We analyze the detailed time evolution of oxygen molecules, in terms of both normal diffusion through and radial diffusion inside the membrane. Diffusion is fast in the more loosely packed interleaflet region, and anisotropic, with oxygen spreading more rapidly in the membrane plane than normal to it. Visualization of the propagator shows that oxygen enters the membrane rapidly, reaching its thermodynamically favored center in about 1 ns, despite the free energy barrier at the headgroup region. Oxygen transport is quantified by computing the oxygen permeability of the membranes and the average radial diffusivity, which confirm the anisotropy of the diffusion. The position-dependent diffusion constants and free energies are used to construct compartmental models and test assumptions used in estimating permeability, including Overton's rule. In particular, a hexadecane slab surrounded by water is found to be a poor model of oxygen transport in membranes because the relevant energy barriers differ substantially.

Retention and diffusion of H, He, O, C impurities in Be

NASA Astrophysics Data System (ADS)

Zhang, Pengbo; Zhao, Jijun; Wen, Bin

2012-04-01

We report the energetics and diffusion behavior of H, He, O, and C impurities in beryllium as fusion materials from first-principles calculations. Among the six interstitial sites in Be, the basal tetrahedral one is most stable for H, He, O, while C prefers to occupy an octahedral site. Solution of O impurity in Be is an exothermic process with solution energy of -2.37 eV, whereas solution of H, C and He is an endothermic process (solution energy: 1.55 eV, 2.46 eV, and 5.70 eV, respectively). Overall speaking, these impurities prefer to diffuse along longer paths. The H and O impurities share the same out-of-plane diffusion path via basal tetrahedral sites, while the He and C impurities in Be mainly diffuse via basal tetrahedral and octahedral sites along the (0 0 1) plane. Diffusion of He in Be is easiest with a lowest barrier of 0.14 eV; whereas H diffusion in Be is also rather fast with migration energies of 0.4 eV. On the contrary, diffusion of C and O impurities is more difficult because of strong bonding with lattice atoms and high energy barriers of 0.42 and 1.63 eV, respectively. Our theoretical results provide the fundamental parameters for understanding the impurity aggregation and bubble formation in early stage of irradiation damage.

Transport and Performance in DIII--D Discharges with Weak or Negative Central Magnetic Shear

NASA Astrophysics Data System (ADS)

Greenfield, C. M.

1996-11-01

The previously reported [B.W. Rice et al., Phys. Plasmas 3, 1983 (1996)] improved performance in DIII-D plasmas with weak or negative central magnetic shear has been additionally enhanced in recent experiments where controlled L-H transitions were used to further broaden the pressure profile and delay detrimental MHD activity [E.A. Lazarus et al., submitted to Phys. Rev. Letters]. These discharges exhibit the highest plasma energy (>=4 MJ) and fusion reactivity (R_DD <= 4.8 × 10^16 s-1, Q_DD <= 0.00146, equivalent Q_DT <= 0.32) yet realized in DIII-D. In such discharges, the core magnetic shear is reversed by tailoring the current profile through application of early, low power, neutral beam injection. These plasmas often undergo a transition to a high performance state, usually following an increase in the applied heating power. At the transition time, we observe the formation of an internal transport barrier near the location of the minimum safety factor, q_min. Formation of this barrier, which can result in central peaking of the temperature and density profiles, is consistent with suppression of turbulence by locally enhanced E×B flow shear. Beam emission spectroscopy and far infrared scattering measurements made in the vicinity of the barrier show that at the time of transition to high performance, fluctuation levels are reduced to below the threshold of detection (tilden/n <= 0.1%). Analysis with the ONETWO and TRANSP transport codes indicates concomitant reductions in the core ion thermal diffusivity to levels at or below Chang-Hinton neoclassical. Smaller reductions are indicated for the electrons. An L-H transition is programmed shortly before the plasma would become MHD unstable in order to broaden the profiles and delay the onset of instabilities. In the resulting state, the region exhibiting ion diffusivities at or below neoclassical is extended to nearly the entire plasma. Analysis to date suggests that the effect of strongly negative vs. weak magnetic shear on transport is negligible, although there is a significant effect on stability. A comparison of transport in strong and weakly sheared discharges will be shown, both in L- (peaked profiles) and H-mode (broadened profiles).

High-throughput ab-initio dilute solute diffusion database

PubMed Central

Wu, Henry; Mayeshiba, Tam; Morgan, Dane

2016-01-01

We demonstrate automated generation of diffusion databases from high-throughput density functional theory (DFT) calculations. A total of more than 230 dilute solute diffusion systems in Mg, Al, Cu, Ni, Pd, and Pt host lattices have been determined using multi-frequency diffusion models. We apply a correction method for solute diffusion in alloys using experimental and simulated values of host self-diffusivity. We find good agreement with experimental solute diffusion data, obtaining a weighted activation barrier RMS error of 0.176 eV when excluding magnetic solutes in non-magnetic alloys. The compiled database is the largest collection of consistently calculated ab-initio solute diffusion data in the world. PMID:27434308

Healing of voids in the aluminum metallization of integrated circuit chips

NASA Technical Reports Server (NTRS)

Cuddihy, Edward F.; Lawton, Russell A.; Gavin, Thomas R.

1990-01-01

The thermal stability of GaAs modulation-doped field effect transistors (MODFETs) is evaluated in order to identify failure mechanisms and validate the reliability of these devices. The transistors were exposed to thermal step-stress and characterized at ambient temperatures to indicate device reliability, especially that of the transistor ohmic contacts with and without molybdenum diffusion barriers. The devices without molybdenum exhibited important transconductance deterioration. MODFETs with molybdenum diffusion barriers were tolerant to temperatures above 300 C. This tolerance indicates that thermally activated failure mechanisms are slow at operational temperatures. Therefore, high-reliability MODFET-based circuits are possible.

Real-time ab initio KMC simulation of the self-assembly and sintering of bimetallic epitaxial nanoclusters: Au + Ag on Ag(100).

PubMed

Han, Yong; Liu, Da-Jiang; Evans, James W

2014-08-13

Far-from-equilibrium shape and structure evolution during formation and post-assembly sintering of bimetallic nanoclusters is extremely sensitive to the periphery diffusion and intermixing kinetics. Precise characterization of the many distinct local-environment-dependent diffusion barriers is achieved for epitaxial nanoclusters using density functional theory to assess interaction energies both with atoms at adsorption sites and at transition states. Kinetic Monte Carlo simulation incorporating these barriers then captures structure evolution on the appropriate time scale for two-dimensional core-ring and intermixed Au-Ag nanoclusters on Ag(100).

Real-Time Ab Initio KMC Simulation of the Self-Assembly and Sintering of Bimetallic Epitaxial Nanoclusters: Au + Ag on Ag(100)

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

Han, Yong; Liu, Da-Jiang; Evans, James W

2014-08-13

Far-from-equilibrium shape and structure evolution during formation and post-assembly sintering of bimetallic nanoclusters is extremely sensitive to the periphery diffusion and intermixing kinetics. Precise characterization of the many distinct local-environment-dependent diffusion barriers is achieved for epitaxial nanoclusters using density functional theory to assess interaction energies both with atoms at adsorption sites and at transition states. Kinetic Monte Carlo simulation incorporating these barriers then captures structure evolution on the appropriate time scale for two-dimensional core-ring and intermixed Au-Ag nanoclusters on Ag(100).

Simulating Radionuclide Migrations of Low-level Wastes in Nearshore Environment

NASA Astrophysics Data System (ADS)

Lu, C. C.; Li, M. H.; Chen, J. S.; Yeh, G. T.

2016-12-01

Tunnel disposal into nearshore mountains was tentatively selected as one of final disposal sites for low-level wastes in Taiwan. Safety assessment on radionuclide migrations in far-filed may involve geosphere processes under coastal environments and into nearshore ocean. In this study the 3-D HYDROFEOCHE5.6 numerical model was used to perform simulations of groundwater flow and radionuclide transport with decay chains. Domain of interest on the surface includes nearby watersheds delineated by digital elevation models and nearshore seabed. As deep as 800 m below the surface and 400 m below sea bed were considered for simulations. The disposal site was located at 200m below the surface. Release rates of radionuclides from near-field was estimated by analytical solutions of radionuclide diffusion with decay out of engineered barriers. Far-field safety assessments were performed starting from the release of radionuclides out of engineered barriers to a time scale of 10,000 years. Sensitivity analyses of geosphere and transport parameters were performed to improve our understanding of safety on final disposal of low-level waste in nearshore environments.

Altered Blood-Brain Barrier Permeability in Patients With Systemic Lupus Erythematosus: A Novel Imaging Approach.

PubMed

Gulati, Gaurav; Jones, Jordan T; Lee, Gregory; Altaye, Mekibib; Beebe, Dean W; Meyers-Eaton, Jamie; Wiley, Kasha; Brunner, Hermine I; DiFrancesco, Mark W

2017-02-01

To evaluate a safe, noninvasive magnetic resonance imaging (MRI) method to measure regional blood-brain barrier integrity and investigate its relationship with neurocognitive function and regional gray matter volume in juvenile-onset systemic lupus erythematosus (SLE). In this cross-sectional, case-control study, capillary permeability was measured as a marker of blood-brain barrier integrity in juvenile SLE patients and matched healthy controls, using a combination of arterial spin labeling and diffusion-weighted brain MRI. Regional gray matter volume was measured by voxel-based morphometry. Correlation analysis was done to investigate the relationship between regional capillary permeability and regional gray matter volume. Formal neurocognitive testing was completed (measuring attention, visuoconstructional ability, working memory, and psychomotor speed), and scores were regressed against regional blood-brain barrier integrity among juvenile SLE patients. Formal cognitive testing confirmed normal cognitive ability in all juvenile SLE subjects (n = 11) included in the analysis. Regional capillary permeability was negatively associated (P = 0.026) with neurocognitive performance concerning psychomotor speed in the juvenile SLE cohort. Compared with controls (n = 11), juvenile SLE patients had significantly greater capillary permeability involving Brodmann's areas 19, 28, 36, and 37 and caudate structures (P < 0.05 for all). There is imaging evidence of increased regional capillary permeability in juvenile SLE patients with normal cognitive performance using a novel noninvasive MRI technique. These blood-brain barrier outcomes appear consistent with functional neuronal network alterations and gray matter volume loss previously observed in juvenile SLE patients with overt neurocognitive deficits, supporting the notion that blood-brain barrier integrity loss precedes the loss of cognitive ability in juvenile SLE. Longitudinal studies are needed to confirm the findings of this pilot study. © 2016, American College of Rheumatology.

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.

Effects of epitaxial structure and processing on electrical characteristics of InAs-based nBn infrared detectors

NASA Astrophysics Data System (ADS)

Du, X.; Savich, G. R.; Marozas, B. T.; Wicks, G. W.

2017-02-01

The conventional processing of the III-V nBn photodetectors defines mesa devices by etching the contact n-layer and stopping immediately above the barrier, i.e., a shallow etch. This processing enables great suppression of surface leakage currents without having to explore surface passivation techniques. However, devices that are made with this processing scheme are subject to lateral diffusion currents. To address the lateral diffusion current, we compare the effects of different processing approaches and epitaxial structures of nBn detectors. The conventional solution for eliminating lateral diffusion current, a deep etch through the barrier and the absorber, creates increased dark currents and an increased device failure rate. To avoid deep etch processing, a new device structure is proposed, the inverted-nBn structure. By comparing with the conventional nBn structure, the results show that the lateral diffusion current is effectively eliminated in the inverted-nBn structure without elevating the dark currents.

Back-diffusion--fact or fiction?

PubMed

Thjodleifsson, B; Wormsley, K G

1977-01-01

Alterations in the concentration of acid in gastric juice secreted at different flow rates and disappearance of acid from the gastric lumen, when the gastric mucosa is exposed to acid luminal contents, have been interpreted as indicating "back-diffusion" of acid into the gastric mucosa from the luminal contents. The loss of acid from the gastric contents increases when the mucosa is exposed to certain drugs or is diseased, giving rise to the suggestion that the increased degree of "back-diffusion" of acid indicates mucosal damage, reflecting a breakdown of the gastric mucosal "barrier" to back-diffusion of acid from the gastric lumen. The change in the "barrier" properties of the gastric mucosa has been found to be associated with change in the electrical properties of the mucosa, so that alterations of the transmucosal potential difference has been considered to denote gastric mucosal damage. The case for every one of these hypotheses and for their underlying assumptions is discussed and found wanting for lack of direct evidence.

An in vitro assay for entry into cilia reveals unique properties of the soluble diffusion barrier

PubMed Central

Breslow, David K.; Koslover, Elena F.; Seydel, Federica; Spakowitz, Andrew J.

2013-01-01

Specific proteins are concentrated within primary cilia, whereas others remain excluded. To understand the mechanistic basis of entry into cilia, we developed an in vitro assay using cells in which the plasma membrane was permeabilized, but the ciliary membrane was left intact. Using a diffusion-to-capture system and quantitative analysis, we find that proteins >9 nm in diameter (∼100 kD) are restricted from entering cilia, and we confirm these findings in vivo. Interference with the nuclear pore complex (NPC) or the actin cytoskeleton in permeabilized cells demonstrated that the ciliary diffusion barrier is mechanistically distinct from those of the NPC or the axon initial segment. Moreover, applying a mass transport model to this system revealed diffusion coefficients for soluble and membrane proteins within cilia that are compatible with rapid exploration of the ciliary space in the absence of active transport. Our results indicate that large proteins require active transport for entry into cilia but not necessarily for movement inside cilia. PMID:24100294

Diffusion of hydrogen into and through γ-iron by density functional theory

NASA Astrophysics Data System (ADS)

Chohan, Urslaan K.; Koehler, Sven P. K.; Jimenez-Melero, Enrique

2018-06-01

This study is concerned with the early stages of hydrogen embrittlement on an atomistic scale. We employed density functional theory to investigate hydrogen diffusion through the (100), (110) and (111) surfaces of γ-Fe. The preferred adsorption sites and respective energies for hydrogen adsorption were established for each plane, as well as a minimum energy pathway for diffusion. The H atoms adsorb on the (100), (110) and (111) surfaces with energies of ∼4.06 eV, ∼3.92 eV and ∼4.05 eV, respectively. The barriers for bulk-like diffusion for the (100), (110) and (111) surfaces are ∼0.6 eV, ∼0.5 eV and ∼0.7 eV, respectively. We compared these calculated barriers with previously obtained experimental data in an Arrhenius plot, which indicates good agreement between experimentally measured and theoretically predicted activation energies. Texturing austenitic steels such that the (111) surfaces of grains are preferentially exposed at the cleavage planes may be a possibility to reduce hydrogen embrittlement.

Inter-diffusion analysis of joint interface of tungsten-rhenium couple

NASA Astrophysics Data System (ADS)

Hua, Y. F.; Li, Z. X.; Zhang, X.; Du, J. H.; Huang, C. L.; Du, M. H.

2011-09-01

The tungsten-rhenium couple was prepared by using glow plasma physical vapor deposition (PVD) on the isotropic fine grained graphite (IG) substrates. Diffusion anneals of the tungsten-rhenium couple were conducted at the temperature from 1100 °C to 1400 °C to investigate the inter-diffusion behaviors. The results showed that the thickness of the inter-diffusion zone increased with increasing annealing temperature. The relationship between the inter-diffusion coefficient and the annealing temperature accorded with the Arrhenius manner. The value of inter-diffusion activation energies was 189 kJ/mole (1.96 eV). The service time of tungsten-rhenium multilayer diffusion barrier was limited by the inter-diffusion for rhenium and tungsten rather than the diffusion of carbon in rhenium.

Controlled growth of vertically aligned carbon nanotubes on metal substrates

NASA Astrophysics Data System (ADS)

Gao, Zhaoli

Carbon nanotube (CNT) is a fascinating material with extraordinary electrical thermal and mechanical properties. Growing vertically aligned CNT (VACNT) arrays on metal substrates is an important step in bringing CNT into practical applications such as thermal interface materials (TIMs) and microelectrodes. However, the growth process is challenging due to the difficulties in preventing catalyst diffusion and controlling catalyst dewetting on metal substrates with physical surface heterogeneity. In this work, the catalyst diffusion mechanism and catalyst dewetting theory were studied for the controlled growth of VACNTs on metal substrates. The diffusion time of the catalyst, the diffusion coefficients for the catalyst in the substrate materials and the number density of catalyst nanoparticles after dewetting are identified as the key parameters, based on which three strategies are developed. Firstly, a fast-heating catalyst pretreatment strategy was used, aiming at preserving the amount of catalyst prior to CNT growth by reducing the catalyst diffusion time. The catalyst lifetime is extended from half an hour to one hour on a patterned Al thin film and a VACNT height of 106 mum, about twenty fold of that reported in the literature, was attained. Secondly, a diffusion barrier layer strategy is employed for a reduction of catalyst diffusion into the substrate materials. Enhancement of VACNT growth on Cu substrates was achieved by adopting a conformal Al2O 3 diffusion barrier layer fabricated by a specially designed atomic layer deposition (ALD) system. Lastly, a novel catalyst glancing angle deposition (GLAD) strategy is performed to manipulate the morphology of a relatively thick catalyst on metal substrates with physical surface heterogeneity, aiming to obtain uniform and dense catalyst nanoparticles after dewetting in the pretreatment process for enhanced VACNT growth. We are able to control the VACNT growth conditions on metal substrates in terms of their distribution, heights and alignments. Catalyst loss is controlled by the catalyst diffusion time and catalyst diffusion coefficients. A shorter catalyst diffusion time and smaller diffusion coefficient enhance VACNT growth on metals due to reduced catalyst loss during the pretreatment process. The dewetting behaviors of the thin film catalysts are influenced by the physical surface heterogeneity of the substrates which leads to non-uniform growth of VACNTs. The GLAD process facilitates the deposition of a relatively thick catalyst layer for the creation of dense and uniform catalyst nanoparticles. Applications of VACNT-metal structures in TIMs and microelectrodes are demonstrated. The VACNT-TIMs fabricated on Al alloy substrates have a typical thermal contact resistivity of 17.1 mm2˙K/W and their effective application in high-brightness LED thermal management was demonstrated. Electrochemical characterization was carried out on VACNT microelectrodes for the development of high resolution retinal prostheses and a satisfactory electrochemical property was again demonstrated.

Fractional Brownian motion with a reflecting wall.

PubMed

Wada, Alexander H O; Vojta, Thomas

2018-02-01

Fractional Brownian motion, a stochastic process with long-time correlations between its increments, is a prototypical model for anomalous diffusion. We analyze fractional Brownian motion in the presence of a reflecting wall by means of Monte Carlo simulations. Whereas the mean-square displacement of the particle shows the expected anomalous diffusion behavior 〈x^{2}〉∼t^{α}, the interplay between the geometric confinement and the long-time memory leads to a highly non-Gaussian probability density function with a power-law singularity at the barrier. In the superdiffusive case α>1, the particles accumulate at the barrier leading to a divergence of the probability density. For subdiffusion α<1, in contrast, the probability density is depleted close to the barrier. We discuss implications of these findings, in particular, for applications that are dominated by rare events.

Measuring the continuity of diffusion barriers on porous films using {gamma}-ray energy spectra of escaping positronium

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

Xu Jun; Mills, Allen P. Jr.; Case, Carlye

2005-08-01

Diffusion barriers for capping porous low dielectric constant films are important for preventing metal migration into a semiconductor circuit. Using the fact that positrons implanted into a porous dielectric form ortho-positronium (o-Ps) copiously, Gidley et al. [D. W. Gidley, W. F. Frieze, T. L. Dull, J. Sun, A. F. Yee, C. V. Nguyen, and D. Y. Yoon, Appl. Phys. Lett. 76, 1282 (2000)], have been able to measure open area fractions as low as 10{sup -5} in porous dielectric film barrier layers from the increase in the ortho-positronium lifetime and intensity associated with positronium escape into vacuum. We demonstrate thatmore » it is possible to obtain comparable sensitivities by measuring the gamma-ray energy spectrum of the escaping positronium.« less

Ab initio and kinetic Monte Carlo study of lithium diffusion in LiSi, Li12Si7, Li13Si5 and Li15Si4

NASA Astrophysics Data System (ADS)

Moon, Janghyuk; Lee, Byeongchan; Cho, Maenghyo; Cho, Kyeongjae

2016-10-01

The kinetics of lithium atoms in various Li-Si binary compounds are investigated using density functional theory calculations and kinetic Monte Carlo calculations. The values of the Li migration energy barriers are identified by NEB calculations with vacancy-mediated, interstitial and exchange migration mechanisms in crystalline LiSi, Li12Si7, Li13Si4, and Li15Si4. A comparison of these NEB results shows that the vacancy-mediated Li migration is identified as the dominant diffusion mechanisms in Li-Si compounds. The diffusion coefficients of Li in Li-Si compounds at room temperature are determined by KMC simulation. From the KMC results, the recalculated migration energy barriers in LiSi, Li12Si7, Li13Si4, and Li15Si4 correspond to 0.306, 0.301, 0.367 and 0.320 eV, respectively. Compared to the Li migration energy barrier of 0.6 eV in crystalline Si, the drastic reduction in the Li migration energy barriers in the lithiated silicon indicates that the initial lithiation of the Si anode is the rate-limiting step. Furthermore, it is also found that Si migration is possible in Li-rich configurations. On the basis of these findings, the underlying mechanisms of kinetics on the atomic scale details are elucidated.

Memory effects in funnel ratchet of self-propelled particles

NASA Astrophysics Data System (ADS)

Hu, Cai-Tian; Wu, Jian-Chun; Ai, Bao-Quan

2017-05-01

The transport of self-propelled particles with memory effects is investigated in a two-dimensional periodic channel. Funnel-shaped barriers are regularly arrayed in the channel. Due to the asymmetry of the barriers, the self-propelled particles can be rectified. It is found that the memory effects of the rotational diffusion can strongly affect the rectified transport. The memory effects do not always break the rectified transport, and there exists an optimal finite value of correlation time at which the rectified efficiency takes its maximal value. We also find that the optimal values of parameters (the self-propulsion speed, the translocation diffusion coefficient, the rotational noise intensity, and the self-rotational diffusion coefficient) can facilitate the rectified transport. When introducing a finite load, particles with different self-propulsion speeds move to different directions and can be separated.

Electronic Devices with Diffusion Barrier and Process for Making Same

DTIC Science & Technology

2001-05-09

conductivity metallization materials such as gold , silver, and platinum. As can be appreciated from the foregoing, a barrier film is needed which... gold ), as well as platinum. These metals are highly attractive 10 for interconnect strategies on account of there intrinsic low resistivity and...the monolayer portion of the barrier -7- material. The monolayer ( monoatomic ) layer of metal atoms and the homoepitaxial film of metal halide

Profiling of barrier capacitance and spreading resistance using a transient linearly increasing voltage technique.

PubMed

Gaubas, E; Ceponis, T; Kusakovskij, J

2011-08-01

A technique for the combined measurement of barrier capacitance and spreading resistance profiles using a linearly increasing voltage pulse is presented. The technique is based on the measurement and analysis of current transients, due to the barrier and diffusion capacitance, and the spreading resistance, between a needle probe and sample. To control the impact of deep traps in the barrier capacitance, a steady state bias illumination with infrared light was employed. Measurements of the spreading resistance and barrier capacitance profiles using a stepwise positioned probe on cross sectioned silicon pin diodes and pnp structures are presented.

A study of dynamical evolution of small two-dimensional Copper islands’ diffusion on Ag(111) surface and observed surface effects

NASA Astrophysics Data System (ADS)

Hayat, Sardar Sikandar; Rehman, Zakirur; Shah, Zulfiqar Ali

2017-11-01

We study the diffusion of two-dimensional Cun(1 ≤ n ≤ 9) islands on Ag(111) surface using molecular dynamics (MD) simulations. The work is the extension of calculations of monomer and dimer Hayat et al. [Phys. Rev. B 82 (2010) 085411] and trimer results Shah et al. [Phys. Lett. A 378 (2014) 1732]. Simulations carried out at three different temperatures — 300, 500, and 700 K — show the concerted motion to be dominant for the smaller islands (2- to 4-atoms), while the shape-changing multiple-atom processes are responsible for the diffusion of larger islands. Arrhenius plots of the diffusion coefficients reveal that the effective energy barrier is less than 260 ± 5 meV for the largest island size of Cu/Ag(111). There is a scaling of the effective energy barrier with size to some extent, but most notably it remains constant for islands with 4- to 6-atoms. The diffusion coefficient increases within a factor of 10 at the three temperatures 300, 500, and 700 K. The observed anharmonic features of the Cun adislands (breakage and pop-up) at Ag(111) surface as well as the surface anharmonicity of the Ag-substrate (fissures, dislocations, vacancy generation, and atomic exchange), are also presented. These findings can serve as an input for kinetic Monte Carlo (KMC) simulations. For the smaller sized islands the variation in the effective energy barrier with the island size is in good agreement with the experimental findings.

Application of minimally invasive pancreatic surgery: an Italian survey.

PubMed

Capretti, Giovanni; Boggi, Ugo; Salvia, Roberto; Belli, Giulio; Coppola, Roberto; Falconi, Massimo; Valeri, Andrea; Zerbi, Alessandro

2018-05-16

The value of minimally invasive pancreatic surgery (MIPS) is still debated. To assess the diffusion of MIPS in Italy and identify the barriers preventing wider implementation, a questionnaire was developed under the auspices of three Scientific Societies (AISP, It-IHPBA, SICE) and was sent to the largest possible number of Italian surgeons also using the mailing list of the two main Italian Surgical Societies (SIC and ACOI). The questionnaire consisted of 25 questions assessing: centre characteristics, facilities and technologies, type of MIPS performed, surgical techniques employed and opinions on the present and future value of MIPS. Only one reply per unit was considered. Fifty-five units answered the questionnaire. While 54 units (98.2%) declared to perform MIPS, the majority of responders were not dedicated to pancreatic surgery. Twenty-five units (45.5%) performed < 20 pancreatic resections/year and 39 (70.9%) < 10 MIPS per year. Forty-nine units (89.1%) performed at least one minimally invasive (MI) distal pancreatectomy (DP), and 10 (18.2%) at least one MI pancreatoduodenectomy (PD). Robotic assistance was used in 18 units (31.7%) (14 DP, 7 PD). The major constraints limiting the diffusion of MIPS were the intrinsic difficulty of the technique and the lack of specific training. The overall value of MIPS was highly rated. Our survey illustrates the current diffusion of MIPS in Italy and underlines the great interest for this approach. Further diffusion of MIPS requires the implementation of standardized protocols of training. Creation of a prospective National Registry should also be considered.

Decontamination systems information and research program. Quarterly report, April--June 1996

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

NONE

This report contains separate reports on the following subtasks: analysis of the Vortec cyclone melting system for remediation of PCB contaminated soils using CFD; drain enhanced soil flushing using prefabricated vertical drains; performance and characteristics evaluation of acrylates as grout barriers; development of standard test protocol barrier design models for desiccation barriers, and for in-situ formed barriers; in-situ bioremediation of chlorinated solvents at Portsmouth Gaseous Diffusion Plant; development of a decision support system and a prototype database for management of the EM50 technology development program; GIS-based infrastructure for site characterization and remediation; treatment of mixed wastes via fluidized bed steammore » reforming; use of centrifugal membrane technology to treat hazardous/radioactive waste; environmental pollution control devices based on novel forms of carbon; development of instrumental methods for analysis of nuclear wastes and environmental materials; production and testing of biosorbents and cleaning solutions for D and D; use of SpinTek centrifugal membrane and sorbents/cleaning solutions for D and D; West Virginia High Tech Consortium Foundation--Environmental support program; small business interaction opportunities; and approach for assessing potential voluntary environmental protection.« less

Current toxicological aspects on drug and chemical transport and metabolism across the human placental barrier.

PubMed

Giaginis, Constantinos; Theocharis, Stamatios; Tsantili-Kakoulidou, Anna

2012-10-01

Placenta plays an obligatory role in fetal growth and development by performing a multitude of functions, including embryo implantation, transport of nutrients and elimination of metabolic waste products and endocrine activity. Drugs and chemicals can transfer across the placental barrier from mother to fetus either by passive diffusion mechanisms and/or via a network of active transporters, which may lead to potential fetotoxicity effects. Placenta also expresses a wide variety of enzymes, being capable of metabolizing a large diversity of drugs and chemicals to metabolites of lower or even higher toxicity than parent compounds. The present review aims to summarize the current toxicological aspects in the emerging topic of drug transport and metabolism across the human placental barrier. There is an emerging demand for accurate assessment of drug transport and metabolism across the human placental barrier, on the basis of a high throughput screening process in the early stages of drug design, to avoid drug candidates from potential fetotoxicity effects. In this aspect, combined studies, which take into account in vivo and in vitro investigations, as well as the ex vivo perfusion method and the recently developed computer-aided technologies, may significantly contribute to this direction.

What is the most efficient respiratory organ for the loricariid air-breathing fish Pterygoplichthys anisitsi, gills or stomach? A quantitative morphological study.

PubMed

da Cruz, André Luis; Fernandes, Marisa Narciso

2016-12-01

The purpose of the present study was to evaluate the morphometric respiratory potential of gills compared to the stomach in obtaining oxygen for aerobic metabolism in Pterygoplichthys anisitsi, a facultative air-breathing fish. The measurements were done using stereological methods. The gills showed greater total volume, volume-to-body mass ratio, potential surface area, and surface-to-volume ratio than the stomach. The water-blood diffusion barrier of the gills is thicker than the air-blood diffusion barrier of the stomach. Taken together, the surface area, the surface-to-volume ratio and the diffusion distance for O 2 transfer from the respiratory medium to blood yield a greater diffusing capacity for gills than for the stomach, suggesting greater importance of aquatic respiration in this species. On the other hand, water breathing is energetically more expensive than breathing air. Under severe hypoxic conditions, O 2 uptake by the stomach is more efficient than by the gills, although the stomach has a much lower diffusing capacity. Thus, P. anisitsi uses gills under normoxic conditions but the stomach may also support aerobic metabolism depending on environmental conditions. Copyright © 2016 Elsevier GmbH. All rights reserved.

