From nucleation to coalescence of Cu2O islands during in situ oxidation of Cu(001)

NASA Astrophysics Data System (ADS)

Yang, J. C.; Evan, D.; Tropia, L.

2002-07-01

The nucleation, growth, and coalescence of Cu2O islands due to oxidation of Cu(001) films were visualized by in situ ultrahigh-vacuum transmission electron microscopy. We have previously demonstrated that the nucleation and initial growth of copper oxides is dominated by oxygen surface diffusion. These surface models have been extended to quantitatively represent the coalescence behavior of copper oxidation in the framework of the Johnson-Mehl-Avrami-Kolmogorov theory. An excellent agreement exists between the experimental data of nucleation to coalescence with the surface model. The implication could be an alternate paradigm for passivation and oxidation, since classic theories assume uniform film growth.

In situ heavy ion irradiation studies of nanopore shrinkage and enhanced radiation tolerance of nanoporous Au

DOE PAGES

Li, Jin; Fan, Cuncai; Ding, Jie; ...

2017-01-03

High energy particle radiations induce severe microstructural damage in metallic materials. Nanoporous materials with a giant surface-to-volume ratio may alleviate radiation damage in irradiated metallic materials as free surface are defect sinks. We show, by using in situ Kr ion irradiation in a transmission electron microscope at room temperature, that nanoporous Au indeed has significantly improved radiation tolerance comparing with coarse-grained, fully dense Au. In situ studies show that nanopores can absorb and eliminate a large number of radiation-induced defect clusters. Meanwhile, nanopores shrink (self-heal) during radiation, and their shrinkage rate is pore size dependent. Furthermore, the in situ studiesmore » show dose-rate-dependent diffusivity of defect clusters. Our study sheds light on the design of radiation-tolerant nanoporous metallic materials for advanced nuclear reactor applications.« less

In situ Visualization of Electrocatalytic Reaction Activity at Quantum Dots for Water Oxidation.

PubMed

Chen, Ying; Fu, Jiaju; Cui, Chen; Jiang, Dechen; Chen, Zixuan; Chen, Hong-Yuan; Zhu, Jun-Jie

2018-06-11

Exploring electrocatalytic reactions on nanomaterial surface can give crucial information for the development of robust catalysts. Here, electrocatalytic reaction activity at single quantum dots (QDs) loaded silica micro-particles involved in water oxidation is visualized using electrochemiluminescence (ECL) microscopy. Under positive potential, the active redox centers at QDs induce the generation of hydroperoxide surface intermediates as coreactant to remarkably enhance ECL emission from luminol derivative for imaging. For the first time, in situ visualization of catalytic activity in water oxidation at QDs catalyst was achieved, supported by a linear relation between ECL intensity and turn over frequency. A very slight diffusion trend attributed to only luminol species proved in situ capture of hydroperoxide surface intermediates at catalytic active sites of QDs. This work provides tremendous potential in on-line imaging of electrocatalytic reaction and visual evaluation of catalyst performance.

Interface chemistry and surface morphology evolution study for InAs/Al2O3 stacks upon in situ ultrahigh vacuum annealing

NASA Astrophysics Data System (ADS)

Wang, Xinglu; Qin, Xiaoye; Wang, Wen; Liu, Yue; Shi, Xiaoran; Sun, Yong; Liu, Chen; Zhao, Jiali; Zhang, Guanhua; Liu, Hui; Cho, Kyeongjae; Wu, Rui; Wang, Jiaou; Zhang, Sen; Wallace, Robert M.; Dong, Hong

2018-06-01

A systematic study of the interfacial chemistry for the HCl pretreated and native oxide InAs(100) samples upon atomic layer deposition (ALD) of Al2O3, and the post deposition annealing (PDA) process has been carried out, using in situ synchrotron radiation photoelectron spectroscopy. The "clean up" effect for the native oxide sample is detected, but it is not observed for the HCl pretreated sample. The out-diffusion and desorption of both In and As oxides have been characterized during the ALD process and the following PDA process. The surface morphology evolution during the PDA process is studied by in situ photo-emission electron microscopy. The bubbles emerged after PDA at 360 °C and grew up at 370 °C. After PDA at 400 °C and at higher temperatures, pits are seen in some areas, and the tear up of the Al2O3 film is seen in other areas with the formation of indium droplets. This study gives insight in the mechanism of elemental diffusion/desorption, which may associate the reliability of III-V semiconductor based devices.

In situ diffusion experiment in granite: Phase I

NASA Astrophysics Data System (ADS)

Vilks, P.; Cramer, J. J.; Jensen, M.; Miller, N. H.; Miller, H. G.; Stanchell, F. W.

2003-03-01

A program of in situ experiments, supported by laboratory studies, was initiated to study diffusion in sparsely fractured rock (SFR), with a goal of developing an understanding of diffusion processes within intact crystalline rock. Phase I of the in situ diffusion experiment was started in 1996, with the purpose of developing a methodology for estimating diffusion parameter values. Four in situ diffusion experiments, using a conservative iodide tracer, were performed in highly stressed SFR at a depth of 450 m in the Underground Research Laboratory (URL). The experiments, performed over a 2 year period, yielded rock permeability estimates of 2×10 -21 m 2 and effective diffusion coefficients varying from 2.1×10 -14 to 1.9×10 -13 m 2/s, which were estimated using the MOTIF code. The in situ diffusion profiles reveal a characteristic "dog leg" pattern, with iodide concentrations decreasing rapidly within a centimeter of the open borehole wall. It is hypothesized that this is an artifact of local stress redistribution and creation of a zone of increased constrictivity close to the borehole wall. A comparison of estimated in situ and laboratory diffusivities and permeabilities provides evidence that the physical properties of rock samples removed from high-stress regimes change. As a result of the lessons learnt during Phase I, a Phase II in situ program has been initiated to improve our general understanding of diffusion in SFR.

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

Li, Jin; Fan, Cuncai; Ding, Jie

High energy particle radiations induce severe microstructural damage in metallic materials. Nanoporous materials with a giant surface-to-volume ratio may alleviate radiation damage in irradiated metallic materials as free surface are defect sinks. We show, by using in situ Kr ion irradiation in a transmission electron microscope at room temperature, that nanoporous Au indeed has significantly improved radiation tolerance comparing with coarse-grained, fully dense Au. In situ studies show that nanopores can absorb and eliminate a large number of radiation-induced defect clusters. Meanwhile, nanopores shrink (self-heal) during radiation, and their shrinkage rate is pore size dependent. Furthermore, the in situ studiesmore » show dose-rate-dependent diffusivity of defect clusters. Our study sheds light on the design of radiation-tolerant nanoporous metallic materials for advanced nuclear reactor applications.« less

Robust determination of surface relaxivity from nuclear magnetic resonance DT2 measurements

NASA Astrophysics Data System (ADS)

Luo, Zhi-Xiang; Paulsen, Jeffrey; Song, Yi-Qiao

2015-10-01

Nuclear magnetic resonance (NMR) is a powerful tool to probe into geological materials such as hydrocarbon reservoir rocks and groundwater aquifers. It is unique in its ability to obtain in situ the fluid type and the pore size distributions (PSD). The T1 and T2 relaxation times are closely related to the pore geometry through the parameter called surface relaxivity. This parameter is critical for converting the relaxation time distribution into the PSD and so is key to accurately predicting permeability. The conventional way to determine the surface relaxivity ρ2 had required independent laboratory measurements of the pore size. Recently Zielinski et al. proposed a restricted diffusion model to extract the surface relaxivity from the NMR diffusion-T2 relaxation (DT2) measurement. Although this method significantly improved the ability to directly extract surface relaxivity from a pure NMR measurement, there are inconsistencies with their model and it relies on a number of preset parameters. Here we propose an improved signal model to incorporate a scalable LT and extend their method to extract the surface relaxivity based on analyzing multiple DT2 maps with varied diffusion observation time. With multiple diffusion observation times, the apparent diffusion coefficient correctly describes the restricted diffusion behavior in samples with wide PSDs, and the new method does not require predetermined parameters, such as the bulk diffusion coefficient and tortuosity. Laboratory experiments on glass beads packs with the beads diameter ranging from 50 μm to 500 μm are used to validate the new method. The extracted diffusion parameters are consistent with their known values and the determined surface relaxivity ρ2 agrees with the expected value within ±7%. This method is further successfully applied on a Berea sandstone core and yields surface relaxivity ρ2 consistent with the literature.

A method to investigate the electron scattering characteristics of ultrathin metallic films by in situ electrical resistance measurements.

PubMed

Trindade, I G; Fermento, R; Leitão, D; Sousa, J B

2009-07-01

In this article, a method to measure the electrical resistivity/conductivity of metallic thin films during layer growth on specific underlayers is described. The in situ monitoring of an underlayer electrical resistance, its change upon the incoming of new material atoms/molecules, and the growth of a new layer are presented. The method is easy to implement and allows obtaining in situ experimental curves of electrical resistivity dependence upon film thickness with a subatomic resolution, providing insight in film growth microstructure characteristics, specular/diffuse electron scattering surfaces, and optimum film thicknesses.

In situ Raman spectroscopy of LiFePO4: size and morphology dependence during charge and self-discharge.

PubMed

Wu, Jing; Dathar, Gopi Krishna Phani; Sun, Chunwen; Theivanayagam, Murali G; Applestone, Danielle; Dylla, Anthony G; Manthiram, Arumugam; Henkelman, Graeme; Goodenough, John B; Stevenson, Keith J

2013-10-25

Previous studies of the size dependent properties of LiFePO4 have focused on the diffusion rate or phase transformation pathways by bulk analysis techniques such as x-ray diffraction (XRD), neutron diffraction and electrochemistry. In this work, in situ Raman spectroscopy was used to study the surface phase change during charge and self-discharge on a more localized scale for three morphologies of LiFePO4: (1) 25 ± 6 nm width nanorods, (2) 225 ± 6 nm width nanorods and (3) ∼2 μm porous microspheres. Both the large nanorod and microsphere geometries showed incomplete delithiation at the end of charge, which was most likely caused by anti-site defects along the 1D diffusion channels in the bulk of the larger particles. Based on the in situ Raman measurements, all of the morphologies studied exhibited self-discharge with time. Among them, the smallest FePO4 particles self-discharged (lithiated) the fastest. While nanostructuring LiFePO4 can offer advantages in terms of lowering anti-site defects within particles, it also creates new problems due to high surface energies that allow self-discharge. The in situ Raman spectroscopy also showed that carbon coating did not provide significant improvement to the stability of the lithiated particles.

In situ TEM study of electron-beam radiation induced boron diffusion and effects on phase and microstructure evolution in nanostructured CoFeB/SiO2 thin film

NASA Astrophysics Data System (ADS)

Liu, B. H.; Teo, H. W.; Mo, Z. H.; Mai, Z. H.; Lam, J.; Xue, J. M.; Zhao, Y. Z.; Tan, P. K.

2017-01-01

Using in situ transmission electron microscopy (TEM), we studied boron diffusion and segregation in CoFeB/SiO2 nanostructured thin film stacks. We also investigated how these phenomena affected the phase and microstructure of CoFeB thin films under electron beam irradiation at 300 kV. A unique phase transformation was observed in CoFeB thin films under high-dose electron irradiation, from a polycrystalline Co3Fe to a unilateral amorphous phase of Co3Fe and nanocrystalline FexCo23-xB6. The unilateral amorphization of the Co3Fe film showed an electron-dose-rate sensitivity with a threshold dose rate. Detailed in situ TEM studies revealed that the unilateral amorphization of the Co3Fe film arose from boron segregation at the bottom of the Co3Fe thin film induced by radiation-enhanced diffusion of boron atoms that were displaced by electron knock-on effects. The radiation-induced nanocrystallization of FexCo23-xB6 was also found to be dose-rate sensitive with a higher electron beam current leading to earlier nucleation and more rapid grain growth. The nanocrystallization of FexCo23-xB6 occurred preferentially at the CoFeB/SiO2 interface. Kinetic studies by in situ TEM revealed the surface crystallization and diffusion-controlled nucleation and grain growth mechanisms. The radiation-enhanced atomic diffusivity and high-concentration of radiation-induced point defects at the Co3Fe/SiO2 interface enhanced the local short-range ordering of Fe, Co, and B atoms, favoring nucleation and grain growth of FexCo23-xB6 at the interface.

Processes for producing low cost, high efficiency silicon solar cells

DOEpatents

Rohatgi, Ajeet; Chen, Zhizhang; Doshi, Parag

1996-01-01

Processes which utilize rapid thermal processing (RTP) are provided for inexpensively producing high efficiency silicon solar cells. The RTP processes preserve minority carrier bulk lifetime .tau. and permit selective adjustment of the depth of the diffused regions, including emitter and back surface field (bsf), within the silicon substrate. Silicon solar cell efficiencies of 16.9% have been achieved. In a first RTP process, an RTP step is utilized to simultaneously diffuse phosphorus and aluminum into the front and back surfaces, respectively, of a silicon substrate. Moreover, an in situ controlled cooling procedure preserves the carrier bulk lifetime .tau. and permits selective adjustment of the depth of the diffused regions. In a second RTP process, both simultaneous diffusion of the phosphorus and aluminum as well as annealing of the front and back contacts are accomplished during the RTP step. In a third RTP process, the RTP step accomplishes simultaneous diffusion of the phosphorus and aluminum, annealing of the contacts, and annealing of a double-layer antireflection/passivation coating SiN/SiO.sub.x.

The Role of Surface Passivation in Controlling Ge Nanowire Faceting.

PubMed

Gamalski, A D; Tersoff, J; Kodambaka, S; Zakharov, D N; Ross, F M; Stach, E A

2015-12-09

In situ transmission electron microscopy observations of nanowire morphologies indicate that during Au-catalyzed Ge nanowire growth, Ge facets can rapidly form along the nanowire sidewalls when the source gas (here, digermane) flux is decreased or the temperature is increased. This sidewall faceting is accompanied by continuous catalyst loss as Au diffuses from the droplet to the wire surface. We suggest that high digermane flux and low temperatures promote effective surface passivation of Ge nanowires with H or other digermane fragments inhibiting diffusion and attachment of Au and Ge on the sidewalls. These results illustrate the essential roles of the precursor gas and substrate temperature in maintaining nanowire sidewall passivation, necessary to ensure the growth of straight, untapered, ⟨111⟩-oriented nanowires.

Temperature effects on the atomic structure and kinetics in single crystal electrochemistry

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

Gründer, Yvonne; Markovic, Nenad M.; Thompson, Paul

2015-01-01

The influence of temperature on the atomic structure at the electrochemical interface has been studied using in-situ surface x-ray scattering (SXS) during the formation of metal monolayers on a Au(111) electrode. For the surface reconstruction of Au(111), higher temperatures increase the mobility of surface atoms in the unreconstructed phase which then determines the surface ordering during the formation of the reconstruction. For the underpotential deposition (UPD) systems, the surface diffusion of the depositing metal adatoms is significantly reduced at low temperatures which results in the frustration of ordered structures in the case of Cu UPD, occurring on a Br-modified surface,more » and in the formation of a disordered Ag monolayer during Ag UPD. The results indicate that temperature changes affect the mass transport and diffusion of metal adatoms on the electrode surface. This demonstrates the importance of including temperature as a variable in studying surface structure and reactions at the electrochemical interface.« less

The role of surface passivation in controlling Ge nanowire faceting

DOE PAGES

Gamalski, A. D.; Tersoff, J.; Kodambaka, S.; ...

2015-11-05

In situ transmission electron microscopy observations of nanowire morphologies indicate that during Au-catalyzed Ge nanowire growth, Ge facets can rapidly form along the nanowire sidewalls when the source gas (here, digermane) flux is decreased or the temperature is increased. This sidewall faceting is accompanied by continuous catalyst loss as Au diffuses from the droplet to the wire surface. We suggest that high digermane flux and low temperatures promote effective surface passivation of Ge nanowires with H or other digermane fragments inhibiting diffusion and attachment of Au and Ge on the sidewalls. Furthermore, these results illustrate the essential roles of themore » precursor gas and substrate temperature in maintaining nanowire sidewall passivation, necessary to ensure the growth of straight, untapered, <111>-oriented nanowires.« less

Diffusion of Magnesium in Led Structures with InGaN/GaN Quantum Wells at True Growth Temperatures 860-980°C of p-GaN

NASA Astrophysics Data System (ADS)

Romanov, I. S.; Prudaev, I. A.; Brudnyi, V. N.

2018-05-01

The results of an investigation of Mg diffusion in blue LED structures with InGaN/GaN quantum wells are presented for various growth temperatures of the p-GaN layer. The values of the diffusion coefficient estimated for true growth temperatures of 860, 910, and 980°C were 7.5·10-17, 2.8·10-16, and 1.2·10-15 cm2/s, respectively. The temperature values given in the work were measured on the surface of the growing layer in situ using a pyrometer. The calculated activation energy for the temperature dependence of the diffusion coefficient was 2.8 eV.

Microwave annealing of Mg-implanted and in situ Be-doped GaN

NASA Astrophysics Data System (ADS)

Aluri, Geetha S.; Gowda, Madhu; Mahadik, Nadeemullah A.; Sundaresan, Siddarth G.; Rao, Mulpuri V.; Schreifels, John A.; Freitas, J. A.; Qadri, S. B.; Tian, Y.-L.

2010-10-01

An ultrafast microwave annealing method, different from conventional thermal annealing, is used to activate Mg-implants in GaN layer. The x-ray diffraction measurements indicated complete disappearance of the defect sublattice peak, introduced by the implantation process for single-energy Mg-implantation, when the annealing was performed at ≥1400 °C for 15 s. An increase in the intensity of Mg-acceptor related luminescence peak (at 3.26 eV) in the photoluminescence spectra confirms the Mg-acceptor activation in single-energy Mg-implanted GaN. In case of multiple-energy implantation, the implant generated defects persisted even after 1500 °C/15 s annealing, resulting in no net Mg-acceptor activation of the Mg-implant. The Mg-implant is relatively thermally stable and the sample surface roughness is 6 nm after 1500 °C/15 s annealing, using a 600 nm thick AlN cap. In situ Be-doped GaN films, after 1300 °C/5 s annealing have shown Be out-diffusion into the AlN layer and also in-diffusion toward the GaN/SiC interface. The in-diffusion and out-diffusion of the Be increased with increasing annealing temperature. In fact, after 1500 °C/5 s annealing, only a small fraction of in situ doped Be remained in the GaN layer, revealing the inadequateness of using Be-implantation for forming p-type doped layers in the GaN.

Slip-activated surface creep with room-temperature super-elongation in metallic nanocrystals

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

Zhong, Li; Sansoz, Frederic; He, Yang

2016-11-28

Atom diffusion assisted by surfaces or interfaces (e.g. Coble creep) has been known to be the origin of large creep rates and superplastic softening in nanosized crystals at low temperature. By contrast, source-limited crystal slip in defect-free nanostructures engenders important strengths, but also premature plastic instability and low ductility. Here, using in-situ transmission electron microscopy, we report a slip-activated surface creep mechanism that suppresses the tendency towards plastic instability without compromising the strength, resulting in ultra-large room-temperature plasticity in face-centered-cubic silver nanocrystals. This phenomenon is shown experimentally and theoretically to prevail over a material-dependent range of diameters where surface dislocationmore » nucleation becomes a stimulus to diffusional creep. This work provides new fundamental insight into coupled diffusive-displacive deformation mechanisms maximizing ductility and strength simultaneously in nanoscale materials.« less

Diagnosing isopycnal diffusivity in an eddying, idealized midlatitude ocean basin via Lagrangian, in Situ, Global, High-Performance Particle Tracking (LIGHT)

DOE PAGES

Wolfram, Phillip J.; Ringler, Todd D.; Maltrud, Mathew E.; ...

2015-08-01

Isopycnal diffusivity due to stirring by mesoscale eddies in an idealized, wind-forced, eddying, midlatitude ocean basin is computed using Lagrangian, in Situ, Global, High-Performance Particle Tracking (LIGHT). Simulation is performed via LIGHT within the Model for Prediction across Scales Ocean (MPAS-O). Simulations are performed at 4-, 8-, 16-, and 32-km resolution, where the first Rossby radius of deformation (RRD) is approximately 30 km. Scalar and tensor diffusivities are estimated at each resolution based on 30 ensemble members using particle cluster statistics. Each ensemble member is composed of 303 665 particles distributed across five potential density surfaces. Diffusivity dependence upon modelmore » resolution, velocity spatial scale, and buoyancy surface is quantified and compared with mixing length theory. The spatial structure of diffusivity ranges over approximately two orders of magnitude with values of O(10 5) m 2 s –1 in the region of western boundary current separation to O(10 3) m 2 s –1 in the eastern region of the basin. Dominant mixing occurs at scales twice the size of the first RRD. Model resolution at scales finer than the RRD is necessary to obtain sufficient model fidelity at scales between one and four RRD to accurately represent mixing. Mixing length scaling with eddy kinetic energy and the Lagrangian time scale yield mixing efficiencies that typically range between 0.4 and 0.8. In conclusion, a reduced mixing length in the eastern region of the domain relative to the west suggests there are different mixing regimes outside the baroclinic jet region.« less

Injectable, in situ forming poly(propylene fumarate)-based ocular drug delivery systems.