Applications and Properties of Ionic Liquid- Based Gels and Soft Solid Composites

NASA Astrophysics Data System (ADS)

Voss, Bret Alan McGinness

2011-12-01

Solid-liquid composites (gels) have a combination of properties that afford new material applications in which high solute diffusion is desirable. These composites have a soft-solid mechanical integrity and will not flow under gravity, but entrain a liquid matrix (i.e. 60-98 mass %) which allows for high diffusion and high reactivity. Room temperature ionic liquid (RTILs) are molten organic salts with a melting point below room temperature and negligible vapor pressure. If the RTILs are used as the liquid component of a gel, then the gel matrix will not evaporate (unlike other organic solvents) and may be used for long term applications. This thesis research applies RTIL gels for two new applications; carbon dioxide/nitrogen separation and chemical warfare agent (CWA) barrier and decontamination. Separating CO2 from the flue gas of coal and gas fired power-plants is an increasingly economically and environmentally important gas separation. In this first study, RTIL gels are cast in a supported membrane and gas permeability and ideal selectivity are measured. The RTIL matrix has an inherent affinity for CO2 and provides a high diffusion, hence high permeability (i.e. 500-700 barrer). The solidifying component is a low molecular-weight organic gelator (LMOG) which through physical bonding interactions (i.e. hydrogen bonding, pi-pi stacking and van der Walls forces) forms an entangled network which provides mechanical stability (i.e. increase trans-membrane pressure required to expel selective material from the support). In these studies two LMOGs and five RTILs are used to make supported gel membranes and determine gas permeability and temperature dependent trends. The second application for RTIL gels is a decontaminating barrier for CWAs and toxic industrial compounds (TICs). In these studies a layer of RTIL gel is applied on top of a substrate contaminated with a CWA simulant (i.e. chloroethylethylsulfide, CEES). The gel performs well as a barrier, preventing CEES vapor from penetrating the gel. Simultaneously, the RTIL gel actively decontaminated the substrate by reacting CEES with a sacrificial amine. The RTIL gel barrier was able to decontaminate up to 98% of the CEES applied to a painted steel substrate. Two gel barriers are tested: (1) RTIL gel with a LMOG solidifying agent, and (2) RTIL gel with a polymeric cross-linked network solidifying agent. The polymer gel provided a more mechanically robust barrier, however, the LMOG gel decontaminated at a faster rate. These new applications are but two of many possible applications for RTIL gels. Their negligible vapor pressure affords long term application in ambient conditions and their unique chemistry allows them to be tailored for specific applications.

Flow control of an elongated jet in cross-flow: Film cooling effectiveness enhancement using surface dielectric barrier discharge plasma actuator

NASA Astrophysics Data System (ADS)

Audier, P.; Fénot, M.; Bénard, N.; Moreau, E.

2016-02-01

The case presented here deals with plasma flow control applied to a cross-flow configuration, more specifically to a film cooling system. The ability of a plasma dielectric barrier discharge actuator for film cooling effectiveness enhancement is investigated through an experimental set-up, including a film injection from an elongated slot into a thermally uniform cross-flow. Two-dimensional particle image velocimetry and infrared-thermography measurements are performed for three different blowing ratios of M = 0.4, 0.5, and 1. Results show that the effectiveness can be increased when the discharge is switched on, as predicted by the numerical results available in literature. Whatever the blowing ratio, the actuator induces a deflection of the jet flow towards the wall, increases its momentum, and delays its diffusion in the cross-flow.

Unconfined lateral diffusion and an estimate of pericellular matrix viscosity revealed by measuring the mobility of gold-tagged lipids

PubMed Central

1993-01-01

Nanovid (video-enhanced) microscopy was used to determine whether lateral diffusion in the plasma membrane of colloidal gold-tagged lipid molecules is confined or is unrestricted. Confinement could be produced by domains within the plane of the plasma membrane or by filamentous barriers within the pericellular matrix. Fluorescein- phosphatidylethanolamine (F1-PE), incorporated into the plasma membranes of cultured fibroblasts, epithelial cells and keratocytes, was labeled with 30-nm colloidal gold conjugated to anti-fluorescein (anti-F1). The trajectories of the gold-labeled lipids were used to compute diffusion coefficients (DG) and to test for restricted motion. On the cell lamella, the gold-labeled lipids diffused freely in the plasma membrane. Since the gold must move through the pericellular matrix as the attached lipid diffuses in the plasma membrane, this result suggests that any extensive filamentous barriers in the pericellular matrix are at least 40 nm from the plasma membrane surface. The average diffusion coefficients ranged from 1.1 to 1.7 x 10(-9) cm2/s. These values were lower than the average diffusion coefficients (DF) (5.4 to 9.5 x 10(-9) cm2/s) obtained by FRAP. The lower DG is partially due to the pericellular matrix as demonstrated by the result that heparinase treatment of keratocytes significantly increased DG to 2.8 x 10(-9) cm2/s, but did not affect DF. Pericellular matrix viscosity was estimated from the frictional coefficients computed from DG and DF and ranged from 0.5 to 0.9 poise for untreated cells. Heparinase treatment of keratocytes decreased the apparent viscosity to approximately 0.1 poise. To evaluate the presence of domains or barriers, the trajectories and corresponding mean square displacement (MSD) plots of gold-labeled lipids were compared to the trajectories and MSD plots resulting from computer simulations of random walks within corrals. Based on these comparisons, we conclude that, if there are domains limiting the diffusion of F1-PE, most are larger than 5 microns in diameter. PMID:8416991

[The mechanism of the transport of organophosphorus compounds across the histo-hematic barriers].

PubMed

Miroshkina, V N; Kosmachev, A B; Salova, L S

1999-01-01

It was demonstrated in experiments on mice [correction of rats] that the transport of organophosphorus compounds (OPC) through membranes of the histohematic barriers (HHB) of the organism occurs by means of diffusion. The rate of this process depends on the interaction of OPC with the specific sites of binding with the tissues, among which the enzyme carboxylesterase plays an important part. It is suggested that both the rate and direction of OPC diffusion are determined by the relationship between the values of affinity of the ligands for the sites of their specific binding found on both sides of the HHB.

Electron-Beam-Induced Deposition as a Technique for Analysis of Precursor Molecule Diffusion Barriers and Prefactors.

PubMed

Cullen, Jared; Lobo, Charlene J; Ford, Michael J; Toth, Milos

2015-09-30

Electron-beam-induced deposition (EBID) is a direct-write chemical vapor deposition technique in which an electron beam is used for precursor dissociation. Here we show that Arrhenius analysis of the deposition rates of nanostructures grown by EBID can be used to deduce the diffusion energies and corresponding preexponential factors of EBID precursor molecules. We explain the limitations of this approach, define growth conditions needed to minimize errors, and explain why the errors increase systematically as EBID parameters diverge from ideal growth conditions. Under suitable deposition conditions, EBID can be used as a localized technique for analysis of adsorption barriers and prefactors.

Study of Nickel Silicide as a Copper Diffusion Barrier in Monocrystalline Silicon Solar Cells

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

Kale, Abhijit; Beese, Emily; Saenz, Theresa

NiSi as a conductive diffusion barrier to silicon has been studied. We demonstrate that the NiSi films formed using the single step annealing process are as good as the two step process using XRD and Raman. Quality of NiSi films formed using e-beam Ni and electroless Ni process has been compared. Incomplete surface coverage and presence of constituents other than Ni are the main challenges with electroless Ni. We also demonstrate that Cu reduces the thermal stability of NiSi films. The detection of Cu has proven to be difficult due to temperature limitations.

Information and communication technology: students' health education in 1st- to 6th-grade South Korea elementary schools.

PubMed

Lee, Eunjoo; Park, Hyejin; Whyte, James; Jeong, Eunhoe

2013-09-01

The purposes of this study were to (1) identify school nurses' awareness of information and communication technology (ICT) use in students' health education and (2) explore the barriers or reasons for the adoption of ICT in school nursing practice, while (3) presenting strategies to speed ICT diffusion and dissemination into practice. For data collection, 209 primary school nurses in K province of Korea were selected and e-mailed the questionnaires. Collected data were analyzed as frequency, percentages, and chi-square tests. The major reasons to adopt ICT were increasing school nurses' confidence in providing health education and improving teaching methods using diverse multimedia. The major barriers to utilization of ICT were lack of time for preparation of educational materials, lack of software availability, and lack of computer skills of school nurses and students. Several strategies were suggested to speed the diffusion of ICT into students' health education, such as integrating a health education course into regular curriculum. It is important to identify barriers and reasons for adoption of ICT in school nursing. In addition, strategies should be emphasized that result in more rapid diffusion of these technologies in school nursing practice. © 2013, American School Health Association.

Controlled release of betamethasone from vitamin E-loaded silicone-based soft contact lenses.

PubMed

Rad, Maryam Shayani; Sajadi Tabassi, Sayyed Abolghasem; Moghadam, Maryam Hassanpour; Mohajeri, Seyed Ahmad

2016-11-01

Betamethasone (BMZ) is an effective drug which is commonly used as an eye drop for the management of ophthalmic inflammations. Due to low ocular bioavailability, it is necessary to prepare and optimize an ocular drug delivery system for BMZ. In this study we tried to use vitamin E diffusion barrier for sustaining BMZ release. Three commercial contact lenses were soaked in vitamin E solutions and swelling percentage, diameter, transmittance, binding capacity and release amount and time were evaluated in comparison with non-vitamin E-loaded pure lenses. The results showed that vitamin E significantly decreased water content of contact lenses whereas, increased the lens diameter in both dry and wet states. It effectively blocked UV radiation which is harmful for the eye surface while had no significant effect on visible transmittance. BMZ loading capacity enhanced and release rate remarkably decreased after using vitamin E as a hydrophobic diffusion barrier. This study revealed that vitamin E can be applied as a hydrophobic diffusion barrier for controlling and sustaining BMZ release from silicone-based soft contact lenses into the lachrymal fluid. It can also protect eye tissues as an antioxidant by blocking the UV radiation.

Low-Resistance Spin Injection into Silicon Using Graphene Tunnel Barriers

DTIC Science & Technology

2012-11-01

compromise spin injection/transport/detection. Ferromagnetic metals readily form silicides even at room tempera- ture19, and diffusion of the ferromagnetic... metal /tunnel barrier/Si contacts using 2 nm SiO2 (triangles), 1.5 nm Al2O3 (diamond) and monolayer graphene (circles) tunnel barriers prepared from...and B. T. Jonker* Spin manipulation in a semiconductor offers a new paradigm for device operation beyond Moore’s law. Ferromagnetic metals are ideal

Multilevel Dual Damascene copper interconnections

NASA Astrophysics Data System (ADS)

Lakshminarayanan, S.

Copper has been acknowledged as the interconnect material for future generations of ICs to overcome the bottlenecks on speed and reliability present with the current Al based wiring. A new set of challenges brought to the forefront when copper replaces aluminum, have to be met and resolved to make it a viable option. Unit step processes related to copper technology have been under development for the last few years. In this work, the application of copper as the interconnect material in multilevel structures with SiO2 as the interlevel dielectric has been explored, with emphasis on integration issues and complete process realization. Interconnect definition was achieved by the Dual Damascene approach using chemical mechanical polishing of oxide and copper. The choice of materials used as adhesion promoter/diffusion barrier included Ti, Ta and CVD TiN. Two different polish chemistries (NH4OH or HNO3 based) were used to form the interconnects. The diffusion barrier was removed during polishing (in the case of TiN) or by a post CMP etch (as with Ti or Ta). Copper surface passivation was performed using boron implantation and PECVD nitride encapsulation. The interlevel dielectric way composed of a multilayer stack of PECVD SiO2 and SixNy. A baseline process sequence which ensured the mechanical and thermal compatibility of the different unit steps was first created. A comprehensive test vehicle was designed and test structures were fabricated using the process flow developed. Suitable modifications were subsequently introduced in the sequence as and when processing problems were encountered. Electrical characterization was performed on the fabricated devices, interconnects, contacts and vias. The structures were subjected to thermal stressing to assess their stability and performance. The measurement of interconnect sheet resistances revealed lower copper loss due to dishing on samples polished using HNO3 based slurry. Interconnect resistances remained stable upto 400oC, 500oC and 600oC for Ti, TiN and Ta barriers respectively. Via resistivity on the order of 10-9/ /Omegacm2 was measured for Cu/Ta/Cu interfaces and no degradation in the via resistance was observed upto 600oC on the 2 μm and 3 μm wide contact windows. Characterization of diode leakage and subthreshold currents of CMOS transistors fabricated with Ta adhesion layers, showed the failure of the Ta barrier at 450oC. Despite the good barrier performance of the CVD TiN films, obtaining low contact resistivity may be a concern. The potential use of Cu-Mg alloy as the backend metallization has also been studied. Fully encapsulated wiring has been fabricated by causing the Mg to out- diffuse towards the Cu/SiO2 interfaces and the free copper surface. The inter-connects exhibited good stability and oxidation resistance, but via resistances were extremely high, probably due to the presence of insulating films like MgO or MgF2 at the interface between the two metal levels. It may be possible to decrease the via resistance to values comparable to Cu/Ta/Cu by altering the process flow and using a suitable via clean. When used at the contact level, undesirable interaction with the CoSi2 film was observed at temperatures as low as 350oC. Another problem was the high contact resistance at the Cu-Mg/CoSi2 interface. Hence the use of this alloy as a contact fill material is not feasible at this time. An additional barrier layer may be required between the Cu-Mg and CoSi2 films to protect the integrity of the silicide and provide low contact resistance.

How to boost the sluggish lithium-ion hopping dynamic in borophene?

NASA Astrophysics Data System (ADS)

Liu, Jia; Chen, Xianfei; Deng, Xiaoyu; Zhang, Wentao; Li, Junfeng; Xiao, Beibei; Pu, Min

2018-05-01

In light of low atomic mass, three types of experimentally synthetized borophene including β12, χ3 and striped t-sheet have been predicted to be promising anode materials for lithium-ion batteries (LIBs) with extremely high capacity. However, the rate performances of β12 and χ3 are quite poor with high diffusion barrier of 0.66-0.81 eV on β12 and 0.60-0.85 eV on χ3 in contrast with that in t-sheet (typically <0.1 eV). Isolation of t-sheet from their blend remains a fundamental challenge in the field of nanotechnology and a mechanistic understanding and control over the hopping dynamic of Li+ therein are thus of extremely important to facilitate the development of borophene-based anode material, but still lacking. In this work, we performed a comprehensive theoretical investigation on the adsorptions and migrations of Li+ on perfect and defective β12 and χ3 based on density functional theory. We determined a new kind of vacancy in β12 that modulates the adsorption and boosts the diffusion of Li+ nearby remarkably. With the aid of charge doping, we uncover a general mechanism (charge-concentration mechanism) involved with the celebrated bonding theory of borophene, where the hopping barrier of Li+ on β12 could be reduced to be 0.06 eV, rationalizing the boosting Li+ hopping as a result of electron deficiency in vacant borophene. By extending our calculations to H functionalized borophene and Ag supported borophene, we further confirm the validity of the "charge-concentration mechanism" under more realistic experimental conditions. The proposed mechanism could be used as a guiding principle to improve or develop new borophene-based electrode materials with high rate performance for LIBs.

Integrating diffusion maps with umbrella sampling: Application to alanine dipeptide

NASA Astrophysics Data System (ADS)

Ferguson, Andrew L.; Panagiotopoulos, Athanassios Z.; Debenedetti, Pablo G.; Kevrekidis, Ioannis G.

2011-04-01

Nonlinear dimensionality reduction techniques can be applied to molecular simulation trajectories to systematically extract a small number of variables with which to parametrize the important dynamical motions of the system. For molecular systems exhibiting free energy barriers exceeding a few kBT, inadequate sampling of the barrier regions between stable or metastable basins can lead to a poor global characterization of the free energy landscape. We present an adaptation of a nonlinear dimensionality reduction technique known as the diffusion map that extends its applicability to biased umbrella sampling simulation trajectories in which restraining potentials are employed to drive the system into high free energy regions and improve sampling of phase space. We then propose a bootstrapped approach to iteratively discover good low-dimensional parametrizations by interleaving successive rounds of umbrella sampling and diffusion mapping, and we illustrate the technique through a study of alanine dipeptide in explicit solvent.

A diffuse argon plume generated by a longitudinal slit jet equipped with a quadri-electrode barrier discharge

NASA Astrophysics Data System (ADS)

Li, Xuechen; Chu, Jingdi; Zhang, Qi; Zhang, Panpan; Jia, Pengying; Dong, Lifang

2018-04-01

A diffuse argon plume at atmospheric pressure is generated downstream of a longitudinal slit jet equipped with a dielectric barrier discharge in a quadri-electrode configuration. Results indicate that both the plume length and the spectral line intensities increase with the increase in the peak voltage. With fast photography it is found that there is a clear difference for discharges with different polarities. The positive discharge is composed of nonuniform branching filaments; however, it is fairly uniform for the negative discharge. Due to the charge overflow of the intra-electrode discharge, the streamer mechanism is involved in the plume discharge. In fact, the positive discharge and the negative one correspond to a cathode-directed streamer and an anode-directed streamer, respectively. The formation mechanisms of the branching filaments and the diffuse background are discussed at last.

The effect of environment on thermal barrier coating lifetime

DOE PAGES

Pint, Bruce A.; Unocic, Kinga A.; Haynes, James Allen

2016-03-15

While the water vapor content of the combustion gas in natural gas-fired land-based turbines is ~10%, it can be 20–85% with coal-derived (syngas or H 2) fuels or innovative turbine concepts for more efficient carbon capture. Additional concepts envisage working fluids with high CO 2 contents to facilitate carbon capture and sequestration. To investigate the effects of changes in the gas composition on thermal barrier coating (TBC) lifetime, furnace cycling tests (1-h and 100-h cycles) were performed in air with 10, 50, and 90 vol. % water vapor and CO 2-10% H 2O and compared to prior results in drymore » air or O 2. Two types of TBCs were investigated: (1) diffusion bond coatings (Pt-diffusion or Pt-modified aluminide) with commercial electron-beam physical vapor-deposited yttria-stabilized zirconia (YSZ) top coatings on second-generation superalloy N5 and N515 substrates and (2) high-velocity oxygen fuel (HVOF) sprayed MCrAlYHfSi bond coatings with air plasma-sprayed YSZ top coatings on superalloys X4, 1483, or 247 substrates. For both types of coatings exposed in 1-h cycles, the addition of water vapor resulted in a decrease in coating lifetime, except for Pt-diffusion coatings which were unaffected by the environment. In 100-h cycles, environment was less critical, perhaps because coating failure was chemical (i.e., due to interdiffusion) rather than mechanical. As a result, in both 1-h and 100-h cycles, CO 2 did not appear to have any negative effect on coating lifetime.« less

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

Marrakchi, G.; Barbier, D.; Guillot, G.

Electrical and deep level transient spectroscopy measurements on Schottky barriers were performed in order to characterize electrically active defects in n-type GaAs (Bridgman substrates or liquid-phase epitaxial layers) after pulsed electron beam annealing. Both surface damage and bulk defects were observed in the Bridgman substrates depending on the pulse energy density. No electron traps were detected in the liquid-phase epitaxial layers before and after annealing for an energy density of 0.4 J/cm/sup 2/. The existence of an interfacial insulating layer at the metal-semiconductor interface, associated with As out-diffusion during the pulsed electron irradiation, was revealed by the abnormally high valuesmore » of the Schottky barrier diffusion potential. Moreover, two new electron traps with activation energy of 0.35 and 0.43 eV, called EP1 and EP2, were introduced in the Bridgman substrates after pulsed electron beam annealing. The presence of these traps, related to the As evaporation, was tentatively attributed to the decrease of the EL2 electron trap signal after 0.4-J/cm/sup 2/ annealing. It is proposed that these new defects states are due to the decomposition of the As/sub Ga/-As/sub i/ complex recently considered as the most probable defect configuration for the dominant EL2 electron trap usually detected in as-grown GaAs substrates.« less

Theoretical study of the ammonia nitridation rate on an Fe (100) surface: a combined density functional theory and kinetic Monte Carlo study.

PubMed

Yeo, Sang Chul; Lo, Yu Chieh; Li, Ju; Lee, Hyuck Mo

2014-10-07

Ammonia (NH3) nitridation on an Fe surface was studied by combining density functional theory (DFT) and kinetic Monte Carlo (kMC) calculations. A DFT calculation was performed to obtain the energy barriers (Eb) of the relevant elementary processes. The full mechanism of the exact reaction path was divided into five steps (adsorption, dissociation, surface migration, penetration, and diffusion) on an Fe (100) surface pre-covered with nitrogen. The energy barrier (Eb) depended on the N surface coverage. The DFT results were subsequently employed as a database for the kMC simulations. We then evaluated the NH3 nitridation rate on the N pre-covered Fe surface. To determine the conditions necessary for a rapid NH3 nitridation rate, the eight reaction events were considered in the kMC simulations: adsorption, desorption, dissociation, reverse dissociation, surface migration, penetration, reverse penetration, and diffusion. This study provides a real-time-scale simulation of NH3 nitridation influenced by nitrogen surface coverage that allowed us to theoretically determine a nitrogen coverage (0.56 ML) suitable for rapid NH3 nitridation. In this way, we were able to reveal the coverage dependence of the nitridation reaction using the combined DFT and kMC simulations.

Characterization of Microstructure and Thermal Properties of YSZ Coatings Obtained by Axial Suspension Plasma Spraying (ASPS)

NASA Astrophysics Data System (ADS)

Ganvir, Ashish; Curry, Nicholas; Björklund, Stefan; Markocsan, Nicolaie; Nylén, Per

2015-10-01

The paper aims at demonstrating various microstructures which can be obtained using the suspension spraying technique and their respective significance in enhancing the thermal insulation property of a thermal barrier coating. Three different types of coating microstructures are discussed which were produced by the Axial Suspension Plasma Spraying. Detailed characterization of coatings was then performed. Optical and scanning electron microscopy were utilized for microstructure evaluations; x-ray diffraction for phase analysis; water impregnation, image analysis, and mercury intrusion porosimetry for porosity analysis, and laser flash analysis for thermal diffusivity measurements were used. The results showed that Axial Suspension Plasma Spraying can generate vertically cracked, porous, and feathery columnar-type microstructures. Pore size distribution was found in micron, submicron, and nanometer range. Higher overall porosity, the lower density of vertical cracks or inter-column spacing, and higher inter-pass porosity favored thermal insulation property of the coating. Significant increase in thermal diffusivity and conductivity was found at higher temperature, which is believed to be due to the pore rearrangement (sintering and pore coarsening). Thermal conductivity values for these coatings were also compared with electron beam physical vapor deposition (EBPVD) thermal barrier coatings from the literature and found to be much lower.

Multilayer Regulation of Atomic Boron Nitride Films to Improve Oxidation and Corrosion Resistance of Cu.

PubMed

Ren, Siming; Cui, Mingjun; Pu, Jibin; Xue, Qunji; Wang, Liping

2017-08-16

The boron nitride (BN) monolayer (1L) with high impermeability and resistivity seems to hold promise as a long-term corrosion barrier for Cu under ambient condition, which is supported by recent researches. Here, we perform a complete study of the alternating temperature tests (the sample is exposed in air for 30 days and subsequently heated at 200 °C for 2 h) and electrochemical measurements on 1L and multilayer BN-coated Cu foils. Results imply that the BN-coated Cu foils are less oxidized than uncoated Cu foils after alternating temperature tests, regardless of the layers of BN. Particularly, the oxidation process proceeds slowly in multilayers because most of the underlying defects are covered with BN layers to suppress the oxygen diffusion in the vertical direction and the oxidation mainly occurs on the wrinkled region of BN films. Electrochemical analyses reveal that the BN layers provide an effective physical barrier against the corrosive medium and inhibit the electron diffusion because of their high electrical insulating behavior and the corrosion resistance of the samples increases with increasing BN layers. These findings indicate that BN films with adequate layers are good candidates for oxidation and corrosion protection at the atomic level, which is vital to many industrial and academic applications.

Interfacial Reaction and Shear Strength of SnAgCu/Ni/Bi2Te3-Based TE Materials During Aging

NASA Astrophysics Data System (ADS)

Jing, Hongyang; Li, Yuan; Xu, Lianyong; Han, Yongdian; Lu, Guoquan; Zhang, Hao

2015-12-01

As a diffusion barrier layer, Ni is widely applied in power electronics packaging, especially in thermoelectric devices. This paper presents the variation of Ni diffusion barrier layer during aging and failure mechanisms of thermoelectric device joints. The thermoelectric joint consists of Sn96.5Ag3.0Cu0.5 (SAC305) solder and Bi2Te3-based thermoelectric materials such as Bi0.5Sb1.5Te3 and Bi1.8Sb0.2Se0.15Te2.85 during service. The result shows that with the increasing aging time, Ni layer was constantly consumed by SAC305 and Bi2Te3-based thermoelectric materials simultaneously. The reaction products are (Cu,Ni)6Sn5 and NiTe or Ni(Bi,Te), respectively. Besides, the shear strength of SAC305/Bi0.5Sb1.5Te3 joint or SAC305/Bi1.8Sb0.2Se0.15Te2.85 joint gets gradually decreased and thermoelectric conversion performance gets worse. Meantime, the different failure mechanisms are also compared between SAC305/Bi0.5Sb1.5Te3 couple joints and SAC305/Bi1.8Sb0.2Se0.15Te2.85 couple joints.

Molecular assemblies as protective barriers and adhesion promotion interlayer

DOEpatents

King, David E.; Czanderna, Alvin W.; Kennedy, Cheryl E.

1996-01-01

A protective diffusion barrier having adhesive qualifies for metalized surfaces is provided by a passivating agent having the formula HS--(CH.sub.2).sub.11 --COOH Which forms a very dense, transparent organized molecular assembly or layer that is impervious to water, alkali, and other impurities and corrosive substances that typically attack metal surfaces.

Spin Transfer Torque in Graphene

NASA Astrophysics Data System (ADS)

Lin, Chia-Ching; Chen, Zhihong

2014-03-01

Graphene is an idea channel material for spin transport due to its long spin diffusion length. To develop graphene based spin logic, it is important to demonstrate spin transfer torque in graphene. Here, we report the experimental measurement of spin transfer torque in graphene nonlocal spin valve devices. Assisted by a small external in-plane magnetic field, the magnetization reversal of the receiving magnet is induced by pure spin diffusion currents from the injector magnet. The magnetization switching is reversible between parallel and antiparallel configurations by controlling the polarity of the applied charged currents. Current induced heating and Oersted field from the nonlocal charge flow have also been excluded in this study. Next, we further enhance the spin angular momentum absorption at the interface of the receiving magnet and graphene channel by removing the tunneling barrier in the receiving magnet. The device with a tunneling barrier only at the injector magnet shows a comparable nonlocal spin valve signal but lower electrical noise. Moreover, in the same preset condition, the critical charge current density for spin torque in the single tunneling barrier device shows a substantial reduction if compared to the double tunneling barrier device.

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.

Probabilistic migration modelling focused on functional barrier efficiency and low migration concepts in support of risk assessment.

PubMed

Brandsch, Rainer

2017-10-01

Migration modelling provides reliable migration estimates from food-contact materials (FCM) to food or food simulants based on mass-transfer parameters like diffusion and partition coefficients related to individual materials. In most cases, mass-transfer parameters are not readily available from the literature and for this reason are estimated with a given uncertainty. Historically, uncertainty was accounted for by introducing upper limit concepts first, turning out to be of limited applicability due to highly overestimated migration results. Probabilistic migration modelling gives the possibility to consider uncertainty of the mass-transfer parameters as well as other model inputs. With respect to a functional barrier, the most important parameters among others are the diffusion properties of the functional barrier and its thickness. A software tool that accepts distribution as inputs and is capable of applying Monte Carlo methods, i.e., random sampling from the input distributions of the relevant parameters (i.e., diffusion coefficient and layer thickness), predicts migration results with related uncertainty and confidence intervals. The capabilities of probabilistic migration modelling are presented in the view of three case studies (1) sensitivity analysis, (2) functional barrier efficiency and (3) validation by experimental testing. Based on the predicted migration by probabilistic migration modelling and related exposure estimates, safety evaluation of new materials in the context of existing or new packaging concepts is possible. Identifying associated migration risk and potential safety concerns in the early stage of packaging development is possible. Furthermore, dedicated material selection exhibiting required functional barrier efficiency under application conditions becomes feasible. Validation of the migration risk assessment by probabilistic migration modelling through a minimum of dedicated experimental testing is strongly recommended.

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

Morphology Effect on Proton Dynamics in Nafion® 117 and Sulfonated Polyether Ether Ketone

NASA Astrophysics Data System (ADS)

Leong, Jun Xing; Diño, Wilson Agerico; Ahmad, Azizan; Daud, Wan Ramli Wan; Kasai, Hideaki

2016-09-01

We report results of our experimental and theoretical studies on the dynamics of proton conductivity in Nafion® 117 and self-fabricated sulfonated polyether ether ketone (SPEEK) membranes. Knowing that the presence of water molecules in the diffusion process results in a lower energy barrier, we determined the diffusion barriers and corresponding tunneling probabilities of Nafion® 117 and SPEEK system using a simple theoretical model that excludes the medium (water molecules) in the initial calculations. We then propose an equation that relates the membrane conductivity to the tunneling probability. We recover the effect of the medium by introducing a correction term into the proposed equation, which takes into account the effect of the proton diffusion distance and the hydration level. We have also experimentally verified that the proposed equation correctly explain the difference in conductivity between Nafion® 117 and SPEEK. We found that membranes that are to be operated in low hydration environments (high temperatures) need to be designed with short diffusion distances to enhance and maintain high conductivity.

Carrier-Mediated Cocaine Transport at the Blood-Brain Barrier as a Putative Mechanism in Addiction Liability

PubMed Central

Chapy, Hélène; Smirnova, Maria; André, Pascal; Schlatter, Joël; Chiadmi, Fouad; Couraud, Pierre-Olivier; Scherrmann, Jean-Michel; Declèves, Xavier

2015-01-01

Background: The rate of entry of cocaine into the brain is a critical factor that influences neuronal plasticity and the development of cocaine addiction. Until now, passive diffusion has been considered the unique mechanism known by which cocaine crosses the blood-brain barrier. Methods: We reassessed mechanisms of transport of cocaine at the blood-brain barrier using a human cerebral capillary endothelial cell line (hCMEC/D3) and in situ mouse carotid perfusion. Results: Both in vivo and in vitro cocaine transport studies demonstrated the coexistence of a carrier-mediated process with passive diffusion. At pharmacological exposure level, passive diffusion of cocaine accounted for only 22.5% of the total cocaine influx in mice and 5.9% in hCMEC/D3 cells, whereas the carrier-mediated influx rate was 3.4 times greater than its passive diffusion rate in vivo. The functional identification of this carrier-mediated transport demonstrated the involvement of a proton antiporter that shared the properties of the previously characterized clonidine and nicotine transporter. The functionnal characterization suggests that the solute carrier (SLC) transporters Oct (Slc22a1-3), Mate (Slc47a1) and Octn (Slc22a4-5) are not involved in the cocaine transport in vivo and in vitro. Diphenhydramine, heroin, tramadol, cocaethylene, and norcocaine all strongly inhibited cocaine transport, unlike benzoylecgonine. Trans-stimulation studies indicated that diphenhydramine, nicotine, 3,4-methylenedioxyamphetamine (ecstasy) and the cathinone compound 3,4-methylenedioxypyrovalerone (MDPV) were also substrates of the cocaine transporter. Conclusions: Cocaine transport at the BBB involves a proton-antiporter flux that is quantitatively much more important than its passive diffusion. The molecular identification and characterization of this transporter will provide new tools to understand its role in addictive mechanisms. PMID:25539501

Impact of homogeneous strain on uranium vacancy diffusion in uranium dioxide

DOE PAGES

Goyal, Anuj; Phillpot, Simon R.; Subramanian, Gopinath; ...

2015-03-03

We present a detailed mechanism of, and the effect of homogeneous strains on, the migration of uranium vacancies in UO 2. Vacancy migration pathways and barriers are identified using density functional theory and the effect of uniform strain fields are accounted for using the dipole tensor approach. We report complex migration pathways and noncubic symmetry associated with the uranium vacancy in UO 2 and show that these complexities need to be carefully accounted for to predict the correct diffusion behavior of uranium vacancies. We show that under homogeneous strain fields, only the dipole tensor of the saddle with respect tomore » the minimum is required to correctly predict the change in the energy barrier between the strained and the unstrained case. Diffusivities are computed using kinetic Monte Carlo simulations for both neutral and fully charged state of uranium single and divacancies. We calculate the effect of strain on migration barriers in the temperature range 800–1800 K for both vacancy types. Homogeneous strains as small as 2% have a considerable effect on diffusivity of both single and divacancies of uranium, with the effect of strain being more pronounced for single vacancies than divacancies. In contrast, the response of a given defect to strain is less sensitive to changes in the charge state of the defect. Further, strain leads to anisotropies in the mobility of the vacancy and the degree of anisotropy is very sensitive to the nature of the applied strain field for strain of equal magnitude. Our results indicate that the influence of strain on vacancy diffusivity will be significantly greater when single vacancies dominate the defect structure, such as sintering, while the effects will be much less substantial under irradiation conditions where divacancies dominate.« less

Radon Diffusion Measurement in Polyethylene based on Alpha Detection

NASA Astrophysics Data System (ADS)

Rau, Wolfgang

2011-04-01

We present a method to measure the diffusion of Radon in solid materials based on the alpha decay of the radon daughter products. In contrast to usual diffusion measurements which detect the radon that penetrates a thin barrier, we let the radon diffuse into the material and then measure the alpha decays of the radon daughter products in the material. We applied this method to regular and ultra high molecular weight poly ethylene and find diffusion lengths of order of mm as expected. However, the preliminary analysis shows significant differences between two different approaches we have chosen. These differences may be explained by the different experimental conditions.

Kinetics of Ta ions penetration into porous low-k dielectrics under bias-temperature stress

NASA Astrophysics Data System (ADS)

He, Ming; Ou, Ya; Wang, Pei-I.; Lu, Toh-Ming

2010-05-01

It is known that Ta, a popular diffusion barrier material, can itself penetrate into low-k dielectrics under bias-temperature stress. In this work, we derived a model which directly correlates the diffusivity of Ta ions to the rate of flatband voltage shift (FBS) of the Ta/methyl silsesquixane (MSQ)/Si capacitors. From our experimentally measured constant FBS rate, the Ta diffusivity and activation energy were determined. It appears that an increase in the porosity of MSQ film enhances the Ta diffusivity but does not affect the associated activation energy. This suggests the Ta ion diffusion is mainly through interconnected pore surfaces.

Balanced improvement of high performance concrete material properties with modified graphite nanomaterials

NASA Astrophysics Data System (ADS)

Peyvandi, Amirpasha

Graphite nanomaterials offer distinct features for effective reinforcement of cementitious matrices in the pre-crack and post-crack ranges of behavior. Thoroughly dispersed and well-bonded nanomaterials provide for effective control of the size and propagation of defects (microcracks) in matrix, and also act as closely spaced barriers against diffusion of moisture and aggressive solutions into concrete. Modified graphite nanomaterials can play multi-faceted roles towards enhancing the mechanical, physical and functional attributes of concrete materials. Graphite nanoplatelets (GP) and carbon nanofibers (CNF) were chosen for use in cementitious materials. Experimental results highlighted the balanced gains in diverse engineering properties of high-performance concrete realized by introduction of graphite nanomaterials. Nuclear Magnetic Resonance (NMR) spectroscopy was used in order to gain further insight into the effects of nanomaterials on the hydration process and structure of cement hydrates. NMR exploits the magnetic properties of certain atomic nuclei, and the sensitivity of these properties to local environments to generate data which enables determination of the internal structure, reaction state, and chemical environment of molecules and bulk materials. 27 Al and 29Si NMR spectroscopy techniques were employed in order to evaluate the effects of graphite nanoplatelets on the structure of cement hydrates, and their resistance to alkali-silica reaction (ASR), chloride ion diffusion, and sulfate attack. Results of 29Si NMR spectroscopy indicated that the percent condensation of C-S-H in cementitious paste was lowered in the presence of nanoplatelets at the same age. The extent of chloride diffusion was assessed indirectly by detecting Friedel's salt as a reaction product of chloride ions with aluminum-bearing cement hydrates. Graphite nanoplatelets were found to significantly reduce the concentration of Friedel's salt at different depths after various periods of exposure to chloride solutions, pointing at the benefits of nanoplatelets towards enhancement of concrete resistance to chloride ion diffusion. It was also found that the intensity of Thaumasite, a key species marking sulfate attack on cement hydrates, was lowered with the addition of graphite nanoplatelets in concrete exposed to sulfate solutions. Experimental evaluations were conducted on scaled-up production of concrete nanocomposite in precast concrete plants. Full-scale reinforced concrete pipes and beams were produced using concrete nanocomposites. Durability and structural tests indicated that the use of graphite nanoplatelets, alone or in combination with synthetic (PVA) fibers, produced significant gains in the durability characteristics, and also benefited the structural performance of precast reinforced concrete products. The material and scaled-up structural investigations conducted in the project concluded that lower-cost graphite nanomaterials (e.g., graphite nanoplatelets) offer significant potentials as multi-functional additives capable of enhancing the barrier, durability and mechanical performance of concrete materials. The benefits of graphite nanomaterials tend to be more pronounced in higher-performance concrete materials.

Surface charge- and space-dependent transport of proteins in crowded environments of nanotailored posts.

PubMed

Choi, Chang Kyoung; Fowlkes, Jason D; Retterer, Scott T; Siuti, Piro; Iyer, Sukanya; Doktycz, Mitchel J

2010-06-22

The reaction and diffusion of molecules across barriers and through crowded environments is integral to biological system function and to separation technologies. Ordered, microfabricated post arrays are a promising route to creating synthetic barriers with controlled chemical and physical characteristics. They can be used to create crowded environments, to mimic aspects of cellular membranes, and to serve as engineered replacements of polymer-based separation media. Here, the translational diffusion of fluorescein isothiocyante and various forms of green fluorescent protein (GFP), including "supercharged" variants, are examined in a silicon-based post array environment. The technique of fluorescence recovery after photobleaching (FRAP) is combined with analytical approximations and numerical simulations to assess the relative effects of reaction and diffusion on molecular transport, respectively. FRAP experiments were conducted for 64 different cases where the molecular species, the density of the posts, and the chemical surface charge of the posts were varied. In all cases, the dense packing of the posts hindered the diffusive transport of the fluorescent species. The supercharged GFPs strongly interacted with oppositely charged surfaces. With similar molecular and surface charges, transport is primarily limited by hindered diffusion. For conventional, enhanced GFP in a positively charged surface environment, transport was limited by the coupled action of hindered diffusion and surface interaction with the posts. Quantification of the size-, space-, time-, and charge-dependent translational diffusion in the post array environments can provide insight into natural processes and guide the design and development of selective membrane systems.

Side chain variations radically alter the diffusion of poly(2-alkyl-2-oxazoline) functionalised nanoparticles through a mucosal barrier.

PubMed

Mansfield, Edward D H; de la Rosa, Victor R; Kowalczyk, Radoslaw M; Grillo, Isabelle; Hoogenboom, Richard; Sillence, Katy; Hole, Patrick; Williams, Adrian C; Khutoryanskiy, Vitaliy V

2016-08-16

Functionalised nanomaterials are gaining popularity for use as drug delivery vehicles and, in particular, mucus penetrating nanoparticles may improve drug bioavailability via the oral route. To date, few polymers have been investigated for their muco-penetration, and the effects of systematic structural changes to polymer architectures on the penetration and diffusion of functionalised nanomaterials through mucosal tissue have not been reported. We investigated the influence of poly(2-oxazoline) alkyl side chain length on nanoparticle diffusion; poly(2-methyl-2-oxazoline), poly(2-ethyl-2-oxazoline), and poly(2-n-propyl-2-oxazoline) were grafted onto the surface of thiolated silica nanoparticles and characterised by FT-IR, Raman and NMR spectroscopy, thermogravimetric analysis, and small angle neutron scattering. Diffusion coefficients were determined in water and in a mucin dispersion (using Nanoparticle Tracking Analysis), and penetration through a mucosal barrier was assessed using an ex vivo fluorescence technique. The addition of a single methylene group in the side chain significantly altered the penetration and diffusion of the materials in both mucin dispersions and mucosal tissue. Nanoparticles functionalised with poly(2-methyl-2-oxazoline) were significantly more diffusive than particles with poly(2-ethyl-2-oxazoline) while particles with poly(2-n-propyl-2-oxazoline) showed no significant increase compared to the unfunctionalised particles. These data show that variations in the polymer structure can radically alter their diffusive properties with clear implications for the future design of mucus penetrating systems.

The diffusion dynamics of PEGylated liposomes in the intact vitreous of the ex vivo porcine eye: A fluorescence correlation spectroscopy and biodistribution study.

PubMed

Eriksen, Anne Z; Brewer, Jonathan; Andresen, Thomas L; Urquhart, Andrew J

2017-04-30

The diffusion dynamics of nanocarriers in the vitreous and the influence of nanocarrier physicochemical properties on these dynamics is an important aspect of the efficacy of intravitreal administered nanomedicines for the treatment of posterior segment eye diseases. Here we use fluorescence correlation spectroscopy (FCS) to determine liposome diffusion coefficients in the intact vitreous (D Vit ) of ex vivo porcine eyes using a modified Miyake-Apple technique to minimize the disruption of the vitreous fine structure. We chose to investigate whether the zeta potential of polyethylene glycol functionalized (i.e. PEGylated) liposomes altered liposome in situ diffusion dynamics in the vitreous. Non-PEGylated cationic nanocarriers have previously shown little to no diffusion in the vitreous, whilst neutral and anionic have shown diffusion. The liposomes investigated had diameters below 150nm and zeta potentials ranging from -20 to +12mV. We observed that PEGylated cationic liposomes had significantly lower D Vit values (1.14μm 2 s -1 ) than PEGylated neutral and anionic liposomes (2.78 and 2.87μm 2 s -1 ). However, PEGylated cationic liposomes had a similar biodistribution profile across the vitreous to the other systems. These results show that PEGylated cationic liposomes with limited cationic charge can diffuse across the vitreous and indicate that the vitreous as a barrier to nanocarriers (Ø<500nm) is more complicated than simply an electrostatic barrier as previously suggested. Copyright © 2017 Elsevier B.V. All rights reserved.

Anisotropic Thermal Diffusivities of Plasma-Sprayed Thermal Barrier Coatings

NASA Astrophysics Data System (ADS)

Akoshima, Megumi; Takahashi, Satoru

2017-09-01

Thermal barrier coatings (TBCs) are used to shield the blades of gas turbines from heat and wear. There is a pressing need to evaluate the thermal conductivity of TBCs in the thermal design of advanced gas turbines with high energy efficiency. These TBCs consist of a ceramic-based top coat and a bond coat on a superalloy substrate. Usually, the focus is on the thermal conductivity in the thickness direction of the TBC because heat tends to diffuse from the surface of the top coat to the substrate. However, the in-plane thermal conductivity is also important in the thermal design of gas turbines because the temperature distribution within the turbine cannot be ignored. Accordingly, a method is developed in this study for measuring the in-plane thermal diffusivity of the top coat. Yttria-stabilized zirconia top coats are prepared by thermal spraying under different conditions. The in-plane and cross-plane thermal diffusivities of the top coats are measured by the flash method to investigate the anisotropy of thermal conduction in a TBC. It is found that the in-plane thermal diffusivity is higher than the cross-plane one for each top coat and that the top coats have significantly anisotropic thermal diffusivity. The cross-sectional and in-plane microstructures of the top coats are observed, from which their porosities are evaluated. The thermal diffusivity and its anisotropy are discussed in detail in relation to microstructure and porosity.

First Principles Study for Proton Transport and Diffusion Behavior in Hydrous Hexagonal WO3

NASA Astrophysics Data System (ADS)

Liu, Chi-Ping; Zhou, Fei; Ozolins, Vidvuds; QPAM Team

2013-03-01

Proton transport is of great importance in biological species and energy storage and conversion systems. Previous studies have shown fast proton conduction in liquids and polymers but seldom in inorganic materials. In this work, first principles density functional theory (DFT) reveals that the formation of hydronium and water chains inside the hexagonal channels plays the key roles for the anomalously fast proton transport, by following modified Grotthuss mechanism. Our DFT study shows the detailed microscopic proton diffusion mechanism along the channel in hydrous WO3 with 50% water composition, which is proper for water chain formation. The water chain in the channel serves as a possible diffusion media for hydronium (H3O +) . With the continuous formation and cleavage of hydrogen bonds in the channel, the hydronium diffuses by hydrogen bonds exchange between water molecules. This mechanism is very similar with Grotthuss relay mechanism for proton transport in liquid. The possible proton diffusion were studied for hydronium is either far away from the water chain bond defect or next to H2O defect at the end of water chain. The diffusion barriers for both conditions are around 150 meV to 200 meV, and water defects reorganization in the chain is the rate-limited step for proton diffusion. These small diffusion barriers could explain the fast 1-D proton transport in hydrous WO3 channel. Further studies about fast proton transport in other inorganic materials could be an important topic in not only biochemistry but also clean energy applications like fuel cell applications.

Fusion cross sections for reactions involving medium and heavy nucleus-nucleus systems

NASA Astrophysics Data System (ADS)

Atta, Debasis; Basu, D. N.

2014-12-01

Existing data on near-barrier fusion excitation functions of medium and heavy nucleus-nucleus systems have been analyzed by using a simple diffused-barrier formula derived assuming the Gaussian shape of the barrier-height distributions. The fusion cross section is obtained by folding the Gaussian barrier distribution with the classical expression for the fusion cross section for a fixed barrier. The energy dependence of the fusion cross section, thus obtained, provides good description to the existing data on near-barrier fusion and capture excitation functions for medium and heavy nucleus-nucleus systems. The theoretical values for the parameters of the barrier distribution are estimated which can be used for fusion or capture cross-section predictions that are especially important for planning experiments for synthesizing new superheavy elements.

Anisotropic diffusion of oxygen on a few layers of black phosphorous

NASA Astrophysics Data System (ADS)

Fernández-Escamilla, Hector Noe; González-Chávez, Víctor Hugo; Martínez-Guerra, Eduardo; Garay-Tapia, Andrés; Martínez-Guerra, Edgar

Recently, phosporene has also been scored well as a functional material for two-dimensional electronic and optoelectronic devices. That is, because in contrast to graphene, black phosphorous has an inherent, direct and appreciable band gap that can be modulated with the numbers of layes. However, the presence of exposed lone pairs at the surface makes phosphorous very reactive to air and humidity and consequently, degradation of its properties. No such fundamental explanation have been made, thus corresponding first principle predictions to evaluate diffusion of O over and along a mono- and a few layers are indispensable. Energy barriers and the mechanisms of oxygen diffusion on mono- and a few layer of black phosphorous were calculated using the NEB(Nudge Elastic band) method as implemented in Quantum Espresso. The electronic states are expanded in plane waves with kinetic-energy cutoffs of 25 and 200 Ry for the wave function and charge density, respectively. Also, as the H2O and O2 are polar molecules, spin-polarized calculations have been carried out. We evaluated the diffusion barriers for O2 and H2O on phosphorene along zigzag, armchair and intermediated directions. Our calculations show that diffusion of O is preferred on zigzag directions and dissociation of O2 is favored as a result of energy gains of about 2 eV. Also, apparently diffusion pathways are blocked along layers.

The impact of aging on epithelial barriers.

PubMed

Parrish, Alan R

2017-10-02

The epithelium has many critical roles in homeostasis, including an essential responsibility in establishing tissue barriers. In addition to the fundamental role in separating internal from external environment, epithelial barriers maintain nutrient, fluid, electrolyte and metabolic waste balance in multiple organs. While, by definition, barrier function is conserved, the structure of the epithelium varies across organs. For example, the skin barrier is a squamous layer of cells with distinct structural features, while the lung barrier is composed of a very thin single cell to minimize diffusion space. With the increased focus on age-dependent alterations in organ structure and function, there is an emerging interest in the impact of age on epithelial barriers. This review will focus on the impact of aging on the epithelial barrier of several organs, including the skin, lung, gastrointestinal tract and the kidney, at a structural and functional level.

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

Ok, Kyung-Chul; Park, Jin-Seong, E-mail: hkim-2@naver.com, E-mail: jsparklime@hanyang.ac.kr; Ko Park, Sang-Hee

We demonstrated the fabrication of flexible amorphous indium gallium zinc oxide thin-film transistors (TFTs) on high-temperature polyimide (PI) substrates, which were debonded from the carrier glass after TFT fabrication. The application of appropriate buffer layers on the PI substrates affected the TFT performance and stability. The adoption of the SiN{sub x}/AlO{sub x} buffer layers as water and hydrogen diffusion barriers significantly improved the device performance and stability against the thermal annealing and negative bias stress, compared to single SiN{sub x} or SiO{sub x} buffer layers. The substrates could be bent down to a radius of curvature of 15 mm and themore » devices remained normally functional.« less

A 3D Real-Scale, Biomimetic, and Biohybrid Model of the Blood-Brain Barrier Fabricated through Two-Photon Lithography.

PubMed

Marino, Attilio; Tricinci, Omar; Battaglini, Matteo; Filippeschi, Carlo; Mattoli, Virgilio; Sinibaldi, Edoardo; Ciofani, Gianni

2018-02-01

The investigation of the crossing of exogenous substances through the blood-brain barrier (BBB) is object of intensive research in biomedicine, and one of the main obstacles for reliable in vitro evaluations is represented by the difficulties at the base of developing realistic models of the barrier, which could resemble as most accurately as possible the in vivo environment. Here, for the first time, a 1:1 scale, biomimetic, and biohybrid BBB model is proposed. Microtubes inspired to the brain capillaries were fabricated through two-photon lithography and used as scaffolds for the co-culturing of endothelial-like bEnd.3 and U87 glioblastoma cells. The constructs show the maturation of tight junctions, good performances in terms of hindering dextran diffusion through the barrier, and a satisfactory trans-endothelial electrical resistance. Moreover, a mathematical model is developed, which assists in both the design of the 3D microfluidic chip and its characterization. Overall, these results show the effective formation of a bioinspired cellular barrier based on microtubes reproducing brain microcapillaries to scale. This system will be exploited as a realistic in vitro model for the investigation of BBB crossing of nanomaterials and drugs, envisaging therapeutic and diagnostic applications for several brain pathologies, including brain cancer. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microvillar Ca++ signaling: a new view of an old problem.

PubMed

Lange, K

1999-07-01

Proceeding from the recent finding that the main components of the Ca++ signal pathway are located in small membrane protrusions on the surface of differentiated cells, called microvilli, a novel concept of cellular Ca++ signaling was developed. The main features of this concept can be summarized as follows: Microvilli are formed on the cell surface of differentiating or resting cells from exocytic membrane domains, growing out from the cell surface by elongation of an internal bundle of actin filaments. The microvillar tip membranes contain all functional important proteins synthesized such as ion channels and transporters for energy-providing substrates and structural components, which are, in rapidly growing undifferentiated cells, distributed over the whole cell surface by lateral diffusion. The microvillar shaft structure, a bundle of actin filaments, forms a dense cytoskeletal matrix tightly covered by the microvillar lipid membrane and represents an effective diffusion barrier separating the microvillar tip compartment (entrance compartment) from the cytoplasm. This diffusion barrier prevents the passage of low molecular components such as Ca++ glucose and other relevant substrates from the entrance compartment into the cytoplasm. The effectiveness of the actin-based diffusion barrier is modulated by various signal pathways and effectors, most importantly, by the actin-depolymerizing/reorganizing activity of the phospholipase C (PLC)-coupled Ca++ signaling. Moreover, the microvillar bundle of actin filaments plays a dual role in Ca++ signaling. It combines the function of a diffusion barrier, preventing Ca++ influx into the resting cell, with that of a high-affinity, ATP-dependent, and IP3-sensitive Ca++ store. Activation of Ca++ signaling via PLC-coupled receptors simultaneously empties Ca++ stores and activates the influx of external Ca++. The presented concept of Ca++ signaling is compatible with all established data on Ca++ signaling. Properties of Ca++ signaling, that could not be reconciled with the basic principles of the current hypothesis, are intrinsic properties of the new concept. Quantal Ca++ release, Ca(++)-induced Ca++ release (CICR), the coupling phenomen between the filling state of the Ca++ store and the activity of the Ca++ influx pathway, as well as the various yet unexplained complex kinetics of Ca++ uptake and release can be explained on a common mechanistic basis.

Intracellular tortuosity underlies slow cAMP diffusion in adult ventricular myocytes.

PubMed

Richards, Mark; Lomas, Oliver; Jalink, Kees; Ford, Kerrie L; Vaughan-Jones, Richard D; Lefkimmiatis, Konstantinos; Swietach, Pawel

2016-06-01

3',5'-Cyclic adenosine monophosphate (cAMP) signals in the heart are often confined to concentration microdomains shaped by cAMP diffusion and enzymatic degradation. While the importance of phosphodiesterases (degradative enzymes) in sculpting cAMP microdomains is well established in cardiomyocytes, less is known about cAMP diffusivity (DcAMP) and factors affecting it. Many earlier studies have reported fast diffusivity, which argues against sharply defined microdomains. [cAMP] dynamics in the cytoplasm of adult rat ventricular myocytes were imaged using a fourth generation genetically encoded FRET-based sensor. The [cAMP]-response to the addition and removal of isoproterenol (β-adrenoceptor agonist) quantified the rates of cAMP synthesis and degradation. To obtain a read out of DcAMP, a stable [cAMP] gradient was generated using a microfluidic device which delivered agonist to one half of the myocyte only. After accounting for phosphodiesterase activity, DcAMP was calculated to be 32 µm(2)/s; an order of magnitude lower than in water. Diffusivity was independent of the amount of cAMP produced. Saturating cAMP-binding sites with the analogue 6-Bnz-cAMP did not accelerate DcAMP, arguing against a role of buffering in restricting cAMP mobility. cAMP diffused at a comparable rate to chemically unrelated but similar sized molecules, arguing for a common physical cause of restricted diffusivity. Lower mitochondrial density and order in neonatal cardiac myocytes allowed for faster diffusion, demonstrating the importance of mitochondria as physical barriers to cAMP mobility. In adult cardiac myocytes, tortuosity due to physical barriers, notably mitochondria, restricts cAMP diffusion to levels that are more compatible with microdomain signalling. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Cardiology.

Search for the source of an apparent interfacial resistance to mass transfer of CnEm surfactants to the water/oil interface.

PubMed

Huston, Kyle J; Kiemen, Ashley; Larson, Ronald G

2018-06-12

Experiments have shown that relaxation of oil/water interfacial tension by adsorption of alkyl ethoxylate surfactants from water onto an oil droplet is delayed relative to diffusion-controlled adsorption. We examine possible causes of this delay, and we show that several are implausible. We find that re-dissolution of the surfactant in the oil droplet cannot explain the apparent interfacial resistance at short times, because the interface will preferentially fill before any such re-dissolution occurs. We also perform umbrella sampling with molecular dynamics simulation and do not find any evidence of a free energy barrier or low-diffusivity zone near the interface. Nor do we find evidence from simulation that pre-micellar aggregation slows diffusion enough to cause the observed resistance to interfacial adsorption. We are therefore unable to pinpoint the cause of the resistance, but we suggest that "dead time" associated with the experimental method could be responsible - specifically a local depletion of surfactant by the ejected droplet when creating the fresh interface between the oil and water.

Enhanced Proton Conductivity in Y-Doped BaZrO3 via Strain Engineering.

PubMed

Fluri, Aline; Marcolongo, Aris; Roddatis, Vladimir; Wokaun, Alexander; Pergolesi, Daniele; Marzari, Nicola; Lippert, Thomas

2017-12-01

The effects of stress-induced lattice distortions (strain) on the conductivity of Y-doped BaZrO 3 , a high-temperature proton conductor with key technological applications for sustainable electrochemical energy conversion, are studied. Highly ordered epitaxial thin films are grown in different strain states while monitoring the stress generation and evolution in situ. Enhanced proton conductivity due to lower activation energies is discovered under controlled conditions of tensile strain. In particular, a twofold increased conductivity is measured at 200 °C along a 0.7% tensile strained lattice. This is at variance with conclusions coming from force-field simulations or the static calculations of diffusion barriers. Here, extensive first-principles molecular dynamic simulations of proton diffusivity in the proton-trapping regime are therefore performed and found to agree with the experiments. The simulations highlight that compressive strain confines protons in planes parallel to the substrate, while tensile strain boosts diffusivity in the perpendicular direction, with the net result that the overall conductivity is enhanced. It is indeed the presence of the dopant and the proton-trapping effect that makes tensile strain favorable for proton conduction.

Thermionic emission current in a single barrier varactor

NASA Technical Reports Server (NTRS)

Hjelmgren, Hans; East, Jack; Kollberg, Erik

1992-01-01

From I-V measurements on Single Barrier Varactors (SBV) at different temperatures we concluded that thermionic emission across the barrier of the actual device is mainly due to transport through the X band. The same structure was also modeled with a one-dimensional drift-diffusion model, including a 'boundary condition' for thermionic emission across the heterojunction interface. By including thermionic field emission through the top of the triangular barrier of a biased diode and the effect of a non-abrupt interface at the heterojunction, we obtained good agreement between the modeled and measured I-V characteristics.

Computing Rates of Small Molecule Diffusion Through Protein Channels Using Markovian Milestoning

NASA Astrophysics Data System (ADS)

Abrams, Cameron

2014-03-01

Measuring diffusion rates of ligands plays a key role in understanding the kinetic processes inside proteins. For example, although many molecular simulation studies have reported free energy barriers to infer rates for CO diffusion in myoglobin (Mb), they typically do not include direct calculation of diffusion rates because of the long simulation times needed to infer these rates with statistical accuracy. We show in this talk how to apply Markovian milestoning along minimum free-energy pathways to calculate diffusion rates of CO inside Mb. In Markovian milestoning, one partitions a suitable reaction coordinate space into regions and performs restrained molecular dynamics in each region to accumulate kinetic statistics that, when assembled across regions, provides an estimate of the mean first-passage time between states. The mean escape time for CO directly from the so-called distal pocket (DP) through the histidine gate (HG) is estimated at about 24 ns, confirming the importance of this portal for CO. But Mb is known to contain several internal cavities, and cavity-to-cavity diffusion rates are also computed and used to build a complete kinetic network as a Markov state model. Within this framework, the effective mean time of escape to the solvent through HG increases to 30 ns. Our results suggest that carrier protein structure may have evolved under pressure to modulate dissolved gas release rates using a network of ligand-accessible cavities. Support: NIH R01GM100472.

Molecular assemblies as protective barriers and adhesion promotion interlayer

DOEpatents

King, D.E.; Czanderna, A.W.; Kennedy, C.E.

1996-01-30

A protective diffusion barrier having adhesive qualities for metalized surfaces is provided by a passivating agent having the formula HS--(CH{sub 2}){sub 11}--COOH which forms a very dense, transparent organized molecular assembly or layer that is impervious to water, alkali, and other impurities and corrosive substances that typically attack metal surfaces. 8 figs.

Performance Enhancement of the Space Shuttle RSRM Nozzle-to-Case Joint Using a Carbon Rope Barrier

NASA Technical Reports Server (NTRS)

Ewing, M. E.; McGuire, J. R.; McWhorter, B. B.; Frost, D. L.