PubMed

Ueda, H; Hacker, M C; Haesslein, A; Jo, S; Ammon, D M; Borazjani, R N; Kunzler, J F; Salamone, J C; Mikos, A G

2007-12-01

This study sought to develop an injectable formulation for long-term ocular delivery of fluocinolone acetonide (FA) by dissolving the anti-inflammatory drug and the biodegradable polymer poly(propylene fumarate) (PPF) in the biocompatible, water-miscible, organic solvent N-methyl-2-pyrrolidone (NMP). Upon injection of the solution into an aqueous environment, a FA-loaded PPF matrix is precipitated in situ through the diffusion/extraction of NMP into surrounding aqueous fluids. Fabrication of the matrices and in vitro release studies were performed in phosphate buffered saline at 37 degrees C. Drug loadings up to 5% were achieved. High performance liquid chromatography was employed to determine the released amount of FA. The effects of drug loading, PPF content of the injectable formulation, and additional photo-crosslinking of the matrix surface were investigated. Overall, FA release was sustained in vitro over up to 400 days. After an initial burst release of 22 to 68% of initial FA loading, controlled drug release driven by diffusion and bulk erosion was observed. Drug release rates in a therapeutic range were demonstrated. Release kinetics were found to be dependent on drug loading, formulation PPF content, and extent of surface crosslinking. The results suggest that injectable, in situ formed PPF matrices are promising candidates for the formulation of long-term, controlled delivery devices for intraocular drug delivery. Copyright 2007 Wiley Periodicals, Inc.

Morphological bubble evolution induced by air diffusion on submerged hydrophobic structures

NASA Astrophysics Data System (ADS)

Lv, Pengyu; Xiang, Yaolei; Xue, Yahui; Lin, Hao; Duan, Huiling

2017-03-01

Bubbles trapped in the cavities always play important roles in the underwater applications of structured hydrophobic surfaces. Air exchange between bubbles and surrounding water has a significant influence on the morphological bubble evolution, which in turn frequently affects the functionalities of the surfaces, such as superhydrophobicity and drag reduction. In this paper, air diffusion induced bubble evolution on submerged hydrophobic micropores under reduced pressures is investigated experimentally and theoretically. The morphological behaviors of collective and single bubbles are observed using confocal microscopy. Four representative evolution phases of bubbles are captured in situ. After depressurization, bubbles will not only grow and coalesce but also shrink and split although the applied pressure remains negative. A diffusion-based model is used to analyze the evolution behavior and the results are consistent with the experimental data. A criterion for bubble growth and shrinkage is also derived along with a phase diagram, revealing that the competition of effective gas partial pressures across the two sides of the diffusion layer dominates the bubble evolution process. Strategies for controlling the bubble evolution behavior are also proposed based on the phase diagram. The current work provides a further understanding of the general behavior of bubble evolution induced by air diffusion and can be employed to better designs of functional microstructured hydrophobic surfaces.

Electron Scattering at Surfaces of Epitaxial Metal Layers

NASA Astrophysics Data System (ADS)

Chawla, Jasmeet Singh

In the field of electron transport in metal films and wires, the 'size effect' refers to the increase in the resistivity of the films and wires as their critical dimensions (thickness of film, width and height of wires) approach or become less than the electron mean free path lambda, which is, for example, 39 nm for bulk copper at room temperature. This size-effect is currently of great concern to the semiconductor industry because the continued downscaling of feature sizes has already lead to Cu interconnect wires in this size effect regime, with a reported 2.5 times higher resistivity for 40 nm wide Cu wires than for bulk Cu. Silver is a possible alternate material for interconnect wires and titanium nitride is proposed as a gate metal in novel field-effect-transistors. Therefore, it is important to develop an understanding of how the growth, the surface morphology, and the microstructure of ultrathin (few nanometers) Cu, Ag and TiN layers affect their electrical properties. This dissertation aims to advance the scientific knowledge of electron scattering at surfaces (external surfaces and grain boundaries), that are, the primary reasons for the size-effect in metal conductors. The effect of surface and grain boundary scattering on the resistivity of Cu thin films and nanowires is separately quantified using (i) in situ transport measurements on single-crystal, atomically smooth Cu(001) layers, (ii) textured polycrystalline Cu(111) layers and patterned wires with independently varying grain size, thickness and line width, and (iii) in situ grown interfaces including Cu-Ta, Cu-MgO, Cu-vacuum and Cu-oxygen. In addition, the electron surface scattering is also measured in situ for single-crystal Ag(001), (111) twinned epitaxial Ag(001), and single-crystal TiN(001) layers. Cu(001), Ag(001), and TiN(001) layers with a minimum continuous thickness of 4, 3.5 and 1.8 nm, respectively, are grown by ultra-high vacuum magnetron sputter deposition on MgO(001) substrates with and without thin epitaxial TiN(001) wetting layers and are studied for structure, crystalline quality, surface morphology, density and composition by a combination of x-ray diffraction theta-2theta scans, o-rocking curves, pole figures, reciprocal space mapping, Rutherford backscattering, x-ray reflectometry and transmission electron microscopy. The TiN(001) surface suppresses Cu and Ag dewetting, yielding lower defect density, no twinning, and smaller surface roughness than if grown on MgO(001). Textured polycrystalline Cu(111) layers 25-50-nm-thick are deposited on a stack of 7.5-nm-Ta on SiO2/Si(001), and subsequent in situ annealing at 350°C followed by sputter etching in Ar plasma yields Cu layers with independently variable thickness and grain size. Cu nanowires, 75 to 350 nm wide, are fabricated from Cu layers with different average grain size using a subtractive patterning process. In situ electron transport measurements at room temperature in vacuum and at 77 K in liquid nitrogen for single-crystal Cu and Ag layers is consistent with the Fuchs-Sondheimer (FS) model and indicates specular scattering at the metal-vacuum boundary with an average specularity parameter p = 0.8 and 0.6, respectively. In contrast, layers measured ex situ show diffuse surface scattering due to sub-monolayer oxidation. Also, addition of Ta atoms on Cu(001) surface perturbs the smooth interface potential and results in completely diffuse scattering at the Cu-Ta interface, and in turn, a higher resistivity of single-crystal Cu layers. In situ exposure of Cu(001) layers to O2 between 10 -3 and 105 Pa-s results in a sequential increase, decrease and increase of the electrical resistance which is attributed to specular surface scattering for clean Cu(001) and for surfaces with a complete adsorbed monolayer, but diffuse scattering at partial coverage and after chemical oxidation. Electron transport measurements for polycrystalline Cu layers and wires show a 10-15% and 7-9% decrease in resistivity, respectively, when increasing the average lateral grain size by a factor of 1.8. The maximum resistivity decrease that can be achieved by increasing the grain size of polycrystalline Cu layers with an average grain size approximately ˜2.5x the layer thickness is 20-26%.

Diffusion Control in the in Situ Synthesis of Iconic Metal-Organic Frameworks within an Ionic Polymer Matrix.

PubMed

Lim, Jungho; Lee, Eun Ji; Choi, Jae Sun; Jeong, Nak Cheon

2018-01-31

Ionic polymers that possess ion-exchangeable sites have been shown to be a greatly useful platform to fabricate mixed matrices (MMs) where metal-organic frameworks (MOFs) can be in situ synthesized, although the in situ synthesis of MOF has been rarely studied. In this study, alginate (ALG), an anionic green polymer that possesses metal-ion-exchangeable sites, is employed as a platform of MMs for the in situ synthesis of iconic MOFs, HKUST-1, and MOF-74(Zn). We demonstrate for the first time that the sequential order of supplying MOF ingredients (metal ion and deprotonated ligand) into the alginate matrix leads to substantially different results because of a difference in the diffusion of the MOF components. For the examples examined, whereas the infusion of BTC 3- ligand into Cu 2+ -exchanged ALG engendered the eggshell-shaped HKUST-1 layers on the surface of MM spheres, the infusion of Cu 2+ ions into BTC 3- -included alginate engendered the high dispersivity and junction contact of HKUST-1 crystals in the alginate matrix. This fundamental property has been exploited to fabricate a flexible MOF-containing mixed matrix membrane by coincorporating poly(vinyl alcohol). Using two molecular dyes, namely, methylene blue and rhodamine 6G, further, we show that this in situ strategy is suitable for fabricating an MOF-MM that exhibits size-selective molecular uptake.

Diffusion of Magnesium in Led Structures with InGaN/GaN Quantum Wells at True Growth Temperatures 860–980°C of p-GaN

NASA Astrophysics Data System (ADS)

Romanov, I. S.; Prudaev, I. A.; Brudnyi, V. N.

2018-05-01

The results of an investigation of Mg diffusion in blue LED structures with InGaN/GaN quantum wells are presented for various growth temperatures of the p-GaN layer. The values of the diffusion coefficient estimated for true growth temperatures of 860, 910, and 980°C were 7.5·10-17, 2.8·10-16, and 1.2·10-15 cm2/s, respectively. The temperature values given in the work were measured on the surface of the growing layer in situ using a pyrometer. The calculated activation energy for the temperature dependence of the diffusion coefficient was 2.8 eV.

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

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

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

Experimental and computational investigation of acetic acid deoxygenation over oxophilic molybdenum carbide: Surface chemistry and active site identity

DOE PAGES

Schaidle, Joshua A.; Blackburn, Jeffrey; Farberow, Carrie A.; ...

2016-01-21

Ex situ catalytic fast pyrolysis (CFP) is a promising route for producing fungible biofuels; however, this process requires bifunctional catalysts that favor C–O bond cleavage, activate hydrogen at near atmospheric pressure and high temperature (350–500 °C), and are stable under high-steam, low hydrogen-to-carbon environments. Recently, early transition-metal carbides have been reported to selectively cleave C–O bonds of alcohols, aldehydes, and oxygenated aromatics, yet there is limited understanding of the metal carbide surface chemistry under reaction conditions and the identity of the active sites for deoxygenation. In this study, we evaluated molybdenum carbide (Mo 2C) for the deoxygenation of acetic acid,more » an abundant component of biomass pyrolysis vapors, under ex situ CFP conditions, and we probed the Mo 2C surface chemistry, identity of the active sites, and deoxygenation pathways using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations.« less

Modeling and in Situ Probing of Surface Reactions in Atomic Layer Deposition.

PubMed

Zheng, Yuanxia; Hong, Sungwook; Psofogiannakis, George; Rayner, G Bruce; Datta, Suman; van Duin, Adri C T; Engel-Herbert, Roman

2017-05-10

Atomic layer deposition (ALD) has matured into a preeminent thin film deposition technique by offering a highly scalable and economic route to integrate chemically dissimilar materials with excellent thickness control down to the subnanometer regime. Contrary to its extensive applications, a quantitative and comprehensive understanding of the reaction processes seems intangible. Complex and manifold reaction pathways are possible, which are strongly affected by the surface chemical state. Here, we report a combined modeling and experimental approach utilizing ReaxFF reactive force field simulation and in situ real-time spectroscopic ellipsometry to gain insights into the ALD process of Al 2 O 3 from trimethylaluminum and water on hydrogenated and oxidized Ge(100) surfaces. We deciphered the origin for the different peculiarities during initial ALD cycles for the deposition on both surfaces. While the simulations predicted a nucleation delay for hydrogenated Ge(100), a self-cleaning effect was discovered on oxidized Ge(100) surfaces and resulted in an intermixed Al 2 O 3 /GeO x layer that effectively suppressed oxygen diffusion into Ge. In situ spectroscopic ellipsometry in combination with ex situ atomic force microscopy and X-ray photoelectron spectroscopy confirmed these simulation results. Electrical impedance characterizations evidenced the critical role of the intermixed Al 2 O 3 /GeO x layer to achieve electrically well-behaved dielectric/Ge interfaces with low interface trap density. The combined approach can be generalized to comprehend the deposition and reaction kinetics of other ALD precursors and surface chemistry, which offers a path toward a theory-aided rational design of ALD processes at a molecular level.

Reactions of SO 2 on hydrated cement particle system for atmospheric pollution reduction: A DRIFTS and XANES study

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

Ramakrishnan, Girish; Wu, Qiyuan; Moon, Juhyuk

An investigation of the adsorptive property of hydrated cement particle system for sulfur dioxide (SO2) removal was conducted. In situ and ex situ experiments using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and X-ray Absorption Near Edge Spectroscopy (XANES) characterization techniques were employed to identify surface species formed during the exposure to SO2. Oxidation of SO2 to sulfate and sulfite species observed during these experiments indicated dominant reaction pathways for SO2 reaction with concrete constituents, such as calcium hydroxide, which were also moderated by adsorption on porous surfaces of crushed aggregates. The impact of variable composition of concrete on itsmore » adsorption capacity and reaction mechanisms was also proposed in this work.« less

Assessment of VIIRS daily BRDF/Albedo product using in situ measurement of SURFRAD sites and MODIS V006 daily BRDF/Albedo product

NASA Astrophysics Data System (ADS)

Liu, Y.; Wang, Z.; Sun, Q.; Schaaf, C.; Roman, M. O.

2014-12-01

Surface albedo is defined as the ratio of upwelling to downwelling radiative flux. It's important for understanding the global energy budget. Remote sensing albedo products provide global time continuous coverage to help capture global energy variability and change. The Visible Infrared Imaging Radiometer Suite (VIIRS) on the Suomi-NPP satellite, launched on October 28, 2011, is aiming to provide continues data record with the MODerate resolution Imaging Spectroradiometer (MODIS), which has been providing Bidirectional Reflectance Distribution Function (BRDF)/Albedo product since 2000. By utilizing the same approach that was used for the most recently V006 daily MODIS BRDF/Albedo product, VIIRS has the ability to keep providing products for research and operational users. Validating albedo product of VIIRS using in situmeasured albedo can assure the quality for land surface climate and biosphere models, and comparing with MODIS product can assure time continues of BRDF/albedo product. The daily BRDF/Albedo product still uses 16-day period multispectral, cloud-cleared, atmospherically-corrected surface reflectances to fit the Ross-Thick/Li-Sparse-Reciprocal semi-empirical BRDF model. But the multiday observations are also weighted based on proximity to the production date in order to emphasis on that individual day. Surface Radiation Budget Network (SURFRAD) was established in 1993 through the support of NOAA's Office of Global Programs. In situ albedo was driven from downwelling and upwelling radiative flux measured from the towers. Fraction of diffuse sky light was calculated using the direct and diffuse solar recorded in the data. It was further used to translate VIIRS, MODIS black sky and white sky albedos into actual albedo at local solar noon. Results show that VIIRS, MODIS and in situ albedo agree well at SURFARD spatially representative sites. While the VIIRS surface reflectance, snow, and cloud algorithms are still undergoing revision, the result shows that VIIRS can provide comparable albedo products with MODIS. The accuracy of both products can meet the requirement for climate and biosphere models. In situ albedo also can be gained from Baseline Surface Radiation Network (BSRN), FLUXNET and Long Term Ecological Research network (LTER) etc., which will be used in future validation work.

Applicability of a Diffuse Reflectance Infrared Fourier Transform handheld spectrometer to perform in situ analyses on Cultural Heritage materials

NASA Astrophysics Data System (ADS)

Arrizabalaga, Iker; Gómez-Laserna, Olivia; Aramendia, Julene; Arana, Gorka; Madariaga, Juan Manuel

2014-08-01

This work studies the applicability of a Diffuse Reflectance Infrared Fourier Transform handheld device to perform in situ analyses on Cultural Heritage assets. This portable diffuse reflectance spectrometer has been used to characterise and diagnose the conservation state of (a) building materials of the Guevara Palace (15th century, Segura, Basque Country, Spain) and (b) different 19th century wallpapers manufactured by the Santa Isabel factory (Vitoria-Gasteiz, Basque Country, Spain) and by the well known Dufour and Leroy manufacturers (Paris, France), all of them belonging to the Torre de los Varona Castle (Villanañe, Basque Country, Spain). In all cases, in situ measurements were carried out and also a few samples were collected and measured in the laboratory by diffuse reflectance spectroscopy (DRIFT) in order to validate the information obtained by the handheld instrument. In the analyses performed in situ, distortions in the diffuse reflectance spectra can be observed due to the presence of specular reflection, showing the inverted bands caused by the Reststrahlen effect, in particular on those IR bands with the highest absorption coefficients. This paper concludes that the results obtained in situ by a diffuse reflectance handheld device are comparable to those obtained with laboratory diffuse reflectance spectroscopy equipment and proposes a few guidelines to acquire good spectra in the field, minimising the influence caused by the specular reflection.

In Situ Graphene Growth Dynamics on Polycrystalline Catalyst Foils

PubMed Central

2016-01-01

The dynamics of graphene growth on polycrystalline Pt foils during chemical vapor deposition (CVD) are investigated using in situ scanning electron microscopy and complementary structural characterization of the catalyst with electron backscatter diffraction. A general growth model is outlined that considers precursor dissociation, mass transport, and attachment to the edge of a growing domain. We thereby analyze graphene growth dynamics at different length scales and reveal that the rate-limiting step varies throughout the process and across different regions of the catalyst surface, including different facets of an individual graphene domain. The facets that define the domain shapes lie normal to slow growth directions, which are determined by the interfacial mobility when attachment to domain edges is rate-limiting, as well as anisotropy in surface diffusion as diffusion becomes rate-limiting. Our observations and analysis thus reveal that the structure of CVD graphene films is intimately linked to that of the underlying polycrystalline catalyst, with both interfacial mobility and diffusional anisotropy depending on the presence of step edges and grain boundaries. The growth model developed serves as a general framework for understanding and optimizing the growth of 2D materials on polycrystalline catalysts. PMID:27576749

Thermal diffusivity determination using heterodyne phase insensitive transient grating spectroscopy

NASA Astrophysics Data System (ADS)

Dennett, Cody A.; Short, Michael P.

2018-06-01

The elastic and thermal transport properties of opaque materials may be measured using transient grating spectroscopy (TGS) by inducing and monitoring periodic excitations in both reflectivity and surface displacement. The "phase grating" response encodes both properties of interest, but complicates quantitative analysis by convolving temperature dynamics with surface displacement dynamics. Thus, thermal transport characteristics are typically determined using the "amplitude grating" response to isolate the surface temperature dynamics. However, this signal character requires absolute heterodyne phase calibration and contains no elastic property information. Here, a method is developed by which phase grating TGS measurements may be consistently analyzed to determine thermal diffusivity with no prior knowledge of the expected properties. To demonstrate this ability, the wavelength-dependent 1D effective thermal diffusivity of pure germanium is measured using this type of response and found to be consistent with theoretical predictions made by solving the Boltzmann transport equation. This ability to determine the elastic and thermal properties from a single set of TGS measurements will be particularly advantageous for new in situ implementations of the technique being used to study dynamic materials systems.

Enhanced Stability of Pt-Cu Single-Atom Alloy Catalysts: In Situ Characterization of the Pt/Cu(111) Surface in an Ambient Pressure of CO

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

Simonovis, Juan Pablo; Hunt, Adrian; Palomino, Robert M.

The interaction between a catalyst and reactants often induce changes in the surface structure and composition of the catalyst, which, in turn, affect its reactivity. Therefore, it is important to study such changes using in situ techniques under well-controlled conditions. We have used ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to study the surface stability of a Pt/Cu(111) single atom alloy (SAA) in an ambient pressure of CO. By directly probing the Pt atoms, we found that CO causes a slight surface segregation of Pt atoms at room temperature. In addition, while the Pt/Cu(111) surface demonstrates poor thermal stability in UHV,more » where surface Pt starts to diffuse to the subsurface layer above 400 K, the presence of adsorbed CO enhances the thermal stability of surface Pt atoms. Furthermore, we also found that temperatures above 450 K cause a restructuring of the subsurface layer, which consequently strengthens the CO binding to the surface Pt sites, likely due to the presence of neighboring subsurface Pt atoms.« less

Enhanced Stability of Pt-Cu Single-Atom Alloy Catalysts: In Situ Characterization of the Pt/Cu(111) Surface in an Ambient Pressure of CO

DOE PAGES

Simonovis, Juan Pablo; Hunt, Adrian; Palomino, Robert M.; ...

2018-02-05

The interaction between a catalyst and reactants often induce changes in the surface structure and composition of the catalyst, which, in turn, affect its reactivity. Therefore, it is important to study such changes using in situ techniques under well-controlled conditions. We have used ambient pressure X-ray photoelectron spectroscopy (AP-XPS) to study the surface stability of a Pt/Cu(111) single atom alloy (SAA) in an ambient pressure of CO. By directly probing the Pt atoms, we found that CO causes a slight surface segregation of Pt atoms at room temperature. In addition, while the Pt/Cu(111) surface demonstrates poor thermal stability in UHV,more » where surface Pt starts to diffuse to the subsurface layer above 400 K, the presence of adsorbed CO enhances the thermal stability of surface Pt atoms. Furthermore, we also found that temperatures above 450 K cause a restructuring of the subsurface layer, which consequently strengthens the CO binding to the surface Pt sites, likely due to the presence of neighboring subsurface Pt atoms.« less

Direct observation of morphological evolution of a catalyst during carbon nanotube forest growth: new insights into growth and growth termination

NASA Astrophysics Data System (ADS)

Jeong, Seojeong; Lee, Jaegeun; Kim, Hwan-Chul; Hwang, Jun Yeon; Ku, Bon-Cheol; Zakharov, Dmitri N.; Maruyama, Benji; Stach, Eric A.; Kim, Seung Min

2016-01-01

In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests.In this study, we develop a new methodology for transmission electron microscopy (TEM) analysis that enables us to directly investigate the interface between carbon nanotube (CNT) arrays and the catalyst and support layers for CNT forest growth without any damage induced by a post-growth TEM sample preparation. Using this methodology, we perform in situ and ex situ TEM investigations on the evolution of the morphology of the catalyst particles and observe the catalyst particles to climb up through CNT arrays during CNT forest growth. We speculate that the lifted catalysts significantly affect the growth and growth termination of CNT forests along with Ostwald ripening and sub-surface diffusion. Thus, we propose a modified growth termination model which better explains various phenomena related to the growth and growth termination of CNT forests. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr05547d

Kinetics of methane-ethane gas replacement in clathrate-hydrates studied by time-resolved neutron diffraction and Raman spectroscopy.