1999-01-01

A carbon rope "thermal barrier" is being considered as a component to enhance performance of the Reusable Solid Rocket Motor (RSRM) nozzle-to-case joint. Fundamental performance characteristics of the rope have been considered in this paper. In particular, resistance to erosion, ability to filter particulate matter, thermal capacitance, and flow resistance have been considered. Testing results have shown the rope to be resistant to the corrosive internal environment of the RSRM. The rope has also been shown to be an effective "slag barrier." A desirable feature of the rope would be the ability to act as a heat sink. However, analyses have indicated that the thermal capacitance of the rope is not large enough to reduce the temperature of an impinging gas stream below the ablation temperature of the 0-ring for significant time periods, The real value of the rope is its ability to act as a flow diffuser. Flow resistance test, were performed on the rope In the course of testing the rope between parallel plates, an undesirable "blow-by" phenomenon was observed when the compressive stress in the rope was smaller than the upstream gas pressure. It was found, however, that in the converging passage of the actual design, the rope would consistently "Self-seat" and thereby prevent blow-by, even in the absence of any precompression. Flow resistance values have been quantified for use in future analyses. The work presented here provides an initial thermal-fluid assessment of the rope for this application, and lays the groundwork for future development.

Oxygen-selective immobilized liquid membranes for operation of lithium-air batteries in ambient air

NASA Astrophysics Data System (ADS)

Zhang, Jian; Xu, Wu; Liu, Wei

In this work, nonaqueous electrolyte-based Li-air batteries with an O 2-selective membrane have been developed for operation in ambient air of 20-30% relative humidity (RH). The O 2 gas is continuously supplied through a membrane barrier layer at the interface of the cathode and ambient air. The membrane allows O 2 to permeate through while blocking moisture. Such membranes can be prepared by loading O 2-selective silicone oils into porous supports such as porous metal sheets and Teflon (PTFE) films. It was found that the silicone oil of high viscosity shows better performance. The immobilized silicone oil membrane in the porous PTFE film enabled the Li-air batteries with carbon black air electrodes to operate in ambient air (at 20% RH) for 16.3 days with a specific capacity of 789 mAh g -1 carbon and a specific energy of 2182 Wh kg -1 carbon. Its performance is much better than a reference battery assembled with a commercial, porous PTFE diffusion membranes as the moisture barrier layer on the cathode, which only had a discharge time of 5.5 days corresponding to a specific capacity of 267 mAh g -1 carbon and a specific energy of 704 Wh kg -1 carbon. The Li-air battery with the present selective membrane barrier layer even showed better performance in ambient air operation (20% RH) than the reference battery tested in the dry air box (<1% RH).

Oxygen-Barrier Coating for Titanium

NASA Technical Reports Server (NTRS)

Clark, Ronald K.; Unnam, Jalaiah

1987-01-01

Oxygen-barrier coating for titanium developed to provide effective and low-cost means for protecting titanium alloys from oxygen in environment when alloys used in high-temperature mechanical or structural applications. Provides protective surface layer, which reduces extent of surface oxidation of alloy and forms barrier to diffusion of oxygen, limiting contamination of substrate alloy by oxygen. Consists of submicron layer of aluminum deposited on surface of titanium by electron-beam evaporation, with submicron layer of dioxide sputtered onto aluminum to form coat.

Deposition and properties of cobalt- and ruthenium-based ultra-thin films

NASA Astrophysics Data System (ADS)

Henderson, Lucas Benjamin

Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165°C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350°C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis(trimethylphosphine)cobalt(0), yields cobalt-phosphorus films without any co-reactant. However, the molecule does not contain sufficient amounts of amorphizing agents to fully eliminate grain boundaries, and the resulting film is nanocrystalline.

TC-99 Decontaminant from heat treated gaseous diffusion membrane -Phase I, Part B

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

Oji, L.; Restivo, M.; Duignan, M.

2017-11-01

Uranium gaseous diffusion cascades represent a significant environmental challenge to dismantle, containerize and dispose as low-level radioactive waste. Baseline technologies rely on manual manipulations involving direct access to technetium-contaminated piping and materials. There is a potential to utilize novel decontamination technologies to remove the technetium and allow for on-site disposal of the very large uranium converters. Technetium entered these gaseous diffusion cascades as a hexafluoride complex in the same fashion as uranium. Technetium, as the isotope Tc-99, is an impurity that follows uranium in the first cycle of the Plutonium and Uranium Extraction (PUREX) process. The technetium speciation or exactmore » form in the gaseous diffusion cascades is not well defined. Several forms of Tc-99 compounds, mostly the fluorinated technetium compounds with varying degrees of volatility have been speculated by the scientific community to be present in these cascades. Therefore, there may be a possibility of using thermal or leaching desorption, which is independent of the technetium oxidation states, to perform an insitu removal of the technetium as a volatile species and trap the radionuclide on sorbent traps which could be disposed as low-level waste. Based on the positive results of the first part of this work1 the use of steam as a thermal decontamination agent was further explored with a second piece of used barrier material from a different location. This new series of tests included exposing more of the material surface to the flow of high temperature steam through the change in the reactor design, subjecting it to alternating periods of stream and vacuum, as well as determining if a lower temperature steam, i.e., 121°C (250°F) would be effective, too. Along with these methods, one other simpler method involving the leaching of the Tc-99 contaminated barrier material with a 1.0 M aqueous solution of ammonium carbonate, with and without sonication, was evaluated.« less

Diffusion anisotropy of poor metal solute atoms in hcp-Ti

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

Scotti, Lucia, E-mail: lxs234@bham.ac.uk; Mottura, Alessandro, E-mail: a.mottura@bham.ac.uk

2015-05-28

Atom migration mechanisms influence a wide range of phenomena: solidification kinetics, phase equilibria, oxidation kinetics, precipitation of phases, and high-temperature deformation. In particular, solute diffusion mechanisms in α-Ti alloys can help explain their excellent high-temperature behaviour. The purpose of this work is to study self- and solute diffusion in hexagonal close-packed (hcp)-Ti, and its anisotropy, from first-principles using the 8-frequency model. The calculated diffusion coefficients show that diffusion energy barriers depend more on bonding characteristics of the solute rather than the size misfit with the host, while the extreme diffusion anisotropy of some solute elements in hcp-Ti is a resultmore » of the bond angle distortion.« less

Nanolaminates with Novel Properties Fabricated Using Atomic Layer Deposition Techniques

DTIC Science & Technology

2006-07-01

Enhance X-Ray Reflectivity of Polysilicon Micro-Mirrors at 1.54 A Wavelength", Proceedings of SPIE 5720, 241-251 (2005). 20. D.C. Miller, C.F...diodes ( OLEDs ). This project has demonstrated that the A120 3 ALD gas diffusion barrier helps to prevent H20 and 02 gases from diffusing through the

Measurement of N-Type 6H SiC Minority-Carrier Diffusion Lengths by Electron Bombardment of Schottky Barriers

NASA Technical Reports Server (NTRS)

Hubbard, S. M.; Tabib-Azar, M.; Balley, S.; Rybickid, G.; Neudeck, P.; Raffaelle, R.

2004-01-01

Minority-Carrier diffusion lengths of n-type 6H-SiC were measured using the electron-beam induced current (EBIC) technique. Experimental values of primary beam current, EBIC, and beam voltage were obtained for a variety of SIC samples. This data was used to calculate experimental diode efficiency vs. beam voltage curves. These curves were fit to theoretically calculated efficiency curves, and the diffusion length and metal layer thickness were extracted. The hole diffusion length in n-6H SiC ranged from 0.93 +/- 0.15 microns.

Investigation of p-type depletion doping for InGaN/GaN-based light-emitting diodes

NASA Astrophysics Data System (ADS)

Zhang, Yiping; Zhang, Zi-Hui; Tan, Swee Tiam; Hernandez-Martinez, Pedro Ludwig; Zhu, Binbin; Lu, Shunpeng; Kang, Xue Jun; Sun, Xiao Wei; Demir, Hilmi Volkan

2017-01-01

Due to the limitation of the hole injection, p-type doping is essential to improve the performance of InGaN/GaN multiple quantum well light-emitting diodes (LEDs). In this work, we propose and show a depletion-region Mg-doping method. Here we systematically analyze the effectiveness of different Mg-doping profiles ranging from the electron blocking layer to the active region. Numerical computations show that the Mg-doping decreases the valence band barrier for holes and thus enhances the hole transportation. The proposed depletion-region Mg-doping approach also increases the barrier height for electrons, which leads to a reduced electron overflow, while increasing the hole concentration in the p-GaN layer. Experimentally measured external quantum efficiency indicates that Mg-doping position is vitally important. The doping in or adjacent to the quantum well degrades the LED performance due to Mg diffusion, increasing the corresponding nonradiative recombination, which is well supported by the measured carrier lifetimes. The experimental results are well numerically reproduced by modifying the nonradiative recombination lifetimes, which further validate the effectiveness of our approach.

Characterization and durability testing of plasma-sprayed zirconia-yttria and hafnia-yttria thermal barrier coatings. Part 2: Effect of spray parameters on the performance of several hafnia-yttria and zirconia-yttria coatings

NASA Technical Reports Server (NTRS)

Miller, Robert A.; Leissler, George W.

1993-01-01

This is the second of two reports which discuss initial experiments on thermal barrier coatings prepared and tested in newly upgraded plasma spray and burner rig test facilities at LeRC. The first report, part 1, describes experiments designed to establish the spray parameters for the baseline zirconia-yttria coating. Coating quality was judged primarily by the response to burner rig exposure, together with a variety of other characterization approaches including thermal diffusivity measurements. That portion of the study showed that the performance of the baseline NASA coating was not strongly sensitive to processing parameters. In this second part of the study, new hafnia-yttria coatings were evaluated with respect to both baseline and alternate zirconia-yttria coatings. The hafnia-yttria and the alternate zirconia-yttria coatings were very sensitive to plasma-spray parameters in that high-quality coatings were obtained only when specific parameters were used. The reasons for this important observation are not understood.

Si/Ge double-layered nanotube array as a lithium ion battery anode.

PubMed

Song, Taeseup; Cheng, Huanyu; Choi, Heechae; Lee, Jin-Hyon; Han, Hyungkyu; Lee, Dong Hyun; Yoo, Dong Su; Kwon, Moon-Seok; Choi, Jae-Man; Doo, Seok Gwang; Chang, Hyuk; Xiao, Jianliang; Huang, Yonggang; Park, Won Il; Chung, Yong-Chae; Kim, Hansu; Rogers, John A; Paik, Ungyu

2012-01-24

Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries. © 2011 American Chemical Society

Outer-membrane translocation of bulky small molecules by passive diffusion

PubMed Central

van den Berg, Bert; Prathyusha Bhamidimarri, Satya; Dahyabhai Prajapati, Jigneshkumar; Kleinekathöfer, Ulrich; Winterhalter, Mathias

2015-01-01

The outer membrane (OM) of gram-negative bacteria forms a protective layer around the cell that serves as a permeability barrier to prevent unrestricted access of noxious substances. The permeability barrier of the OM results partly from the limited pore diameters of OM diffusion channels. As a consequence, there is an “OM size-exclusion limit,” and the uptake of bulky molecules with molecular masses of more than ∼600 Da is thought to be mediated by TonB-dependent, active transporters. Intriguingly, the OM protein CymA from Klebsiella oxytoca does not depend on TonB but nevertheless mediates efficient OM passage of cyclodextrins with diameters of up to ∼15 Å. Here we show, by using X-ray crystallography, molecular dynamics simulations, and single-channel electrophysiology, that CymA forms a monomeric 14-stranded β-barrel with a large pore that is occluded on the periplasmic side by the N-terminal 15 residues of the protein. Representing a previously unidentified paradigm in OM transport, CymA mediates the passive diffusion of bulky molecules via an elegant transport mechanism in which a mobile element formed by the N terminus acts as a ligand-expelled gate to preserve the permeability barrier of the OM. PMID:26015567

First-Principles Analysis of Defect Thermodynamics and Ion Transport in Inorganic SEI Compounds: LiF and NaF

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

Yildirim, Handan; Kinaci, Alper; Chan, Maria K. Y.

The formation mechanism and composition of the solid electrolyte interphase (SEI) in lithium ion batteries has been widely explored. However, relatively little is known about the function of the SEI as a transport medium. Such critical information is directly relevant to battery rate performance, power loss, and capacity fading. To partially bridge this gap in the case of inorganic SEI compounds, we report herein the results of first-principles calculations on the defect thermodynamics, the dominant diffusion carriers, and the diffusion pathways associated with crystalline LiF and NaF, which are stable components of the SEI in Li-ion and Na-ion batteries, respectively.more » The thermodynamics of common point defects are computed, and the dominant diffusion carriers are determined over a voltage range of 0-4 V, corresponding to conditions relevant to both anode and cathode SEI's. Our analyses reveal that for both compounds, vacancy defects are energetically more favorable, therefore form more readily than interstitials, due to the close-packed nature of the crystal structures. However, the vacancy concentrations are very small for the diffusion processes facilitated by defects. Ionic conductivities are calculated as a function of voltage, considering the diffusion carrier concentration and the diffusion barriers as determined by nudged elastic band calculations. These conductivities are more than ten orders of magnitude smaller in NaF than in LiF. As compared to the diffusivity of Li in other common inorganic SEI compounds, such as Li2CO3 and Li2O,the cation diffusivity in LiF and NaF is quite low, with at least three orders of magnitude lower ionic conductivities. The results quantify the extent to which fluorides pose rate limitations in Li and Na batteries.« less

Morphological respiratory diffusion capacity of the lungs of ball pythons (Python regius).

PubMed

Starck, J Matthias; Aupperle, Heike; Kiefer, Ingmar; Weimer, Isabel; Krautwald-Junghanns, Maria-Elisabeth; Pees, Michael

2012-08-01

This study aims at a functional and morphological characterization of the lung of a boid snake. In particular, we were interested to see if the python's lungs are designed with excess capacity as compared to resting and working oxygen demands. Therefore, the morphological respiratory diffusion capacity of ball pythons (Python regius) was examined following a stereological, hierarchically nested approach. The volume of the respiratory exchange tissue was determined using computed tomography. Tissue compartments were quantified using stereological methods on light microscopic images. The tissue diffusion barrier for oxygen transport was characterized and measured using transmission electron micrographs. We found a significant negative correlation between body mass and the volume of respiratory tissue; the lungs of larger snakes had relatively less respiratory tissue. Therefore, mass-specific respiratory tissue was calculated to exclude effects of body mass. The volume of the lung that contains parenchyma was 11.9±5.0mm(3)g(-1). The volume fraction, i.e., the actual pulmonary exchange tissue per lung parenchyma, was 63.22±7.3%; the total respiratory surface was, on average, 0.214±0.129m(2); it was significantly negatively correlated to body mass, with larger snakes having proportionally smaller respiratory surfaces. For the air-blood barrier, a harmonic mean of 0.78±0.05μm was found, with the epithelial layer representing the thickest part of the barrier. Based on these findings, a median diffusion capacity of the tissue barrier ( [Formula: see text] ) of 0.69±0.38ml O(2)min(-1)mmHg(-1) was calculated. Based on published values for blood oxygen concentration, a total oxygen uptake capacity of 61.16mlO(2)min(-1)kg(-1) can be assumed. This value exceeds the maximum demand for oxygen in ball pythons by a factor of 12. We conclude that healthy individuals of P. regius possess a considerable spare capacity for tissue oxygen exchange. Copyright © 2012 Elsevier GmbH. All rights reserved.

The NASA/DOD aerospace knowledge diffusion research project: A research agenda

NASA Technical Reports Server (NTRS)

Pinelli, Thomas E.; Kennedy, John M.

1990-01-01

The project has both immediate and long term purposes. In the first instance it provides a practical and pragmatic basis for understanding how the results of NASA/DoD research diffuse into the aerospace R and D process. Over the long term it provides an empirical basis for understanding the aerospace knowledge diffusion process itself, and its implications at the individual, organizational, national, and international levels. The project is studying the major barriers to effective knowledge diffusion. This project will provide descriptive and analytical data regarding the flow of scientific and technical information (STI). It will examine both channels used to communicate information and the social system of the aerospace knowledge diffusion process.

Comparing electrochemical performance of transition metal silicate cathodes and chevrel phase Mo6S8 in the analogous rechargeable Mg-ion battery system

NASA Astrophysics Data System (ADS)

Chen, Xinzhi; Bleken, Francesca L.; Løvvik, Ole Martin; Vullum-Bruer, Fride

2016-07-01

Polyanion based silicate materials, MgMSiO4 (M = Fe, Mn, Co), previously reported to be promising cathode materials for Mg-ion batteries, have been re-examined. Both the sol-gel and molten salt methods are employed to synthesize MgMSiO4 composites. Mo6S8 is synthesized by a molten salt method combined with Cu leaching and investigated in the equivalent electrochemical system as a bench mark. Electrochemical measurements for Mo6S8 performed using the 2nd generation electrolyte show similar results to those reported in literature. Electrochemical performance of the silicate materials on the other hand, do not show the promising results previously reported. A thorough study of these published results are presented here, and compared to the current experimental data on the same material system. It appears that there are certain inconsistencies in the published results which cannot be explained. To further corroborate the present experimental results, atomic-scale calculations from first principles are performed, demonstrating that diffusion barriers are very high for Mg diffusion in MgMSiO4. In conclusion, MgMSiO4 (M = Fe, Mn, Co) olivine materials do not seem to be such good candidates for cathode materials in Mg-ion batteries as previously reported.

Deterioration of reflecting coatings by intermetallic diffusion.

PubMed

Hunter, W R; Mikes, T L; Hass, G

1972-07-01

Gold diffraction gratings overcoated with Al + MgF(2) to increase their efficiency in the vacuum ultraviolet suffered a severe loss in efficiency within six months to a year after coating; for example, from 50% to 2% at lambda1216 A. The cause of this loss was assumed to be interdiffusion of Au and Al; therefore, a more complete study of Au-Al film combinations was performed. The coatings were aged at room and elevated temperatures. Reflectance measurements were made in the visible and vacuum ultraviolet spectral regions. For wavelengths longer than lambda900 A, the measurements show very little change until the diffusion boundary reaches the penetration depth of the radiation. If Al is the first surface layer, however, reflectance measurements at lambda584 A permit measuring the progress of the diffusion boundary toward the Al surface because of the low absorptance of Al at this wavelength. Interdiffusion can be effectively eliminated by the use of thin dielectric layers uch as SiO and the natural oxide of Al. Such protected coatings have been exposed for one week at a temperature of 170 degrees C with no visible sign of diffusion, whereas a similar coating without the barrier layer would become useless in less than 1 h. Some preliminary studies have been made with Pt-Al film combinations.

Variation in diffusion of gases through PDMS due to plasma surface treatment and storage conditions.

PubMed

Markov, Dmitry A; Lillie, Elizabeth M; Garbett, Shawn P; McCawley, Lisa J

2014-02-01

Polydimethylsiloxane (PDMS) is a commonly used polymer in the fabrication of microfluidic devices due to such features as transparency, gas permeability, and ease of patterning with soft lithography. The surface characteristics of PDMS can also be easily changed with oxygen or low pressure air plasma converting it from a hydrophobic to a hydrophilic state. As part of such a transformation, surface methyl groups are removed and replaced with hydroxyl groups making the exposed surface to resemble silica, a gas impermeable substance. We have utilized Platinum(II)-tetrakis(pentaflourophenyl)porphyrin immobilized within a thin (~1.5 um thick) polystyrene matrix as an oxygen sensor, Stern-Volmer relationship, and Fick's Law of simple diffusion to measure the effects of PDMS composition, treatment, and storage on oxygen diffusion through PDMS. Results indicate that freshly oxidized PDMS showed a significantly smaller diffusion coefficient, indicating that the SiO2 layer formed on the PDMS surface created an impeding barrier. This barrier disappeared after a 3-day storage in air, but remained significant for up to 3 weeks if PDMS was maintained in contact with water. Additionally, higher density PDMS formulation (5:1 ratio) showed similar diffusion characteristics as normal (10:1 ratio) formulation, but showed 60 % smaller diffusion coefficient after plasma treatment that never recovered to pre-treatment levels even after a 3-week storage in air. Understanding how plasma surface treatments contribute to oxygen diffusion will be useful in exploiting the gas permeability of PDMS to establish defined normoxic and hypoxic oxygen conditions within microfluidic bioreactor systems.

Variation in diffusion of gases through PDMS due to plasma surface treatment and storage conditions

PubMed Central

Markov, Dmitry A.; Lillie, Elizabeth M.; Garbett, Shawn P.; McCawley, Lisa J.

2013-01-01

Polydimethylsiloxane (PDMS) is a commonly used polymer in the fabrication of microfluidic devices due to such features as transparency, gas permeability, and ease of patterning with soft lithography. The surface characteristics of PDMS can also be easily changed with oxygen or low pressure air converting it from a hydrophobic to a hydrophilic state. As part of such a transformation, surface methyl groups are removed and replaced with hydroxyl groups making the exposed surface to resemble silica, a gas impermeable substance. We have utilized Platinum(II)-tetrakis(pentaflourophenyl)porphyrin immobilized within a thin (~1.5 um thick) polystyrene matrix as an oxygen sensor, Stern-Volmer relationship, and Fick's Law of simple diffusion to measure the effects of PDMS composition, treatment, and storage on oxygen diffusion through PDMS. Results show that freshly oxidized PDMS showed a significantly smaller diffusion coefficient, indicating that the SiO2 layer formed on the PDMS surface created an impeding barrier. This barrier disappeared after a three-day storage in air, but remained significant for up to three weeks if PDMS was maintained in contact with water. Additionally, higher density PDMS formulation (5:1 ratio) showed similar diffusion characteristics as normal (10:1 ratio) formulation, but showed 60% smaller diffusion coefficient after plasma treatment that never recovered to pre-treatment levels even after a three-week storage in air. Understanding how plasma surface treatments contribute to oxygen diffusion will be useful in exploiting the gas permeability of PDMS to establish defined normoxic and hypoxic oxygen conditions within microfluidic bioreactor systems. PMID:24065585

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.

Barrier Coatings for Refractory Metals and Superalloys

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

SM Sabol; BT Randall; JD Edington

2006-02-23

In the closed working fluid loop of the proposed Prometheus space nuclear power plant (SNPP), there is the potential for reaction of core and plant structural materials with gas phase impurities and gas phase transport of interstitial elements between superalloy and refractory metal alloy components during service. Primary concerns are surface oxidation, interstitial embrittlement of refractory metals and decarburization of superalloys. In parallel with kinetic investigations, this letter evaluates the ability of potential coatings to prevent or impede communication between reactor and plant components. Key coating requirements are identified and current technology coating materials are reviewed relative to these requirements.more » Candidate coatings are identified for future evaluation based on current knowledge of design parameters and anticipated environment. Coatings were identified for superalloys and refractory metals to provide diffusion barriers to interstitial transport and act as reactive barriers to potential oxidation. Due to their high stability at low oxygen potential, alumina formers are most promising for oxidation protection given the anticipated coolant gas chemistry. A sublayer of iridium is recommended to provide inherent diffusion resistance to interstitials. Based on specific base metal selection, a thin film substrate--coating interdiffusion barrier layer may be necessary to meet mission life.« less

Tunneling-Magnetoresistance Ratio Comparison of MgO-Based Perpendicular-Magnetic-Tunneling-Junction Spin Valve Between Top and Bottom Co2Fe6B2 Free Layer Structure.

PubMed

Lee, Du-Yeong; Lee, Seung-Eun; Shim, Tae-Hun; Park, Jea-Gun

2016-12-01

For the perpendicular-magnetic-tunneling-junction (p-MTJ) spin valve with a nanoscale-thick bottom Co2Fe6B2 free layer ex situ annealed at 400 °C, which has been used as a common p-MTJ structure, the Pt atoms of the Pt buffer layer diffused into the MgO tunneling barrier. This transformed the MgO tunneling barrier from a body-centered cubic (b.c.c) crystallized layer into a mixture of b.c.c, face-centered cubic, and amorphous layers and rapidly decreased the tunneling-magnetoresistance (TMR) ratio. The p-MTJ spin valve with a nanoscale-thick top Co2Fe6B2 free layer could prevent the Pt atoms diffusing into the MgO tunneling barrier during ex situ annealing at 400 °C because of non-necessity of a Pt buffer layer, demonstrating the TMR ratio of ~143 %.

Effects of heat treatment on U-Mo fuel foils with a zirconium diffusion barrier

NASA Astrophysics Data System (ADS)

Jue, Jan-Fong; Trowbridge, Tammy L.; Breckenridge, Cynthia R.; Moore, Glenn A.; Meyer, Mitchell K.; Keiser, Dennis D.

2015-05-01

A monolith fuel design based on U-Mo alloy has been selected as the fuel type for conversion of the United States' high performance research reactors (HPRRs) from highly enriched uranium (HEU) to low-enriched uranium (LEU). In this fuel design, a thin layer of zirconium is used to eliminate the direct interaction between the U-Mo fuel meat and the aluminum-alloy cladding during irradiation. The co-rolling process used to bond the Zr barrier layer to the U-Mo foil during fabrication alters the microstructure of both the U-10Mo fuel meat and the U-Mo/Zr interface. This work studied the effects of post-rolling annealing treatment on the microstructure of the co-rolled U-Mo fuel meat and the U-Mo/Zr interaction layer. Microscopic characterization shows that the grain size of U-Mo fuel meat increases with the annealing temperature, as expected. The grain sizes were ∼9, ∼13, and ∼20 μm for annealing temperature of 650, 750, and 850 °C, respectively. No abnormal grain growth was observed. The U-Mo/Zr interaction-layer thickness increased with the annealing temperature with an Arrhenius constant for growth of 184 kJ/mole, consistent with a previous diffusion-couple study. The interaction layer thickness was 3.2 ± 0.5 μm, 11.1 ± 2.1 μm, 27.1 ± 0.9 μm for annealing temperature of 650, 750, to 850 °C, respectively. The homogeneity of Mo improves with post rolling annealing temperature and with U-Mo coupon homogenization. The phases in the Zr/U-Mo interaction layer produced by co-rolling, however, differ from those reported in the previous diffusion couple studies.

Effects of heat treatment on U–Mo fuel foils with a zirconium diffusion barrier

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

Jue, Jan-Fong; Trowbridge, Tammy L.; Breckenridge, Cynthia R.

A monolith fuel design based on U–Mo alloy has been selected as the fuel type for conversion of the United States’ high performance research reactors (HPRRs) from highly enriched uranium (HEU) to low-enriched uranium (LEU). In this fuel design, a thin layer of zirconium is used to eliminate the direct interaction between the U–Mo fuel meat and the aluminum-alloy cladding during irradiation. The co-rolling process used to bond the Zr barrier layer to the U–Mo foil during fabrication alters the microstructure of both the U–10Mo fuel meat and the U–Mo/Zr interface. This work studied the effects of post-rolling annealing treatmentmore » on the microstructure of the co-rolled U–Mo fuel meat and the U–Mo/Zr interaction layer. Microscopic characterization shows that the grain size of U–Mo fuel meat increases with the annealing temperature, as expected. The grain sizes were ~9, ~13, and ~20 μm for annealing temperature of 650, 750, and 850 °C, respectively. No abnormal grain growth was observed. The U–Mo/Zr interaction-layer thickness increased with the annealing temperature with an Arrhenius constant for growth of 184 kJ/mole, consistent with a previous diffusion-couple study. The interaction layer thickness was 3.2 ± 0.5 μm, 11.1 ± 2.1 μm, 27.1 ± 0.9 μm for annealing temperature of 650, 750, to 850 °C, respectively. The homogeneity of Mo improves with post rolling annealing temperature and with U–Mo coupon homogenization. The phases in the Zr/U–Mo interaction layer produced by co-rolling, however, differ from those reported in the previous diffusion couple studies.« less

Interstitial diffusion in lithium-ion battery electrodes and structural phase transitions in crystalline solids from first principles

NASA Astrophysics Data System (ADS)

Bhattacharya, Jishnu

We perform first-principles investigations of thermally activated phase transitions and diffusion in solids. The atomic scale energy landscapes are evaluated with first-principles total energy calculations for different structural and configurational microstates. Effective Hamiltonians constructed from the total energies are subjected to Monte Carlo simulations to study thermodynamic and kinetic properties of the solids at finite temperatures. Cubic to tetragonal martensitic phase transitions are investigated beyond the harmonic approximation. As an example, stoichiometric TiH2 is studied where a cubic phase becomes stable at high temperature while ab-initio energy calculations predict the cubic phase to be mechanically unstable with respect to tetragonal distortions at zero Kelvin. An anharmonic Hamiltonian is used to explain the stability of the cubic phase at higher temperature. The importance of anharmonic terms is emphasized and the true nature of the high temperature phase is elucidated beyond the traditional Landau-like explanation. In Li-ion battery electrodes, phase transitions due to atomic redistribution with changes in Li concentration occur with insertion (removal) of Li-ions during discharge (charge). A comprehensive study of the thermodynamics and the non-dilute Li-diffusion mechanisms in spinel-Li1+xTi2 O4 is performed. Two distinct phases are predicted at different lithium compositions. The predicted voltage curve qualitatively matches with experimental observation. The predicted fast diffusion arises from crystallographic features unique to the spinel crystal structure elucidating the crucial role of crystal structure on Li diffusion in intercalation compounds. Effects of anion and guest species on diffusion are elucidated with Li- and Cu-diffusion in spinel-LixTiS2. We predict strong composition dependence of the diffusion coefficients. A unique feature about spinel-LixTiS2 is that the intermediate site of a Li-hop is coordinated by four Li-sites. This results in di- and triple-vacancy mechanisms at non-dilute concentrations with very different migration barriers. The strong dependence of hop mechanisms on local Li-arrangement is at the origin of large concentration dependence of the diffusion coefficients. This contrasts with spinel-Li xTiO2 where the transition states are coordinated only by the end states of the hop, thereby restricting hops to a single vacancy mechanism. Cu ions are predicted to have much slower diffusion rate in TiS 2 host compared to Li ions.

Currency target-zone modeling: An interplay between physics and economics.

PubMed

Lera, Sandro Claudio; Sornette, Didier

2015-12-01

We study the performance of the euro-Swiss franc exchange rate in the extraordinary period from September 6, 2011 to January 15, 2015 when the Swiss National Bank enforced a minimum exchange rate of 1.20 Swiss francs per euro. Within the general framework built on geometric Brownian motions and based on the analogy between Brownian motion in finance and physics, the first-order effect of such a steric constraint would enter a priori in the form of a repulsive entropic force associated with the paths crossing the barrier that are forbidden. Nonparametric empirical estimates of drift and volatility show that the predicted first-order analogy between economics and physics is incorrect. The clue is to realize that the random-walk nature of financial prices results from the continuous anticipation of traders about future opportunities, whose aggregate actions translate into an approximate efficient market with almost no arbitrage opportunities. With the Swiss National Bank's stated commitment to enforce the barrier, traders' anticipation of this action leads to a vanishing drift together with a volatility of the exchange rate that depends on the distance to the barrier. This effect is described by Krugman's model [P. R. Krugman, Target zones and exchange rate dynamics, Q. J. Econ. 106, 669 (1991)]. We present direct quantitative empirical evidence that Krugman's theoretical model provides an accurate description of the euro-Swiss franc target zone. Motivated by the insights from the economic model, we revise the initial economics-physics analogy and show that, within the context of hindered diffusion, the two systems can be described with the same mathematics after all. Using a recently proposed extended analogy in terms of a colloidal Brownian particle embedded in a fluid of molecules associated with the underlying order book, we derive that, close to the restricting boundary, the dynamics of both systems is described by a stochastic differential equation with a very small constant drift and a linear diffusion coefficient. As a side result, we present a simplified derivation of the linear hydrodynamic diffusion coefficient of a Brownian particle close to a wall.

Currency target-zone modeling: An interplay between physics and economics

NASA Astrophysics Data System (ADS)

Lera, Sandro Claudio; Sornette, Didier

2015-12-01

We study the performance of the euro-Swiss franc exchange rate in the extraordinary period from September 6, 2011 to January 15, 2015 when the Swiss National Bank enforced a minimum exchange rate of 1.20 Swiss francs per euro. Within the general framework built on geometric Brownian motions and based on the analogy between Brownian motion in finance and physics, the first-order effect of such a steric constraint would enter a priori in the form of a repulsive entropic force associated with the paths crossing the barrier that are forbidden. Nonparametric empirical estimates of drift and volatility show that the predicted first-order analogy between economics and physics is incorrect. The clue is to realize that the random-walk nature of financial prices results from the continuous anticipation of traders about future opportunities, whose aggregate actions translate into an approximate efficient market with almost no arbitrage opportunities. With the Swiss National Bank's stated commitment to enforce the barrier, traders' anticipation of this action leads to a vanishing drift together with a volatility of the exchange rate that depends on the distance to the barrier. This effect is described by Krugman's model [P. R. Krugman, Target zones and exchange rate dynamics, Q. J. Econ. 106, 669 (1991), 10.2307/2937922]. We present direct quantitative empirical evidence that Krugman's theoretical model provides an accurate description of the euro-Swiss franc target zone. Motivated by the insights from the economic model, we revise the initial economics-physics analogy and show that, within the context of hindered diffusion, the two systems can be described with the same mathematics after all. Using a recently proposed extended analogy in terms of a colloidal Brownian particle embedded in a fluid of molecules associated with the underlying order book, we derive that, close to the restricting boundary, the dynamics of both systems is described by a stochastic differential equation with a very small constant drift and a linear diffusion coefficient. As a side result, we present a simplified derivation of the linear hydrodynamic diffusion coefficient of a Brownian particle close to a wall.

Escape rate of Brownian particles from a metastable potential well under time derivative Ornstein-Uhlenbeck noise

NASA Astrophysics Data System (ADS)

Bai, Zhan-Wu; Wang, Ping

2016-03-01

We investigate the escape rate of Brownian particles that move in a cubic metastable potential subjected to an internal time derivative Ornstein-Uhlenbeck noise (DOUN). This noise can induce the ballistic diffusion of force-free Brownian particles. Some new features are found. The escape rate for DOUN shows qualitative different dependence on potential well width compared with OUN which induces normal diffusion. As the potential barrier height decreases, the escape rate of DOUN deviates from Arrhenius law considerably earlier than that of Ornstein-Uhlenbeck noise (OUN). The Brownian particles escape faster under DOUN than that under OUN. A quasi-periodic oscillation occurs in transient state. A solvable case is presented to demonstrate the significant cancellation behavior in the barrier region that governs most of these phenomena. The physical mechanism of the findings can be clarified by the noise features. These characteristics should be common for internal noises that induce superdiffusion, especially the ballistic diffusion.

Oxygen impurity effects at metal/silicide interfaces - Formation of silicon oxide and suboxides in the Ni/Si system

NASA Technical Reports Server (NTRS)

Grunthaner, P. J.; Grunthaner, F. J.; Scott, D. M.; Nicolet, M.-A.; Mayer, J. W.

1981-01-01

The effect of implanted oxygen impurities on the Ni/Ni2Si interface is investigated using X-ray photoelectron spectroscopy, He-4(+) backscattering and O(d, alpha)-16 N-14 nuclear reactions. Oxygen dosages corresponding to concentrations of 1, 2, and 3 atomic percent were implanted into Ni films evaporated on Si substrates. The oxygen, nickel, and silicon core lines were monitored as a function of time during in situ growth of the Ni silicide to determine the chemical nature of the diffusion barrier which forms in the presence of oxygen impurities. Analysis of the Ni, Si, and O core levels demonstrates that the formation of SiO2 is responsible for the Ni diffusion barrier rather than Ni oxide or mixed oxides, such as Ni2SiO4. It is determined that 2.2 x 10 to the 16th O/qu cm is sufficient to prevent Ni diffusion under UHV annealing conditions.

Reflectance spectroscopy can quantify cutaneous haemoglobin oxygenation by oxygen uptake from the atmosphere after epidermal barrier disruption.

PubMed

Heise, H M; Lampen, P; Stücker, M

2003-11-01

The supply of oxygen to the viable skin tissue within the upper layers is not only secured by the cutaneous blood vascular system, but to a significant part also by oxygen diffusion from the atmosphere through the horny layer. The aim of this study was to examine whether changes in haemoglobin oxygenation can be observed within the isolated perfused bovine udder skin used as a skin model by removing the upper horny layer by adhesive tape stripping. Diffuse reflectance spectroscopy in the visible spectral range was used for non-invasive characterisation of haemoglobin oxygenation in skin under in vitro conditions. Mid-infrared attenuated total reflectance spectroscopy was employed for analysing the surface layer of the stratum corneum with respect to keratin, water and lipid components. Skin barrier disruption was achieved by repeated stripping of superficial corneocyte layers by adhesive tape. Significant changes in skin haemoglobin oxygenation were observed for skin areas with reduced lipid concentration and a reduced stratum corneum layer, as determined from the quantitative evaluation of the diffuse reflectance skin spectra. The result can be interpreted as an increase of oxygen diffusion after the removal of the upper horny layer.

Ab initio study of novel carbon nanofoam structure as an anode material for Li secondary battery

NASA Astrophysics Data System (ADS)

Park, Hanjin; Park, Sora; Kang, Seoung-Hun; Kwon, Young-Kyun

2014-03-01

Using ab inito density functional theory, we investigate the adsorption and diffusion properties of Li atoms on a new carbon nanostructure, which may be used as an anode of Li secondary battery. We focus on a special carbon nanofoam structure consisting of Schwarzite structures with negative Gaussian curvature as core parts, which are interconnected through (4,4) CNT segments. Considering the symmetry of the nanofoam structure, we find various Li adsorption sites exhibiting relatively large binding energies (>= 2 . 00 eV). Based on these adsorption sites, we identify several diffusion paths on the outside or inside surface of the nanofoam structure and examine the diffusion barriers along the paths. Our results show that Li atom can diffuse almost freely due to its low energy barriers on both outside and inside surfaces. Finally, we also evaluate the energy gain tendency and the volume expansion as well as the average binding energy while adding Li atoms to estimate the Li-capacity and recyclability of the system, which are important characterisitics for anode materials. We conclude that the carbon nanofoam structure would be better as an anode material than graphite in Li capacity and volume expansion.

Ag Transport Through Non-Irradiated and Irradiated SiC

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

Szlufarska, Izabela; Morgan, Dane; Blanchard, James

Silicon carbide is the main barrier to diffusion of fission products in the current design of TRistuctural ISOtropic (TRISO) coated fuel particles, and Ag is one of the few fission products that have been shown to escape through this barrier. Because the SiC coating in TRISO is exposed to radiation throughout the lifetime of the fuel, understanding of how radiation changes the transport of the fission products is essential for the safety of the reactor. The goals of this project are: (i) to determine whether observed variation in integral release measurements of Ag through SiC can be explained by differencesmore » in grain size and grain boundary (GB) types among the samples; (2) to identify the effects of irradiation on diffusion of Ag through SiC; (3) to discover phenomena responsible for significant solubility of Ag in polycrystalline SiC. To address these goals, we combined experimental analysis of SiC diffusion couples with modeling studies of diffusion mechanisms through bulk and GBs of this material. Comparison between results obtained for pristine and irradiated samples brings in insights into the effects of radiation on Ag transport.« less

Transition from diffuse to self-organized discharge in a high frequency dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Belinger, Antoine; Naudé, Nicolas; Gherardi, Nicolas

2017-05-01

Depending on the operating conditions, different regimes can be obtained in a dielectric barrier discharge (DBD): filamentary, diffuse (also called homogeneous) or self-organized. For a plane-to-plane DBD operated at high frequency (160 kHz) and at atmospheric pressure in helium gas, we show that the addition of a small amount of nitrogen induces a transition from the diffuse regime to a self-organized regime characterized by the appearance of filaments at the exit of the discharge. In this paper, we detail mechanisms that could be responsible of the transition from diffuse mode to this self-organized mode. We point out the critical role of the power supply and the importance of the gas memory effect from one discharge to the following one on the transition to the self-organised mode. The self-organized mode is usually attributed to a surface memory effect. In this work, we show an additional involvement of the gas memory effect on the self-organized mode. Contribution to the topical issue "The 15th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE XV)", edited by Nicolas Gherardi and Tomáš Hoder

Bond lifetime and diffusion coefficient in colloids with short-range interactions.

PubMed

Ndong Mintsa, E; Germain, Ph; Amokrane, S

2015-03-01

We use molecular dynamics simulations to study the influence of short-range structures in the interaction potential between hard-sphere-like colloidal particles. Starting from model potentials and effective potentials in binary mixtures computed from the Ornstein-Zernike equations, we investigate the influence of the range and strength of a possible tail beyond the usual core repulsion or the presence of repulsive barriers. The diffusion coefficient and mean "bond" lifetimes are used as indicators of the effect of this structure on the dynamics. The existence of correlations between the variations of these quantities with the physical parameters is discussed to assess the interpretation of dynamics slowing down in terms of long-lived bonds. We also discuss the question of a universal behaviour determined by the second virial coefficient B ((2)) and the interplay of attraction and repulsion. While the diffusion coefficient follows the B ((2)) law for purely attractive tails, this is no longer true in the presence of repulsive barriers. Furthermore, the bond lifetime shows a dependence on the physical parameters that differs from that of the diffusion coefficient. This raises the question of the precise role of bonds on the dynamics slowing down in colloidal gels.

Classification Order of Surface-Confined Intermixing at Epitaxial Interface

NASA Astrophysics Data System (ADS)

Michailov, M.

The self-organization phenomena at epitaxial interface hold special attention in contemporary material science. Being relevant to the fundamental physical problem of competing, long-range and short-range atomic interactions in systems with reduced dimensionality, these phenomena have found exacting academic interest. They are also of great technological importance for their ability to bring spontaneous formation of regular nanoscale surface patterns and superlattices with exotic properties. The basic phenomenon involved in this process is surface diffusion. That is the motivation behind the present study which deals with important details of diffusion scenarios that control the fine atomic structure of epitaxial interface. Consisting surface imperfections (terraces, steps, kinks, and vacancies), the interface offers variety of barriers for surface diffusion. Therefore, the adatoms and clusters need a certain critical energy to overcome the corresponding diffusion barriers. In the most general case the critical energies can be attained by variation of the system temperature. Hence, their values define temperature limits of system energy gaps associated with different diffusion scenarios. This systematization imply classification order of surface alloying: blocked, incomplete, and complete. On that background, two diffusion problems, related to the atomic-scale surface morphology, will be discussed. The first problem deals with diffusion of atomic clusters on atomically smooth interface. On flat domains, far from terraces and steps, we analyzed the impact of size, shape, and cluster/substrate lattice misfit on the diffusion behavior of atomic clusters (islands). We found that the lattice constant of small clusters depends on the number N of building atoms at 1 < N ≤ 10. In heteroepitaxy, this effect of variable lattice constant originates from the enhanced charge transfer and the strong influence of the surface potential on cluster atomic arrangement. At constant temperature, the variation of the lattice constant leads to variable misfit which affects the island migration. The cluster/substrate commensurability influences the oscillation behavior of the diffusion coefficient caused by variation in the cluster shape. We discuss the results in a physical model that implies cluster diffusion with size-dependent cluster/substrate misfit. The second problem is devoted to diffusion phenomena in the vicinity of atomic terraces on stepped or vicinal surfaces. Here, we develop a computational model that refines important details of diffusion behavior of adatoms accounting for the energy barriers at specific atomic sites (smooth domains, terraces, and steps) located on the crystal surface. The dynamic competition between energy gained by mixing and substrate strain energy results in diffusion scenario where adatoms form alloyed islands and alloyed stripes in the vicinity of terrace edges. Being in agreement with recent experimental findings, the observed effect of stripe and island alloy formation opens up a way regular surface patterns to be configured at different atomic levels on the crystal surface. The complete surface alloying of the entire interface layer is also briefly discussed with critical analysis and classification of experimental findings and simulation data.

COATED CARBON ELEMENT FOR USE IN NUCLEAR REACTORS AND THE PROCESS OF MAKING THE ELEMENT

DOEpatents

Pyle, R.J.; Allen, G.L.

1963-01-15

S>This patent relates to a carbide-nitride-carbide coating for carbon bodies that are to be subjected to a high temperature nuclear reactor atmosphere, and a method of applying the same. This coating is a highly efficient diffusion barrier and protects the C body from corrosion and erosion by the reactor atmosphere. Preferably, the innermost coating is Zr carbide, the middle coatlng is Zr nitride, and the outermost coating is a mixture of Zr and Nb carbide. The nitride coating acts as a diffusion barrier, while the innermost carbide bonds the nitride to the C body and prevents deleterious reaction between the nitride and C body. The outermost carbide coating protects the nitride coating from the reactor atmosphere. (AEC)

Convective diffusion of nanoparticles from the epithelial barrier toward regional lymph nodes.

PubMed

Dukhin, Stanislav S; Labib, Mohamed E

2013-11-01

Drug delivery using nanoparticles as drug carriers has recently attracted the attention of many investigators. Targeted delivery of nanoparticles to the lymph nodes is especially important to prevent cancer metastasis or infection, and to diagnose disease stage. However, systemic injection of nanoparticles often results in organ toxicity because they reach and accumulate in all the lymph nodes in the body. An attractive strategy would be to deliver the drug-loaded nanoparticles to a subset of draining lymph nodes corresponding to a specific site or organ to minimize systemic toxicity. In this respect, mucosal delivery of nanoparticles to regional draining lymph nodes of a selected site creates a new opportunity to accomplish this task with minimal toxicity. One example is the delivery of nanoparticles from the vaginal lumen to draining lymph nodes to prevent the transmission of HIV in women. Other known examples include mucosal delivery of vaccines to induce immunity. In all cases, molecular and particle transport by means of diffusion and convective diffusion play a major role. The corresponding transport processes have common inherent regularities and are addressed in this review. Here we use nanoparticle delivery from the vaginal lumen to the lymph nodes as an example to address the many aspects of associated transport processes. In this case, nanoparticles penetrate the epithelial barrier and move through the interstitium (tissue) to the initial lymphatics until they finally reach the lymph nodes. Since the movement of interstitial liquid near the epithelial barrier is retarded, nanoparticle transport was found to take place through special foci present in the epithelium. Immediately after nanoparticles emerge from the foci, they move through the interstitium due to diffusion affected by convection (convective diffusion). Specifically, the convective transport of nanoparticles occurs due to their convection together with interstitial fluid through the interstitium toward the initial lymph capillaries. Afterwards, nanoparticles move together with the lymph flow along the initial lymph capillaries and then enter the afferent lymphatics and ultimately reach the lymph node. As the liquid moves through the interstitium toward the initial lymph capillaries due to the axial movement of lymph along the lymphatics, the theory for coupling between lymph flow and concomitant flow through the interstitium is developed to describe this general case. The developed theory is applied to interpret the large uptake of Qdots by lymph nodes during inflammation, which is induced by pre-treating mouse vagina with the surfactant Nonoxynol-9 prior to instilling the Qdots. Inflammation is viewed here to cause broadening of the pores within the interstitium with the concomitant formation of transport channels which function as conduits to transport the nanoparticles to the initial lymph capillaries. We introduced the term "effective channels" to denote those channels which interconnect with foci present in the epithelial barrier and which function to transport nanoparticles to initial lymph capillaries. The time of transport toward the lymph node, predicated by the theory, increases rapidly with increasing the distance y0 between the epithelial barrier and the initial lymph capillaries. Transport time is only a few hours, when y0 is small, about some R (where R is the initial lymph capillary radius), due to the predomination of a rather rapid convection in this case. This transport time to the lymph nodes may be tens of hours (or longer) when y0 is essentially larger and the slow diffusion controls the transport rate in a zone not far from the epithelial barrier, where convection is weak at large y0. Accounting for transport by diffusion only, which is mainly considered in many relevant publications, is not sufficient to explain our nanoparticle uptake kinetics because the possibility of fast transport due to convection is overlooked. Our systematic investigations have revealed that the information about the main transport conditions, namely, y0 and the pore broadening up to the dimension of the interstitial transport channels, is necessary to create the quantitative model of enhanced transport during inflammation with the use of the proposed model as a prerequisite. The modeling for convective diffusion of nanoparticles from the epithelial barrier to the lymph node has been mainly accomplished here, while the diffusion only scenario is accounted for in other studies. This first modeling is a semi-quantitative one. A more rigorous mathematical approach is almost impossible at this stage because the transport properties of the model are introduced here for the first time. These properties include: discovery of foci in the epithelium, formation of transport channels, definition of channels interconnecting with foci (effective foci and channels), generation of flow in the interstitium toward the initial lymph capillaries due to axial flow within afferent lymphatics, deformation of this flow due to hydrodynamic impermeability of the squamous layer with the formation of the hydrodynamic stagnation zone near the epithelial barrier, predomination of slow diffusion transport within the above zone, and predomination of fast convection of nanoparticles near the initial lymph capillaries. Copyright © 2013 Elsevier B.V. All rights reserved.

Convective diffusion of nanoparticles from the epithelial barrier towards regional lymph nodes

PubMed Central

Dukhin, Stanislav S; Labib, Mohamed E.

2013-01-01

Drug delivery using nanoparticles as drug carriers has recently attracted the attention of many investigators. Targeted delivery of nanoparticles to lymph nodes is especially important to prevent cancer metastasis or infection, and to diagnose disease stage. However, systemic injection of nanoparticles often results in organ toxicity because they reach and accumulate in all the lymph nodes in the body. An attractive strategy would be to deliver the drug-loaded nanoparticles to a subset of draining lymph nodes corresponding to a specific site or organ to minimize systemic toxicity. In this respect, mucosal delivery of nanoparticles to regional draining lymph nodes of a selected site creates a new opportunity to accomplish this task with minimal toxicity. One example is the delivery of nanoparticles from the vaginal lumen to draining lymph nodes to prevent the transmission of HIV in women. Other known examples include mucosal delivery of vaccines to induce immunity. In all cases, molecular and particle transport by means of diffusion and convective diffusion play a major role. The corresponding transport processes have common inherent regularities and are addressed in this review. Here we use nanoparticles delivery from the vaginal lumen to lymph nodes as an example to address the many aspects of associated transport processes. In this case, nanoparticles penetrate the epithelial barrier and move through the interstitium (tissue) to the initial lymphatics until they finally reach the lymph nodes. Since the movement of interstitial liquid near the epithelial barrier is retarded, nanoparticles transport was found to take place through special foci present in the epithelium. Immediately after nanoparticles emerge from the foci, they move through the interstitium due to diffusion affected by convection (convective diffusion). Specifically, the convective transport of nanoparticles occurs due to their convection together with interstitial fluid through the interstitium towards the initial lymph capillaries. Afterwards, nanoparticles move together with the lymph flow along the initial lymph capillaries and then enter the afferent lymphatics and ultimately reach the lymph node. As the liquid moves through the interstitium towards the initial lymph capillaries due to the axial movement of lymph along the lymphatics, the theory for coupling between lymph flow and concomitant flow through the interstitium is developed to describe this general case. The developed theory is applied to interpret the large uptake of Qdots by lymph nodes during inflammation, which is induced by pre-treating mouse vagina with the surfactant Nonoxynol-9 prior to instilling the Qdots. Inflammation is viewed here to cause broadening of the pores within the interstitium with the concomitant formation of transport channels which function as conduits to transport the nanoparticles to the initial lymph capillaries. We introduced the term “effective channels” to denote those channels which interconnect with foci present in the epithelial barrier and which function to transport nanoparticles to initial lymph capillaries. The time of transport towards the lymph node, predicated by the theory, increases rapidly with increasing the distance y0 between the epithelial barrier and the initial lymph capillaries. Transport time is only a few hours, when y0 is small, about some R (where R is the initial lymph capillary radius), due to the predomination of a rather rapid convection in this case. This transport time to lymph nodes may be tens of hours (or longer) when y0 is essentially larger and the slow diffusion controls the transport rate in a zone not far from the epithelial barrier, where convection is weak at large y0. Accounting for transport by diffusion only, which is mainly considered in many relevant publications, is not sufficient to explain our nanoparticles uptake kinetics because the possibility of fast transport due to convection is overlooked. Our systematic investigations have revealed that the information about the main transport conditions, namely, y0 and the pore broadening up to the dimension of the interstitial transport channels, is necessary to create the quantitative model of enhanced transport during inflammation with the use of the proposed model as a prerequisite. The modeling for convective diffusion of nanoparticles from the epithelial barrier to the lymph node has been mainly accomplished here, while the diffusion only scenario is accounted for in other studies. This first modeling is a semi-quantitative one. A more rigorous mathematical approach is almost impossible at this stage because the transport properties of the model are introduced here for the first time. These properties include: discovery of foci in the epithelium, formation of transport channels, definition of channels interconnecting with foci (effective foci and channels), generation of flow in the interstitium towards the initial lymph capillaries due to axial flow within afferent lymphatics, deformation of this flow due to hydrodynamic impermeability of the squamous layer with the formation of the hydrodynamic stagnation zone near the epithelial barrier, predomination of slow diffusion transport within the above zone, and predomination of fast convection of nanoparticles near the initial lymph capillaries. PMID:23859221

Mechanism of anisotropic surface self-diffusivity at the prismatic ice-vapor interface.

PubMed

Gladich, Ivan; Oswald, Amrei; Bowens, Natalie; Naatz, Sam; Rowe, Penny; Roeselova, Martina; Neshyba, Steven

2015-09-21

Predictive theoretical models for mesoscopic roughening of ice require improved understanding of attachment kinetics occurring at the ice-vapor interface. Here, we use classical molecular dynamics to explore the generality and mechanics of a transition from anisotropic to isotropic self-diffusivity on exposed prismatic surfaces. We find that self-diffusion parallel to the crystallographic a-axis is favored over the c-axis at sub-melt temperatures below about -35 °C, for three different representations of the water-water intermolecular potential. In the low-temperature anisotropic regime, diffusion results from interstitial admolecules encountering entropically distinct barriers to diffusion in the two in-plane directions. At higher temperatures, isotropic self-diffusion occurring deeper within the quasi-liquid layer becomes the dominant mechanism, owing to its larger energy of activation.

Universal time-dependent dispersion properties for diffusion in a one-dimensional critically tilted potential

NASA Astrophysics Data System (ADS)

Guérin, T.; Dean, D. S.

2017-01-01

We consider the time-dependent dispersion properties of overdamped tracer particles diffusing in a one-dimensional periodic potential under the influence of an additional constant tilting force F . The system is studied in the region where the force is close to the critical value Fc at which the barriers separating neighboring potential wells disappear. We show that, when F crosses the critical value, the shape of the mean-square displacement (MSD) curves is strongly modified. We identify a diffusive regime at intermediate-time scales with an effective diffusion coefficient which is much larger than the late-time diffusion coefficient for F >Fc , whereas for F

Improving oxidation resistance and thermal insulation of thermal barrier coatings by intense pulsed electron beam irradiation

NASA Astrophysics Data System (ADS)

Mei, Xianxiu; Liu, Xiaofei; Wang, Cunxia; Wang, Younian; Dong, Chuang

2012-12-01

In this paper, intense pulsed electron beam was used for the irradiation treatment of 6-8% Y2O3-stablized ZrO2 thermal barrier coating prepared by electron beam-physical vapor deposition to achieve the "sealing" of columnar crystals, thus improving their thermal insulation properties and high temperature oxidation resistance. The electron beam parameters used were: pulse duration 200 μs, electron voltage 15 kV, energy density 3, 5, 8, 15, 20 J/cm2, and pulsed numbers 30. 1050 °C cyclic oxidation and static oxidation experiments were used for the research on oxidation resistance of the coatings. When the energy density of the electron beam was larger than 8 J/cm2, ZrO2 ceramic coating surface was fully re-melted and became smooth, dense and shiny. The coating changed into a smooth polycrystalline structure, thus achieving the "sealing" effect of the columnar crystals. After irradiations with the energy density of 8-15 J/cm2, the thermally grown oxide coating thickness decreased significantly in comparison with non-irradiated coatings, showing that the re-melted coating improved the oxidation resistance of the coatings. The results of thermal diffusivity test by laser flash method showed that the thermal diffusion rate of the irradiated coating was lower than that of the coating without irradiation treatment, and the thermal insulation performance of irradiated coating was improved.

Theoretical study of the ammonia nitridation rate on an Fe (100) surface: A combined density functional theory and kinetic Monte Carlo study

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

Yeo, Sang Chul; Lee, Hyuck Mo, E-mail: hmlee@kaist.ac.kr; Lo, Yu Chieh

2014-10-07

Ammonia (NH{sub 3}) nitridation on an Fe surface was studied by combining density functional theory (DFT) and kinetic Monte Carlo (kMC) calculations. A DFT calculation was performed to obtain the energy barriers (E{sub b}) of the relevant elementary processes. The full mechanism of the exact reaction path was divided into five steps (adsorption, dissociation, surface migration, penetration, and diffusion) on an Fe (100) surface pre-covered with nitrogen. The energy barrier (E{sub b}) depended on the N surface coverage. The DFT results were subsequently employed as a database for the kMC simulations. We then evaluated the NH{sub 3} nitridation rate onmore » the N pre-covered Fe surface. To determine the conditions necessary for a rapid NH{sub 3} nitridation rate, the eight reaction events were considered in the kMC simulations: adsorption, desorption, dissociation, reverse dissociation, surface migration, penetration, reverse penetration, and diffusion. This study provides a real-time-scale simulation of NH{sub 3} nitridation influenced by nitrogen surface coverage that allowed us to theoretically determine a nitrogen coverage (0.56 ML) suitable for rapid NH{sub 3} nitridation. In this way, we were able to reveal the coverage dependence of the nitridation reaction using the combined DFT and kMC simulations.« less

Method of making dense, conformal, ultra-thin cap layers for nanoporous low-k ILD by plasma assisted atomic layer deposition

DOEpatents

Jiang, Ying-Bing [Albuquerque, NM; Cecchi, Joseph L [Albuquerque, NM; Brinker, C Jeffrey [Albuquerque, NM

2011-05-24

Barrier layers and methods for forming barrier layers on a porous layer are provided. The methods can include chemically adsorbing a plurality of first molecules on a surface of the porous layer in a chamber and forming a first layer of the first molecules on the surface of the porous layer. A plasma can then be used to react a plurality of second molecules with the first layer of first molecules to form a first layer of a barrier layer. The barrier layers can seal the pores of the porous material, function as a diffusion barrier, be conformal, and/or have a negligible impact on the overall ILD k value of the porous material.

Numerical analysis of similarity of barrier discharges in the 0.95 Ne/0.05 Xe mixture

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

Avtaeva, S. V.; Kulumbaev, E. B.

2009-04-15

Established dynamic regimes of similar (with a scale factor of 10) barrier discharges in the 0.95 Ne/0.05 Xe mixture are simulated in a one-dimensional drift-diffusion model. The similarity is examined of barrier discharges excited in gaps of lengths 0.4 and 4 mm at gas pressures of 350 and 35 Torr and dielectric layer thicknesses of 0.2 and 2 mm, the frequencies of the 400-V ac voltage applied to the discharge electrodes being 100 and 10 kHz, respectively.

A computational ab initio study of surface diffusion of sulfur on the CdTe (111) surface

NASA Astrophysics Data System (ADS)

Naderi, Ebadollah; Ghaisas, S. V.

2016-08-01

In order to discern the formation of epitaxial growth of CdS shell over CdTe nanocrystals, kinetics related to the initial stages of the growth of CdS on CdTe is investigated using ab-initio methods. We report diffusion of sulfur adatom on the CdTe (111) A-type (Cd-terminated) and B-type (Te-terminated) surfaces within the density functional theory (DFT). The barriers are computed by applying the climbing Nudge Elastic Band (c-NEB) method. From the results surface hopping emerges as the major mode of diffusion. In addition, there is a distinct contribution from kick-out type diffusion in which a CdTe surface atom is kicked out from its position and is replaced by the diffusing sulfur atom. Also, surface vacancy substitution contributes to the concomitant dynamics. There are sites on the B- type surface that are competitively close in terms of the binding energy to the lowest energy site of epitaxy on the surface. The kick-out process is more likely for B-type surface where a Te atom of the surface is displaced by a sulfur adatom. Further, on the B-type surface, subsurface migration of sulfur is indicated. Furthermore, the binding energies of S on CdTe reveal that on the A-type surface, epitaxial sites provide relatively higher binding energies and barriers than on B-type.