PubMed

Murshed, M Mangir; Schmidt, Burkhard C; Kuhs, Werner F

2010-01-14

The kinetics of CH(4)-C(2)H(6) replacement in gas hydrates has been studied by in situ neutron diffraction and Raman spectroscopy. Deuterated ethane structure type I (C(2)H(6) sI) hydrates were transformed in a closed volume into methane-ethane mixed structure type II (CH(4)-C(2)H(6) sII) hydrates at 5 MPa and various temperatures in the vicinity of 0 degrees C while followed by time-resolved neutron powder diffraction on D20 at ILL, Grenoble. The role of available surface area of the sI starting material on the formation kinetics of sII hydrates was studied. Ex situ Raman spectroscopic investigations were carried out to crosscheck the gas composition and the distribution of the gas species over the cages as a function of structure type and compared to the in situ neutron results. Raman micromapping on single hydrate grains showed compositional and structural gradients between the surface and core of the transformed hydrates. Moreover, the observed methane-ethane ratio is very far from the one expected for a formation from a constantly equilibrated gas phase. The results also prove that gas replacement in CH(4)-C(2)H(6) hydrates is a regrowth process involving the nucleation of new crystallites commencing at the surface of the parent C(2)H(6) sI hydrate with a progressively shrinking core of unreacted material. The time-resolved neutron diffraction results clearly indicate an increasing diffusion limitation of the exchange process. This diffusion limitation leads to a progressive slowing down of the exchange reaction and is likely to be responsible for the incomplete exchange of the gases.

Applicability of a Diffuse Reflectance Infrared Fourier Transform handheld spectrometer to perform in situ analyses on Cultural Heritage materials.

PubMed

Arrizabalaga, Iker; Gómez-Laserna, Olivia; Aramendia, Julene; Arana, Gorka; Madariaga, Juan Manuel

2014-08-14

This work studies the applicability of a Diffuse Reflectance Infrared Fourier Transform handheld device to perform in situ analyses on Cultural Heritage assets. This portable diffuse reflectance spectrometer has been used to characterise and diagnose the conservation state of (a) building materials of the Guevara Palace (15th century, Segura, Basque Country, Spain) and (b) different 19th century wallpapers manufactured by the Santa Isabel factory (Vitoria-Gasteiz, Basque Country, Spain) and by the well known Dufour and Leroy manufacturers (Paris, France), all of them belonging to the Torre de los Varona Castle (Villanañe, Basque Country, Spain). In all cases, in situ measurements were carried out and also a few samples were collected and measured in the laboratory by diffuse reflectance spectroscopy (DRIFT) in order to validate the information obtained by the handheld instrument. In the analyses performed in situ, distortions in the diffuse reflectance spectra can be observed due to the presence of specular reflection, showing the inverted bands caused by the Reststrahlen effect, in particular on those IR bands with the highest absorption coefficients. This paper concludes that the results obtained in situ by a diffuse reflectance handheld device are comparable to those obtained with laboratory diffuse reflectance spectroscopy equipment and proposes a few guidelines to acquire good spectra in the field, minimising the influence caused by the specular reflection. Copyright © 2014 Elsevier B.V. All rights reserved.

Intensity-Value Corrections for Integrating Sphere Measurements of Solid Samples Measured Behind Glass

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

Johnson, Timothy J.; Bernacki, Bruce E.; Redding, Rebecca L.

2014-11-01

Accurate and calibrated directional-hemispherical reflectance spectra of solids are important for both in situ and remote sensing. Many solids are in the form of powders or granules and to measure their diffuse reflectance spectra in the laboratory, it is often necessary to place the samples behind a transparent medium such as glass for the ultraviolet (UV), visible, or near-infrared spectral regions. Using both experimental methods and a simple optical model, we demonstrate that glass (fused quartz in our case) leads to artifacts in the reflectance values. We report our observations that the measured reflectance values, for both hemispherical and diffusemore » reflectance, are distorted by the additional reflections arising at the air–quartz and sample–quartz interfaces. The values are dependent on the sample reflectance and are offset in intensity in the hemispherical case, leading to measured values up to ~6% too high for a 2% reflectance surface, ~3.8% too high for 10% reflecting surfaces, approximately correct for 40–60% diffuse-reflecting surfaces, and ~1.5% too low for 99% reflecting Spectralon® surfaces. For the case of diffuse-only reflectance, the measured values are uniformly too low due to the polished glass, with differences of nearly 6% for a 99% reflecting matte surface. The deviations arise from the added reflections from the quartz surfaces, as verified by both theory and experiment, and depend on sphere design. Finally, empirical correction factors were implemented into post-processing software to redress the artifact for hemispherical and diffuse reflectance data across the 300–2300 nm range.« less

Methods for characterizing subsurface volatile contaminants using in-situ sensors

DOEpatents

Ho, Clifford K [Albuquerque, NM

2006-02-21

An inverse analysis method for characterizing diffusion of vapor from an underground source of volatile contaminant using data taken by an in-situ sensor. The method uses one-dimensional solutions to the diffusion equation in Cartesian, cylindrical, or spherical coordinates for isotropic and homogenous media. If the effective vapor diffusion coefficient is known, then the distance from the source to the in-situ sensor can be estimated by comparing the shape of the predicted time-dependent vapor concentration response curve to the measured response curve. Alternatively, if the source distance is known, then the effective vapor diffusion coefficient can be estimated using the same inverse analysis method. A triangulation technique can be used with multiple sensors to locate the source in two or three dimensions. The in-situ sensor can contain one or more chemiresistor elements housed in a waterproof enclosure with a gas permeable membrane.

Origin of Quantum Ring Formation During Droplet Epitaxy

NASA Astrophysics Data System (ADS)

Zhou, Z. Y.; Zheng, C. X.; Tang, W. X.; Tersoff, J.; Jesson, D. E.

2013-07-01

Droplet epitaxy of GaAs is studied in real time using in situ surface electron microscopy. The resulting movies motivate a theoretical model for quantum ring formation which can explain the origin of nanoscale features such as double rings observed under a variety of experimental conditions. Inner rings correspond to GaAs deposition at the droplet edge, while outer rings result from the reaction of Ga and As atoms diffusing along the surface. The observed variety of morphologies primarily reflects relative changes in the outer rings with temperature and As flux.

Processes for producing low cost, high efficiency silicon solar cells

DOEpatents

Rohatgi, Ajeet; Doshi, Parag; Tate, John Keith; Mejia, Jose; Chen, Zhizhang

1998-06-16

Processes which utilize rapid thermal processing (RTP) are provided for inexpensively producing high efficiency silicon solar cells. The RTP processes preserve minority carrier bulk lifetime .tau. and permit selective adjustment of the depth of the diffused regions, including emitter and back surface field (bsf), within the silicon substrate. In a first RTP process, an RTP step is utilized to simultaneously diffuse phosphorus and aluminum into the front and back surfaces, respectively, of a silicon substrate. Moreover, an in situ controlled cooling procedure preserves the carrier bulk lifetime .tau. and permits selective adjustment of the depth of the diffused regions. In a second RTP process, both simultaneous diffusion of the phosphorus and aluminum as well as annealing of the front and back contacts are accomplished during the RTP step. In a third RTP process, the RTP step accomplishes simultaneous diffusion of the phosphorus and aluminum, annealing of the contacts, and annealing of a double-layer antireflection/passivation coating SiN/SiO.sub.x. In a fourth RTP process, the process of applying front and back contacts is broken up into two separate respective steps, which enhances the efficiency of the cells, at a slight time expense. In a fifth RTP process, a second RTP step is utilized to fire and adhere the screen printed or evaporated contacts to the structure.

The Ehrlich-Schwoebel barrier on an oxide surface: a combined Monte-Carlo and in situ scanning tunneling microscopy approach.

PubMed

Gianfrancesco, Anthony G; Tselev, Alexander; Baddorf, Arthur P; Kalinin, Sergei V; Vasudevan, Rama K

2015-11-13

The controlled growth of epitaxial films of complex oxides requires an atomistic understanding of key parameters determining final film morphology, such as termination dependence on adatom diffusion, and height of the Ehrlich-Schwoebel (ES) barrier. Here, through an in situ scanning tunneling microscopy study of mixed-terminated La5/8Ca3/8MnO3 (LCMO) films, we image adatoms and observe pile-up at island edges. Image analysis allows determination of the population of adatoms at the edge of islands and fractions on A-site and B-site terminations. A simple Monte-Carlo model, simulating the random walk of adatoms on a sinusoidal potential landscape using Boltzmann statistics is used to reproduce the experimental data, and provides an estimate of the ES barrier as ∼0.18 ± 0.04 eV at T = 1023 K, similar to those of metal adatoms on metallic surfaces. These studies highlight the utility of in situ imaging, in combination with basic Monte-Carlo methods, in elucidating the factors which control the final film growth in complex oxides.

The Ehrlich-Schwoebel barrier on an oxide surface: a combined Monte-Carlo and in situ scanning tunneling microscopy approach

NASA Astrophysics Data System (ADS)

Gianfrancesco, Anthony G.; Tselev, Alexander; Baddorf, Arthur P.; Kalinin, Sergei V.; Vasudevan, Rama K.

2015-11-01

The controlled growth of epitaxial films of complex oxides requires an atomistic understanding of key parameters determining final film morphology, such as termination dependence on adatom diffusion, and height of the Ehrlich-Schwoebel (ES) barrier. Here, through an in situ scanning tunneling microscopy study of mixed-terminated La5/8Ca3/8MnO3 (LCMO) films, we image adatoms and observe pile-up at island edges. Image analysis allows determination of the population of adatoms at the edge of islands and fractions on A-site and B-site terminations. A simple Monte-Carlo model, simulating the random walk of adatoms on a sinusoidal potential landscape using Boltzmann statistics is used to reproduce the experimental data, and provides an estimate of the ES barrier as ˜0.18 ± 0.04 eV at T = 1023 K, similar to those of metal adatoms on metallic surfaces. These studies highlight the utility of in situ imaging, in combination with basic Monte-Carlo methods, in elucidating the factors which control the final film growth in complex oxides.

The effect of metal (hydr)oxide nano-enabling on intraparticle mass transport of organic contaminants in hybrid granular activated carbon.

PubMed

Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D

2017-05-15

The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.

Solar Ion Processing of Major Element Surface Compositions of Mature Mare Soils: Insights from Combined XPS and Analytical TEM Observations

NASA Technical Reports Server (NTRS)

Christoffersen, R.; Dukes, C.; Keller, L. P.; Baragiola, R.

2012-01-01

Solar wind ions are capable of altering the sur-face chemistry of the lunar regolith by a number of mechanisms including preferential sputtering, radiation-enhanced diffusion and sputter erosion of space weathered surfaces containing pre-existing compositional profiles. We have previously reported in-situ ion irradiation experiments supported by X-ray photoelectron spectroscopy (XPS) and analytical TEM that show how solar ions potentially drive Fe and Ti reduction at the monolayer scale as well as the 10-100 nm depth scale in lunar soils [1]. Here we report experimental data on the effect of ion irradiation on the major element surface composition in a mature mare soil.

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

NASA Astrophysics Data System (ADS)

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

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

Mask aligner for ultrahigh vacuum with capacitive distance control

NASA Astrophysics Data System (ADS)

Bhaskar, Priyamvada; Mathioudakis, Simon; Olschewski, Tim; Muckel, Florian; Bindel, Jan Raphael; Pratzer, Marco; Liebmann, Marcus; Morgenstern, Markus

2018-04-01

We present a mask aligner driven by three piezomotors which guides and aligns a SiN shadow mask under capacitive control towards a sample surface. The three capacitors for read out are located at the backside of the thin mask such that the mask can be placed at a μm distance from the sample surface, while keeping it parallel to the surface, without touching the sample by the mask a priori. Samples and masks can be exchanged in-situ and the mask can additionally be displaced parallel to the surface. We demonstrate an edge sharpness of the deposited structures below 100 nm, which is likely limited by the diffusion of the deposited Au on Si(111).

Interfacial nano-mixing in a miniaturised platform enables signal enhancement and in situ detection of cancer biomarkers.

PubMed

Wuethrich, Alain; Sina, Abu Ali Ibn; Ahmed, Mostak; Lin, Ting-Yun; Carrascosa, Laura G; Trau, Matt

2018-06-14

Interfacial biosensing performs the detection of biomolecules at the bare-metal interface for disease diagnosis by comparing how biological species derived from patients and healthy individuals interact with bare metal surfaces. This technique retrieves clinicopathological information without complex surface functionalisation which is a major limitation of conventional techniques. However, it is still challenging to detect subtle molecular changes by interfacial biosensing, and the detection often requires prolonged sensing times due to the slow diffusion process of the biomolecules towards the sensor surface. Herein, we report on a novel strategy for interfacial biosensing which involves in situ electrochemical detection under the action of an electric field-induced nanoscopic flow at nanometre distance to the sensing surface. This nanomixing significantly increases target adsorption, reduces sensing time, and enables the detection of small molecular changes with enhanced sensitivity. Using a multiplex electrochemical microdevice that enables nanomixing and in situ label-free electrochemical detection, we demonstrate the detection of multiple cancer biomarkers on the same device. We present data for the detection of aberrant phosphorylation in the EGFR protein and hypermethylation in the EN1 gene region. Our method significantly shortens the assay period (from 40 min and 20 min to 3 minutes for protein and DNA, respectively), increases the sensitivity by up to two orders of magnitude, and improves detection specificity.

Self-organized nickel nanoparticles on nanostructured silicon substrate intermediated by a titanium oxynitride (TiNxOy) interface

NASA Astrophysics Data System (ADS)

Morales, M.; Droppa, R., Jr.; de Mello, S. R. S.; Figueroa, C. A.; Zanatta, A. R.; Alvarez, F.

2018-01-01

In this work we report an experimental approach by combining in situ sequential top-down and bottom-up processes to induce the organization of nanosized nickel particles. The top-down process consists in xenon ion bombardment of a crystalline silicon substrate to generate a pattern, followed by depositing a ˜15 nm titanium oxynitride thin film to act as a metallic diffusion barrier. Then, metallic nanoparticles are deposited by argon ion sputtering a pure nickel target, and the sample is annealed to promote the organization of the nickel nanoparticles (a bottom-up process). According to the experimental results, the surface pattern and the substrate biaxial surface strain are the driving forces behind the alignment and organization of the nickel nanoparticles. Moreover, the ratio between the F of metallic atoms arriving at the substrate relative to its surface diffusion mobility determines the nucleation regime of the nickel nanoparticles. These features are presented and discussed considering the existing technical literature on the subject.

Intraparticle reduction of arsenite (As(III)) by nanoscale zerovalent iron (nZVI) investigated with In Situ X-ray absorption spectroscopy.

PubMed

Yan, Weile; Vasic, Relja; Frenkel, Anatoly I; Koel, Bruce E

2012-07-03

While a high efficiency of contaminant removal by nanoscale zerovalent iron (nZVI) has often been reported for several contaminants of great concern, including aqueous arsenic species, the transformations and translocation of contaminants at and within the nanoparticles are not clearly understood. By analysis using in situ time-dependent X-ray absorption spectroscopy (XAS) of the arsenic core level for nZVI in anoxic As(III) solutions, we have observed that As(III) species underwent two stages of transformation upon adsorption at the nZVI surface. The first stage corresponds to breaking of As-O bonds at the particle surface, and the second stage involves further reduction and diffusion of arsenic across the thin oxide layer enclosing the nanoparticles, which results in arsenic forming an intermetallic phase with the Fe(0) core. Extended X-ray absorption fine-structure (EXAFS) data from experiments conducted at different iron/arsenic ratios indicate that the reduced arsenic species tend to be enriched at the surface of the Fe(0) core region and had limited mobility into the interior of the metal core within the experimental time frame (up to 22 h). Therefore, there was an accumulation of partially reduced arsenic at the Fe(0)/oxide interface when a relatively large arsenic content was present in the solid phase. These results illuminate the role of intraparticle diffusion and reduction in affecting the chemical state and spatial distribution of arsenic in nZVI materials.

Gold diffusion in mercury cadmium telluride grown by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Selamet, Yusuf; Singh, Rasdip; Zhao, Jun; Zhou, Yong D.; Sivananthan, Sivalingam; Dhar, Nibir K.

2003-12-01

The growth and characterization of Au-doped HgCdTe layers on (211)B CdTe/Si substrates grown by molecular beam epitaxy reported. The electrical properties of these layers studied for diffusion are presented. For ex-situ experiments, thin Au layers were deposited by evaporation and annealed at various temperatures and times to investigate the p-type doping properties and diffusion of Au in HgCdTe. The atomic distribution of the diffused Au was determined by secondary ion mass spectroscopy. We found clear evidence for p-type doping of HgCdTe:Au by in-situ and ex-situ methods. For in-situ doped layers, we found that, the Au cell temperature needs to be around 900°C to get p-type behavior. The diffusion coefficient of Au in HgCdTe was calculated by fitting SIMS profiles after annealing. Both complementary error functions and gaussian fittings were used, and were in full agreement. Diffusion coefficient as low as 8x10-14cm2/s observed for a sample annealed at 250°C and slow component of a diffusion coefficient as low as 2x10-15 cm2/s observed for a sample annealed at 300°C. Our preliminary results indicate no appreciable diffusion of Au in HgCdTe under the conditions used in these studies. Further work is in progress to confirm these results and to quantify our SIMS profiles.

Ex situ n+ doping of GeSn alloys via non-equilibrium processing

NASA Astrophysics Data System (ADS)

Prucnal, S.; Berencén, Y.; Wang, M.; Rebohle, L.; Böttger, R.; Fischer, I. A.; Augel, L.; Oehme, M.; Schulze, J.; Voelskow, M.; Helm, M.; Skorupa, W.; Zhou, S.

2018-06-01

Full integration of Ge-based alloys like GeSn with complementary-metal-oxide-semiconductor technology would require the fabrication of p- and n-type doped regions for both planar and tri-dimensional device architectures which is challenging using in situ doping techniques. In this work, we report on the influence of ex situ doping on the structural, electrical and optical properties of GeSn alloys. n-type doping is realized by P implantation into GeSn alloy layers grown by molecular beam epitaxy (MBE) followed by flash lamp annealing. We show that effective carrier concentration of up to 1 × 1019 cm‑3 can be achieved without affecting the Sn distribution. Sn segregation at the surface accompanied with an Sn diffusion towards the crystalline/amorphous GeSn interface is found at P fluences higher than 3 × 1015 cm‑2 and electron concentration of about 4 × 1019 cm‑3. The optical and structural properties of ion-implanted GeSn layers are comparable with the in situ doped MBE grown layers.

Polymer Nanocomposite Film with Metal Rich Surface Prepared by In Situ Single-Step Formation of Palladium Nanoparticles: An Interesting Way to Combine Specific Functional Properties.

PubMed

Thompson, David; Kranbuehl, David; Espuche, Eliane

2016-10-18

This paper presents a continuous single-step route that permits preparation of a thermostable polymer/metal nanocomposite film and to combine different functional properties in a unique material. More precisely, palladium nanoparticles are in situ generated in a polyimide matrix thanks to a designed curing cycle which is applied to a polyamic acid/metal precursor solution cast on a glass plate. A metal-rich surface layer which is strongly bonded to the bulk film is formed in addition to homogeneously dispersed metal nanoparticles. This specific morphology leads to obtaining an optically reflective film. The metal nanoparticles act as gas diffusion barriers for helium, oxygen, and carbon dioxide; they induce a tortuosity effect which allows dividing the gas permeation coefficients by a factor near to 2 with respect to the neat polyimide matrix. Moreover, the ability of the in situ synthesized palladium nanoparticles to entrap hydrogen is evidenced. The nanocomposite film properties can be modulated as a function of the location of the film metal-rich surface with respect to the hydrogen feed. The synthesized nanocomposite could represent a major interest for a wide variety of applications, from specific coatings for aerospace or automotive industry, to catalysis applications or sensors.

Rain Impact Model Assessment of Near-Surface Salinity Stratification Following Rainfall

NASA Astrophysics Data System (ADS)

Drushka, K.; Jones, L.; Jacob, M. M.; Asher, W.; Santos-Garcia, A.

2016-12-01

Rainfall over oceans produces a layer of fresher surface water, which can have a significant effect on the exchanges between the surface and the bulk mixed layer and also on satellite/in-situ comparisons. For satellite sea surface salinity (SSS) measurements, the standard is the Hybrid Coordinate Ocean Model (HYCOM), but there is a significant difference between the remote sensing sampling depth of 0.01 m and the typical range of 5-10 m of in-situ instruments. Under normal conditions the upper layer of the ocean is well mixed and there is uniform salinity; however, under rainy conditions, there is a dilution of the near-surface salinity that mixes downward by diffusion and by mechanical mixing (gravity waves/wind speed). This significantly modifies the salinity gradient in the upper 1-2 m of the ocean, but these transient salinity stratifications dissipate in a few hours, and the upper layer becomes well mixed at a slightly fresher salinity. Based upon research conducted within the NASA/CONAE Aquarius/SAC-D mission, a rain impact model (RIM) was developed to estimate the change in SSS due to rainfall near the time of the satellite observation, with the objective to identify the probability of salinity stratification. RIM uses HYCOM (which does not include the short-term rain effects) and a NOAA global rainfall product CMORPH to model changes in the near-surface salinity profile in 0.5 h increments. Based upon SPURS-2 experimental near-surface salinity measurements with rain, this paper introduces a term in the RIM model that accounts for the effect of wind speed in the mechanical mixing, which translates into a dynamic vertical diffusivity; whereby a Generalized Ocean Turbulence Model (GOTM) is used to investigate the response to rain events of the upper few meters of the ocean. The objective is to determine how rain and wind forcing control the thickness, stratification strength, and lifetime of fresh lenses and to quantify the impacts of rain-formed fresh lenses on the fresh bias in satellite retrievals of salinity. Results will be presented of comparisons of RIM measurements at depth of a few meters with measurements from in-situ salinity instruments. Also, analytical results will be shown, which assess the accuracy of RIM salinity profiles under a variety of rain rate, wind/wave conditions.