A computational ab initio study of surface diffusion of sulfur on the CdTe (111) surface

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

Naderi, Ebadollah, E-mail: enaderi42@gmail.com; Ghaisas, S. V.

2016-08-15

In order to discern the formation of epitaxial growth of CdS shell over CdTe nanocrystals, kinetics related to the initial stages of the growth of CdS on CdTe is investigated using ab-initio methods. We report diffusion of sulfur adatom on the CdTe (111) A-type (Cd-terminated) and B-type (Te-terminated) surfaces within the density functional theory (DFT). The barriers are computed by applying the climbing Nudge Elastic Band (c-NEB) method. From the results surface hopping emerges as the major mode of diffusion. In addition, there is a distinct contribution from kick-out type diffusion in which a CdTe surface atom is kicked outmore » from its position and is replaced by the diffusing sulfur atom. Also, surface vacancy substitution contributes to the concomitant dynamics. There are sites on the B- type surface that are competitively close in terms of the binding energy to the lowest energy site of epitaxy on the surface. The kick-out process is more likely for B-type surface where a Te atom of the surface is displaced by a sulfur adatom. Further, on the B-type surface, subsurface migration of sulfur is indicated. Furthermore, the binding energies of S on CdTe reveal that on the A-type surface, epitaxial sites provide relatively higher binding energies and barriers than on B-type.« less

Diffusion of anthracene derivatives on Cu(111) studied by STM and DFT

NASA Astrophysics Data System (ADS)

Wyrick, Jonathan; Bartels, Ludwig; Einstein, Theodore

2014-03-01

Substituted anthracenes have drawn attention due to their ability to diffuse uniaxially on a Cu(111) surface. We compare anthracene to three of its derivatives whose 9,10 hydrogens are replaced by elements of the chalcogen group that act as linkers binding the molecules to a Cu(111) substrate. DFT calculations shed light on STM imaging and diffusion studies on the three substituted species. We present an analysis of the DFT results in which energetic contributions to the diffusion barriers are partitioned among the Kohn-Sham orbitals, allowing us to make assignments as to how each orbital affects diffusion for each species and draw comparisons between them. Present address: Center for Nanoscale Science and Technology, NIST, Gaithersburg, MD.

Simulation of atomic diffusion in the Fcc NiAl system: A kinetic Monte Carlo study

DOE PAGES

Alfonso, Dominic R.; Tafen, De Nyago

2015-04-28

The atomic diffusion in fcc NiAl binary alloys was studied by kinetic Monte Carlo simulation. The environment dependent hopping barriers were computed using a pair interaction model whose parameters were fitted to relevant data derived from electronic structure calculations. Long time diffusivities were calculated and the effect of composition change on the tracer diffusion coefficients was analyzed. These results indicate that this variation has noticeable impact on the atomic diffusivities. A reduction in the mobility of both Ni and Al is demonstrated with increasing Al content. As a result, examination of the pair interaction between atoms was carried out formore » the purpose of understanding the predicted trends.« less

SIEST-A-RT: a study of vacancy diffusion in crystalline silicon using a local-basis first-principle (SIESTA) activation technique (ART).

NASA Astrophysics Data System (ADS)

El Mellouhi, Fedwa; Mousseau, Normand; Ordejón, Pablo

2003-03-01

We report on a first-principle study of vacancy-induced self-diffusion in crystalline silicon. Our simulations are performed on supercells containing 63 and 215 atoms. We generate the diffusion paths using the activation-relaxation technique (ART) [1], which can sample efficiently the energy landscape of complex systems. The forces and energy are evaluated using SIESTA [2], a selfconsistent density functional method using standard norm-conserving pseudopotentials and a flexible numerical linear combination of atomic orbitals basis set. Combining these two methods allows us to identify diffusion paths that would not be reachable with this degree of accuracy, using other methods. After a full relaxation of the neutral vacancy, we proceed to search for local diffusion paths. We identify various mechanisms like the formation of the four fold coordinated defect, and the recombination of dangling bonds by WWW process. The diffusion of the vacancy proceeds by hops to first nearest neighbor with an energy barrier of 0.69 eV. This work is funded in part by NSERC and NATEQ. NM is a Cottrell Scholar of the Research Corporation. [1] G. T. Barkema and N. Mousseau, Event-based relaxation of continuous disordered systems, Phys. Rev. Lett. 77, 4358 (1996); N. Mousseau and G. T. Barkema, Traveling through potential energy landscapes of disordered materials: ART, Phys. Rev. E 57, 2419 (1998). [2] Density functional method for very large systems with LCAO basis sets D. Sánchez-Portal, P. Ordejón, E. Artacho and J. M. Soler, Int. J. Quant. Chem. 65, 453 (1997).

Carrier-mediated cocaine transport at the blood-brain barrier as a putative mechanism in addiction liability.

PubMed

Chapy, Hélène; Smirnova, Maria; André, Pascal; Schlatter, Joël; Chiadmi, Fouad; Couraud, Pierre-Olivier; Scherrmann, Jean-Michel; Declèves, Xavier; Cisternino, Salvatore

2014-10-31

The rate of entry of cocaine into the brain is a critical factor that influences neuronal plasticity and the development of cocaine addiction. Until now, passive diffusion has been considered the unique mechanism known by which cocaine crosses the blood-brain barrier. We reassessed mechanisms of transport of cocaine at the blood-brain barrier using a human cerebral capillary endothelial cell line (hCMEC/D3) and in situ mouse carotid perfusion. Both in vivo and in vitro cocaine transport studies demonstrated the coexistence of a carrier-mediated process with passive diffusion. At pharmacological exposure level, passive diffusion of cocaine accounted for only 22.5% of the total cocaine influx in mice and 5.9% in hCMEC/D3 cells, whereas the carrier-mediated influx rate was 3.4 times greater than its passive diffusion rate in vivo. The functional identification of this carrier-mediated transport demonstrated the involvement of a proton antiporter that shared the properties of the previously characterized clonidine and nicotine transporter. The functionnal characterization suggests that the solute carrier (SLC) transporters Oct (Slc22a1-3), Mate (Slc47a1) and Octn (Slc22a4-5) are not involved in the cocaine transport in vivo and in vitro. Diphenhydramine, heroin, tramadol, cocaethylene, and norcocaine all strongly inhibited cocaine transport, unlike benzoylecgonine. Trans-stimulation studies indicated that diphenhydramine, nicotine, 3,4-methylenedioxyamphetamine (ecstasy) and the cathinone compound 3,4-methylenedioxypyrovalerone (MDPV) were also substrates of the cocaine transporter. Cocaine transport at the BBB involves a proton-antiporter flux that is quantitatively much more important than its passive diffusion. The molecular identification and characterization of this transporter will provide new tools to understand its role in addictive mechanisms. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Innovations In Diabetes Care Around the World: Case Studies Of Care Transformation Through Accountable Care Reforms.

PubMed

Thoumi, Andrea; Udayakumar, Krishna; Drobnick, Elizabeth; Taylor, Andrea; McClellan, Mark

2015-09-01

The rising prevalence, health burden, and cost of chronic diseases such as diabetes have accelerated global interest in innovative care models that use approaches such as community-based care and information technology to improve or transform disease prevention, diagnosis, and treatment. Although evidence on the effectiveness of innovative care models is emerging, scaling up or extending these models beyond their original setting has been difficult. We developed a framework to highlight policy barriers-institutional, regulatory, and financial-to the diffusion of transformative innovations in diabetes care. The framework builds on accountable care principles that support higher-value care, or better patient-level outcomes at lower cost. We applied this framework to three case studies from the United States, Mexico, and India to describe how innovators and policy leaders have addressed barriers, with a focus on important financing barriers to provider and consumer payment. The lessons have implications for policy reform to promote innovation through new funding approaches, institutional reforms, and performance measures with the goal of addressing the growing burdens of diabetes and other chronic diseases. Project HOPE—The People-to-People Health Foundation, Inc.

Lost in translation? Moving contingency management and cognitive behavioral therapy into clinical practice.

PubMed

Carroll, Kathleen M

2014-10-01

In the treatment of addictions, the gap between the availability of evidence-based therapies and their limited implementation in practice has not yet been bridged. Two empirically validated behavioral therapies, contingency management (CM) and cognitive behavioral therapy (CBT), exemplify this challenge. Both have a relatively strong level of empirical support but each has weak and uneven adoption in clinical practice. This review highlights examples of how barriers to their implementation in practice have been addressed systematically, using the Stage Model of Behavioral Therapies Development as an organizing framework. For CM, barriers such as cost and ideology have been addressed through the development of lower-cost and other adaptations to make it more community friendly. For CBT, barriers such as relative complexity, lack of trained providers, and need for supervision have been addressed via conversion to standardized computer-assisted versions that can serve as clinician extenders. Although these and other modifications have rendered both interventions more disseminable, diffusion of innovation remains a complex, often unpredictable process. The existing specialty addiction-treatment system may require significant reforms to fully implement CBT and CM, particularly greater focus on definable treatment goals and performance-based outcomes. © 2014 New York Academy of Sciences.

Carbon diffusion paths and segregation at high-angle tilt grain boundaries in α-Fe studied by using a kinetic activation-relation technique

NASA Astrophysics Data System (ADS)

Restrepo, Oscar A.; Mousseau, Normand; Trochet, Mickaël; El-Mellouhi, Fedwa; Bouhali, Othmane; Becquart, Charlotte S.

2018-02-01

Carbon diffusion and segregation in iron is fundamental to steel production but is also associated with corrosion. Using the kinetic activation-relaxation technique (k-ART), a kinetic Monte Carlo (KMC) algorithm with an on-the-fly catalog that allows to obtain diffusion properties over large time scales taking into account long-range elastic effects coupled with an EAM force field, we study the motion of a carbon impurity in four Fe systems with high-angle grain boundaries (GB), focusing on the impact of these extended defects on the long-time diffusion of C. Short and long-time stability of the various GBs is first analyzed, which allows us to conclude that the Σ 3 (1 1 1 ) θ =109 .53∘<110 > GB is unstable, with Fe migration barriers of ˜0.1 eV or less, and C acts as a pinning center. Focusing on three stable GBs, in all cases, these extended defects trap C in energy states lower than found in the crystal. Yet, contrary to general understanding, we show, through simulations extending to 0.1 s, that even tough C diffusion takes place predominantly in the GB, it is not necessarily faster than in the bulk and can even be slower by one to two orders of magnitude depending on the GB type. Analysis of the energy landscape provided by k-ART also shows that the free cavity volume around the impurity is not a strong predictor of diffusion barrier height. Overall, results show rather complex diffusion kinetics intimately dependent on the local environment.

Adsorption and diffusion of Au atoms on the (001) surface of Ti, Zr, Hf, V, Nb, Ta, and Mo carbides.

PubMed

Florez, Elizabeth; Viñes, Francesc; Rodriguez, Jose A; Illas, Francesc

2009-06-28

The adsorption of atomic Au on the (001) surface of TiC, ZrC, HfC, VC, NbC, TaC, and delta-MoC and the mechanism of diffusion of this adatom through the surface have been studied in terms of a periodic density functional theory based approach. In all the cases, the Au adsorption energies are in the range of 1.90-2.35 eV. The moderately large adsorption energies allow the Au diffusion before desorption could take place. For TiC(001), ZrC(001), and HfC(001), atomic Au is adsorbed directly on top of C atoms and diffusion takes place along the diagonal of the squares formed by M-C-M-C atoms with the transition state located above the hollow sites. For the rest of transition metal carbides the situation is less simple with the appearance of more than one stable adsorption site, as for NbC and TaC, of a small energy barrier for diffusion around the most stable adsorption site and of a more complex diffusion pathway. The small energy barrier for diffusion around the most stable site will result in a highly mobile Au species which could be observed in scanning tunnel microscope experiments. After depositing Au on metal-carbide surfaces, there is a noticeable charge transfer from the substrate to the adsorbed Au atom. The electronic perturbations on Au increase when going from TiC to ZrC or TaC. Our results indicate that metal carbides should be better supports for the chemical activation of Au than metal oxides.

Universal time-dependent dispersion properties for diffusion in a one-dimensional critically tilted potential.

PubMed

Guérin, T; Dean, D S

2017-01-01

We consider the time-dependent dispersion properties of overdamped tracer particles diffusing in a one-dimensional periodic potential under the influence of an additional constant tilting force F. The system is studied in the region where the force is close to the critical value F_{c} at which the barriers separating neighboring potential wells disappear. We show that, when F crosses the critical value, the shape of the mean-square displacement (MSD) curves is strongly modified. We identify a diffusive regime at intermediate-time scales with an effective diffusion coefficient which is much larger than the late-time diffusion coefficient for F>F_{c}, whereas for F

Macromolecule diffusion and confinement in prokaryotic cells.

PubMed

Mika, Jacek T; Poolman, Bert

2011-02-01

We review recent observations on the mobility of macromolecules and their spatial organization in live bacterial cells. We outline the major fluorescence microscopy-based methods to determine the mobility and thus the diffusion coefficients (D) of molecules, which is not trivial in small cells. The extremely high macromolecule crowding of prokaryotes is used to rationalize the reported lower diffusion coefficients as compared to eukaryotes, and we speculate on the nature of the barriers for diffusion observed for proteins (and mRNAs) in vivo. Building on in vitro experiments and modeling studies, we evaluate the size dependence of diffusion coefficients for macromolecules in vivo, in case of both water-soluble and integral membrane proteins. We comment on the possibilities of anomalous diffusion and provide examples where the macromolecule mobility may be limiting biological processes. Copyright © 2010 Elsevier Ltd. All rights reserved.

[Simulation on contamination forecast and control of groundwater in a certain hazardous waste landfill].

PubMed

Ma, Zhi-Fei; An, Da; Jiang, Yong-Hai; Xi, Bei-Dou; Li, Ding-Long; Zhang, Jin-Bao; Yang, Yu

2012-01-01

On the basis of site investigation and data collection of a certain hazardous waste landfill, the groundwater flow and solute transport coupled models were established by applying Visual Modflow software, which was used to conduct a numerical simulation that forecast the transport process of Cr6+ in groundwater and the effects of three control measures (ground-harden, leakage-proof barriers and drainage ditches) of contaminants transport after leachate leakage happened in impermeable layer of the landfill. The results show that the contamination plume of Cr6+ transports with groundwater flow direction, the contamination rang would reach the pool's boundary in 10 years, and the distance of contamination transport is 1 450 m. But the diffusion range of contamination plume would not be obviously expanded between 10 and 20 years. While the ground is hardened, the contamination plume would not reach the pool's boundary in 20 years. When the leakage-proof barrier is set in the bottom of water table aquifer, the concentration of Cr6+ is higher than that the leakage-proof barrier is unset, but the result is just opposite when setting the leakage-proof barrier in the bottom of underlying aquifer. The range of contamination plume is effectively controlled by setting drainage ditches that water discharge is 2 642 m3 x d(-1), which makes the monitoring wells would not be contaminated in 20 years. Moreover, combining the ground-harden with drainage ditches can get the best effect in controlling contaminants diffusion, and meanwhile, the drainage ditches' daily discharge is reduced to 1 878 m3 x d(-1). Therefore, it is suggested that the control measure combining the ground-harden with drainage ditches should apply to prevent contamination diffusion in groundwater when leachate leakage have happened in impermeable layer of the landfill.

Impact of volume and surface processes on the pre-ionization of dielectric barrier discharges: advanced diagnostics and fluid modeling

NASA Astrophysics Data System (ADS)

Nemschokmichal, Sebastian; Tschiersch, Robert; Höft, Hans; Wild, Robert; Bogaczyk, Marc; Becker, Markus M.; Loffhagen, Detlef; Stollenwerk, Lars; Kettlitz, Manfred; Brandenburg, Ronny; Meichsner, Jürgen

2018-05-01

The phenomenology and breakdown mechanism of dielectric barrier discharges are strongly determined by volume and surface memory effects. In particular, the pre-ionization provided by residual species in the volume or surface charges on the dielectrics influences the breakdown behavior of filamentary and diffuse discharges. This was investigated by advanced diagnostics such as streak camera imaging, laser photodetachment of negative ions and laser photodesorption of electrons from dielectric surfaces in correlation with 1D fluid modeling. The streak camera images show that an increasing number of residual charges in the volume changes the microdischarge breakdown in air-like gas mixtures from a cathode-directed streamer to a simultaneous propagation of cathode- and anode-directed streamers. In contrast, seed electrons are important for the pre-ionization if the density of residual charges in the volume is low. One source of seed electrons are negative ions, whose density exceeds the electron density during the pre-phase of diffuse helium-oxygen barrier discharges as indicated by the laser photodetachment experiments. Electrons desorbed from the cathodic dielectric have an even larger influence. They induce a transition from the glow-like to the Townsend-like discharge mode in nominally pure helium. Apart from analyzing the importance of the pre-ionization for the breakdown mechanism, the opportunities for manipulating the lateral structure and discharge modes are discussed. For this purpose, the intensity and diameter of a diffuse discharge in helium are controlled by an illuminated semiconducting barrier. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications

PubMed Central

Genovese, Laura

2017-01-01

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O2 and CO2) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients (D) and solubility (S) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate (GTR) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content. PMID:28867806

How Stress Treatments Influence the Performance of Biodegradable Poly(Butylene Succinate)-Based Copolymers with Thioether Linkages for Food Packaging Applications.

PubMed

Siracusa, Valentina; Genovese, Laura; Munari, Andrea; Lotti, Nadia

2017-08-30

Biodegradable poly(butylene succinate) (PBS)-based random copolymers containing thioether linkages (P(BSxTDGSy)) of various compositions have been investigated and characterized from the gas barrier, thermal, and mechanical point of view, after food contact simulants or thermal and photoaging processes. Each stress treatment was performed on thin films and the results obtained have been compared to the same untreated film, used as a standard. Barrier properties with different gases (O₂ and CO₂) were evaluated, showing that the polymer chemical composition strongly influenced the permeability behavior. The relationships between the diffusion coefficients ( D ) and solubility ( S ) with polymer composition were also investigated. The results highlighted a correlation between polymer chemical structure and treatment. Gas transmission rate ( GTR ) mainly depending on the performed treatment, as GTR increased with the increase of TDGS co-unit amount. Thermal and mechanical tests allowed for the recording of variations in the degree of crystallinity and in the tensile properties. An increase in the crystallinity degree was recorded after contact with simulant liquids and aging treatments, together with a molecular weight decrease, a slight enhancement of the elastic modulus and a decrement of the elongation at break, proportional to the TDGS co-unit content.

Release from the cone ribbon synapse under bright light conditions can be controlled by the opening of only a few Ca2+ channels

PubMed Central

Bartoletti, Theodore M.; Jackman, Skyler L.; Babai, Norbert; Mercer, Aaron J.; Kramer, Richard H.

2011-01-01

Light hyperpolarizes cone photoreceptors, causing synaptic voltage-gated Ca2+ channels to open infrequently. To understand neurotransmission under these conditions, we determined the number of L-type Ca2+ channel openings necessary for vesicle fusion at the cone ribbon synapse. Ca2+ currents (ICa) were activated in voltage-clamped cones, and excitatory postsynaptic currents (EPSCs) were recorded from horizontal cells in the salamander retina slice preparation. Ca2+ channel number and single-channel current amplitude were calculated by mean-variance analysis of ICa. Two different comparisons—one comparing average numbers of release events to average ICa amplitude and the other involving deconvolution of both EPSCs and simultaneously recorded cone ICa—suggested that fewer than three Ca2+ channel openings accompanied fusion of each vesicle at the peak of release during the first few milliseconds of stimulation. Opening fewer Ca2+ channels did not enhance fusion efficiency, suggesting that few unnecessary channel openings occurred during strong depolarization. We simulated release at the cone synapse, using empirically determined synaptic dimensions, vesicle pool size, Ca2+ dependence of release, Ca2+ channel number, and Ca2+ channel properties. The model replicated observations when a barrier was added to slow Ca2+ diffusion. Consistent with the presence of a diffusion barrier, dialyzing cones with diffusible Ca2+ buffers did not affect release efficiency. The tight clustering of Ca2+ channels, along with a high-Ca2+ affinity release mechanism and diffusion barrier, promotes a linear coupling between Ca2+ influx and vesicle fusion. This may improve detection of small light decrements when cones are hyperpolarized by bright light. PMID:21880934

Knowledge barriers to PACS adoption and implementation in hospitals.

PubMed

Paré, Guy; Trudel, Marie-Claude

2007-01-01

Drawing on the classical theory of diffusion of innovations advanced by Rogers [E.M. Rogers, Diffusion of Innovations, 4th ed., Free Press, New York, NY, 1995] and on the theory of barriers to innovation [P. Attewell, Technology diffusion and organizational learning: the case of business computing. Organ. Sci. 3 (1992) 1-19; H. Tanriverdi, C.S. Iacono, Knowledge barriers to diffusion of telemedicine. Proceedings of the 20th International Conference on Information Systems, Charlotte, NC, 1999, pp. 39-50; S. Nambisan, Y.-M. Wang, Roadblocks to web technology adoption? Commun. ACM, 42 (1) (1999) 98-101], this study seeks a better understanding of challenges faced in PACS implementations in hospitals and of the strategies required to ensure their success. To attain this objective, we describe and analyze the process used to adopt and implement PACS at two Canadian hospitals. Our findings clearly demonstrate the importance of treating any PACS deployment not simply as a rollout of new technology but as a project that will transform the organization. Proponents of these projects must not lose sight of the fact that, even if technological complexity represents a significant issue, it must not garner all the project team's attention. This situation is even more dangerous, inasmuch as the greatest risk to the implementation often lies elsewhere. It would also appear to be crucial to anticipate and address organizational and behavioral challenges from the very first phase of the innovation process, in order to ensure that all participants will be committed to the project. In order to maximize the likelihood of PACS success, it appears crucial to adopt a proactive implementation strategy, one that takes into consideration all the technical, economic, organizational, and human factors, and does so from the first phase of the innovation process.

Release from the cone ribbon synapse under bright light conditions can be controlled by the opening of only a few Ca(2+) channels.

PubMed

Bartoletti, Theodore M; Jackman, Skyler L; Babai, Norbert; Mercer, Aaron J; Kramer, Richard H; Thoreson, Wallace B

2011-12-01

Light hyperpolarizes cone photoreceptors, causing synaptic voltage-gated Ca(2+) channels to open infrequently. To understand neurotransmission under these conditions, we determined the number of L-type Ca(2+) channel openings necessary for vesicle fusion at the cone ribbon synapse. Ca(2+) currents (I(Ca)) were activated in voltage-clamped cones, and excitatory postsynaptic currents (EPSCs) were recorded from horizontal cells in the salamander retina slice preparation. Ca(2+) channel number and single-channel current amplitude were calculated by mean-variance analysis of I(Ca). Two different comparisons-one comparing average numbers of release events to average I(Ca) amplitude and the other involving deconvolution of both EPSCs and simultaneously recorded cone I(Ca)-suggested that fewer than three Ca(2+) channel openings accompanied fusion of each vesicle at the peak of release during the first few milliseconds of stimulation. Opening fewer Ca(2+) channels did not enhance fusion efficiency, suggesting that few unnecessary channel openings occurred during strong depolarization. We simulated release at the cone synapse, using empirically determined synaptic dimensions, vesicle pool size, Ca(2+) dependence of release, Ca(2+) channel number, and Ca(2+) channel properties. The model replicated observations when a barrier was added to slow Ca(2+) diffusion. Consistent with the presence of a diffusion barrier, dialyzing cones with diffusible Ca(2+) buffers did not affect release efficiency. The tight clustering of Ca(2+) channels, along with a high-Ca(2+) affinity release mechanism and diffusion barrier, promotes a linear coupling between Ca(2+) influx and vesicle fusion. This may improve detection of small light decrements when cones are hyperpolarized by bright light.

Investigation of nanosecond pulsed dielectric barrier discharge using plate-to-plate electrode with asymmetric dielectric arrangement in airflow

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

Qi, Haicheng; School of Physics Science and Technology, Anshan Normal University, Anshan 114005; Fan, Zhihui

Atmospheric pressure dielectric barrier discharge plasma is produced in airflow by applying nanosecond high voltage pulses with peak voltage about 35 kV and rising time about 40 ns on a plate-to-plate electrode arrangement. The effects of airflow rate (0–50 m/s) on the discharge characteristics are investigated under different barrier conditions (the bare anode case and the bare cathode case). For both cases, the breakdown voltage and the time lag increase distinctly and the discharge intensity decreases sharply when the airflow rate increases from 0 to 30 m/s, and then keep almost constant until the airflow rate is further increased to 50 m/s. For the baremore » anode case (the cathode is covered by dielectric plate), the discharge mode transforms gradually from filamentary to diffuse discharge with the increasing airflow rate. While for the bare cathode case, some micro-discharge channels are still excited, though the discharge becomes more diffuse when the airflow rate is higher than 30 m/s. By acquiring the time-resolved images of the discharge, it is proved that it is the primary discharge which becomes diffuse when airflow is introduced and the following two discharges of the same voltage pulse occur principally at the positions where the primary discharge is more intense. And in both cases, the plasma temperatures are reduced, but the degree is different. All the phenomena can be explained mainly by the variation of the space charge distribution when the airflow is introduced into the discharge gap. And it is indicated that the bare anode case has an advantage in obtaining diffuse discharge.« less

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.

Preliminary study of a solar selective coating system using black cobalt oxide for high temperature solar collectors

NASA Technical Reports Server (NTRS)

Mcdonald, G.

1980-01-01

Black cobalt oxide coatings (high solar absorptance layer) were deposited on thin layers of silver or gold (low emittance layer) which had been previously deposited on oxidized (diffusion barrier layer) stainless steel substrates. The reflectance properties of these coatings were measured at various thicknesses of cobalt for integrated values of the solar and infrared spectrum. The values of absorptance and emittance were calculated from the measured reflectance values, before and after exposure in air at 650 C for approximately 1000 hours. Absorptance and emittance were interdependent functions of the weight of cobalt oxide. Also, these cobalt oxide/noble metal/oxide diffusion barrier coatings have absorptances greater than 0.90 and emittances of approximately 0.20 even after about 1000 hours at 650 C.

Nano-Nucleation Characteristic of Cu-Ag Alloy Directly Electrodeposited on W Diffusion Barrier for Microelectronic Device Interconnect.

PubMed

Kim, Kang O; Kim, Sunjung

2016-05-01

Cu-Ag alloy interconnect is promising for ultra-large-scale integration (ULSI) microelectronic system of which device dimension keeps shrinking. In this study, seedless electrodeposition of Cu-Ag alloy directly on W diffusion barrier as interconnect technology is presented in respect of nano-nucleation control. Chemical equilibrium state of electrolyte was fundamentally investigated according to the pH of electrolyte because direct nano-nucleation of Cu-Ag alloy on W surface is challenging. Chelation behavior of Cu2+ and Ag+ ions with citrate (Cit) and ammonia ligands was dependent on the pH of electrolyte. The amount and kind of Cu- and Ag-based complexes determine the deposition rate, size, elemental composition, and surface morphology of Cu-Ag alloy nano-nuclei formed on W surface.

Fast Mg2+ diffusion in Mo3(PO4)3O for Mg batteries.

PubMed

Rong, Ziqin; Xiao, Penghao; Liu, Miao; Huang, Wenxuan; Hannah, Daniel C; Scullin, William; Persson, Kristin A; Ceder, Gerbrand

2017-07-13

In this work, we identify a new potential Mg battery cathode structure Mo 3 (PO 4 ) 3 O, which is predicted to exhibit ultra-fast Mg 2+ diffusion and relatively high voltage based on first-principles density functional theory calculations. Nudged elastic band calculations reveal that the migration barrier of the percolation channel is only ∼80 meV, which is remarkably low, and comparable to the best Li-ion conductors. This low barrier is verified by ab initio molecular dynamics and kinetic Monte Carlo simulations. The voltage and specific energy are predicted to be ∼1.98 V and ∼173 W h kg -1 , respectively. If confirmed by experiments, this material would have the highest known Mg mobility among inorganic compounds.

Microstructural analysis of as-processed U-10 wt.%Mo monolithic fuel plate in AA6061 matrix with Zr diffusion barrier

NASA Astrophysics Data System (ADS)

Perez, E.; Yao, B.; Keiser, D. D., Jr.; Sohn, Y. H.

2010-07-01

For higher U-loading in low-enriched U-10 wt.%Mo fuels, monolithic fuel plate clad in AA6061 is being developed as a part of Reduced Enrichment for Research and Test Reactor (RERTR) program. This paper reports the first characterization results from a monolithic U-10 wt.%Mo fuel plate with a Zr diffusion barrier that was fabricated as part of a plate fabrication campaign for irradiation testing in the Advanced Test Reactor (ATR). Both scanning and transmission electron microscopy (SEM and TEM) were employed for analysis. At the interface between the Zr barrier and U-10 wt.%Mo, going from Zr to U(Mo), UZr 2, γ-UZr, Zr solid-solution and Mo 2Zr phases were observed. The interface between AA6061 cladding and Zr barrier plate consisted of four layers, going from Al to Zr, (Al, Si) 2Zr, (Al, Si)Zr 3 (Al, Si) 3Zr, and AlSi 4Zr 5. Irradiation behavior of these intermetallic phases is discussed based on their constituents. Characterization of as-fabricated phase constituents and microstructure would help understand the irradiation behavior of these fuel plates, interpret post-irradiation examination, and optimize the processing parameters of monolithic fuel system.

Activated dynamics in dense fluids of attractive nonspherical particles. II. Elasticity, barriers, relaxation, fragility, and self-diffusion

NASA Astrophysics Data System (ADS)

Tripathy, Mukta; Schweizer, Kenneth S.

2011-04-01

In paper II of this series we apply the center-of-mass version of Nonlinear Langevin Equation theory to study how short-range attractive interactions influence the elastic shear modulus, transient localization length, activated dynamics, and kinetic arrest of a variety of nonspherical particle dense fluids (and the spherical analog) as a function of volume fraction and attraction strength. The activation barrier (roughly the natural logarithm of the dimensionless relaxation time) is predicted to be a rich function of particle shape, volume fraction, and attraction strength, and the dynamic fragility varies significantly with particle shape. At fixed volume fraction, the barrier grows in a parabolic manner with inverse temperature nondimensionalized by an onset value, analogous to what has been established for thermal glass-forming liquids. Kinetic arrest boundaries lie at significantly higher volume fractions and attraction strengths relative to their dynamic crossover analogs, but their particle shape dependence remains the same. A limited universality of barrier heights is found based on the concept of an effective mean-square confining force. The mean hopping time and self-diffusion constant in the attractive glass region of the nonequilibrium phase diagram is predicted to vary nonmonotonically with attraction strength or inverse temperature, qualitatively consistent with recent computer simulations and colloid experiments.

Thin coatings in packaging: Fundamental and practical aspects

NASA Astrophysics Data System (ADS)

Thorne, N. A.

1996-01-01

A beverage or food can is very much a functionalized product, the overall performance characteristics being achieved by the use of several materials each of which provides a specific property. Schematically, the metal substrate provides the mechanical and barrier properties, whereby the chemical resistance is provided by specific surface treatments to the metal surface and the application of a thin organic coating. Between about 4-15 μm in thickness, this organic coating has a double protective role, as it must protect the substrate from the foodstuff (corrosion) and the foodstuff from the substrate (taste..) over the required shelflife of the product. To give an idea of the industrial importance of this application, over 100 billion beverage cans per year are produced worldwide, each being individually sprayed with a protective organic layer. To perform correctly these coatings need to possess the following characteristics: —ability to be applied in thin, homogeneous layers without macroscopic or microscopic defects, —sufficient adhesion with the substrate and possess considerable interface stability —mechanical properties sufficient to withstand the can forming operations —intrinsic diffusion barrier properties necessary to prevent significant interaction with the substrate —sufficient chemical resistance to withstand any significant modification of the coating structure and hence intrinsic properties induced by the foodstuff Whereas a considerable amount of scientific attention has been applied to ``bulk'' systems, such as the mechanical properties of epoxies used for composite materials, diffusion in polymer packaging..., little published work is available concerning the specific properties of these thin coatings. The task is not helped by the commercial nature of the resin formulations used, the need to adapt these formulations to the multitude of industrial operations and the physical size of the coatings. The above coating properties will be discussed in relation to the ability to understand the underlying mechanisms involved, to measure the required properties and in the long term predict coating performance.

Role of constant value of surface diffuseness in alpha decay half-lives of superheavy nuclei

NASA Astrophysics Data System (ADS)

Dehghani, V.; Alavi, S. A.; Benam, Kh.

2018-05-01

By using WKB method and considering deformed Woods-Saxon nuclear potential, deformed Coulomb potential, and centrifugal potential, the alpha decay half-lives of 68 superheavy alpha emitters have been calculated. The effect of the constant value of surface diffuseness parameter in the range of 0.1 ≤ a ≤ 0.9 (fm) on the potential barrier, tunneling probability, assault frequency, and alpha decay half-lives has been investigated. Significant differences were observed for alpha decay half-lives and decay quantities in this range of surface diffuseness. Good agreement between calculated half-lives with fitted surface diffuseness parameter a = 0.54 (fm) and experiment was observed.

ICP-MS measurement of iodine diffusion in IG-110 graphite for HTGR/VHTR

NASA Astrophysics Data System (ADS)

Carter, L. M.; Brockman, J. D.; Robertson, J. D.; Loyalka, S. K.

2016-05-01

Graphite functions as a structural material and as a barrier to fission product release in HTGR/VHTR designs, and elucidation of transport parameters for fission products in reactor-grade graphite is thus required for reactor source terms calculations. We measured iodine diffusion in spheres of IG-110 graphite using a release method based on Fickain diffusion kinetics. Two sources of iodine were loaded into the graphite spheres; molecular iodine (I2) and cesium iodide (CsI). Measurements of the diffusion coefficient were made over a temperature range of 873-1293 K. We have obtained the following Arrhenius expressions for iodine diffusion:DI , CsI infused =(6 ×10-12 2/s) exp(30,000 J/mol RT) And,DI , I2 infused =(4 ×10-10 m2/s) exp(-11,000 J/mol RT ) The results indicate that iodine diffusion in IG-110 graphite is not well-described by Fickan diffusion kinetics. To our knowledge, these are the first measurements of iodine diffusion in IG-110 graphite.

Enhancing Cation Diffusion and Suppressing Anion Diffusion via Lewis-Acidic Polymer Electrolytes.

PubMed

Savoie, Brett M; Webb, Michael A; Miller, Thomas F

2017-02-02

Solid polymer electrolytes (SPEs) have the potential to increase both the energy density and stability of lithium-based batteries, but low Li + conductivity remains a barrier to technological viability. SPEs are designed to maximize Li + diffusivity relative to the anion while maintaining sufficient salt solubility. It is thus remarkable that poly(ethylene oxide) (PEO), the most widely used SPE, exhibits Li + diffusivity that is an order of magnitude smaller than that of typical counterions at moderate salt concentrations. We show that Lewis-basic polymers like PEO favor slow cation and rapid anion diffusion, while this relationship can be reversed in Lewis-acidic polymers. Using molecular dynamics, polyboranes are identified that achieve up to 10-fold increases in Li + diffusivities and significant decreases in anion diffusivities, relative to PEO in the dilute-ion regime. These results illustrate a general principle for increasing Li + diffusivity and transference number with chemistries that exhibit weaker cation and stronger anion coordination.

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

Capurro, O. A.; Niello, J. O. Fernandez; Pacheco, A. J.

We have investigated experimental quasielastic cross sections measured at backward angles and at deep sub-barrier energies for the {sup 35}Cl+{sup 105,106,110}Pd and {sup 32}S+{sup 110}Pd systems. Since coupling effects are almost negligible at very low bombarding energies, the quasielastic data allow one to determine the diffuseness parameter of the ion-ion potential. For the analyzed reactions we have obtained a surface diffuseness parameter value around 0.58{+-}0.04 fm.

Impact of diffusion barriers to small cytotoxic molecules on the efficacy of immunotherapy in breast cancer.

PubMed

Das, Hiranmoy; Wang, Zhihui; Niazi, M Khalid Khan; Aggarwal, Reeva; Lu, Jingwei; Kanji, Suman; Das, Manjusri; Joseph, Matthew; Gurcan, Metin; Cristini, Vittorio

2013-01-01

Molecular-focused cancer therapies, e.g., molecularly targeted therapy and immunotherapy, so far demonstrate only limited efficacy in cancer patients. We hypothesize that underestimating the role of biophysical factors that impact the delivery of drugs or cytotoxic cells to the target sites (for associated preferential cytotoxicity or cell signaling modulation) may be responsible for the poor clinical outcome. Therefore, instead of focusing exclusively on the investigation of molecular mechanisms in cancer cells, convection-diffusion of cytotoxic molecules and migration of cancer-killing cells within tumor tissue should be taken into account to improve therapeutic effectiveness. To test this hypothesis, we have developed a mathematical model of the interstitial diffusion and uptake of small cytotoxic molecules secreted by T-cells, which is capable of predicting breast cancer growth inhibition as measured both in vitro and in vivo. Our analysis shows that diffusion barriers of cytotoxic molecules conspire with γδ T-cell scarcity in tissue to limit the inhibitory effects of γδ T-cells on cancer cells. This may increase the necessary ratios of γδ T-cells to cancer cells within tissue to unrealistic values for having an intended therapeutic effect, and decrease the effectiveness of the immunotherapeutic treatment.

Diffusion in quasi-one-dimensional channels: A small system n, p, T, transition state theory for hopping times.

PubMed

Ahmadi, Sheida; Bowles, Richard K

2017-04-21

Particles confined to a single file, in a narrow quasi-one-dimensional channel, exhibit a dynamic crossover from single file diffusion to Fickian diffusion as the channel radius increases and the particles begin to pass each other. The long time diffusion coefficient for a system in the crossover regime can be described in terms of a hopping time, which measures the time it takes for a particle to escape the cage formed by its neighbours. In this paper, we develop a transition state theory approach to the calculation of the hopping time, using the small system isobaric-isothermal ensemble to rigorously account for the volume fluctuations associated with the size of the cage. We also describe a Monte Carlo simulation scheme that can be used to calculate the free energy barrier for particle hopping. The theory and simulation method correctly predict the hopping times for a two-dimensional confined ideal gas system and a system of confined hard discs over a range of channel radii, but the method breaks down for wide channels in the hard discs' case, underestimating the height of the hopping barrier due to the neglect of interactions between the small system and its surroundings.

Thermochemical Compatibility and Oxidation Resistance of Advanced LWR Fuel Cladding

DOE PAGES

Besmann, T. M.; Yamamoto, Y.; Unocic, K. A.

2016-06-21

We assessed the thermochemical compatibility of potential replacement cladding materials for zirconium alloys in light water reactors. Considered were FeCrAl steel (similar to Kanthal APMT), Nb-1%Zr (similar to PWC-11), and a hybrid SiC-composite with a metallic barrier layer. The niobium alloy was also seen as requiring an oxidation protective layer, and a diffusion silicide was investigated. Metallic barrier layers for the SiC-composite reviewed included a FeCrAl alloy, Nb-1%Zr, and chromium. Thermochemical calculations were performed to determine oxidation behavior of the materials in steam, and for hybrid SiC-composites possible interactions between the metallic layer and SiC. Additionally, experimental exposures of SiC-alloymore » reaction couples at 673K, 1073K, and 1273K for 168 h in an inert atmosphere were made and microanalysis performed. Whereas all materials were determined to oxidize under higher oxygen partial pressures in the steam environment, these varied by material with expected protective oxides forming. Finally, the computed and experimental results indicate the formation of liquid phase eutectic in the FeCrAl-SiC system at the higher temperatures.« less

Electron-stimulated desorption from polished and vacuum fired 316LN stainless steel coated with Ti-Zr-Hf-V

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

Malyshev, Oleg B., E-mail: oleg.malyshev@stfc.ac.uk; Valizadeh, Reza; Hogan, Benjamin T.

2014-11-01

In this study, two identical 316LN stainless steel tubular samples, which had previously been polished and vacuum-fired and then used for the electron-stimulated desorption (ESD) experiments, were coated with Ti-Zr-Hf-V with different morphologies: columnar and dense. ESD measurement results after nonevaporable getter (NEG) activation to 150, 180, 250, and 350 °C indicated that the values for the ESD yields are significantly (2–20 times) lower than the data from our previous study with similar coatings on nonvacuum-fired samples. Based on these results, the lowest pressure and best long-term performance in particle accelerators will be achieved with a vacuum-fired vacuum chamber coated withmore » dense Ti-Zr-Hf-V coating activated at 180 °C. This is likely due to the following facts: after NEG activation, the hydrogen concentration inside the NEG was lower than in the bulk stainless steel substrate; the NEG coating created a barrier for gas diffusion from the sample bulk to vacuum; the dense NEG coating performed better as a barrier than the columnar NEG coating.« less

Proton radiation effect on performance of InAs/GaSb complementary barrier infrared detector

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

Soibel, Alexander; Rafol, Sir B.; Khoshakhlagh, Arezou

In this work, we investigated the effect of proton irradiation on the performance of long wavelength infrared InAs/GaSb photodiodes (λ{sub c} = 10.2 μm), based on the complementary barrier infrared detector design. We found that irradiation with 68 MeV protons causes a significant increase of the dark current from j{sub d} = 5 × 10{sup −5} A/cm{sup 2} to j{sub d} = 6 × 10{sup −3} A/cm{sup 2}, at V{sub b} = 0.1 V, T = 80 K and fluence 19.2 × 10{sup 11 }H{sup +}/cm{sup 2}. Analysis of the dark current as a function of temperature and bias showed that the dominant contributor to the dark current in these devices changes from diffusion current to tunneling current after proton irradiation.more » This change in the dark current mechanism can be attributed to the onset of surface leakage current, generated by trap-assisted tunneling processes in proton displacement damage areas located near the device sidewalls.« less

Adsorption, vibration and diffusion of oxygen on Ag(110)

NASA Astrophysics Data System (ADS)

Rawal, Takat; Hong, Sampyo; Pulkkinen, Aki; Alatalo, Matti; Rahman, Talat

2015-03-01

We have performed density functional theory calculations for the adsorption, vibration and diffusion of oxygen on Ag(110). At low coverage, O2 adsorbs at the four-fold hollow (FFH) with the molecular axis aligned along the [ 1 1 0 ] direction. The dissociation of O2 is easier along the [001] direction than along the [ 1 1 0 ] direction. For O2 species in FFH aligned along the [001] the O-O intra-molecular stretching mode is coupled with the substrate vibration and thus its dissociation can be induced by surface phonon. In addition, O diffusion barrier from FFH to next FFH along the [ 1 1 0 ] is small (0.07 eV only) but is by far larger (0.4 eV) along [001]. On the other hand, O species in the short-bride (SB) site prefers to diffuse along the [001] (to FFH) rather than along the [ 1 1 0 ] direction (to next SB). Finally, the preference of atomic oxygen to form O-Ag-O complex on Ag(110) is responsible for disordering of the surface by means of substantial lateral and vertical displacements of Ag atoms in the topmost layer. In fact, such disordering phase of Ag(110) may act as a precursor of the reconstructed phase of Ag(110). Work supported in part by NSF under Grant CHE-1310327.

Nanopipette Delivery of Individual Molecules to Cellular Compartments for Single-Molecule Fluorescence Tracking

PubMed Central

Bruckbauer, Andreas; James, Peter; Zhou, Dejian; Yoon, Ji Won; Excell, David; Korchev, Yuri; Jones, Roy; Klenerman, David

2007-01-01

We have developed a new method, using a nanopipette, for controlled voltage-driven delivery of individual fluorescently labeled probe molecules to the plasma membrane which we used for single-molecule fluorescence tracking (SMT). The advantages of the method are 1), application of the probe to predefined regions on the membrane; 2), release of only one or a few molecules onto the cell surface; 3), when combined with total internal reflection fluorescence microscopy, very low background due to unbound molecules; and 4), the ability to first optimize the experiment and then repeat it on the same cell. We validated the method by performing an SMT study of the diffusion of individual membrane glycoproteins labeled with Atto 647-wheat germ agglutin in different surface domains of boar spermatozoa. We found little deviation from Brownian diffusion with a mean diffusion coefficient of 0.79 ± 0.04 μm2/s in the acrosomal region and 0.10 ± 0.02 μm2/s in the postacrosomal region; this difference probably reflects different membrane structures. We also showed that we can analyze diffusional properties of different subregions of the cell membrane and probe for the presence of diffusion barriers. It should be straightforward to extend this new method to other probes and cells, and it can be used as a new tool to investigate the cell membrane. PMID:17631532

Unstable vicinal crystal growth from cellular automata

NASA Astrophysics Data System (ADS)

Krasteva, A.; Popova, H.; KrzyŻewski, F.; Załuska-Kotur, M.; Tonchev, V.

2016-03-01

In order to study the unstable step motion on vicinal crystal surfaces we devise vicinal Cellular Automata. Each cell from the colony has value equal to its height in the vicinal, initially the steps are regularly distributed. Another array keeps the adatoms, initially distributed randomly over the surface. The growth rule defines that each adatom at right nearest neighbor position to a (multi-) step attaches to it. The update of whole colony is performed at once and then time increases. This execution of the growth rule is followed by compensation of the consumed particles and by diffusional update(s) of the adatom population. Two principal sources of instability are employed - biased diffusion and infinite inverse Ehrlich-Schwoebel barrier (iiSE). Since these factors are not opposed by step-step repulsion the formation of multi-steps is observed but in general the step bunches preserve a finite width. We monitor the developing surface patterns and quantify the observations by scaling laws with focus on the eventual transition from diffusion-limited to kinetics-limited phenomenon. The time-scaling exponent of the bunch size N is 1/2 for the case of biased diffusion and 1/3 for the case of iiSE. Additional distinction is possible based on the time-scaling exponents of the sizes of multi-step Nmulti, these are 0.36÷0.4 (for biased diffusion) and 1/4 (iiSE).

Integrin-based diffusion barrier separates membrane domains enabling the formation of microbiostatic frustrated phagosomes

PubMed Central

Maxson, Michelle E; Naj, Xenia; O'Meara, Teresa R; Plumb, Jonathan D; Cowen, Leah E

2018-01-01

Candida albicans hyphae can reach enormous lengths, precluding their internalization by phagocytes. Nevertheless, macrophages engulf a portion of the hypha, generating incompletely sealed tubular phagosomes. These frustrated phagosomes are stabilized by a thick cuff of F-actin that polymerizes in response to non-canonical activation of integrins by fungal glycan. Despite their continuity, the surface and invaginating phagosomal membranes retain a strikingly distinct lipid composition. PtdIns(4,5)P2 is present at the plasmalemma but is not detectable in the phagosomal membrane, while PtdIns(3)P and PtdIns(3,4,5)P3 co-exist in the phagosomes yet are absent from the surface membrane. Moreover, endo-lysosomal proteins are present only in the phagosomal membrane. Fluorescence recovery after photobleaching revealed the presence of a diffusion barrier that maintains the identity of the open tubular phagosome separate from the plasmalemma. Formation of this barrier depends on Syk, Pyk2/Fak and formin-dependent actin assembly. Antimicrobial mechanisms can thereby be deployed, limiting the growth of the hyphae. PMID:29553370

Corrosion Properties of Dissimilar Friction Stir Welded 6061 Aluminum and HT590 Steel

NASA Astrophysics Data System (ADS)

Seo, Bosung; Song, Kuk Hyun; Park, Kwangsuk

2018-05-01

Corrosion properties of dissimilar friction stir welded 6061 aluminum and HT590 steel were investigated to understand effects of galvanic corrosion. As cathode when coupled, HT590 was cathodically protected. However, the passivation of AA6061 made the aluminum alloy cathode temporarily, which leaded to corrosion of HT590. From the EIS analysis showing Warburg diffusion plot in Nyquist plots, it can be inferred that the stable passivation layer was formed on AA6061. However, the weld as well as HT590 did not show Warburg diffusion plot in Nyquist plots, suggesting that there was no barrier for corrosion or even if it exists, the barrier had no function for preventing and/or retarding charge transport through the passivation layer. The open circuit potential measurements showed that the potential of the weld was similar to that of HT590, which lied in the pitting region for AA6061, making the aluminum alloy part of the weld keep corrosion state. That resulted in the cracked oxide film on AA6061 of the weld, which could not play a role of corrosion barrier.

Influence of ion transport on discharge propagation of nanosecond dielectric barrier discharge plasma actuator

NASA Astrophysics Data System (ADS)

Hua, Weizhuo; Koji, Fukagata

2017-11-01

A numerical study has been conducted to understand the streamer formation and propagation of nanosecond pulsed surface dielectric barrier discharge of positive polarity. First we compared the result of different grid configuration to investigate the influence of x and y direction grid spacing on the streamer propagation. The streamer propagation is sensitive to y grid spacing especially at the dielectric surface. The streamer propagation velocity can reach 0.2 cm/ns when the voltage magnitude is 12 kV. A narrow gap was found between the streamer and dielectric barrier, where the plasma density is several orders of magnitude smaller than the streamer region. Analyses on the ion transport in the gap and streamer regions show the different ion transport mechanisms in the two different region. In the gap region, the diffusion of electron toward the dielectric layer decreases the seed electron in the beginning of voltage pulse, resulting that ionization avalanche does not occur. The streamer region is not significantly affected by the diffusion flux toward the dielectric layer, so that ionization avalanche takes place and leads to dramatic increase of plasma density.

Tight junctions and the modulation of barrier function in disease

PubMed Central

2008-01-01

Tight junctions create a paracellular barrier in epithelial and endothelial cells protecting them from the external environment. Two different classes of integral membrane proteins constitute the tight junction strands in epithelial cells and endothelial cells, occludin and members of the claudin protein family. In addition, cytoplasmic scaffolding molecules associated with these junctions regulate diverse physiological processes like proliferation, cell polarity and regulated diffusion. In many diseases, disruption of this regulated barrier occurs. This review will briefly describe the molecular composition of the tight junctions and then present evidence of the link between tight junction dysfunction and disease. PMID:18415116

Influence of interface inhomogeneities in thin-film Schottky diodes

NASA Astrophysics Data System (ADS)

Wilson, Joshua; Zhang, Jiawei; Li, Yunpeng; Wang, Yiming; Xin, Qian; Song, Aimin

2017-11-01

The scalability of thin-film transistors has been well documented, but there have been very few investigations into the effects of device scalability in Schottky diodes. Indium-gallium-zinc-oxide (IGZO) Schottky diodes were fabricated with IGZO thicknesses of 50, 150, and 250 nm. Despite the same IGZO-Pt interface and Schottky barrier being formed in all devices, reducing the IGZO thickness caused a dramatic deterioration of the current-voltage characteristics, most notably increasing the reverse current by nearly five orders of magnitude. Furthermore, the forward characteristics display an increase in the ideality factor and a reduction in the barrier height. The origins of this phenomenon have been elucidated using device simulations. First, when the semiconductor layer is fully depleted, the electric field increases with the reducing thickness, leading to an increased diffusion current. However, the effects of diffusion only offer a small contribution to the huge variations in reverse current seen in the experiments. To fully explain this effect, the role of inhomogeneities in the Schottky barrier height has been considered. Contributions from lower barrier regions (LBRs) are found to dominate the reverse current. The conduction band minimum below these LBRs is strongly dependent upon thickness and bias, leading to reverse current variations as large as several orders of magnitude. Finally, it is demonstrated that the thickness dependence of the reverse current is exacerbated as the magnitude of the inhomogeneities is increased and alleviated in the limit where the LBRs are large enough not to be influenced by the adjacent higher barrier regions.

Defining the Interaction of HIV-1 with the Mucosal Barriers of the Female Reproductive Tract

PubMed Central

Carias, Ann M.; McCoombe, Scott; McRaven, Michael; Anderson, Meegan; Galloway, Nicole; Vandergrift, Nathan; Fought, Angela J.; Lurain, John; Duplantis, Maurice; Veazey, Ronald S.

2013-01-01

Worldwide, HIV-1 infects millions of people annually, the majority of whom are women. To establish infection in the female reproductive tract (FRT), HIV-1 in male ejaculate must overcome numerous innate and adaptive immune factors, traverse the genital epithelium, and establish infection in underlying CD4+ target cells. How the virus achieves this remains poorly defined. By utilizing a new technique, we define how HIV-1 interacts with different tissues of the FRT using human cervical explants and in vivo exposure in the rhesus macaque vaginal transmission model. Despite previous claims of the squamous epithelium being an efficient barrier to virus entry, we reveal that HIV-1 can penetrate both intact columnar and squamous epithelial barriers to depths where the virus can encounter potential target cells. In the squamous epithelium, we identify virus entry occurring through diffusive percolation, penetrating areas where cell junctions are absent. In the columnar epithelium, we illustrate that virus does not transverse barriers as well as previously thought due to mucus impediment. We also show a statistically significant correlation between the viral load of inocula and the ability of HIV-1 to pervade the squamous barrier. Overall, our results suggest a diffusive percolation mechanism for the initial events of HIV-1 entry. With these data, we also mathematically extrapolate the number of HIV-1 particles that penetrate the mucosa per coital act, providing a biological description of the mechanism for HIV-1 transmission during the acute and chronic stages of infection. PMID:23966398

Tribological properties of ceramic-(Ti3Al-Nb) sliding couples for use as candidate seal materials to 700 C

NASA Technical Reports Server (NTRS)

Dellacorte, Christhopher; Steinetz, Bruce M.; Brindley, Pamela K.

1990-01-01

Tribological properties of Ti3Al-Nb intermetallic disks sliding against alumina-boria-silicate fabric were ascertained in air at temperatures from 25 to 700 C. These materials are candidates for sliding seal applications for the National AeroSpace Plane. The tests were done using a pin on disk tribometer. Sliding was unidirectional at 0.27 m/sec under a nominal contact stress of 340 kPa. Gold sputter or ion plating deposited films were used to reduce friction and wear. Rhodium and palladium films were used beneath the gold lubricating films to prevent diffusion of the substrate into the gold at high temperature. The friction and wear of the unlubricated specimens was unacceptable. Friction coefficients were generally greater than 1.0. The ion plated gold films, when used with a rhodium diffusion barrier reduced friction by almost a factor of 2. Wear was also substantially reduced. The sputter deposited films were not adherent unless the substrate was sputter cleaned immediately prior to film deposition. Palladium did not function as a diffusion barrier.

Tribological properties of ceramic/Ti3Al-Nb sliding couples for use as candidate seal materials to 700 deg C

NASA Technical Reports Server (NTRS)

Dellacorte, Christopher; Steinetz, Bruce M.; Brindley, Pamela K.

1989-01-01

Tribological properties of Ti3Al-Nb intermetallic disks sliding against alumina-boria-silicate fabric were ascertained in air at temperatures from 25 to 700 C. These materials are candidates for sliding seal applications for the National AeroSpace Plane. The tests were done using a pin on disk tribometer. Sliding was unidirectional at 0.27 m/sec under a nominal contact stress of 340 kPa. Gold sputter or ion plating deposited films were used to reduce friction and wear. Rhodium and palladium films were used beneath the gold lubricating films to prevent diffusion of the substrate into the gold at high temperature. The friction and wear of the unlubricated specimens was unacceptable. Friction coefficients were generally greater than 1.0. The ion plated gold films, when used with a rhodium diffusion barrier reduced friction by almost a factor of 2. Wear was also substantially reduced. The sputter deposited films were not adherent unless the substrate was sputter cleaned immediately prior to film deposition. Palladium did not function as a diffusion barrier.

Markov Chain Monte Carlo in the Analysis of Single-Molecule Experimental Data

NASA Astrophysics Data System (ADS)

Kou, S. C.; Xie, X. Sunney; Liu, Jun S.

2003-11-01

This article provides a Bayesian analysis of the single-molecule fluorescence lifetime experiment designed to probe the conformational dynamics of a single DNA hairpin molecule. The DNA hairpin's conformational change is initially modeled as a two-state Markov chain, which is not observable and has to be indirectly inferred. The Brownian diffusion of the single molecule, in addition to the hidden Markov structure, further complicates the matter. We show that the analytical form of the likelihood function can be obtained in the simplest case and a Metropolis-Hastings algorithm can be designed to sample from the posterior distribution of the parameters of interest and to compute desired estiamtes. To cope with the molecular diffusion process and the potentially oscillating energy barrier between the two states of the DNA hairpin, we introduce a data augmentation technique to handle both the Brownian diffusion and the hidden Ornstein-Uhlenbeck process associated with the fluctuating energy barrier, and design a more sophisticated Metropolis-type algorithm. Our method not only increases the estimating resolution by several folds but also proves to be successful for model discrimination.

Structure and Barrier Properties of Multinanolayered Biodegradable PLA/PBSA Films: Confinement Effect via Forced Assembly Coextrusion.

PubMed

Messin, Tiphaine; Follain, Nadège; Guinault, Alain; Sollogoub, Cyrille; Gaucher, Valérie; Delpouve, Nicolas; Marais, Stéphane

2017-08-30

Multilayer coextrusion processing was applied to produce 2049-layer film of poly(butylene succinate-co-butylene adipate) (PBSA) confined against poly(lactic acid) (PLA) using forced assembly, where the PBSA layer thickness was about 60 nm. This unique technology allowed to process semicrystalline PBSA as confined polymer and amorphous PLA as confining polymer in a continuous manner. The continuity of PBSA layers within the 80/20 wt % PLA/PBSA layered films was clearly evidenced by atomic force microscopy (AFM). Similar thermal events to the reference films were revealed by thermal studies; indicating no diffusion of polymers during the melt-processing. Mechanical properties were measured for the multilayer film and the obtained results were those expected considering the fraction of each polymer, revealing the absence of delamination in the PLA/PBSA multinanolayer film. The confinement effect induced by PLA led to a slight orientation of the crystals, an increase of the rigid amorphous fraction (RAF) in PBSA with a densification of this fraction without changing film crystallinity. These structural changes allowed to strongly improve the water vapor and gas barrier properties of the PBSA layer into the multilayer film up to two decades in the case of CO 2 gas. By confining the PBSA structure in very thin and continuous layers, it was then possible to improve the barrier performances of a biodegradable system and the resulting barrier properties were successfully correlated to the effect of confinement on the microstructure and the chain segment mobility of the amorphous phase. Such investigation on these multinanolayers of PLA/PBSA with the aim of evidencing relationships between microstructure implying RAF and barrier performances has never been performed yet. Besides, gas and water permeation results have shown that the barrier improvement obtained from the multilayer was mainly due to the reduction of solubility linked to the reduction of the free volume while the tortuosity effect, as usually expected, was not really observed. This work brings new insights in the field of physicochemical behaviors of new multilayer films made of biodegradable polyesters but also in interfacial processes due to the confinement effect induced in these multinanolayer structures obtained by the forced assembly coextrusion. This original coextrusion process was a very advantageous technique to produce eco-friendly materials with functional properties without the help of tie layer, additives, solvents, surface treatments, or inorganic fillers.

Effect of hole transport on performance of infrared type-II superlattice light emitting diodes

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

Lin, Youxi; Suchalkin, Sergey; Kipshidze, Gela

2015-04-28

The effect of hole transport on the performance of infrared light emitting diodes (LED) was investigated. The active area of the LEDs comprised two type-II superlattices with different periods and widths connected in series. Electroluminescence spectra of the devices with different positions of long wave and mid wave superlattice sections were mostly contributed by the superlattice closest to the p-contact. The experimental results indicate that due to suppressed vertical hole transport, the recombination of electrically injected electrons and holes in a type II superlattice LED active region takes place within a few superlattice periods near p-barrier. Possible reason for themore » effect is reduction of hole diffusion coefficient in an active area of a superlattice LED under bias.« less

Hot chemistry in the diffuse medium: spectral signature in the H2 rotational lines

NASA Astrophysics Data System (ADS)

Verstraete, L.; Falgarone, E.; Pineau des Forets, G.; Flower, D.; Puget, J. L.