Island dynamics and anisotropy during vapor phase epitaxy of m-plane GaN

DOE PAGES

Perret, Edith; Xu, Dongwei; Highland, M. J.; ...

2017-12-04

Using in situ grazing-incidence x-ray scattering, we have measured the diffuse scattering from islands that form during layer-by-layer growth of GaN by metal-organic vapor phase epitaxy on the (10more » $$\\bar{1}$$0) m-plane surface. The diffuse scattering is extended in the (0001) in-plane direction in reciprocal space, indicating a strong anisotropy with islands elongated along [1$$\\bar{2}$$10] and closely spaced along [0001]. This is confirmed by atomic force microscopy of a quenched sample. Islands were characterized as a function of growth rate F and temperature. Furthermore, the island spacing along [0001] observed during the growth of the first monolayer obeys a power-law dependence on growth rate F -n, with an exponent n=0.25±0.02. Our results are in agreement with recent kinetic Monte Carlo simulations, indicating that elongated islands result from the dominant anisotropy in step edge energy and not from surface diffusion anisotropy. The observed power-law exponent can be explained using a simple steady-state model, which gives n = 1/4.« less

Island dynamics and anisotropy during vapor phase epitaxy of m-plane GaN

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

Perret, Edith; Xu, Dongwei; Highland, M. J.

Using in situ grazing-incidence x-ray scattering, we have measured the diffuse scattering from islands that form during layer-by-layer growth of GaN by metal-organic vapor phase epitaxy on the (1010) m-plane surface. The diffuse scattering is extended in the (0001) in-plane direction in reciprocal space, indicating a strong anisotropy with islands elongated along [1210] and closely spaced along [0001]. This is confirmed by atomic force microscopy of a quenched sample. Islands were characterized as a function of growth rate F and temperature. The island spacing along [0001] observed during the growth of the first monolayer obeys a power-law dependence on growthmore » rate F-n, with an exponent n = 0:25 + 0.02. The results are in agreement with recent kinetic Monte Carlo simulations, indicating that elongated islands result from the dominant anisotropy in step edge energy and not from surface diffusion anisotropy. The observed power-law exponent can be explained using a simple steady-state model, which gives n = 1/4.« less

Island dynamics and anisotropy during vapor phase epitaxy of m-plane GaN

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

Perret, Edith; Xu, Dongwei; Highland, M. J.

Using in situ grazing-incidence x-ray scattering, we have measured the diffuse scattering from islands that form during layer-by-layer growth of GaN by metal-organic vapor phase epitaxy on the (10more » $$\\bar{1}$$0) m-plane surface. The diffuse scattering is extended in the (0001) in-plane direction in reciprocal space, indicating a strong anisotropy with islands elongated along [1$$\\bar{2}$$10] and closely spaced along [0001]. This is confirmed by atomic force microscopy of a quenched sample. Islands were characterized as a function of growth rate F and temperature. Furthermore, the island spacing along [0001] observed during the growth of the first monolayer obeys a power-law dependence on growth rate F -n, with an exponent n=0.25±0.02. Our results are in agreement with recent kinetic Monte Carlo simulations, indicating that elongated islands result from the dominant anisotropy in step edge energy and not from surface diffusion anisotropy. The observed power-law exponent can be explained using a simple steady-state model, which gives n = 1/4.« less

Oxide ion diffusion mechanism related to Co and Fe ions in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ using in-situ X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Itoh, Takanori; Imai, Hideto

2018-03-01

The time changes of the white line and pre-edge intensities of Co and Fe K-edge in (Ba0.5Sr0.5)(Co0.8Fe0.2)O3-δ (BSCF) were observed to estimate the oxide ion diffusion related to Co and Fe ions by using in - situ X-ray absorption spectroscopy (XAS) during oxidation. The 20 μm self-standing BSCF film was prepared for in - situ XAS measurements. The time changes of absorption were fitted to the exponential decay function with two terms. The longer relaxation time (τ), related to the oxide ion diffusion during the oxidation of BSCF, is dependent on temperature. The oxide ion diffusion coefficients (D) were calculated from the τ s estimated by in - situ XAS. The values of the activation energy (Ea) for D related to Co K-edge white line, Co pre-edge, and Fe pre-edge were 1.8-2.0 eV. The value of Ea for D related to Fe K-edge white line, however, was higher than other absorption values at approximately 2.3 eV. We discussed the oxide ion diffusion mechanism related to Co and Fe ions in BSCF using in - situ XAS.

Nanostructural evolution and behavior of H and Li in ion-implanted γ-LiAlO 2

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

Jiang, Weilin; Zhang, Jiandong; Edwards, Danny J.

In-situ He+ ion irradiation is performed under a helium ion microscope to study nanostructural evolution in polycrystalline gamma-LiAlO2 pellets. Various locations within a grain, across grain boundaries and at a cavity are selected. The results exhibit He bubble formation, grain-boundary cracking, nanoparticle agglomeration, increasing surface brightness with dose, and material loss from the surface. Similar brightening effects at grain boundaries are also observed under a scanning electron microscope. Li diffusion and loss from polycrystalline gamma-LiAlO2 is faster than its monocrystalline counterpart during H2+ ion implantation at elevated temperatures. There is also more significant H diffusion and release from polycrystalline pelletsmore » during thermal annealing of 300 K implanted samples. Grain boundaries and cavities could provide a faster pathway for H and Li diffusion. H release is slightly faster from the 573 K implanted monocrystalline gamma-LiAlO2 during annealing at 773 K. Metal hydrides could be formed preferentially along the grain boundaries to immobilize hydrogen.« less

Normalized sensitivities and parameter identifiability of in situ diffusion experiments on Callovo Oxfordian clay at Bure site

NASA Astrophysics Data System (ADS)

Samper, J.; Dewonck, S.; Zheng, L.; Yang, Q.; Naves, A.

Diffusion of inert and reactive tracers (DIR) is an experimental program performed by ANDRA at Bure underground research laboratory in Meuse/Haute Marne (France) to characterize diffusion and retention of radionuclides in Callovo-Oxfordian (C-Ox) argillite. In situ diffusion experiments were performed in vertical boreholes to determine diffusion and retention parameters of selected radionuclides. C-Ox clay exhibits a mild diffusion anisotropy due to stratification. Interpretation of in situ diffusion experiments is complicated by several non-ideal effects caused by the presence of a sintered filter, a gap between the filter and borehole wall and an excavation disturbed zone (EdZ). The relevance of such non-ideal effects and their impact on estimated clay parameters have been evaluated with numerical sensitivity analyses and synthetic experiments having similar parameters and geometric characteristics as real DIR experiments. Normalized dimensionless sensitivities of tracer concentrations at the test interval have been computed numerically. Tracer concentrations are found to be sensitive to all key parameters. Sensitivities are tracer dependent and vary with time. These sensitivities are useful to identify which are the parameters that can be estimated with less uncertainty and find the times at which tracer concentrations begin to be sensitive to each parameter. Synthetic experiments generated with prescribed known parameters have been interpreted automatically with INVERSE-CORE 2D and used to evaluate the relevance of non-ideal effects and ascertain parameter identifiability in the presence of random measurement errors. Identifiability analysis of synthetic experiments reveals that data noise makes difficult the estimation of clay parameters. Parameters of clay and EdZ cannot be estimated simultaneously from noisy data. Models without an EdZ fail to reproduce synthetic data. Proper interpretation of in situ diffusion experiments requires accounting for filter, gap and EdZ. Estimates of the effective diffusion coefficient and the porosity of clay are highly correlated, indicating that these parameters cannot be estimated simultaneously. Accurate estimation of De and porosities of clay and EdZ is only possible when the standard deviation of random noise is less than 0.01. Small errors in the volume of the circulation system do not affect clay parameter estimates. Normalized sensitivities as well as the identifiability analysis of synthetic experiments provide additional insight on inverse estimation of in situ diffusion experiments and will be of great benefit for the interpretation of real DIR in situ diffusion experiments.

Pathology of carcinoma in situ of the urinary bladder and related lesions.

PubMed

Farrow, G M

1992-01-01

In the United States, nearly all cases of bladder cancer are of the transitional cell type, and epidemiological evidence indicates that among these, approximately 80% present initially as more or less well-differentiated, superficial papillary neoplasms with a tendency for multifocal or diffuse involvement of the urothelial surface and/or recurrent tumor episodes, but with limited potential for invasive growth or a lethal outcome. Bladder tumors with lethal potential generally begin as poorly differentiated, sessile growths that are usually invasive at first diagnosis. Carcinoma in situ is a change that must be elicited among intact surface cells before progressive proliferation results in a tumor mass. Evidence for such an association is both temporal and spatial. Since most transitional cell carcinomas begin as well-differentiated tumors, i.e., resembling normal urothelium, recognition of early neoplastic alteration before a papillary structure forms is unlikely and most of the evidence is spatial based upon urothelial changes adjacent to papillary tumors. The morphologic definition of carcinoma in situ is arbitrary and generally defined as a total replacement of the urothelial surface by cells which bear morphologic features of carcinoma, but which lack architectural alteration other than an increase in the number of cell layers, i.e., a flat lesion. The Union Internationále Contra Cancer/American Joint Committee on Cancer (UICC/AJCC) staging scheme for bladder cancer distinguishes non-invasive papillary growths as Ta and carcinoma in situ as Tis. Because detection of carcinoma in situ, either by cytology or biopsy, depends upon recognizable malignant morphologic characteristics, studies of the lesion tend to be limited to the higher grade or more anaplastic examples.(ABSTRACT TRUNCATED AT 250 WORDS)

Horizon Partitioning of Soil CO2 Sources and their Isotopic Composition (13C) in a Pinus Sylvestris Stand

NASA Astrophysics Data System (ADS)

Goffin, S.; Parent, F.; Plain, C.; Maier, M.; Schack-Kirchner, H.; Aubinet, M.; Longdoz, B.

2012-12-01

The overall aim of this study is to contribute to a better understanding of mechanisms behind soil CO2 efflux using carbon stable isotopes. The approach combines a soil multilayer analysis and the isotopic tool in an in situ study. The specific goal of this work is to quantify the origin and the determinism of 13CO2 and 12CO2 production processes in the different soil layers using the gradient-efflux approach. To meet this, the work includes an experimental setup and a modeling approach. The experimental set up (see also communication of Parent et al., session B008) comprised a combination of different systems, which were installed in a Scot Pine temperate forest at the Hartheim site (Southwestern Germany). Measurements include (i) half hourly vertical profiles of soil CO2 concentration (using soil CO2 probes), soil water content and temperature; (ii) half hourly soil surface CO2 effluxes (automatic chambers); (iii) half hourly isotopic composition of surface CO2 efflux and soil CO2 concentration profile and (iv) estimation of soil diffusivity through laboratory measurements conducted on soil samples taken at several depths. Using the data collected in the experimental part, we developed and used a diffusive transport model to simulate CO2 (13CO2 and 12CO2) flows inside and out of the soil based on Fick's first law. Given the horizontal homogeneity of soil physical parameters in Hartheim, we treated the soil as a structure consisting of distinctive layers of 5 cm thick and expressed the Fick's first law in a discrete formalism. The diffusion coefficient used in each layer was derived from (i) horizon specific relationships, obtained from laboratory measurements, between soil relative diffusivity and its water content and (ii) the soil water content values measured in situ. The concentration profile was obtained from in situ measurements. So, the main model inputs are the profiles of (i) CO2 (13CO2 and 12CO2) concentration, (ii) soil diffusion coefficient and (iii) soil water content. Once the diffusive fluxes deduced at each layer interface, the CO2 (13CO2 and 12CO2) production profile was calculated using the (discretized) mass balance equation in each layer. The results of the Hartheim measurement campaign will be presented. The CO2 source vertical profile and its link with the root and the Carbon organic content distribution will be showed. The dynamic of CO2 sources and their isotopic signature will be linked to climatic variables such soil temperature and soil water content. For example, we will show that the dynamics of CO2 sources was mainly related to temperature while changing of isotopic signature was more correlated to soil moisture.

Processes for producing low cost, high efficiency silicon solar cells

DOEpatents

Rohatgi, A.; Doshi, P.; Tate, J.K.; Mejia, J.; Chen, Z.

1998-06-16

Processes which utilize rapid thermal processing (RTP) are provided for inexpensively producing high efficiency silicon solar cells. The RTP processes preserve minority carrier bulk lifetime {tau} and permit selective adjustment of the depth of the diffused regions, including emitter and back surface field (bsf), within the silicon substrate. In a first RTP process, an RTP step is utilized to simultaneously diffuse phosphorus and aluminum into the front and back surfaces, respectively, of a silicon substrate. Moreover, an in situ controlled cooling procedure preserves the carrier bulk lifetime {tau} and permits selective adjustment of the depth of the diffused regions. In a second RTP process, both simultaneous diffusion of the phosphorus and aluminum as well as annealing of the front and back contacts are accomplished during the RTP step. In a third RTP process, the RTP step accomplishes simultaneous diffusion of the phosphorus and aluminum, annealing of the contacts, and annealing of a double-layer antireflection/passivation coating SiN/SiO{sub x}. In a fourth RTP process, the process of applying front and back contacts is broken up into two separate respective steps, which enhances the efficiency of the cells, at a slight time expense. In a fifth RTP process, a second RTP step is utilized to fire and adhere the screen printed or evaporated contacts to the structure. 28 figs.

Quantifying the Stable Boundary Layer Structure and Evolution during T-REX 2006

DTIC Science & Technology

2014-09-30

integrating surface observations, data from in-situ measurements, and a nested numerical model with two related topics was conducted in this project. the WRF ...as well as quantify differences at a fine scale model output using the different turbulent mixing/diffusion options in the WRF -ARW model; and (2... WRF model planetary boundary layer schemes were also conducted to study a downslope windstorm and rotors in Las Vegas valley. Two events (March 20

Mechanically Assisted Self-Healing of Ultrathin Gold Nanowires.

PubMed

Wang, Binjun; Han, Ying; Xu, Shang; Qiu, Lu; Ding, Feng; Lou, Jun; Lu, Yang

2018-04-17

As the critical feature sizes of integrated circuits approaching sub-10 nm, ultrathin gold nanowires (diameter <10 nm) have emerged as one of the most promising candidates for next-generation interconnects in nanoelectronics. Also due to their ultrasmall dimensions, however, the structures and morphologies of ultrathin gold nanowires are more prone to be damaged during practical services, for example, Rayleigh instability can significantly alter their morphologies upon Joule heating, hindering their applications as interconnects. Here, it is shown that upon mechanical perturbations, predamaged, nonuniform ultrathin gold nanowires can quickly recover into uniform diameters and restore their smooth surfaces, via a simple mechanically assisted self-healing process. By examining the local self-healing process through in situ high-resolution transmission electron microscopy, the underlying mechanism is believed to be associated with surface atomic diffusion as evidenced by molecular dynamics simulations. In addition, mechanical manipulation can assist the atoms to overcome the diffusion barriers, as suggested by ab initio calculations, to activate more surface adatoms to diffuse and consequently speed up the self-healing process. This result can provide a facile method to repair ultrathin metallic nanowires directly in functional devices, and quickly restore their microstructures and morphologies by simple global mechanical perturbations. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azimuthal ULF Structure and Radial Transport of Charged Particles

NASA Astrophysics Data System (ADS)

Ali, A.; Elkington, S. R.

2015-12-01

The Van Allen radiation belts contain highly energetic particles which interact with a variety of plasma and MHD waves. Waves with frequencies in the ULF range are understood to play an important role in loss and acceleration of energetic particles. There is still much to be understood about the interaction between charged particles and ULF waves in the inner magnetosphere and how they influence particle diffusion. We investigate how ULF wave power distribution in azimuth affects radial diffusion of charged particles. Analytic treatments of the diffusion coefficients generally assume uniform distribution of power in azimuth but in situ measurements suggest otherwise. The power profiles obtained from in situ measurements will be used to conduct particle simulations to see how well do the simulated diffusion coefficients agree with diffusion coefficients estimated directly from in situ measurements. We also look at the ULF wave power distribution across different modes. In order to use in situ point measurements from spacecraft, it is typically assumed that all of the wave power exists in m=1 mode. How valid is this assumption? Do higher modes contain a major fraction of the total power? If yes, then under what conditions? One strategy is to use the obtained realistic azimuthal power profiles from in situ measurements (such as from the Van Allen Probes) to drive simulations and see how the power distributions across modes larger than one depends on parameters such as the level of geomagnetic activity.

Obtaining the porewater composition of a clay rock by modeling the in- and out-diffusion of anions and cations from an in-situ experiment.

PubMed

Appelo, C A J; Vinsot, A; Mettler, S; Wechner, S

2008-10-23

A borehole in the Callovo-Oxfordian clay rock in ANDRA's underground research facility was sampled during 1 year and chemically analyzed. Diffusion between porewater and the borehole solution resulted in concentration changes which were modeled with PHREEQC's multicomponent diffusion module. In the model, the clay rock's pore space is divided in free porewater (electrically neutral) and diffuse double layer water (devoid of anions). Diffusion is calculated separately for the two domains, and individually for all the solute species while a zero-charge flux is maintained. We explain how the finite difference formulas for radial diffusion can be translated into mixing factors for solutions. Operator splitting is used to calculate advective flow and chemical reactions such as ion exchange and calcite dissolution and precipitation. The ion exchange reaction is formulated in the form of surface complexation, which allows distributing charge over the fixed sites and the diffuse double layer. The charge distribution affects pH when calcite dissolves, and modeling of the experimental data shows that about 7% of the cation exchange capacity resides in the diffuse double layer. The model calculates the observed concentration changes very well and provides an estimate of the pristine porewater composition in the clay rock.

Dry Reforming of Ethane and Butane with CO 2 over PtNi/CeO 2 Bimetallic Catalysts

DOE PAGES

Yan, Binhang; Yang, Xiaofang; Yao, Siyu; ...

2016-09-21

Dry reforming is a potential process to convert CO 2 and light alkanes into syngas (H 2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce 4+ to Ce 3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS),more » X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

Dry Reforming of Ethane and Butane with CO 2 over PtNi/CeO 2 Bimetallic Catalysts

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

Yan, Binhang; Yang, Xiaofang; Yao, Siyu

Dry reforming is a potential process to convert CO 2 and light alkanes into syngas (H 2 and CO), which can be subsequently transformed to chemicals and fuels. Here in this work, PtNi bimetallic catalysts have been investigated for dry reforming of ethane and butane using both model surfaces and supported powder catalysts. The PtNi bimetallic catalyst shows an improvement in both activity and stability as compared to the corresponding monometallic catalysts. The formation of PtNi alloy and the partial reduction of Ce 4+ to Ce 3+ under reaction conditions are demonstrated by in-situ Ambient Pressure X-ray Photoemission Spectroscopy (AP-XPS),more » X-ray Diffraction (XRD) and X-ray Absorption Fine Structure (XAFS) measurements. A Pt-rich bimetallic surface is revealed by Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) following CO adsorption. Combined in-situ experimental results and Density Functional Theory (DFT) calculations suggest that the Pt-rich PtNi bimetallic surface structure would weaken the binding of surface oxygenates/carbon species and reduce the activation energy for C-C bond scission, leading to an enhanced dry reforming activity.« less

Study of Ag induced bimetallic (Au-Ag) nanowires on silicon (5 5 12) surfaces: Experiment and theoretical aspects

NASA Astrophysics Data System (ADS)

Bhukta, Anjan; Bagarti, Trilochan; Guha, Puspendu; Ravulapalli, Sathyavathi; Satpati, Biswarup; Rakshit, Bipul; Maiti, Paramita; Parlapalli, Venkata Satyam

2017-10-01

The reconstructed vicinal (high index) silicon surfaces, such as, Si (5 5 12) composes row-like structures that can be used as templates for growing aligned nanowires. By using a sub-monolayers of Ag, prior to Au deposition on reconstructed Si (5 512) surface, intermixing of Au and Ag, enhancement of aspect ratio of bimetallic Au-Ag nanowires with tunable morphology is reported. This is attributed to a combined effect of pre-grown Ag strips as nucleation centers for incoming Au ad-atoms and anisotropic Au-Ag intermixing. To achieve optimum conditions for the growth of larger aspect ratio Au-Ag nanostructures, the growth kinetics have been studied by varying growth and annealing temperatures. At ≈400 °C, the Ag diffused into silicon substrate and the inter-diffusion found to inhibit the formation of Au-Ag bimetallic nanostructures. Controlled experiments under ultra-high vacuum condition in a molecular beam epitaxy system and in-situ scanning tunneling microscopy measurements along with ex-situ scanning transmission and secondary electron microscopy measurements have been carried out to understand the bimetallic nanostructure growth. Kinetic Monte Carlo (KMC) simulations based on kinematics of ad-atoms on an anisotropic template with a solid on solid model in which the relative ratios of binding energies (that are obtained from the Density Functional Theory) have been used and the KMC simulations results agree with the experimental observations. Advantage of having bimetallic structures as effective substrates for Surface enhanced Raman spectroscopy application is demonstrated by detecting Rhodamine 6 G (R6G) molecule at the concentration of 10-7M.

In situ analysis of capacity fade in thin-film anodes for high performance Li-ion all-solid-state batteries

NASA Astrophysics Data System (ADS)

Leite, Marina S.; Gong, Chen; Ruzmetov, Dmitry; Talin, A. Alec

There is still a pressing need to understand how the solid-interfaces in Li-ion all-solid-batteries form, including their chemical composition and electrical characteristics. In order to resolve the origin of the degradation mechanism in Al anodes, we combine in situ scanning electron microscopy in ultra-high vacuum with electrochemical cycling, in addition to ex situ characterization of the morphological, chemical, and electrical changes of the Al anodes upon lithiation. An AlLi alloy capped by a stable Al-Li-O is formed on the top surface of the anode, trapping Li, which results in the capacity fade, from 48.0 to 41.5 μ.Ah/cm2 in two cycles. The addition of a Cu capping layer is insufficient to prevent the device degradation because of the fast Li diffusion within Al. Yet, Si present extremely stable cycling: >92% of capacity retention after 100 cycles, with average Coulombic efficiency of 98%. Our in situ measurements represent a new platform for probing the real-time degradation of electrodes in all-solid-state batteries for energy storage devices.

Remote fluorescence imaging of dynamic concentration profiles with micrometer resolution using a coherent optical fiber bundle.

PubMed

Amatore, Christian; Chovin, Arnaud; Garrigue, Patrick; Servant, Laurent; Sojic, Neso; Szunerits, Sabine; Thouin, Laurent

2004-12-15

Dynamic concentration profiles within the diffusion layer of an electrode were imaged in situ using fluorescence detection through a multichannel imaging fiber. In this work, a coherent optical fiber bundle is positioned orthogonal to the surface of an electrode and is used to report spatial and temporal micrometric changes in the fluorescence intensity of an initial fluorescent species. The fluorescence signal is directly related to the local concentration of a redox fluorescent reagent, which is electrochemically modulated by the electrode. Fluorescence images are collected through the optical fiber bundle during the oxidation of tris(2,2'-bipyridine)ruthenium(II) to ruthenium(III) at a diffusion-limited rate and allow the concentration profiles of Ru(II) reagent to be monitored in situ as a function of time. Tris(2,2'-bipyridine)ruthenium(II) is excited at 485 nm and emits fluorescence at 605 nm, whereas the Ru(III) oxidation state is not fluorescent. Our experiments emphasize the influence of two parameters on the micrometer spatial resolution: the numerical aperture of optical fibers within the bundle and the Ru(II) bulk concentration. The extent of the volume probed by each individual fiber of the bundle is discussed qualitatively in terms of a primary inner-filter effect and refractive index gradient. Experimentally measured fluorescence intensity profiles were found to be in very good agreement with concentration profiles predicted upon considering planar diffusion and thus validate the concept of this new application of imaging fibers. The originality of this remote approach is to provide a global view of the entire diffusion layer at a given time through one single image and to allow the time expansion of the diffusion layer to be followed quantitatively in real time.

Assessment of satellite derived diffuse attenuation coefficients ...

EPA Pesticide Factsheets

Optical data collected in coastal waters off South Florida and in the Caribbean Sea between January 2009 and December 2010 were used to evaluate products derived with three bio-optical inversion algorithms applied to MOIDS/Aqua, MODIS/Terra, and SeaWiFS satellite observations. The products included the diffuse attenuation coefficient at 490 nm (Kd_490) and for the visible range (Kd_PAR), and euphotic depth (Zeu, corresponding to 1% of the surface incident photosynthetically available radiation or PAR). Above-water hyperspectral reflectance data collected over optically shallow waters of the Florida Keys between June 1997 and August 2011 were used to help understand algorithm performance over optically shallow waters. The in situ data covered a variety of water types in South Florida and the Caribbean Sea, ranging from deep clear waters, turbid coastal waters, and optically shallow waters (Kd_490 range of ~0.03 – 1.29m-1). An algorithm based on Inherent Optical Properties (IOPs) showed the best performance (RMSD < 13% and R2 ~1.0 for MODIS/Aqua and SeaWiFS). Two algorithms based on empirical regressions performed well for offshore clear waters, but underestimated Kd_490 and Kd_PAR in coastal waters due to high turbidity or shallow bottom contamination. Similar results were obtained when only in situ data were used to evaluate algorithm performance. The excellent agreement between satellite-derived remote sensing reflectance (Rrs) and in situ Rrs suggested that

Investigation of hurricane Ivan using the coupled ocean-atmosphere-wave-sediment transport (COAWST) model

USGS Publications Warehouse

Zambon, Joseph B.; He, Ruoying; Warner, John C.

2014-01-01

The coupled ocean–atmosphere–wave–sediment transport (COAWST) model is used to hindcast Hurricane Ivan (2004), an extremely intense tropical cyclone (TC) translating through the Gulf of Mexico. Sensitivity experiments with increasing complexity in ocean–atmosphere–wave coupled exchange processes are performed to assess the impacts of coupling on the predictions of the atmosphere, ocean, and wave environments during the occurrence of a TC. Modest improvement in track but significant improvement in intensity are found when using the fully atmosphere–ocean-wave coupled configuration versus uncoupled (e.g., standalone atmosphere, ocean, or wave) model simulations. Surface wave fields generated in the fully coupled configuration also demonstrates good agreement with in situ buoy measurements. Coupled and uncoupled model-simulated sea surface temperature (SST) fields are compared with both in situ and remote observations. Detailed heat budget analysis reveals that the mixed layer temperature cooling in the deep ocean (on the shelf) is caused primarily by advection (equally by advection and diffusion).

In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Wang, Fei; Wang, Hua-Lin; Qiu, Yang; Chang, Yu-Long; Long, Yi-Tao

2015-12-01

In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation.

In situ arsenic-doped polycrystalline silicon as a low thermal budget emitter contact for Si/Si1 - xGex heterojunction bipolar transistors

NASA Astrophysics Data System (ADS)

King, C. A.; Johnson, R. W.; Pinto, M. R.; Luftman, H. S.; Munanka, J.

1996-01-01

A low thermal budget emitter contact with low specific contact resistivity (ρc) with the absence of transient enhanced diffusion (TED) effects is essential to fabricate integratable high performance Si/SiGe heterojunction bipolar transistors (HBTs). We report the use of in situ As-doped polycrystalline silicon (polysilicon) from a low base pressure rapid thermal episystem for this purpose and find that it meets all the requirements. We used secondary ion mass spectrometry to find that 18 nm, heavily B-doped layers remain intact after implantation into the surface polysilicon and annealing at 800 °C for 40 s. Similar samples without the surface polylayer displayed extreme broadening of B profile. Kelvin crossbridge resistors together with 2D device simulations revealed that ρc is an extremely low value of 1.2×10-8 Ω cm2 in as-deposited material. Fabrication of simple 30×30 μm2 mesa isolated HBT devices showed IC to be more than two decades higher in devices with only an in situ As-doped polyemitter compared with devices that incorporated a surface implant into the single crystal portion of the emitter before polysilicon deposition. These results demonstrate that this doped polycrystalline silicon material is an excellent choice for emitter contacts to HBT devices.

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

NASA Technical Reports Server (NTRS)

Heinemann, K.; Rao, D. B.; Douglass, D. L.

1975-01-01

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

A versatile optical profilometer based on conoscopic holography sensors for acquisition of specular and diffusive surfaces in artworks

NASA Astrophysics Data System (ADS)

Gaburro, Nicola; Marchioro, Giacomo; Daffara, Claudia

2017-07-01

Surface metrology of artworks requires the design of suitable devices for in-situ non-destructive measurement together with reliable procedures for an effective analysis of such non-engineered variegate objects. To advance the state-of-the-art it has been implemented a versatile optical micro-profilometry taking advantage of the adapt- ability of conoscopic holography sensors, able to operate with irregular shapes and composite materials (diffusive, specular, and polychrome) of artworks. The scanning technique is used to obtain wide field and high spatially resolved areal profilometry. The prototype has a modular scheme based on a set of conoscopic sensors, extending the typical design based on a scanning stage and a single probe with a limited bandwidth, thus allowing the collection of heights data from surface with different scales and materials with variegate optical response. The system was optimized by characterizing the quality of the measurement with the probes triggered in continuous scanning modality. The results obtained on examples of cultural heritage objects (2D paintings, 3D height-relief) and materials (pictorial, metallic) demonstrate the versatility of the implemented device.

Defect Detection in Fuel Cell Gas Diffusion Electrodes Using Infrared Thermography

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

Ulsh, Michael; Porter, Jason M.; Bittinat, Daniel C.

2016-04-01

Polymer electrolyte membrane fuel cells are energy conversion devices that offer high power densities and high efficiencies for mobile and other applications. Successful introduction into the marketplace requires addressing cost barriers such as production volumes and platinum loading. For cost reduction, it is vital to minimize waste and maximize quality during the manufacturing of platinum-containing electrodes, including gas diffusion electrodes (GDEs). In this work, we report on developing a quality control diagnostic for GDEs, involving creating an ex situ exothermic reaction on the electrode surface and using infrared thermography to measure the resulting temperature profile. Experiments with a moving GDEmore » containing created defects were conducted to demonstrate the applicability of the diagnostic for real-time web-line inspection.« less

Oxidative dissolution of biogenic uraninite in groundwater at Old Rifle, CO

USGS Publications Warehouse

Campbell, Kate M.; Veeramani, Harish; Ulrich, Kai-Uwe; Blue, Lisa Y.; Giammar, Dianiel E.; Bernier-Latmani, Rizlan; Stubbs, Joanne E.; Suvorova, Elena; Yabusaki, Steve; Lezama-Pacheco, Juan S.; Mehta, Apurva; Long, Philip E.; Bargar, John R.

2011-01-01

Reductive bioremediation is currently being explored as a possible strategy for uranium-contaminated aquifers such as the Old Rifle site (Colorado). The stability of U(IV) phases under oxidizing conditions is key to the performance of this procedure. An in situ method was developed to study oxidative dissolution of biogenic uraninite (UO2), a desirable U(VI) bioreduction product, in the Old Rifle, CO, aquifer under different variable oxygen conditions. Overall uranium loss rates were 50–100 times slower than laboratory rates. After accounting for molecular diffusion through the sample holders, a reactive transport model using laboratory dissolution rates was able to predict overall uranium loss. The presence of biomass further retarded diffusion and oxidation rates. These results confirm the importance of diffusion in controlling in-aquifer U(IV) oxidation rates. Upon retrieval, uraninite was found to be free of U(VI), indicating dissolution occurred via oxidation and removal of surface atoms. Interaction of groundwater solutes such as Ca2+ or silicate with uraninite surfaces also may retard in-aquifer U loss rates. These results indicate that the prolonged stability of U(IV) species in aquifers is strongly influenced by permeability, the presence of bacterial cells and cell exudates, and groundwater geochemistry.

Parent zonation in thermochronometers - resolving complexity revealed by ID-TIMS U-Pb dates and implications for the application of decay-based thermochronometers

NASA Astrophysics Data System (ADS)

Navin Paul, Andre; Spikings, Richard; Chew, David; Daly, J. Stephen; Ulyanov, Alexey

2017-04-01

High temperature (>350℃) U-Pb thermochronometers primarily use accessory minerals such as apatite, titanite and rutile, and assume that daughter isotopes are lost by thermally activated volume diffusion while the parent remains immobile. Studies exploiting such behaviour have been successfully used to reconstruct thermal histories spanning several hundred million years (e.g. Cochrane et al., 2014). However, outliers in date (ID-TIMS) vs diffusion length space are frequently observed, and grains are frequently found to be either too young or too old for expected thermal history solutions using the diffusion data of Cherniak et al. (2010). These deviations of single grain apatite U-Pb dates from expected behaviour could be caused by a combination of i) metamorphic (over-)growth, ii) fluid-aided Pb mobilisation during alteration/recrystallization, iii) parent isotope zonation, iv) metamictisation, and v) changes in diffusion length with time (e.g. fracturing). We present a large data set from the northern Andes of South America, where we compare apatite U-Pb ID-TIMS-(TEA) data with LA-ICP-MS element maps and in-situ apatite U-Pb LA-(MC)-ICP-MS dates. These are combined with U-Pb zircon and 40Ar/39Ar (muscovite) data to attempt to distinguish between thermally activated volume diffusion and secondary overgrowth/recrystallization. We demonstrate that in young (e.g. Phanerozoic) apatites that have not recrystallized or experienced metasomatic overgrowths, U-Pb dates are dominantly controlled by volume diffusion and intra-crystal uranium zonation. This implies that ID-TIMS analyses of apatites with zoned parent isotope distributions will not usually recover accurate thermal history solutions, and an in-situ dating method is required. Recovering the uranium distribution during in-situ analysis provides a means to account for parent zonation, substantially increasing the accuracy of the modelled t-T-paths. We present in-situ data from apatites where scatter in date v diffusion length scale is observed and compare t-T-paths from single grain and in-situ modelling. Modelling of in-situ data will further show if all apatites from a single hand specimen record the same thermal history using Cherniak et al. (2010) diffusion data, or if the Pb-in-apatite diffusion parameters are a function of composition. U zonation is ubiquitous in the studied rocks (Triassic apatites extracted from peraluminous leucosomes), implying that these conclusions may also apply to lower temperature thermochronometers that are based on uranium decay, such as (U-Th)/He dating.

Importance of Trimethylaluminum Diffusion in Three-Step ABC Molecular Layer Deposition Using Trimethylaluminum, Ethanolamine, and Maleic Anhydride

DTIC Science & Technology

2010-01-01

Crystal Microbalance Analysis. A detailed description of the in situQCM experimental setup has been given elsewhere.22,23 The QCM sensors were AT-cut...quartz crystals with a polishedAu face and a 6MHz oscillation frequency. These QCM sensors were obtained from Colorado Crystal Corp (Loveland, CO...larger than typical mass gains for surface reactions. The quartz crystal microbalance ( QCM ) mass profiles during the TMA reaction were consistent with

Formation mechanism of photo-induced nested wrinkles on siloxane-photomonomer hybrid film

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

Suzuki, Kazumasa; International Laboratory of Materials Science and Nanotechnology; Laboratorio di Scienz

Nested wrinkle structures, hierarchical surface wrinkles of different periodicities of sub-μm and tens-μm, have been fabricated on a siloxane-photomonomer hybrid film via a photo-induced surface polymerization of acrylamide. The formation mechanism of the nested wrinkle structures is examined based on a time-dependent structure observation and chemical composition analyses. In-situ observation of the evolving surface structure showed that sub-μm scale wrinkles first formed, subsequently the tens-μm scale ones did. In-situ FT-IR analysis indicated that the nested wrinkles formation took place along with the development of siloxane network of under layer. A cross sectional observation of the film revealed that the filmmore » was composed of three layers. FT-IR spectra of the film revealed that the surface and interior layers were polyacrylamide rich layer and siloxane-polymer rich layer, respectively. The intermediate layer formed as a diffusion layer by migration of acrylamide from interior to the surface. These three layers have different chemical compositions and therefore different mechanical characteristics, which allows the wrinkle formation. Shrinkage of siloxane-polymer interior layers, as a result of polycondensation of siloxane network, induced mechanical instabilities at interlayers, to form the nested wrinkle structures.« less

Quantitatively in Situ Imaging Silver Nanowire Hollowing Kinetics

DOE PAGES

Yu, Le; Yan, Zhongying; Cai, Zhonghou; ...

2016-09-28

We report the in-situ investigation of the morphological evolution of silver nanowires to hollow silver oxide nanotubes using transmission x-ray microscopy (TXM). Complex silver diffusion kinetics and hollowing process via the Kirkendall effect have been captured in real time. Further quantitative x-ray absorption analysis reveals the difference between the longitudinal and radial diffusions. In conclusion, the diffusion coefficient of silver in its oxide nanoshell is, for the first time, calculated to be 1.2 × 10 -13 cm 2/s from the geometrical parameters extracted from the TXM images.

Fractal growth of platinum electrodeposits revealed by in situ electron microscopy.

PubMed

Wang, Lifen; Wen, Jianguo; Sheng, Huaping; Miller, Dean J

2016-10-06

Fractals are commonly observed in nature and elucidating the mechanisms of fractal-related growth is a compelling issue for both fundamental science and technology. Here we report an in situ electron microscopy study of dynamic fractal growth of platinum during electrodeposition in a miniaturized electrochemical cell at varying growth conditions. Highly dendritic growth - either dense branching or ramified islands - are formed at the solid-electrolyte interface. We show how the diffusion length of ions in the electrolyte influences morphology selection and how instability induced by initial surface roughness, combined with local enhancement of electric field, gives rise to non-uniform branched deposition as a result of nucleation/growth at preferred locations. Comparing the growth behavior under these different conditions provides new insight into the fundamental mechanisms of platinum nucleation.

Fabrication of Polyimide Membrane Incorporated with Functional Graphene Oxide for CO2 Separation: The Effects of GO Surface Modification on Membrane Performance.

PubMed

Wang, Ting; Cheng, Cheng; Wu, Li-Guang; Shen, Jiang-Nan; Van der Bruggen, Bart; Chen, Qian; Chen, Di; Dong, Chun-Ying

2017-06-06

Two kinds of isocyanate were used to modify graphene oxide (GO) samples. Then, polyimide (PI) hybrid membranes containing GO and modified GO were prepared by in situ polymerization. The permeation of CO 2 and N 2 was studied using these novel membranes. The morphology experiments showed that the isocyanate groups were successfully grafted on the surface of GO by replacement of the oxygen-containing functional groups. After modification, the surface polarity of the GO increased, and more defect structures were introduced into the GO surface. This resulted in a good distribution of more modified GO samples in the PI polymer matrix. Thus, the PI hybrid membranes incorporated by modified GO samples showed a high gas permeability and ideal selectivity of membranes. In addition, enhancement of the selectivity due to the solubility of CO 2 played a major role in the increase in the separation performance of the hybrid membranes for CO 2 , although the diffusion coefficients for CO 2 also increased. Both the higher condensability and the strong affinity between CO 2 molecules and GO in the polymer matrix caused an enhancement of the solubility selectivity higher than the diffusion selectivity after GO surface modification.

A new in-situ method to determine the apparent gas diffusion coefficient of soils

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Paulus, Sinikka; Schack-Kirchner, Helmer; Maier, Martin

2015-04-01

Soil aeration is an important factor for the biological activity in the soil and soil respiration. Generally, gas exchange between soil and atmosphere is assumed to be governed by diffusion and Fick's Law is used to describe the fluxes in the soil. The "apparent soil gas diffusion coefficient" represents the proportional factor between the flux and the gas concentration gradient in the soil and reflects the ability of the soil to "transport passively" gases through the soil. One common way to determine this coefficient is to take core samples in the field and determine it in the lab. Unfortunately this method is destructive and needs laborious field work and can only reflect a small fraction of the whole soil. As a consequence insecurity about the resulting effective diffusivity on the profile scale must remain. We developed a new in-situ method using new gas sampling device, tracer gas and inverse soil gas modelling. The gas sampling device contains several sampling depths and can be easily installed into vertical holes of an auger, which allows for fast installation of the system. At the lower end of the device inert tracer gas is injected continuously. The tracer gas diffuses into the surrounding soil. The resulting distribution of the tracer gas concentrations is used to deduce the diffusivity profile of the soil. For Finite Element Modeling of the gas sampling device/soil system the program COMSOL is used. We will present the results of a field campaign comparing the new in-situ method with lab measurements on soil cores. The new sampling pole has several interesting advantages: it can be used in-situ and over a long time; so it allows following modifications of diffusion coefficients in interaction with rain but also vegetation cycle and wind.

Atomic steps on an ultraflat Si(111) surface upon sublimation

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

Sitnikov, S. V., E-mail: sitnikov@isp.nsc.ru; Latyshev, A. V.; Kosolobov, S. S.

2016-05-15

The kinetics of atomic steps on an ultraflat Si(111) surface is studied by in situ ultrahigh-vacuum reflection electron microscopy at temperatures of 1050–1350°C. For the first time it is experimentally shown that the rate of displacement of an atomic step during sublimation nonlinearly depends on the width of the adjacent terrace. It is established that the atomic mechanism of mass-transport processes at the surface at temperatures higher than 1200°C is controlled by nucleation and the diffusion of surface vacancies rather than of adsorbed Si atoms. The studies make it possible to estimate the activation energy of the dissolution of vacanciesmore » from the surface into the bulk of Si. The estimated activation energy is (4.3 ± 0.05) eV.« less

Nanoscale charge transfer and diffusion at the MoS2/SiO2 interface by atomic force microscopy: contact injection versus triboelectrification.

PubMed

Xu, Rui; Ye, Shili; Xu, Kunqi; Lei, Le; Hussain, Sabir; Zheng, Zhiyue; Pang, Fei; Xing, Shuya; Liu, Xinmeng; Ji, Wei; Cheng, Zhihai

2018-08-31

Understanding the process of charge generation, transfer, and diffusion between two-dimensional (2D) materials and their supporting substrates is very important for potential applications of 2D materials. Compared with the systematic studies of triboelectric charging in a bulk sample, a fundamental understanding of the triboelectrification of the 2D material/insulator system is rather limited. Here, the charge transfer and diffusion of both the SiO 2 surface and MoS 2 /SiO 2 interface through contact electrification and frictional electrification are investigated systematically in situ by scanning Kelvin probe microscopy and dual-harmonic electrostatic force microscopy. Different from the simple static charge transfer between SiO 2 and the PtSi alloy atomic force microscope (AFM) tip, the charge transfer between the tip and the MoS 2 /SiO 2 system is complicated. Triboelectric charges, generated by contact or frictional electrification with the AFM tip, are trapped at the MoS 2 /SiO 2 interface and act as floating gates. The local charge discharge processes can be obtained by monitoring the surface potential. The charge decay time (τ) of the MoS 2 /SiO 2 interface is one (or two) orders of magnitude larger than the decay time τ of the SiO 2 surface. This work facilitates an understanding of the triboelectric and de-electrification of the interface between 2D materials and substrates. In addition to the charge transfer and diffusion, we demonstrate the nanopatterns of surface and interfacial charges, which have great potential for the application of self-assembly of charged nanostructures.