1999-03-01

Most of the diffuse interstellar medium is cold, but it must harbor pockets of hot gas to explain the large observed abundances of molecules like CH+ and HCO+. Because they dissipate locally large amounts of kinetic energy, MHD shocks and coherent vortices in turbulence can drive endothermic chemical reactions or reactions with large activation barriers. We predict the spectroscopic signatures in the H2 rotational lines of MHD shocks and vortices and compare them to those observed with the ISO-SWS along a line of sight through the Galaxy which samples 20 magnitudes of mostly diffuse gas.

Removing the barrier to the calculation of activation energies: Diffusion coefficients and reorientation times in liquid water.

PubMed

Piskulich, Zeke A; Mesele, Oluwaseun O; Thompson, Ward H

2017-10-07

General approaches for directly calculating the temperature dependence of dynamical quantities from simulations at a single temperature are presented. The method is demonstrated for self-diffusion and OH reorientation in liquid water. For quantities which possess an activation energy, e.g., the diffusion coefficient and the reorientation time, the results from the direct calculation are in excellent agreement with those obtained from an Arrhenius plot. However, additional information is obtained, including the decomposition of the contributions to the activation energy. These results are discussed along with prospects for additional applications of the direct approach.

First-principles-based kinetic Monte Carlo studies of diffusion of hydrogen in Ni–Al and Ni–Fe binary alloys

DOE PAGES

Tafen, De Nyago

2015-02-14

The diffusion of dilute hydrogen in fcc Ni–Al and Ni–Fe binary alloys was examined using kinetic Monte Carlo method with input kinetic parameters obtained from first-principles density functional theory. The simulation involves the implementation of computationally efficient energy barrier model that describes the configuration dependence of the hydrogen hopping. The predicted hydrogen diffusion coefficients in Ni and Ni 89.4Fe 10.6 are compared well with the available experimental data. In Ni–Al, the model predicts lower hydrogen diffusivity compared to that in Ni. Overall, diffusion prefactors and the effective activation energies of H in Ni–Fe and Ni–Al are concentration dependent of themore » alloying element. Furthermore, the changes in their values are the results of the short-range order (nearest-neighbor) effect on the interstitial diffusion of hydrogen in fcc Ni-based alloys.« less

Surface diffusion on SrTiO3 (100): A temperature accelerated dynamics and first principles study

NASA Astrophysics Data System (ADS)

Hong, Minki; Wohlwend, Jennifer L.; Behera, Rakesh K.; Phillpot, Simon R.; Sinnott, Susan B.; Uberuaga, Blas P.

2013-11-01

Temperature accelerated dynamics (TAD) with an empirical potential is used to predict diffusion mechanisms and energy barriers associated with surface diffusion of adatoms and surface vacancies on (100) SrTiO3 (STO). Specifically, Sr, O, and Ti adatoms and vacancies are investigated on each termination - SrO and TiO2 - of the SrTiO3 surface. We find that the empirical potential predicts different surface mobility of adatoms depending on the surface termination: they are mobile with relatively low diffusion barriers on the SrO-terminated surface, whereas they are largely immobile on the TiO2-terminated surface. One important finding is that, of the two binding sites on the SrO-terminated surface, one is typically very close in energy to the saddle point. Thus, one of the two sites is a good estimator of the migration energy of the adatom, a conclusion supported by select density functional theory (DFT) calculations. Motivated by this result, we calculate the migration energies for a number of metal elements on the SrO-terminated surface: Ti, Ba, La, and Al. The DFT results also reveal that the details of the migration mechanism depend on the charge state of the diffusing species and that the ability of the empirical potential to properly estimate the migration mechanism depends on the magnitude and variability of the charge transfer between the adatom and the surface.

Genetic and Functional Drivers of Diffuse Large B Cell Lymphoma.

PubMed

Reddy, Anupama; Zhang, Jenny; Davis, Nicholas S; Moffitt, Andrea B; Love, Cassandra L; Waldrop, Alexander; Leppa, Sirpa; Pasanen, Annika; Meriranta, Leo; Karjalainen-Lindsberg, Marja-Liisa; Nørgaard, Peter; Pedersen, Mette; Gang, Anne O; Høgdall, Estrid; Heavican, Tayla B; Lone, Waseem; Iqbal, Javeed; Qin, Qiu; Li, Guojie; Kim, So Young; Healy, Jane; Richards, Kristy L; Fedoriw, Yuri; Bernal-Mizrachi, Leon; Koff, Jean L; Staton, Ashley D; Flowers, Christopher R; Paltiel, Ora; Goldschmidt, Neta; Calaminici, Maria; Clear, Andrew; Gribben, John; Nguyen, Evelyn; Czader, Magdalena B; Ondrejka, Sarah L; Collie, Angela; Hsi, Eric D; Tse, Eric; Au-Yeung, Rex K H; Kwong, Yok-Lam; Srivastava, Gopesh; Choi, William W L; Evens, Andrew M; Pilichowska, Monika; Sengar, Manju; Reddy, Nishitha; Li, Shaoying; Chadburn, Amy; Gordon, Leo I; Jaffe, Elaine S; Levy, Shawn; Rempel, Rachel; Tzeng, Tiffany; Happ, Lanie E; Dave, Tushar; Rajagopalan, Deepthi; Datta, Jyotishka; Dunson, David B; Dave, Sandeep S

2017-10-05

Diffuse large B cell lymphoma (DLBCL) is the most common form of blood cancer and is characterized by a striking degree of genetic and clinical heterogeneity. This heterogeneity poses a major barrier to understanding the genetic basis of the disease and its response to therapy. Here, we performed an integrative analysis of whole-exome sequencing and transcriptome sequencing in a cohort of 1,001 DLBCL patients to comprehensively define the landscape of 150 genetic drivers of the disease. We characterized the functional impact of these genes using an unbiased CRISPR screen of DLBCL cell lines to define oncogenes that promote cell growth. A prognostic model comprising these genetic alterations outperformed current established methods: cell of origin, the International Prognostic Index comprising clinical variables, and dual MYC and BCL2 expression. These results comprehensively define the genetic drivers and their functional roles in DLBCL to identify new therapeutic opportunities in the disease. Copyright © 2017 Elsevier Inc. All rights reserved.

Host and adsorbate dynamics in silicates with flexible frameworks: Empirical force field simulation of water in silicalite

NASA Astrophysics Data System (ADS)

Bordat, Patrice; Cazade, Pierre-André; Baraille, Isabelle; Brown, Ross

2010-03-01

Molecular dynamics simulations are performed on the pure silica zeolite silicalite (MFI framework code), maintaining via a new force field both framework flexibility and realistic account of electrostatic interactions with adsorbed water. The force field is similar to the well-known "BKS" model [B. W. H. van Beest et al., Phys. Rev. Lett. 64, 1955 (1990)], but with reduced partial atomic charges and reoptimized covalent bond potential wells. The present force field reproduces the monoclinic to orthorhombic transition of silicalite. The force field correctly represents the hydrophobicity of pure silica silicalite, both the adsorption energy, and the molecular diffusion constants of water. Two types of adsorption, specific and weak unspecific, are predicted on the channel walls and at the channel intersection. We discuss molecular diffusion of water in silicalite, deducing a barrier to crossing between the straight and the zigzag channels. Analysis of the thermal motion shows that at room temperature, framework oxygen atoms incurring into the zeolite channels significantly influence the dynamics of adsorbed water.

Collective phenomena in volume and surface barrier discharges

NASA Astrophysics Data System (ADS)

Kogelschatz, U.

2010-11-01

Barrier discharges are increasingly used as a cost-effective configuration to produce non-equilibrium plasmas at atmospheric pressure. This way, copious amounts of electrons, ions, free radicals and excited species can be generated without significant heating of the background gas. In most applications the barrier is made of dielectric material. Major applications utilizing mainly dielectric barriers include ozone generation, surface cleaning and modification, polymer and textile treatment, sterilization, pollution control, CO2 lasers, excimer lamps, plasma display panels (flat TV screens). More recent research efforts are devoted to biomedical applications and to plasma actuators for flow control. Sinusoidal feeding voltages at various frequencies as well as pulsed excitation schemes are used. Volume as well as surface barrier discharges can exist in the form of filamentary, regularly patterned or diffuse, laterally homogeneous discharges. The physical effects leading to collective phenomena in volume and surface barrier discharges are discussed in detail. Special attention is paid to self-organization of current filaments and pattern formation. Major similarities of the two types of barrier discharges are elaborated.

Regenerative switching CMOS system

DOEpatents

Welch, James D.

1998-01-01

Complementary Metal Oxide Semiconductor (CMOS) Schottky barrier Field Effect Transistor systems, which are a seriesed combination of N and P-Channel MOSFETS, in which Source Schottky barrier junctions of the N and P-Channel Schottky barrier MOSFETS are electically interconnected, (rather than the Drains as in conventional diffused junction CMOS), which Schottky barrier MOSFET system demonstrates Regenerative Inverting Switching Characteristics in use are disclosed. Both the N and P-Channel Schottky barrier MOSFET devices are unique in that they provide operational Drain Current vs. Drain to Source voltage as a function of Gate voltage only where the polarities of the Drain voltage and Gate voltage are opposite, referenced to the Source as a common terminal, and where the polarity of the voltage applied to the Gate is appropriate to cause Channel inversion. Experimentally derived results which demonstrate and verify the operation of N and P-Channel Schottky barrier MOSFETS actually fabricated on P and N-type Silicon respectively, by a common procedure using vacuum deposited Chromium as a Schottky barrier forming metal, are also provided.

Regenerative switching CMOS system

DOEpatents

Welch, J.D.

1998-06-02

Complementary Metal Oxide Semiconductor (CMOS) Schottky barrier Field Effect Transistor systems, which are a series combination of N and P-Channel MOSFETS, in which Source Schottky barrier junctions of the N and P-Channel Schottky barrier MOSFETS are electrically interconnected, (rather than the Drains as in conventional diffused junction CMOS), which Schottky barrier MOSFET system demonstrates Regenerative Inverting Switching Characteristics in use are disclosed. Both the N and P-Channel Schottky barrier MOSFET devices are unique in that they provide operational Drain Current vs. Drain to Source voltage as a function of Gate voltage only where the polarities of the Drain voltage and Gate voltage are opposite, referenced to the Source as a common terminal, and where the polarity of the voltage applied to the Gate is appropriate to cause Channel inversion. Experimentally derived results which demonstrate and verify the operation of N and P-Channel Schottky barrier MOSFETS actually fabricated on P and N-type Silicon respectively, by a common procedure using vacuum deposited Chromium as a Schottky barrier forming metal, are also provided. 14 figs.

Chromatographic behaviour predicts the ability of potential nootropics to permeate the blood-brain barrier.

PubMed

Farsa, Oldřich

2013-01-01

The log BB parameter is the logarithm of the ratio of a compound's equilibrium concentrations in the brain tissue versus the blood plasma. This parameter is a useful descriptor in assessing the ability of a compound to permeate the blood-brain barrier. The aim of this study was to develop a Hansch-type linear regression QSAR model that correlates the parameter log BB and the retention time of drugs and other organic compounds on a reversed-phase HPLC containing an embedded amide moiety. The retention time was expressed by the capacity factor log k'. The second aim was to estimate the brain's absorption of 2-(azacycloalkyl)acetamidophenoxyacetic acids, which are analogues of piracetam, nefiracetam, and meclofenoxate. Notably, these acids may be novel nootropics. Two simple regression models that relate log BB and log k' were developed from an assay performed using a reversed-phase HPLC that contained an embedded amide moiety. Both the quadratic and linear models yielded statistical parameters comparable to previously published models of log BB dependence on various structural characteristics. The models predict that four members of the substituted phenoxyacetic acid series have a strong chance of permeating the barrier and being absorbed in the brain. The results of this study show that a reversed-phase HPLC system containing an embedded amide moiety is a functional in vitro surrogate of the blood-brain barrier. These results suggest that racetam-type nootropic drugs containing a carboxylic moiety could be more poorly absorbed than analogues devoid of the carboxyl group, especially if the compounds penetrate the barrier by a simple diffusion mechanism.

Simple realization of efficient barrier performance of a single layer silicon nitride film via plasma chemistry.

PubMed

Lee, Jun Suk; Sahu, Bibhuti Bhusan; Han, Jeon Geon

2016-11-30

Due to the problem of degradation by moisture or oxygen, there is growing interest in efficient gas diffusion barriers for organic optoelectronic devices. Additionally, for the continuous and long-term operation of a device, dedicated flexible thin film encapsulation is required, which is the foremost challenge. Many efforts are being undertaken in the plasma assisted deposition process control for the optimization of film properties. Control of the plasma density along with the energy of the principal plasma species is critical to inducing alteration of the plasma reactivity, chemistry, and film properties. Here, we have used the radio frequency (RF) plasma enhanced chemical vapor deposition (PECVD) technique to deposit amorphous silicon nitride (SiN x ) barrier films onto a plastic substrate at different pressures. A large part of our efforts is devoted to a detailed study of the process parameters controlling the plasma treatment. Numerous plasma diagnostic techniques combined with various characterization tools are purposefully used to characterize and investigate the plasma environment and the associated film properties. This contribution also reports a study of the correlations between the plasma chemistry and the chemical, mechanical, barrier, and optical properties of the deposited films. The data reveal that the film possesses a very low stress for the condition where the net energy imparted on the substrate is at a minimum. Simultaneously, a relatively high ion flux and high energy of the ions impinging on the film growth surfaces are crucial for controlling the film stress and the resulting barrier properties.

Development of Spray on Bag for manufacturing of large composites parts: Diffusivity analysis

NASA Astrophysics Data System (ADS)

Dempah, Maxime Joseph

Bagging materials are utilized in many composites manufacturing processes. The selection is mainly driven by cost, temperature requirements, chemical compatibility and tear properties of the bag. The air barrier properties of the bag are assumed to be adequate or in many cases are not considered at all. However, the gas barrier property of a bag is the most critical parameter, as it can negatively affect the quality of the final laminate. The barrier property is a function of the bag material, uniformity, thickness and temperature. Improved barrier properties are needed for large parts, high pressure consolidated components and structures where air stays entrapped on the part surface. The air resistance property of the film is defined as permeability and is investigated in this thesis. A model was developed to evaluate the gas transport through the film and an experimental cell was implemented to characterize various commercial films. Understanding and characterizing the transport phenomena through the film allows optimization of the bagging material for various manufacturing processes. Spray-on-Bag is a scalable alternative bagging method compared to standard films. The approach allows in-situ fabrication of the bag on large and complex geometry structures where optimization of the bag properties can be varied on a local level. An experimental setup was developed and implemented using a six axis robot and an automated spraying system. Experiments were performed on a flat surface and specimens were characterized and compared to conventional films. Air barrier properties were within range of standard film approaches showing the potential to fabricate net shape bagging structures in an automated process.

Textural break foundation wall construction modules

DOEpatents

Phillips, Steven J.

1990-01-01

Below-grade, textural-break foundation wall structures are provided for inhibiting diffusion and advection of liquids and gases into and out from a surrounding hydrogeologic environment. The foundation wall structure includes a foundation wall having an interior and exterior surface and a porous medium disposed around a portion of the exterior surface. The structure further includes a modular barrier disposed around a portion of the porous medium. The modular barrier is substantially removable from the hydrogeologic environment.

First-principles estimates of free energy barriers for Mg desolvation and intercalation at electrolyte/electrode interfaces

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2014-03-01

There is a growing interest in developing multivalent ion batteries that could, in principle, double or triple the energy density compared to the monovalent Li-ion batteries. However, the strong electrostatic interaction caused by the extra charge also makes it very challenging to find appropriate intercalation compounds that allow for relatively fast and reversible ion transport. An established working multivalent battery is comprised of Mg(AlCl2BuEt)2 salts in THF solution as the electrolyte, and Mg metal and Mo6S8 Chevrel phase as the anode and cathode, respectively. Currently, we lack a clear understanding of the mechanism for Mg desolvation and intercalation at the interface between the electrolyte and Chevrel phase surfaces, which is critical in designing new advanced battery systems with improved ion diffusion rate. Here, we present a theoretical investigation of the dynamics and kinetics of the Mg desolvation/intercalation process. The surface properties of Mo6S8 are studied for the first time using density functional theory (DFT) and its interaction with the electrolyte is simulated via an ab initio molecular dynamics (AIMD) approach. The free energy barrier for Mg diffusing through the interface is then calculated by performing a set of biased AIMD simulations. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Realization of improved metallization-Ti/Al/Ti/W/Au ohmic contacts to n-GaN for high temperature application

NASA Astrophysics Data System (ADS)

Motayed, A.; Davydov, A. V.; Boettinger, W. J.; Josell, D.; Shapiro, A. J.; Levin, I.; Zheleva, T.; Harris, G. L.

2005-05-01

Tungsten metal layer was used for the first time as an effective diffusion barrier for the standard Ti/Al/Ti/Au ohmic metallization scheme to obtain thermally stable ohmic contact suitable for high temperature applications. Comparative studies were performed on three distinct metallization schemes: 1) standard GaN/Ti/Al/Ti/Au, 2) GaN/Ti/Al/W/Au, and 3) GaN/Ti/Al/Ti/W/Au. For the GaN with doping level of 5 × 1017 cm-3, the lowest specific contact resistance for the Ti/Al/Ti/W/Au metallization scheme annealed in argon at 750 °C for 30 sec was 5 × 10-6 .cm2, which is comparable to the standard Ti/Al/Ti/Au scheme. X-ray diffractions (XRD), auger electron spectroscopy (AES) depth profiling, field-emission scanning electron microscopy (FE-SEM), atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM) revealed that the Ti/Al/Ti/W/Au metallization has superior morphology and microstructural properties compared to standard Ti/Al/Ti/Au metallizations. Remarkably, this metallization was able to withstand thermal aging at 500 °C for 50 hrs with only marginal morphological and electrical deterioration. These studies revealed that the utilization of a compound diffusion barrier stack, as in the Ti/Al/Ti/W/Au metallization, yields electrically, structurally, and morphologically superior metallizations with exceptional thermal stability.

Effect of carbon ion irradiation on Ag diffusion in SiC

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

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Effect of carbon ion irradiation on Ag diffusion in SiC

DOE PAGES

Leng, Bin; Ko, Hyunseok; Gerczak, Tyler J.; ...

2015-11-14

Transport of Ag fission product through the silicon-carbide (SiC) diffusion barrier layer in TRISO fuel particles is of considerable interest given the application of this fuel type in high temperature gas-cooled reactor (HTGR) and other future reactor concepts. The reactor experiments indicate that radiation may play an important role in release of Ag; however so far the isolated effect of radiation on Ag diffusion has not been investigated in controlled laboratory experiments. In this study, we investigate the diffusion couples of Ag and polycrystalline 3C–SiC, as well as Ag and single crystalline 4H–SiC samples before and after irradiation with Cmore » 2+ ions. The diffusion couple samples were exposed to temperatures of 1500 °C, 1535 °C, and 1569 °C, and the ensuing diffusion profiles were analyzed by secondary ion mass spectrometry (SIMS). We found that diffusion coefficients calculated from these measurements indicate that Ag diffusion was greatly enhanced by carbon irradiation due to a combined effect of radiation damage on diffusion and the presence of grain boundaries in polycrystalline SiC samples.« less

Simulation of stationary glow patterns in dielectric barrier discharges at atmospheric pressure

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

Liu, Fucheng, E-mail: hdlfc@hbu.cn; He, Yafeng; Dong, Lifang

2014-12-15

Self-organized stationary patterns in dielectric barrier discharges operating in glow regime at atmospheric pressure are investigated by a self-consistent two-dimensional fluid model. The simulation results show that two different modes, namely, the diffuse mode and the static patterned mode, can be formed in different ranges of the driving frequency. The discharge operates in Townsend regime in the diffuse mode, while it operates in a glow regime inside the filaments and in a Townsend regime outside the filaments in the stable pattered mode. The forming process of the stationary filaments can be divided into three stages, namely, destabilizing stage, self-assembling stage,more » and stable stage. The space charge associated with residual electron density and surface charge is responsible for the formation of these stationary glow patterns.« less

An entropic barriers diffusion theory of decision-making in multiple alternative tasks

PubMed Central

Sigman, Mariano; Cecchi, Guillermo A.

2018-01-01

We present a theory of decision-making in the presence of multiple choices that departs from traditional approaches by explicitly incorporating entropic barriers in a stochastic search process. We analyze response time data from an on-line repository of 15 million blitz chess games, and show that our model fits not just the mean and variance, but the entire response time distribution (over several response-time orders of magnitude) at every stage of the game. We apply the model to show that (a) higher cognitive expertise corresponds to the exploration of more complex solution spaces, and (b) reaction times of users at an on-line buying website can be similarly explained. Our model can be seen as a synergy between diffusion models used to model simple two-choice decision-making and planning agents in complex problem solving. PMID:29499036

Lithium and sodium adsorption properties of two-dimensional aluminum nitride

NASA Astrophysics Data System (ADS)

Sengupta, Amretashis

2018-09-01

In this work the lithiation and sodiation properties of 2-dimensional (2D) AlN sheets are studied from density functional theory (DFT) simulations. 2D AlN showed theoretical specific capacity of 500.8 and 385.3 mA h g-1, maximum open circuit voltage of 1.49 and 1.86 V and diffusion barriers 0.40 and 0.15 eV, for Li and Na adsorption respectively. The calculations show 2D AlN as a possible alternative as anode material in Li-ion and Na-ion batteries. Further the high specific capacity and small diffusion barriers for Na atoms can make 2D AlN useful in supercapacitors. The change in carrier transport properties due to Li/Na adsorption on monolayer AlN can also be useful in chemical/bio-sensors and nanoelectronics devices.

In-pile test results of U-silicide or U-nitride coated U-7Mo particle dispersion fuel in Al

NASA Astrophysics Data System (ADS)

Kim, Yeon Soo; Park, J. M.; Lee, K. H.; Yoo, B. O.; Ryu, H. J.; Ye, B.

2014-11-01

U-silicide or U-nitride coated U-Mo particle dispersion fuel in Al (U-Mo/Al) was in-pile tested to examine the effectiveness of the coating as a diffusion barrier between the U-7Mo fuel kernels and Al matrix. This paper reports the PIE data and analyses focusing on the effectiveness of the coating in terms of interaction layer (IL) growth and general fuel performance. The U-silicide coating showed considerable success, but it also provided evidence for additional improvement for coating process. The U-nitride coated specimen showed largely inefficient results in reducing IL growth. From the test, important observations were also made that can be utilized to improve U-Mo/Al fuel performance. The heating process for coating turned out to be beneficial to suppress fuel swelling. The use of larger fuel particles confirmed favorable effects on fuel performance.

Minority carrier diffusion length and edge surface-recombination velocity in InP

NASA Technical Reports Server (NTRS)

Hakimzadeh, Roshanak; Bailey, Sheila G.

1993-01-01

A scanning electron microscope was used to obtain the electron-beam-induced current (EBIC) profiles in InP specimens containing a Schottky barrier perpendicular to the scanned (edge) surface. An independent technique was used to measure the edge surface-recombination velocity. These values were used in a fit of the experimental EBIC data with a theoretical expression for normalized EBIC (Donolato, 1982) to obtain the electron (minority carrier) diffusion length.

Magnetic resonance imaging of blood-brain barrier permeability in ischemic stroke using diffusion-weighted arterial spin labeling in rats.

PubMed

Tiwari, Yash V; Lu, Jianfei; Shen, Qiang; Cerqueira, Bianca; Duong, Timothy Q

2017-08-01

Diffusion-weighted arterial spin labeling magnetic resonance imaging has recently been proposed to quantify the rate of water exchange (K w ) across the blood-brain barrier in humans. This study aimed to evaluate the blood-brain barrier disruption in transient (60 min) ischemic stroke using K w magnetic resonance imaging with cross-validation by dynamic contrast-enhanced magnetic resonance imaging and Evans blue histology in the same rats. The major findings were: (i) at 90 min after stroke (30 min after reperfusion), group K w magnetic resonance imaging data showed no significant blood-brain barrier permeability changes, although a few animals showed slightly abnormal K w . Dynamic contrast-enhanced magnetic resonance imaging confirmed this finding in the same animals. (ii) At two days after stroke, K w magnetic resonance imaging revealed significant blood-brain barrier disruption. Regions with abnormal K w showed substantial overlap with regions of hyperintense T 2 (vasogenic edema) and hyperperfusion. Dynamic contrast-enhanced magnetic resonance imaging and Evans blue histology confirmed these findings in the same animals. The K w values in the normal contralesional hemisphere and the ipsilesional ischemic core two days after stroke were: 363 ± 17 and 261 ± 18 min -1 , respectively (P < 0.05, n = 9). K w magnetic resonance imaging is sensitive to blood-brain barrier permeability changes in stroke, consistent with dynamic contrast-enhanced magnetic resonance imaging and Evans blue extravasation. K w magnetic resonance imaging offers advantages over existing techniques because contrast agent is not needed and repeated measurements can be made for longitudinal monitoring or averaging.

Microimaging of transient guest profiles to monitor mass transfer in nanoporous materials

NASA Astrophysics Data System (ADS)

Kärger, Jörg; Binder, Tomas; Chmelik, Christian; Hibbe, Florian; Krautscheid, Harald; Krishna, Rajamani; Weitkamp, Jens

2014-04-01

The intense interactions of guest molecules with the pore walls of nanoporous materials is the subject of continued fundamental research. Stimulated by their thermal energy, the guest molecules in these materials are subject to a continuous, irregular motion, referred to as diffusion. Diffusion, which is omnipresent in nature, influences the efficacy of nanoporous materials in reaction and separation processes. The recently introduced techniques of microimaging by interference and infrared microscopy provide us with a wealth of information on diffusion, hitherto inaccessible from commonly used techniques. Examples include the determination of surface barriers and the sticking coefficient's analogue, namely the probability that, on colliding with the particle surface, a molecule may continue its diffusion path into the interior. Microimaging is further seen to open new vistas in multicomponent guest diffusion (including the detection of a reversal in the preferred diffusion pathways), in guest-induced phase transitions in nanoporous materials and in matching the results of diffusion studies under equilibrium and non-equilibrium conditions.

First-principles investigation of diffusion and defect properties of Fe and Ni in Cr2O3

NASA Astrophysics Data System (ADS)

Rak, Zs.; Brenner, D. W.

2018-04-01

Diffusion of Fe and Ni and the energetics of Fe- and Ni-related defects in chromium oxide (α-Cr2O3) are investigated using first-principles Density Functional Theory calculations in combination with the climbing-image nudged elastic band method. The orientations of the spin magnetic moments of the migrating ions are taken into account and their effects on migration barriers are examined. Several possible diffusion pathways were explored through interstitial and vacancy mechanisms, and it was found that the principal mode of ion transport in Cr2O3 is via vacancies. Both interstitial- and vacancy-mediated diffusions are anisotropic, with diffusion being faster in the z-direction. The energetics of defect formation indicates that the Ni-related defects are less stable than the Fe-related ones. This is consistent with Ni-diffusion being faster than Fe-diffusion. The results are compared with previous theoretical and experimental data and possible implications in corrosion control are discussed.

Influence of deformed surface diffuseness on alpha decay half-lives of actinides and lanthanides

NASA Astrophysics Data System (ADS)

Dahmardeh, S.; Alavi, S. A.; Dehghani, V.

2017-07-01

By using semiclassical WKB method and taking into account the Bohr-Sommerfeld quantization condition, the alpha decay half-lives of some deformed lanthanide (with 151 ≤ A ≤ 160 and 66 ≤ Z ≤ 73) and rare-earth nuclei (with 217 ≤ A ≤ 261 and 92 ≤ Z ≤ 104) have been calculated. The effective potential has been considered as sum of deformed Woods-Saxon nuclear potential, deformed Coulomb potential, and centrifugal potential. The influence of deformed surface diffuseness on the potential barrier, transmission coefficient at each angle, assault frequency, and alpha decay half-lives has been investigated. Good agreement between calculated half-lives with deformed surface diffuseness and experiment is observed. Relative differences between calculated half-lives with deformed surface diffuseness and with constant surface diffuseness were significant.

Hetero-diffusion of Au epitaxy on stepped Ag(110) surface: Study of the jump rate and diffusion coefficient

NASA Astrophysics Data System (ADS)

Benlattar, M.; El koraychy, E.; Kotri, A.; Mazroui, M.

2017-12-01

We have used molecular dynamics simulations combined with an interatomic potential derived from the embedded atom method, to investigate the hetero-diffusion of Au adatom near a stepped Ag(110) surface with the height of one monoatomic layer. The activation energies for different diffusion processes, which occur on the terrace and near the step edge, are calculated both by molecular statics and molecular dynamics simulations. Static energies are found by the drag method, whereas the dynamic barriers are computed at high temperature from the Arrhenius plots. Our numerical results reveal that the jump process requires very high activation energy compared to the exchange process either on the terrace or near the step edge. In this work, other processes, such as upward and downward diffusion at step edges, have also been discussed.

Multiple relaxations of the cluster surface diffusion in a homoepitaxial SrTiO3 layer

NASA Astrophysics Data System (ADS)

Woo, Chang-Su; Chu, Kanghyun; Song, Jong-Hyun; Yang, Chan-Ho

2018-03-01

We examine the surface diffusion process of adatomic clusters on a (001)-oriented SrTiO3 single crystal using reflection high energy electron diffraction (RHEED). We find that the recovery curve of the RHEED intensity acquired after a homoepitaxial half-layer growth can be accurately fit into a double exponential function, indicating the existence of two dominant relaxation mechanisms. The characteristic relaxation times at selected growth temperatures are investigated to determine the diffusion activation barriers of 0.67 eV and 0.91 eV, respectively. The Monte Carlo simulation of the cluster hopping model suggests that the decrease in the number of dimeric and trimeric clusters during surface diffusion is the origin of the observed relaxation phenomena.