In Situ, High-Resolution Profiles of Labile Metals in Sediments of Lake Taihu

PubMed Central

Wang, Dan; Gong, Mengdan; Li, Yangyang; Xu, Lv; Wang, Yan; Jing, Rui; Ding, Shiming; Zhang, Chaosheng

2016-01-01

Characterizing labile metal distribution and biogeochemical behavior in sediments is crucial for understanding their contamination characteristics in lakes, for which in situ, high-resolution data is scare. The diffusive gradient in thin films (DGT) technique was used in-situ at five sites across Lake Taihu in the Yangtze River delta in China to characterize the distribution and mobility of eight labile metals (Fe, Mn, Zn, Ni, Cu, Pb, Co and Cd) in sediments at a 3 mm spatial resolution. The results showed a great spatial heterogeneity in the distributions of redox-sensitive labile Fe, Mn and Co in sediments, while other metals had much less marked structure, except for downward decreases of labile Pb, Ni, Zn and Cu in the surface sediment layers. Similar distributions were found between labile Mn and Co and among labile Ni, Cu and Zn, reflecting a close link between their geochemical behaviors. The relative mobility, defined as the ratio of metals accumulated by DGT to the total contents in a volume of sediments with a thickness of 10 mm close to the surface of DGT probe, was the greatest for Mn and Cd, followed by Zn, Ni, Cu and Co, while Pb and Fe had the lowest mobility; this order generally agreed with that defined by the modified BCR approach. Further analyses showed that the downward increases of pH values in surface sediment layer may decrease the lability of Pb, Ni, Zn and Cu as detected by DGT, while the remobilization of redox-insensitive metals in deep sediment layer may relate to Mn cycling through sulphide coprecipitation, reflected by several corresponding minima between these metals and Mn. These in situ data provided the possibility for a deep insight into the mechanisms involved in the remobilization of metals in freshwater sediments. PMID:27608033

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

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

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Thin film surface modifications of thin/tunable liquid/gas diffusion layers for high-efficiency proton exchange membrane electrolyzer cells

DOE PAGES

Kang, Zhenye; Mo, Jingke; Yang, Gaoqiang; ...

2017-09-14

We present that a proton exchange membrane electrolyzer cell (PEMEC) is one of the most promising devices for high-efficiency and low-cost energy storage and ultrahigh purity hydrogen production. As one of the critical components in PEMECs, the titanium thin/tunable LGDL (TT-LGDL) with its advantages of small thickness, planar surface, straight-through pores, and well-controlled pore morphologies, achieved superior multifunctional performance for hydrogen and oxygen production from water splitting even at low temperature. Different thin film surface treatments on the novel TT-LGDLs for enhancing the interfacial contacts and PEMEC performance were investigated both in-situ and ex-situ for the first time. Surface modifiedmore » TT-LGDLs with about 180 nm thick Au thin film yielded performance improvement (voltage reduction), from 1.6849 V with untreated TT-LGDLs to only 1.6328 V with treated TT-LGDLs at 2.0 A/cm 2 and 80°C. Furthermore, the hydrogen/oxygen production rate was increased by about 28.2% at 1.60 V and 80°C. The durability test demonstrated that the surface treated TT-LGDL has good stability as well. Finally, the gold electroplating surface treatment is a promising method for the PEMEC performance enhancement and titanium material protection even in harsh environment.« less

Plasma nitriding induced growth of Pt-nanowire arrays as high performance electrocatalysts for fuel cells

NASA Astrophysics Data System (ADS)

Du, Shangfeng; Lin, Kaijie; Malladi, Sairam K.; Lu, Yaxiang; Sun, Shuhui; Xu, Qiang; Steinberger-Wilckens, Robert; Dong, Hanshan

2014-09-01

In this work, we demonstrate an innovative approach, combing a novel active screen plasma (ASP) technique with green chemical synthesis, for a direct fabrication of uniform Pt nanowire arrays on large-area supports. The ASP treatment enables in-situ N-doping and surface modification to the support surface, significantly promoting the uniform growth of tiny Pt nuclei which directs the growth of ultrathin single-crystal Pt nanowire (2.5-3 nm in diameter) arrays, forming a three-dimensional (3D) nano-architecture. Pt nanowire arrays in-situ grown on the large-area gas diffusion layer (GDL) (5 cm2) can be directly used as the catalyst electrode in fuel cells. The unique design brings in an extremely thin electrocatalyst layer, facilitating the charge transfer and mass transfer properties, leading to over two times higher power density than the conventional Pt nanoparticle catalyst electrode in real fuel cell environment. Due to the similar challenges faced with other nanostructures and the high availability of ASP for other material surfaces, this work will provide valuable insights and guidance towards the development of other new nano-architectures for various practical applications.

Nanoscale Silicon as a Catalyst for Graphene Growth: Mechanistic Insight from in Situ Raman Spectroscopy

DOE PAGES

Share, Keith; Carter, Rachel E.; Nikolaev, Pavel; ...

2016-06-08

Nanoscale carbons are typically synthesized by thermal decomposition of a hydrocarbon at the surface of a metal catalyst. Whereas the use of silicon as an alternative to metal catalysts could unlock new techniques to seamlessly couple carbon nanostructures and semiconductor materials, stable carbide formation renders bulk silicon incapable of the precipitation and growth of graphitic structures. In this article, we provide evidence supported by comprehensive in situ Raman experiments that indicates nanoscale grains of silicon in porous silicon (PSi) scaffolds act as catalysts for hydrocarbon decomposition and growth of few-layered graphene at temperatures as low as 700 K. Self-limiting growthmore » kinetics of graphene with activation energies measured between 0.32–0.37 eV elucidates the formation of highly reactive surface-bound Si radicals that aid in the decomposition of hydrocarbons. Nucleation and growth of graphitic layers on PSi exhibits striking similarity to catalytic growth on nickel surfaces, involving temperature dependent surface and subsurface diffusion of carbon. Lastly, this work elucidates how the nanoscale properties of silicon can be exploited to yield catalytic properties distinguished from bulk silicon, opening an important avenue to engineer catalytic interfaces combining the two most technologically important materials for modern applications—silicon and nanoscale carbons.« less

Development of In Situ Gelling and Bio Adhesive 5-Fluorouracil Enema

PubMed Central

Wang, Lu-Lu; Zheng, Wen-Sheng; Chen, Shao-Hua; Fang, Xia-Qin

2013-01-01

In this study, a novel 5-Fluorouracil (5-FU) enema with good bio adhesion and temperature sensitivity was developed using in situ gelling technology. The preparation was formulated as a free-flowing liquid before use, while a layer of gel film was quickly formed when administered in the rectum, with a large contact surface area. It also demonstrated good biocompatibility, appropriate gel strength and bio adhesive force with excellent adhesion to rectal mucosa and prolonged action time, allowing more effective drug absorption and diffusion to surrounding tissues. Poloxamer 407 and poloxamer 188 were applied to adjust the gelling temperature. With the addition of carbopol and polycarbophil (bio adhesive substances), the solubility of 5-FU and gel strength increased, the temperature of gelation and the surface area of drug contact on mucous epithelium decreased. Decreased adhesive force between the preparation and the mucous membrane of the rectum was demonstrated with improving carbopol and polycarbophil’s concentration. In vitro release demonstrated that 5-FU in situ gelling enema with different bases had a rapid and almost complete drug release. We used an optimized formulation of P407/P188/polycarbophil/5-FU (17/2.5/0.2/1.0) for animal experiments. The result showed that the drug evenly covered the surface of the rectum and there was no leakage in 6 hours. The in situ gelling enema showed significantly higher rectal tissue levels of 5-FU compared with suppository and intravenous administration, indicating that 5-FU could be well absorbed due to the enlarged releasing area, longer retention time and larger amount of dissolved active ingredients. Systemically, 5-FU levels in the enema group were similar to those in the suppository group and significantly lower than the intravenous group. The enema was not associated with morphological damage to rectal tissue. These results suggest that the bio adhesive and in situ gelling enema could be a more effective rectal delivery system of 5-FU. PMID:23976976

Development of in situ gelling and bio adhesive 5-Fluorouracil enema.

PubMed

Wang, Lu-Lu; Zheng, Wen-Sheng; Chen, Shao-Hua; Fang, Xia-Qin

2013-01-01

In this study, a novel 5-Fluorouracil (5-FU) enema with good bio adhesion and temperature sensitivity was developed using in situ gelling technology. The preparation was formulated as a free-flowing liquid before use, while a layer of gel film was quickly formed when administered in the rectum, with a large contact surface area. It also demonstrated good biocompatibility, appropriate gel strength and bio adhesive force with excellent adhesion to rectal mucosa and prolonged action time, allowing more effective drug absorption and diffusion to surrounding tissues. Poloxamer 407 and poloxamer 188 were applied to adjust the gelling temperature. With the addition of carbopol and polycarbophil (bio adhesive substances), the solubility of 5-FU and gel strength increased, the temperature of gelation and the surface area of drug contact on mucous epithelium decreased. Decreased adhesive force between the preparation and the mucous membrane of the rectum was demonstrated with improving carbopol and polycarbophil's concentration. In vitro release demonstrated that 5-FU in situ gelling enema with different bases had a rapid and almost complete drug release. We used an optimized formulation of P407/P188/polycarbophil/5-FU (17/2.5/0.2/1.0) for animal experiments. The result showed that the drug evenly covered the surface of the rectum and there was no leakage in 6 hours. The in situ gelling enema showed significantly higher rectal tissue levels of 5-FU compared with suppository and intravenous administration, indicating that 5-FU could be well absorbed due to the enlarged releasing area, longer retention time and larger amount of dissolved active ingredients. Systemically, 5-FU levels in the enema group were similar to those in the suppository group and significantly lower than the intravenous group. The enema was not associated with morphological damage to rectal tissue. These results suggest that the bio adhesive and in situ gelling enema could be a more effective rectal delivery system of 5-FU.

Effect of drug loading method against drug dissolution mechanism of encapsulated amoxicillin trihydrate in matrix of semi-IPN chitosan-poly(N-vinylpyrrolidone) hydrogel with KHCO3 as pore forming agent in floating drug delivery system

NASA Astrophysics Data System (ADS)

Fimantari, Khansa; Budianto, Emil

2018-04-01

Helicobacterpylori infection can be treated using trihydrate amoxicillin. However, this treatment is not effective enough, as the conventional dosage treatment has a relatively short retention time in the human stomach. In the present study, the amoxicillin trihydrate drug will be encapsulated into a semi-IPN K-PNVP hydrogel matrix with 7,5% KHCO3 as a pore-forming agent. The encapsulated drug is tested with in vitro method to see the efficiency of its encapsulation and dissolution. The hydrogel in situ loading produces an encapsulation efficiency value. The values of the encapsulation efficiency are 95% and 98%, while post loading hydrogel yields an encapsulation efficiency value is 77% and the dissolution is 84%. The study of drug dissolution mechanism was done by using mathematical equation model to know its kinetics and its mechanism of dissolution. The post loading hydrogel was done by using thefirst-order model, while hydrogel in situ loading used Higuchi model. The Korsmeyer-Peppas model shows that post loading hydrogel dissolution mechanism is a mixture of diffusion and erosion, and in situ loading hydrogel in the form of diffusion. It is supported by the results of hydrogel characterization, before and after dissolution test with an optical microscope. The results of the optical microscope show that the hydrogel surface before and after the dissolution tested for both methods shows the change becomes rougher.

Surface dynamics of micellar diblock copolymer films

NASA Astrophysics Data System (ADS)

Song, Sanghoon; Cha, Wonsuk; Kim, Hyunjung; Jiang, Zhang; Narayanan, Suresh

2011-03-01

We studied the structure and surface dynamics of poly(styrene)-b-poly(dimethylsiloxane) (PS-b-PDMS) diblock copolymer films with micellar PDMS surrounded by PS shells. By `in-situ' high resolution synchrotron x-ray reflectivity and diffuse scattering, we obtained exact thickness, electron density and surface tension. A segregation layer near the top surface was appeared with increasing temperature Surface dynamics were measured as a function of film thickness and temperature by x-ray photon correlation spectroscopy. The best fit to relaxation time constants as a function of in-plane wavevectors were analyzed with a theory based on capillary waves with hydrodynamics with bilayer model Finally the viscosities for the top segregated layer as well as for the bottom layer are obtained at given temperatures This work was supported by National Research Foundation of Korea (R15-2008-006-01001-0), Seoul Research and Business Development Program (10816), and Sogang University Research Grant (2010).

Porous V2O5/RGO/CNT hierarchical architecture as a cathode material: Emphasis on the contribution of surface lithium storage

PubMed Central

Palanisamy, Kowsalya; Um, Ji Hyun; Jeong, Mihee; Yoon, Won-Sub

2016-01-01

A three dimensional vanadium pentoxide/reduced graphene oxide/carbon nanotube (3D V2O5/RGO/CNT) composite is synthesized by microwave-assisted hydrothermal method. The combination of 2D RGO and 1D CNT establishes continuous 3D conductive network, and most notably, the 1D CNT is designed to form hierarchically porous structure by penetrating into V2O5 microsphere assembly constituted of numerous V2O5 nanoparticles. The highly porous V2O5 microsphere enhances electrolyte contact and shortens Li+ diffusion path as a consequence of its developed surface area and mesoporosity. The successive phase transformations of 3D V2O5/RGO/CNT from α-phase to ε-, δ-, γ-, and ω-phase and its structural reversibility upon Li+ intercalation/de-intercalation are investigated by in situ XRD analysis, and the electronic and local structure reversibility around vanadium atom in 3D V2O5/RGO/CNT is observed by in situ XANES analysis. The 3D V2O5/RGO/CNT achieves a high capacity of 220 mAh g−1 at 1 C after 80 cycles and an excellent rate capability of 100 mAh g−1 even at a considerably high rate of 20 C. The porous 3D V2O5/RGO/CNT structure not only provides facile Li+ diffusion into bulk but contributes to surface Li+ storage as well, which enables the design of 3D V2O5/RGO/CNT composite to become a promising cathode architecture for high performance LIBs. PMID:27511434

Lithium-ions diffusion kinetic in LiFePO4/carbon nanoparticles synthesized by microwave plasma chemical vapor deposition for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Gao, Chao; Zhou, Jian; Liu, Guizhen; Wang, Lin

2018-03-01

Olivine structure LiFePO4/carbon nanoparticles are synthesized successfully using a microwave plasma chemical vapor deposition (MPCVD) method. Microwave is an effective method to synthesize nanomaterials, the LiFePO4/carbon nanoparticles with high crystallinity can shorten diffusion routes for ionic transfer and electron tunneling. Meanwhile, a high quality, complete and homogenous carbon layer with appropriate thickness coating on the surface of LiFePO4 particles during in situ chemical vapor deposition process, which can ensure that electrons are able to transfer fast enough from all sides. Electrochemical impedance spectroscopy (EIS) is carried out to collect information about the kinetic behavior of lithium diffusion in LiFePO4/carbon nanoparticles during the charging and discharging processes. The chemical diffusion coefficients of lithium ions, DLi, are calculated in the range of 10-15-10-9 cm2s-1. Nanoscale LiFePO4/carbon particles show the longer regions of the faster solid-solution diffusion, and corresponding to the narrower region of the slower two-phase diffusion during the insertion/exaction of lithium ions. The CV and galvanostatic charge-discharge measurements show that the LiFePO4/carbon nanoparticles perform an excellent electrochemical performance, especially the high rate capacity and cycle life.

Bio-Optical Properties of the Arabian Sea as Determined by In Situ and Sea WiFS Data

NASA Technical Reports Server (NTRS)

Trees, Charles C.

1997-01-01

The overall objective of this work was to characterize optical and fluorescence properties in the euphotic zone during two British Ocean Flux Study (BOFS) Arabian Sea cruises. This was later expanded in 1995 to include three U.S. JGOFS Arabian Sea Cruises. The region was to be divided into one or more "bio-optical provinces," within each of which a single set of regression models was to be developed to relate the vertical distribution of irradiance attenuation and normalized fluorescence (SF and NF) to remote sensing reflectance and diffuse attenuation coefficient. The working hypothesis was that over relatively large spatial and temporal scales, the vertical profiles of bio-optical properties were predictable. The specific technical objectives were: (1) To characterize the vertical distribution of the inherent and apparent optical properties by measuring downwelling and upwelling irradiances, upwelling radiances, scalar irradiance of PAR, and beam transmissions at each station - from these data, spectral diffuse attenuation coefficients, irradiance reflectances, remote sensing reflectances, surface-leaving radiances and beam attenuation coefficients were determined; (2) To characterize the spectral absorption of total particulate, detrital, and dissolved organic material at each station from discrete water samples; (3) To describe the vertical distribution of photoadaptive properties in the water column by measuring profiles of stimulated (SF) and natural (NF) fluorescence and examining relationships between SF and NF as a function of diffuse optical depth, pigment biomass and primary productivity; and (4) To establish locally derived, in-water algorithms relating remote sensing reflectance spectra to diffuse attenuation coefficients, phytoplankton pigment concentrations and primary productivity, through intercomparisons with in situ measurements, for application to SeaWiFS data.

Photocatalytic reduction of CO2 with H2O to CH4 on Cu(I) supported TiO2 nanosheets with defective {001} facets.

PubMed

Zhu, Shuying; Liang, Shijing; Tong, Yuecong; An, Xiaohan; Long, Jinlin; Fu, Xianzhi; Wang, Xuxu

2015-04-21

Highly dispersed Cu2O clusters loaded on TiO2 nanosheets with dominant exposed {001} facets are prepared by a hydrothermal treatment followed by photodeposition. The physicochemical properties of the as-prepared samples are characterized carefully. The deposition position and chemical state of the Cu2O clusters are characterized by X-ray diffraction, transmission electron microscopy, UV-vis diffuse reflectance spectroscopy, EPR spectroscopy, and in situ CO-adsorbed FTIR spectroscopy, respectively. The results show that in situ Cu deposition leads to in situ formation of abundant oxygen vacancies (Vo) on the surface of the TiO2 nanosheets. Interestingly, the co-existence of Vo and Cu2O clusters could promote the photoactivity of CO2 reduction efficiently. The surface Vo play a significant role in the reduction of CO2. Meanwhile, the deposited Cu(I) species serve also as active sites for the formation of CH4, and then protect CH4 from degradation by generated oxidation species. For the photoreduction of CO2 to CH4, it is found that the content level of Cu2O has a significant influence on the activity. Cu-TiO2-1.0 shows the highest photocatalytic activity, which is over 30 times higher than that of the parent TiO2. This great enhancement of photocatalytic activity may be contributed by high CO2 adsorption capacity, high electron mobility, and high concentration of Vo. However, the effect of the surface area of the samples on the activity is negligible. All of this evidence is obtained by CO2-sorption, electrochemistry, in situ FTIR spectroscopy, in situ ERP techniques, etc. The reaction intermediates are detected by in situ FTIR spectroscopy. Finally, a probable mechanism is proposed based on the experimental results. It is hoped that our work could render one of the most effective strategies to achieve advanced properties over photofunctional materials for solar energy conversion of CO2.

In situ analysis of dynamic laminar flow extraction using surface-enhanced Raman spectroscopy

PubMed Central

Wang, Fei; Wang, Hua-Lin; Qiu, Yang; Chang, Yu-Long; Long, Yi-Tao

2015-01-01

In this study, we performed micro-scale dynamic laminar flow extraction and site-specific in situ chloride concentration measurements. Surface-enhanced Raman spectroscopy was utilized to investigate the diffusion process of chloride ions from an oil phase to a water phase under laminar flow. In contrast to common logic, we used SERS intensity gradients of Rhodamine 6G to quantitatively calculate the concentration of chloride ions at specific positions on a microfluidic chip. By varying the fluid flow rates, we achieved different extraction times and therefore different chloride concentrations at specific positions along the microchannel. SERS spectra from the water phase were recorded at these different positions, and the spatial distribution of the SERS signals was used to map the degree of nanoparticle aggregation. The concentration of chloride ions in the channel could therefore be obtained. We conclude that this method can be used to explore the extraction behaviour and efficiency of some ions or molecules that enhance the SERS intensity in water or oil by inducing nanoparticle aggregation. PMID:26687436

Enhancement of surface graft density of MPEG on alginate/chitosan hydrogel microcapsules for protein repellency.

PubMed

Zheng, Jiani; Xie, Hongguo; Yu, Weiting; Tan, Mingqian; Gong, Faquan; Liu, Xiudong; Wang, Feng; Lv, Guojun; Liu, Wanfa; Zheng, Guoshuang; Yang, Yan; Xie, Weiyang; Ma, Xiaojun

2012-09-18

Alginate/chitosan/alginate (ACA) hydrogel microcapsules were modified with methoxy poly(ethylene glycol) (MPEG) to improve protein repellency and biocompatibility. Increased MPEG surface graft density (n(S)) on hydrogel microcapsules was achieved by controlling the grafting parameters including the buffer layer substrate, membrane thickness, and grafting method. X-ray photoelectron spectroscopy (XPS) model was employed to quantitatively analyze n(S) on this three-dimensional (3D) hydrogel network structure. Our results indicated that neutralizing with alginate, increasing membrane thickness, and in situ covalent grafting could increase n(S) effectively. ACAC(PEG) was more promising than ACC(PEG) in protein repellency because alginate supplied more -COO(-) negative binding sites and prevented MPEG from diffusing. The n(S) increased with membrane thickness, showing better protein repellency. Moreover, the in situ covalent grafting provided an effective way to enhance n(S), and 1.00 ± 0.03 chains/nm(2) was achieved, exhibiting almost complete immunity to protein adsorption. This antifouling hydrogel biomaterial is expected to be useful in transplantation in vivo.

Surface charge dynamics and OH and H number density distributions in near-surface nanosecond pulse discharges at a liquid / vapor interface

NASA Astrophysics Data System (ADS)

Winters, Caroline; Petrishchev, Vitaly; Yin, Zhiyao; Lempert, Walter R.; Adamovich, Igor V.

2015-10-01

The present work provides insight into surface charge dynamics and kinetics of radical species reactions in nanosecond pulse discharges sustained at a liquid-vapor interface, above a distilled water surface. The near-surface plasma is sustained using two different discharge configurations, a surface ionization wave discharge between two exposed metal electrodes and a double dielectric barrier discharge. At low discharge pulse repetition rates (~100 Hz), residual surface charge deposition after the discharge pulse is a minor effect. At high pulse repetition rates (~10 kHz), significant negative surface charge accumulation over multiple discharge pulses is detected, both during alternating polarity and negative polarity pulse trains. Laser induced fluorescence (LIF) and two-photon absorption LIF (TALIF) line imaging are used for in situ measurements of spatial distributions of absolute OH and H atom number densities in near-surface, repetitive nanosecond pulse discharge plasmas. Both in a surface ionization wave discharge and in a double dielectric barrier discharge, peak measured H atom number density, [H] is much higher compared to peak OH number density, due to more rapid OH decay in the afterglow between the discharge pulses. Higher OH number density was measured near the regions with higher plasma emission intensity. Both OH and especially H atoms diffuse out of the surface ionization wave plasma volume, up to several mm from the liquid surface. Kinetic modeling calculations using a quasi-zero-dimensional H2O vapor / Ar plasma model are in qualitative agreement with the experimental data. The results demonstrate the experimental capability of in situ radical species number density distribution measurements in liquid-vapor interface plasmas, in a simple canonical geometry that lends itself to the validation of kinetic models.

In Situ Three-Dimensional Reciprocal-Space Mapping of Diffuse Scattering Intensity Distribution and Data Analysis for Precursor Phenomenon in Shape-Memory Alloy

NASA Astrophysics Data System (ADS)

Cheng, Tian-Le; Ma, Fengde D.; Zhou, Jie E.; Jennings, Guy; Ren, Yang; Jin, Yongmei M.; Wang, Yu U.

2012-01-01

Diffuse scattering contains rich information on various structural disorders, thus providing a useful means to study the nanoscale structural deviations from the average crystal structures determined by Bragg peak analysis. Extraction of maximal information from diffuse scattering requires concerted efforts in high-quality three-dimensional (3D) data measurement, quantitative data analysis and visualization, theoretical interpretation, and computer simulations. Such an endeavor is undertaken to study the correlated dynamic atomic position fluctuations caused by thermal vibrations (phonons) in precursor state of shape-memory alloys. High-quality 3D diffuse scattering intensity data around representative Bragg peaks are collected by using in situ high-energy synchrotron x-ray diffraction and two-dimensional digital x-ray detector (image plate). Computational algorithms and codes are developed to construct the 3D reciprocal-space map of diffuse scattering intensity distribution from the measured data, which are further visualized and quantitatively analyzed to reveal in situ physical behaviors. Diffuse scattering intensity distribution is explicitly formulated in terms of atomic position fluctuations to interpret the experimental observations and identify the most relevant physical mechanisms, which help set up reduced structural models with minimal parameters to be efficiently determined by computer simulations. Such combined procedures are demonstrated by a study of phonon softening phenomenon in precursor state and premartensitic transformation of Ni-Mn-Ga shape-memory alloy.

Segregation Phenomena on the Crystal Surface of Chemical Compounds

NASA Astrophysics Data System (ADS)

Tomashpol'skii, Yu. Ya.

2018-06-01

The current state of the theoretical and experimental studies of changes in the chemical structure and composition caused by segregation phenomena on the surface of chemical compounds was reviewed. The review considers the experimental data obtained exclusively on single crystals, which were studied by modern instrumental methods, including in situ Auger electron spectrometry, X-ray spectral microanalysis, high-resolution scanning and transmission electron microscopy, secondary electron emission, and atomic force microscopy. The models that suggest the crystal-chemical diffusion and liquid-phase mechanisms of segregation were described. The parameters of the theory include the type of chemical bond, elastic constants, and crystal-chemical characteristics of substances. The models make it possible to predict the nature of changes in the surface composition: segregation tendency, segregant type, and degree of nonstoichiometry. A new direction in surface segregation was considered, which is promising for nanoelectronics and emission electronics.

Determination of pollutant diffusion coefficients in naturally formed biofilms using a single tube extractive membrane bioreactor

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

Zhang, S.F.; Splendiani, A.; Freitas dos Santos, L.M.

A novel technique has been used to determine the effective diffusion coefficients for 1,1,2-trichloroethane (TCE), a nonreacting tracer, in biofilms growing on the external surface of a silicone rubber membrane tube during degradation of 1,2-dichloroethane (DCE) by Xanthobacter autotrophicus GJ10 and monochlorobenzene (MCB) by Pseudomonas JS150. Experiments were carried out in a single tube extractive membrane bioreactor (STEMB), whose configuration makes it possible to measure the transmembrane flux of substrates. A video imaging technique (VIT) was employed for in situ biofilm thickness measurement and recording. Diffusion coefficients of TCE in the biofilms and TCE mass transfer coefficients in the liquidmore » films adjacent to the biofilms were determined simultaneously using a resistances-in-series diffusion model. It was found that the flux and overall mass transfer coefficient of TCE decrease with increasing biofilm thickness, showing the importance of biofilm diffusion on the mass transfer process. Similar fluxes were observed for the nonreacting tracer (TCE) and the reactive substrates (MCB or DCE), suggesting that membrane-attached biofilm systems can be rate controlled primarily by substrate diffusion. The TCE diffusion coefficient in the JS150 biofilm appeared to be dependent on biofilm thickness, decreasing markedly for biofilm thicknesses of >1 mm. The values of the TCE diffusion coefficients in the JS150 biofilms <1-mm thick are approximately twice those in water and fall to around 30% of the water value for biofilms >1-mm thick.« less

Impact of oxygen diffusion on superconductivity in YBa2Cu3O7 -δ thin films studied by positron annihilation spectroscopy

NASA Astrophysics Data System (ADS)

Reiner, M.; Gigl, T.; Jany, R.; Hammerl, G.; Hugenschmidt, C.

2018-04-01

The oxygen deficiency δ in YBa2Cu3O7 -δ (YBCO) plays a crucial role for affecting high-temperature superconductivity. We apply (coincident) Doppler broadening spectroscopy of the electron-positron annihilation line to study in situ the temperature dependence of the oxygen concentration and its depth profile in single crystalline YBCO film grown on SrTiO3 (STO) substrates. The oxygen diffusion during tempering is found to lead to a distinct depth dependence of δ , which is not accessible using x-ray diffraction. A steady state reached within a few minutes is defined by both, the oxygen exchange at the surface and at the interface to the STO substrate. Moreover, we reveal the depth-dependent critical temperature Tc in the as prepared and tempered YBCO film.

Investigation and Application of a New Passive Sampling Technique for in Situ Monitoring of Illicit Drugs in Waste Waters and Rivers.

PubMed

Guo, Changsheng; Zhang, Tingting; Hou, Song; Lv, Jiapei; Zhang, Yuan; Wu, Fengchang; Hua, Zhendong; Meng, Wei; Zhang, Hao; Xu, Jian

2017-08-15

Illicit drugs constitute a class of emerging contaminants that has been drawing significant concern due to its potent pharmacological and biological activities. In this study, an in situ passive sampling approach that uses diffusive gradients in thin films (DGT) was successfully tested for measuring ketamine (KET), methamphetamine (METH), and amphetamine (AMP) in water. The diffusion coefficients of KET, METH, and AMP in diffusive gel were (8.13 ± 0.12) × 10 -6 , (8.55 ± 0.14) × 10 -6 , and (7.72 ± 0.18) × 10 -6 cm 2 s -1 at 22 °C, respectively. The capacities of an XAD binding gel for KET, METH, and AMP were 92, 57, and 45 μg per binding gel disc, which were suitable for long-term environmental monitoring. The DGT measurement of these drugs was not influenced by the pH (4 to 9) and the ionic strength (0.001 M - 0.1 M) and unaffected by the water flow, demonstrating the effectiveness of the XAD-based DGT for the in situ monitoring of illicit drugs. DGT samplers were deployed in a WWTP influent and natural rivers in Beijing, China. The ng L -1 levels of the drugs were high in the wastewater influent and low in river waters, with an insignificant fluctuation during the seven-day monitoring. The DGT-measured concentrations were comparable to the average concentrations determined by SPE method, which suggested that the average data measured by DGT could be substituted for high-frequency grab sampling. This study has demonstrated systematically for the first time that DGT is effective and accurate for monitoring illicit drugs in wastewater and surface waters, and provides a powerful tool to investigating the presence, transport, and environmental behaviors of these drugs in the aquatic ecosystem.

In situ study of mass transfer in aqueous solutions under high pressures via Raman spectroscopy: A new method for the determination of diffusion coefficients of methane in water near hydrate formation conditions

USGS Publications Warehouse

Lu, W.J.; Chou, I.-Ming; Burruss, R.C.; Yang, M.Z.

2006-01-01

A new method was developed for in situ study of the diffusive transfer of methane in aqueous solution under high pressures near hydrate formation conditions within an optical capillary cell. Time-dependent Raman spectra of the solution at several different spots along the one-dimensional diffusion path were collected and thus the varying composition profile of the solution was monitored. Diffusion coefficients were estimated by the least squares method based on the variations in methane concentration data in space and time in the cell. The measured diffusion coefficients of methane in water at the liquid (L)-vapor (V) stable region and L-V metastable region are close to previously reported values determined at lower pressure and similar temperature. This in situ monitoring method was demonstrated to be suitable for the study of mass transfer in aqueous solution under high pressure and at various temperature conditions and will be applied to the study of nucleation and dissolution kinetics of methane hydrate in a hydrate-water system where the interaction of methane and water would be more complicated than that presented here for the L-V metastable condition. ?? 2006 Society for Applied Spectroscopy.

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

Wolfram, Phillip J.; Ringler, Todd D.; Maltrud, Mathew E.

Isopycnal diffusivity due to stirring by mesoscale eddies in an idealized, wind-forced, eddying, midlatitude ocean basin is computed using Lagrangian, in Situ, Global, High-Performance Particle Tracking (LIGHT). Simulation is performed via LIGHT within the Model for Prediction across Scales Ocean (MPAS-O). Simulations are performed at 4-, 8-, 16-, and 32-km resolution, where the first Rossby radius of deformation (RRD) is approximately 30 km. Scalar and tensor diffusivities are estimated at each resolution based on 30 ensemble members using particle cluster statistics. Each ensemble member is composed of 303 665 particles distributed across five potential density surfaces. Diffusivity dependence upon modelmore » resolution, velocity spatial scale, and buoyancy surface is quantified and compared with mixing length theory. The spatial structure of diffusivity ranges over approximately two orders of magnitude with values of O(10 5) m 2 s –1 in the region of western boundary current separation to O(10 3) m 2 s –1 in the eastern region of the basin. Dominant mixing occurs at scales twice the size of the first RRD. Model resolution at scales finer than the RRD is necessary to obtain sufficient model fidelity at scales between one and four RRD to accurately represent mixing. Mixing length scaling with eddy kinetic energy and the Lagrangian time scale yield mixing efficiencies that typically range between 0.4 and 0.8. In conclusion, a reduced mixing length in the eastern region of the domain relative to the west suggests there are different mixing regimes outside the baroclinic jet region.« less

Unusual plastic deformation and damage features in titanium: Experimental tests and constitutive modeling

NASA Astrophysics Data System (ADS)

Revil-Baudard, Benoit; Cazacu, Oana; Flater, Philip; Chandola, Nitin; Alves, J. L.

2016-03-01

In this paper, we present an experimental study on plastic deformation and damage of polycrystalline pure HCP Ti, as well as modeling of the observed behavior. Mechanical characterization data were conducted, which indicate that the material is orthotropic and displays tension-compression asymmetry. The ex-situ and in-situ X-ray tomography measurements conducted reveal that damage distribution and evolution in this HCP Ti material is markedly different than in a typical FCC material such as copper. Stewart and Cazacu (2011) anisotropic elastic/plastic damage model is used to describe the behavior. All the parameters involved in this model have a clear physical significance, being related to plastic properties, and are determined from very few simple mechanical tests. It is shown that this model predicts correctly the anisotropy in plastic deformation, and its strong influence on damage distribution and damage accumulation. Specifically, for a smooth axisymmetric specimen subject to uniaxial tension, damage initiates at the center of the specimen, and is diffuse; the level of damage close to failure being very low. On the other hand, for a notched specimen subject to the same loading the model predicts that damage initiates at the outer surface of the specimen, and further grows from the outer surface to the center of the specimen, which corroborates with the in-situ tomography data.

Probing and mapping electrode surfaces in solid oxide fuel cells.

PubMed

Blinn, Kevin S; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A; Liu, Meilin

2012-09-20

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen (1-7). The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion(2). Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation(8-12). It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition(8, 10, 13, 14) ("coking") and sulfur poisoning(11, 15) and the manner in which surface modifications stave off this degradation(16). The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated(17-22). In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode.

Probing and Mapping Electrode Surfaces in Solid Oxide Fuel Cells

PubMed Central

Blinn, Kevin S.; Li, Xiaxi; Liu, Mingfei; Bottomley, Lawrence A.; Liu, Meilin

2012-01-01

Solid oxide fuel cells (SOFCs) are potentially the most efficient and cost-effective solution to utilization of a wide variety of fuels beyond hydrogen 1-7. The performance of SOFCs and the rates of many chemical and energy transformation processes in energy storage and conversion devices in general are limited primarily by charge and mass transfer along electrode surfaces and across interfaces. Unfortunately, the mechanistic understanding of these processes is still lacking, due largely to the difficulty of characterizing these processes under in situ conditions. This knowledge gap is a chief obstacle to SOFC commercialization. The development of tools for probing and mapping surface chemistries relevant to electrode reactions is vital to unraveling the mechanisms of surface processes and to achieving rational design of new electrode materials for more efficient energy storage and conversion2. Among the relatively few in situ surface analysis methods, Raman spectroscopy can be performed even with high temperatures and harsh atmospheres, making it ideal for characterizing chemical processes relevant to SOFC anode performance and degradation8-12. It can also be used alongside electrochemical measurements, potentially allowing direct correlation of electrochemistry to surface chemistry in an operating cell. Proper in situ Raman mapping measurements would be useful for pin-pointing important anode reaction mechanisms because of its sensitivity to the relevant species, including anode performance degradation through carbon deposition8, 10, 13, 14 ("coking") and sulfur poisoning11, 15 and the manner in which surface modifications stave off this degradation16. The current work demonstrates significant progress towards this capability. In addition, the family of scanning probe microscopy (SPM) techniques provides a special approach to interrogate the electrode surface with nanoscale resolution. Besides the surface topography that is routinely collected by AFM and STM, other properties such as local electronic states, ion diffusion coefficient and surface potential can also be investigated17-22. In this work, electrochemical measurements, Raman spectroscopy, and SPM were used in conjunction with a novel test electrode platform that consists of a Ni mesh electrode embedded in an yttria-stabilized zirconia (YSZ) electrolyte. Cell performance testing and impedance spectroscopy under fuel containing H2S was characterized, and Raman mapping was used to further elucidate the nature of sulfur poisoning. In situ Raman monitoring was used to investigate coking behavior. Finally, atomic force microscopy (AFM) and electrostatic force microscopy (EFM) were used to further visualize carbon deposition on the nanoscale. From this research, we desire to produce a more complete picture of the SOFC anode. PMID:23023264

Effect of in situ annealing on the structural and electrical properties and infrared photodetection of III-Sb on GaAs using interfacial misfit array

NASA Astrophysics Data System (ADS)

Jia, Bo Wen; Tan, Kian Hua; Loke, Wan Khai; Wicaksono, Satrio; Yoon, Soon Fatt

2018-01-01

This work presents the effects of in situ thermal annealing under antimony overpressure on the structural, electrical, and optical properties of III-Sb (GaSb and InSb) grown on (100) GaAs using an interfacial misfit array to accommodate the lattice mismatch. Both the sample growth and the in situ thermal annealing were carried out in the in the molecular beam epitaxy system, and the temperature of the as-grown sample was increased to exceed its growth temperature during the annealing. X-ray diffraction demonstrates nearly fully relaxed as-grown and annealed III-Sb layers. The optimal annealing temperatures and durations are for 590 °C, 5 min for GaSb and 420 °C, 15 min for InSb, respectively. In situ annealing decreased the surface roughness of the III-Sb layers. X-ray reciprocal space mapping and transmission electron microscopy observation showed stable interfacial misfit arrays, and no interfacial diffusion occurred in the annealed III-Sb layers. A Hall measurement of unintentionally doped III-Sb layers showed greater carrier mobility and a lower carrier concentration in the annealed samples at both 77 and 300 K. In situ annealing improved the photoresponsivity of GaSb and InSb photoconductors grown on GaAs in the near- and mid-infrared ranges, respectively.

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

DOE PAGES

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

2015-03-02

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

In situ microscopy of rapidly heated nano-Al and nano-Al/WO{sub 3} thermites

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

Sullivan, Kyle T.; Zachariah, Michael R.; Chiou, Wen-An

2010-09-27

The initiation and reaction mechanism of nano-Al and nano-Al thermites in rapid heating environments is investigated in this work. A semiconductor-based grid/stage was used, capable of in situ heating of a sample from room temperature to 1473 K, and at a rate of 10{sup 6} K/s, inside an electron microscope. Nano-Al was rapidly heated in a transmission electron microscope, and before and after images indicate that the aluminum migrates through the shell, consistent with a diffusion-based mechanism. A nano-Al/WO{sub 3} composite was then heated in a scanning electron microscope. The results indicate that a reactive sintering mechanism is occurring formore » the nano-Al/WO{sub 3} thermite, as the products are found to be in surface contact and significantly deformed after the heating pulse.« less

Novel instruments for in situ continuous Rn-222 measurement in groundwater and the application to river bank infiltration.

PubMed

Gilfedder, B S; Hofmann, H; Cartwright, I

2013-01-15

There is little known about the short-term dynamics of groundwater-surface water exchange in losing rivers. This is partly due to the paucity of chemical techniques that can autonomously collect high-frequency data in groundwater bores. Here we present two new instruments for continuous in situ (222)Rn measurement in bores for quantifying the surface water infiltration rate into an underlying or adjacent aquifer. These instruments are based on (222)Rn diffusion through silicone tube membranes, either wrapped around a pole (MonoRad) or strung between two hollow end pieces (OctoRad). They are combined with novel, robust, low-cost Geiger counter (222)Rn detectors which are ideal for long-term autonomous measurement. The down-hole instruments have a quantitative response time of about a day during low flow, but this decreases to <12 h during high-flow events. The setup was able to trace river water bank infiltration during moderate to high river flow during two field experiments. Mass-balance calculations using the (222)Rn data gave a maximum infiltration rate of 2 m d(-1). These instruments offer the first easily constructible system for continuous (222)Rn analysis in groundwater, and could be used to trace surface water infiltration in many environments including rivers, lakes, wetlands, and coastal settings.

Grain boundary imaging, gallium diffusion and the fracture behavior of Al-Zn Alloy - An in situ study

NASA Astrophysics Data System (ADS)

Tsai, W. L.; Hwu, Y.; Chen, C. H.; Chang, L. W.; Je, J. H.; Lin, H. M.; Margaritondo, G.

2003-01-01

Phase contrast radiology using unmonochromatic synchrotron X-ray successfully imaged the grain boundaries of Al and AlZn alloy without contrast agent. Combining the high penetration of X-ray and the possibility of 3D reconstruction by tomorgraphy or stereography method, this approach can be very used for nondestructive characterization of polycrystalline materials. By examine the images with 3D perspective, we were able locate the observed void-like defects which lies exclusively on the grain boundary and identify their origin from last stage of the rolling process. We studied the Ga Liquid metal diffusion in the AlZn alloy, under different temperature and stress conditions. High resolution images, ˜2 μm, of Ga liquid metal diffusion in AlZn were obtained in real time and diffusion paths alone grain boundaries and surfaces were clearly identified. Embrittled AlZn responses to the tensile stress and fractures in a drastic different manner than the pure AlZn. These results, although very much expected from the known weakening effect of the liquid metal embrittlement demonstrated, however, that this particular radiology method is fully capable of dynamic study in the micrometer scale.

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

NASA Astrophysics Data System (ADS)

Schampera, Birgit; Dultz, Stefan

2013-04-01

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

Thermal annealing dynamics of carbon-coated LiFePO4 nanoparticles studied by in-situ analysis

NASA Astrophysics Data System (ADS)

Krumeich, Frank; Waser, Oliver; Pratsinis, Sotiris E.

2016-10-01

The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO4-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO4-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO4 starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further to T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO4 particles (diameter in the range 300-400 nm), in agreement with ex-situ experiments.

Sediment entrainment by debris flows: In situ measurements from the headwaters of a steep catchment

USGS Publications Warehouse

McCoy, S.W.; Kean, Jason W.; Coe, Jeffrey A.; Tucker, G.E.; Staley, Dennis M.; Wasklewicz, T.A.

2012-01-01

Debris flows can dramatically increase their volume, and hence their destructive potential, by entraining sediment. Yet quantitative constraints on rates and mechanics of sediment entrainment by debris flows are limited. Using an in situ sensor network in the headwaters of a natural catchment we measured flow and bed properties during six erosive debris-flow events. Despite similar flow properties and thicknesses of bed sediment entrained across all events, time-averaged entrainment rates were significantly faster for bed sediment that was saturated prior to flow arrival compared with rates for sediment that was dry. Bed sediment was entrained from the sediment-surface downward in a progressive fashion and occurred during passage of dense granular fronts as well as water-rich, inter-surge flow.En massefailure of bed sediment along the sediment-bedrock interface was never observed. Large-magnitude, high-frequency fluctuations in total normal basal stress were dissipated within the upper 5 cm of bed sediment. Within this near surface layer, concomitant fluctuations in Coulomb frictional resistance are expected, irrespective of the influence of pore fluid pressure or fluctuations in shear stress. If the near-surface sediment was wet as it was overridden by a flow, additional large-magnitude, high-frequency pore pressure fluctuations were measured in the near-surface bed sediment. These pore pressure fluctuations propagated to depth at subsonic rates and in a diffusive manner. The depth to which large excess pore pressures propagated was typically less than 10 cm, but scaled as (D/fi)0.5, in which D is the hydraulic diffusivity and fi is the frequency of a particular pore pressure fluctuation. Shallow penetration depths of granular-normal-stress fluctuations and excess pore pressures demonstrate that only near-surface bed sediment experiences the full dynamic range of effective-stress fluctuations, and as a result, can be more easily entrained than deeper sediment. These data provide robust tests for mechanical models of entrainment and demonstrate that a debris flow over wet bed sediment will be larger than the same flow over dry bed sediment.

Synergistic reaction between SO2 and NO2 on mineral oxides: a potential formation pathway of sulfate aerosol.

PubMed

Liu, Chang; Ma, Qingxin; Liu, Yongchun; Ma, Jinzhu; He, Hong

2012-02-07

Sulfate is one of the most important aerosols in the atmosphere. A new sulfate formation pathway via synergistic reactions between SO(2) and NO(2) on mineral oxides was proposed. The heterogeneous reactions of SO(2) and NO(2) on CaO, α-Fe(2)O(3), ZnO, MgO, α-Al(2)O(3), TiO(2), and SiO(2) were investigated by in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (in situ DRIFTS) at ambient temperature. Formation of sulfate from adsorbed SO(2) was promoted by the coexisting NO(2), while surface N(2)O(4) was observed as the crucial oxidant for the oxidation of surface sulfite. This process was significantly promoted by the presence of O(2). The synergistic effect between SO(2) and NO(2) was not observed on other mineral particles (such as CaCO(3) and CaSO(4)) probably due to the lack of the surface reactive oxygen sites. The synergistic reaction between SO(2) and NO(2) on mineral oxides resulted in the formation of internal mixtures of sulfate, nitrate, and mineral oxides. The change of mixture state will affect the physicochemical properties of atmospheric particles and therefore further influence their environmental and climate effects.

Biofilm three-dimensional architecture influences in situ pH distribution pattern on the human enamel surface

PubMed Central

Xiao, Jin; Hara, Anderson T; Kim, Dongyeop; Zero, Domenick T; Koo, Hyun; Hwang, Geelsu

2017-01-01

To investigate how the biofilm three-dimensional (3D) architecture influences in situ pH distribution patterns on the enamel surface. Biofilms were formed on human tooth enamel in the presence of 1% sucrose or 0.5% glucose plus 0.5% fructose. At specific time points, biofilms were exposed to a neutral pH buffer to mimic the buffering of saliva and subsequently pulsed with 1% glucose to induce re-acidification. Simultaneous 3D pH mapping and architecture of intact biofilms was performed using two-photon confocal microscopy. The enamel surface and mineral content characteristics were examined successively via optical profilometry and microradiography analyses. Sucrose-mediated biofilm formation created spatial heterogeneities manifested by complex networks of bacterial clusters (microcolonies). Acidic regions (pH<5.5) were found only in the interior of microcolonies, which impedes rapid neutralization (taking more than 120 min for neutralization). Glucose exposure rapidly re-created the acidic niches, indicating formation of diffusion barriers associated with microcolonies structure. Enamel demineralization (white spots), rougher surface, deeper lesion and more mineral loss appeared to be associated with the localization of these bacterial clusters at the biofilm-enamel interface. Similar 3D architecture was observed in plaque-biofilms formed in vivo in the presence of sucrose. The formation of complex 3D architectures creates spatially heterogeneous acidic microenvironments in close proximity of enamel surface, which might correlate with the localized pattern of the onset of carious lesions (white spot like) on teeth. PMID:28452377

Improved solar-driven photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} prepared in-situ

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

Zhong, Junbo, E-mail: junbozhong@163.com; Li, Jianzhang, E-mail: lschmanuscript@163.com; Huang, Shengtian

Highlights: • Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} photocatalysts were prepared in-situ. • The photo-induced charge separation rate has been greatly increased. • The photocatalytic activity has been greatly promoted. - Abstract: Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} composites have been fabricated in-situ via a facile parallel flaw co-precipitation method. The specific surface area, structure, morphology, and the separation rate of photo-induced charge pairs of the photocatalysts were characterized by Brunauer–Emmett–Teller (BET) method, X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy(DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), and surface photovoltage (SPV) spectroscopy, respectively. XRD patterns and DRS demonstrated that Ag{submore » 2}CO{sub 3} has no effect on the crystal phase and bandgap of (BiO){sub 2}CO{sub 3}. The existence of Ag{sub 2}CO{sub 3} in the composites enhances the separation rate of photo-induced charge pairs of the photocatalysts. The photocatalytic performance of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} was evaluated by the decolorization of methyl orange (MO) aqueous solution under simulated solar irradiation. It was found that the simulated solar-induced photocatalytic activity of Ag{sub 2}CO{sub 3}/(BiO){sub 2}CO{sub 3} copmposites was significantly improved, which was mainly attributed to the enhanced surface area and the separation rate of photo-induced charge pairs.« less

Imaging and histologic prognostic factors in triple-negative breast cancer and carcinoma in situ as a prognostic factor.

PubMed

Sebastián Sebastián, C; García Mur, C; Cruz Ciria, S; Rosero Cuesta, D S; Gros Bañeres, B

2016-01-01

To analyze what factors in magnetic resonance imaging (MRI) and histological study of triple-negative breast cancers are related to tumor recurrence and to shorter disease-free survival. To analyze survival and recurrence in function of the presence of an in situ component. This was a retrospective study of MRI staging examinations in 122 women with triple-negative breast cancer done from 2007 through 2014. In the MRI, we evaluated morphological variables (size, margins, morphology, internal signal in T2-weighted sequences) and dynamic variables (perfusion and diffusion). In the histological study, we evaluated Ki67, p53, CK5/6, nuclear grade, and Scarff-Bloom grade, as well as the presence of an in situ component and tumor grade (high grade or not high grade). We compared the variables between patients with tumor recurrence and those without, and we conducted a survival analysis. Non-nodular enhancement was more common in patients with tumor recurrence (p=0.038) and was associated with shorter disease-free survival (p=0.023). Neither diffusion restriction (p=0.079) nor ki67 (p=0.052) was associated with a worse prognosis. An in situ component was detected in 44% of triple-negative tumors, and a greater proportion of patients in the group with tumor recurrence had an in situ component; however, the presence of an in situ component was not associated with shorter survival (p = 0.185). Non-nodular enhancement was associated with a worse prognosis. Diffusion restriction, ki67, and the presence of an in situ component were not associated with shorter disease-free survival. Copyright © 2016 SERAM. Publicado por Elsevier España, S.L.U. All rights reserved.

Removal of PCB and Other Halogenated Organic Contaminants found in Ex Situ Structures

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline (Inventor); Clausen, Christian (Inventor); Geiger, Cherie L. (Inventor); Coon, Christina (Inventor); Berger, Cristina M. (Inventor); Filipek, Laura B. (Inventor); Milum, Kristen M. (Inventor)

2007-01-01

Emulsified systems or a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

Removal of PCB and other halogenated organic contaminants found in ex situ structures

NASA Technical Reports Server (NTRS)

Quinn, Jacqueline (Inventor); Clausen, Christian (Inventor); Geiger, Cherie L. (Inventor); Coon, Christina (Inventor); Berger, Cristina M. (Inventor); Filipek, Laura B. (Inventor); Milum, Kristen M. (Inventor)

2007-01-01

Emulsified systems of a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

Removal of PCB and other halogenated organic contaminants found in ex situ structures

NASA Technical Reports Server (NTRS)

Clausen, Christian A. (Inventor); Milum, Kristen M. (Inventor); Quinn, Jacqueline W. (Inventor); Berger, Cristina M. (Inventor); Geiger, Cherie L. (Inventor); Filipek, Laura B. (Inventor); Coon, Christina (Inventor)

2009-01-01

Emulsified systems of a surfactant-stabilized, biodegradable water-in-solvent emulsion with bimetallic particles contained with the emulsion droplets are useful at removing PCBs from ex situ structures. The hydrophobic emulsion system draws PCBs through the solvent/surfactant membrane. Once inside the membrane, the PCBs diffuse into the bimetallic particles and undergo degradation. The PCBs continue to enter, diffuse, degrade, and biphenyl will exit the particle maintaining a concentration gradient across the membrane and maintaining a driving force of the reaction.

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

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

Mombrú, Dominique; Romero, Mariano, E-mail: mromero@fq.edu.uy; Faccio, Ricardo, E-mail: rfaccio@fq.edu.uy

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. Inmore » addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of ~3–8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications. - Highlights: • In situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion. • Polyaniline charge carriers at the interface and charge interactions between quantum dots. • Easy extrapolation to sol-gel derived quantum dots into polymer host as potential electrode materials.« less

Single-Nanowire Electrochemical Probe Detection for Internally Optimized Mechanism of Porous Graphene in Electrochemical Devices.

PubMed

Hu, Ping; Yan, Mengyu; Wang, Xuanpeng; Han, Chunhua; He, Liang; Wei, Xiujuan; Niu, Chaojiang; Zhao, Kangning; Tian, Xiaocong; Wei, Qiulong; Li, Zijia; Mai, Liqiang

2016-03-09

Graphene has been widely used to enhance the performance of energy storage devices due to its high conductivity, large surface area, and excellent mechanical flexibility. However, it is still unclear how graphene influences the electrochemical performance and reaction mechanisms of electrode materials. The single-nanowire electrochemical probe is an effective tool to explore the intrinsic mechanisms of the electrochemical reactions in situ. Here, pure MnO2 nanowires, reduced graphene oxide/MnO2 wire-in-scroll nanowires, and porous graphene oxide/MnO2 wire-in-scroll nanowires are employed to investigate the capacitance, ion diffusion coefficient, and charge storage mechanisms in single-nanowire electrochemical devices. The porous graphene oxide/MnO2 wire-in-scroll nanowire delivers an areal capacitance of 104 nF/μm(2), which is 4.0 and 2.8 times as high as those of reduced graphene oxide/MnO2 wire-in-scroll nanowire and MnO2 nanowire, respectively, at a scan rate of 20 mV/s. It is demonstrated that the reduced graphene oxide wrapping around the MnO2 nanowire greatly increases the electronic conductivity of the active materials, but decreases the ion diffusion coefficient because of the shielding effect of graphene. By creating pores in the graphene, the ion diffusion coefficient is recovered without degradation of the electron transport rate, which significantly improves the capacitance. Such single-nanowire electrochemical probes, which can detect electrochemical processes and behavior in situ, can also be fabricated with other active materials for energy storage and other applications in related fields.

Direct in situ observations of single Fe atom catalytic processes and anomalous diffusion at graphene edges

PubMed Central

Zhao, Jiong; Deng, Qingming; Avdoshenko, Stanislav M.; Fu, Lei; Eckert, Jürgen; Rümmeli, Mark H.

2014-01-01

Single-atom catalysts are of great interest because of their high efficiency. In the case of chemically deposited sp2 carbon, the implementation of a single transition metal atom for growth can provide crucial insight into the formation mechanisms of graphene and carbon nanotubes. This knowledge is particularly important if we are to overcome fabrication difficulties in these materials and fully take advantage of their distinct band structures and physical properties. In this work, we present atomically resolved transmission EM in situ investigations of single Fe atoms at graphene edges. Our in situ observations show individual iron atoms diffusing along an edge either removing or adding carbon atoms (viz., catalytic action). The experimental observations of the catalytic behavior of a single Fe atom are in excellent agreement with supporting theoretical studies. In addition, the kinetics of Fe atoms at graphene edges are shown to exhibit anomalous diffusion, which again, is in agreement with our theoretical investigations. PMID:25331874

Optical properties of Zn-diffused InP layers for the planar-type InGaAs/InP photodetectors

NASA Astrophysics Data System (ADS)

Chen, Guifeng; Wang, Mengxue; Yang, Wenxian; Tan, Ming; Wu, Yuanyuan; Dai, Pan; Huang, Yuyang; Lu, Shulong

2017-12-01

Zn diffusion into InP was carried out ex-situ using a new Zn diffusion technique with zinc phosphorus particles placed around InP materials as zinc source in a semi-closed chamber formed by a modified diffusion furnace. The optical characteristics of the Zn-diffused InP layer for the planar-type InGaAs/InP PIN photodetectors grown by molecular beam epitaxy (MBE) has been investigated by photoluminescence (PL) measurements. The temperature-dependent PL spectrum of Zn-diffused InP samples at different diffusion temperatures showed that band-to-acceptor transition dominates the PL emission, which indicates that Zn was commendably diffused into InP layer as the acceptor. High quality Zn-diffused InP layer with typically smooth surface was obtained at 580 °C for 10 min. Furthermore, more interstitial Zn atoms were activated to act as acceptors after a rapid annealing process. Based on the above Zn-diffusion technique, a 50 μm planar-type InGaAs/InP PIN photodector device was fabricated and exhibited a low dark current of 7.73 pA under a reverse bias potential of -5 V and a high breakdown voltage of larger than 41 V (I < 10 μA). In addition, a high responsivity of 0.81 A/W at 1.31 μm and 0.97 A/W at 1.55 μm was obtained in the developed PIN photodetector. Project supported by the Key R&D Program of Jiangsu Province (No. BE2016085) , the National Natural Science Foundation of China (Nos. 61674051), and the External Cooperation Program of BIC, Chinese Academy of Sciences (No. 121E32KYSB20160071).

Structures of Cu surfaces developing in benzotriazole solutions: Effect of pH

NASA Astrophysics Data System (ADS)

Kondoh, Eiichi; Kawakami, Tatsuya; Watanabe, Mitsuhiro; Jin, Linhua; Hamada, Satomi; Shima, Shohei; Hiyama, Hirokuni

2017-07-01

The effect of pH on layer formation onto clean Cu surfaces in benzotriazole (BTA) aqueous solutions was studied by in situ spectroscopic ellipsometry. The effect of H2O2 addition was also investigated. Time changes in the ellipsometric parameters Ψ and Δ, which correspond to the structural changes of the layers on Cu, were discussed. In acidic solutions, a BTA or a Cu-BTA complex layer grows directly on Cu. The out-diffusion of Cu is suppressed at the Cu layer interface. When H2O2 was mixed, the Cu surface is eroded in acidic solutions. In alkaline solutions, the BTA layer grows on the oxidized Cu layer, or no growth occurs, depending on the composition of the solutions. In neutral solutions, the Cu-BTA complex layer forms on Cu, and the uncovered part is oxidized in the presence of H2O2.

Permanganate diffusion and reaction in sedimentary rocks.

PubMed

Huang, Qiuyuan; Dong, Hailiang; Towne, Rachael M; Fischer, Timothy B; Schaefer, Charles E

2014-04-01

In situ chemical oxidation using permanganate has frequently been used to treat chlorinated solvents in fractured bedrock aquifers. However, in systems where matrix back-diffusion is an important process, the ability of the oxidant to migrate and treat target contaminants within the rock matrix will likely determine the overall effectiveness of this remedial approach. In this study, a series of diffusion experiments were performed to measure the permanganate diffusion and reaction in four different types of sedimentary rocks (dark gray mudstone, light gray mudstone, red sandstone, and tan sandstone). Results showed that, within the experimental time frame (~2 months), oxidant migration into the rock was limited to distances less than 500 μm. The observed diffusivities for permanganate into the rock matrices ranged from 5.3 × 10(-13) to 1.3 × 10(-11) cm(2)/s. These values were reasonably predicted by accounting for both the rock oxidant demand and the effective diffusivity of the rock. Various Mn minerals formed as surface coatings from reduction of permanganate coupled with oxidation of total organic carbon (TOC), and the nature of the formed Mn minerals was dependent upon the rock type. Post-treatment tracer testing showed that these Mn mineral coatings had a negligible impact on diffusion through the rock. Overall, our results showed that the extent of permanganate diffusion and reaction depended on rock properties, including porosity, mineralogy, and organic carbon. These results have important implications for our understanding of long-term organic contaminant remediation in sedimentary rocks using permanganate. Copyright © 2014 Elsevier B.V. All rights reserved.

In Situ Scanning Tunneling Microscopy Topography Changes of Gold (111) in Aqueous Sulfuric Acid Produced by Electrochemical Surface Oxidation and Reduction and Relaxation Phenomena

NASA Astrophysics Data System (ADS)

Pasquale, M. A.; Nieto, F. J. Rodríguez; Arvia, A. J.

The electrochemical formation and reduction of O-layers on gold (111) films in 1 m sulfuric acid under different potentiodynamic routines are investigated utilizing in situ scanning tunneling microscopy. The surface dynamics is interpreted considering the anodic and cathodic reaction pathways recently proposed complemented with concurrent relaxation phenomena occurring after gold (111) lattice mild disruption (one gold atom deep) and moderate disruption (several atoms deep). The dynamics of both oxidized and reduced gold topographies depends on the potentiodynamic routine utilized to form OH/O surface species. The topography resulting from a mild oxidative disruption is dominated by quasi-2D holes and hillocks of the order of 5 nm, involving about 500-600 gold atoms each, and their coalescence. A cooperative turnover process at the O-layer, in which the anion ad-layer and interfacial water play a key role, determines the oxidized surface topography. The reduction of these O-layers results in gold clusters, their features depending on the applied potential routine. A moderate oxidative disruption produces a surface topography of hillocks and holes several gold atoms high and deep, respectively. The subsequent reduction leads to a spinodal gold pattern. Concurrent coalescence appears to be the result of an Ostwald ripening that involves the surface diffusion of both gold atoms and clusters. These processes produce an increase in surface roughness and an incipient gold faceting. The dynamics of different topographies can be qualitatively explained employing the arguments from colloidal science theory. For 1.1 V ≤ E ≅ Epzc weak electrostatic repulsions favor gold atom/cluster coalescence, whereas for E < Epzc the attenuated electrostatic repulsions among gold surfaces stabilize small clusters over the substrate producing string-like patterns.

Nano- and Macro-wear of Bio-carbo-nitrided AISI 8620 Steel Surfaces

NASA Astrophysics Data System (ADS)

Arthur, Emmanuel Kwesi; Ampaw, Edward; Zebaze Kana, M. G.; Adetunji, A. R.; Olusunle, S. O. O.; Adewoye, O. O.; Soboyejo, W. O.

2015-12-01

This paper presents the results of an experimental study of nano- and macro-scale wear in a carbo-nitrided AISI 8620 steel. Carbo-nitriding is carried out using a novel method that involves the use of dried, cyanide-containing cassava leaves, as sources of carbon and nitrogen. These are used in a pack cementation that is used to diffuse carbon and nitrogen into case layers at intermediate temperatures [673.15 K, 723.15 K, 773.15 K, and 823.15 K (400 °C, 450 °C, 500 °C, and 550 °C)]. Nano- and macro-scale wear properties are studied in the case-hardened surfaces, using a combination of nano-scratch and pin-on-disk experiments. The measured wear volumes (at both nano- and macro-length scales) are shown to increase with decreasing pack cyaniding temperature. The nano- and macro-wear resistances are also shown to be enhanced by the in situ diffusion of carbon and nitrogen from cyanide-containing bio-processed waste. The underlying wear mechanisms are also elucidated via atomic force microscopy and scanning electron microscopy observations of the wear tracks. The implications of the results are discussed for the design of hardened carbo-nitrided steel surfaces with improved wear resistance.

In-situ diagnostics for metalorganic chemical vapor deposition of yttrium barium copper oxide

NASA Astrophysics Data System (ADS)

Tripathi, Ashok Burton

A new stagnation flow MOCVD research reactor is described that is designed to serve as a testbed to develop tools for "intelligent" thin film deposition, such as in-situ sensors and diagnostics, control algorithms, and thin film growth models. The reactor is designed in particular for the deposition of epitaxial YBa2Cu3O 7-delta on MgO, although with minor modifications it would be suitable for deposition of any metal-oxide thin films. The reactor is specifically designed to permit closed-loop thermal and stoichiometric control of the film growth process. Closed-loop control of precursor flow rates is accomplished by using ultraviolet absorption spectroscopy on each precursor line. Also integrated into the design is a Fourier Transform Infrared (FTIR) spectroscopy system which collects real-time, in-situ infrared polarized reflectance spectra of the film as it grows. Numerical simulation was used extensively to optimize the fluid dynamics and heat transfer to provide uniform fluxes to the substrate. As a result, thickness uniformity across the substrate is typically within 3% from the center to the edge of the substrate. Experimental studies of thin films grown in the Y/Ba/Cu/O system have been carried out. The films have been characterized by Rutherford Backscattering Spectrometry and X-ray Diffraction. Results indicate c-axis oriented grains with pure 1:2:3 phase YBCO, good spatial uniformity, and a low degree of c-axis wobble. Experimental growth data is used in a gas phase and surface chemistry model to calculate sticking coefficients for yttrium oxide, barium oxide, and copper oxide on YBCO. In-situ FTIR and Coherent Gradient Sensing (CGS) analysis of growing films has been performed, yielding accurate substrate temperature, film thickness monitoring, and full-field, real-time curvature maps of the films. In addition, we have implemented CGS to obtain full-field in-situ images of local curvature during oxygenation and deoxygenation of YBCO films. An analysis of the oxygen diffusion is performed, and diffusivity constants are presented for a variety of temperature and film conditions.

Integration of In Situ Radon Modeling with High Resolution Aerial Remote Sensing for Mapping and Quantifying Local to Regional Flow and Transport of Submarine Groundwater Discharge from Coastal Aquifers

NASA Astrophysics Data System (ADS)

Glenn, C. R.; Kennedy, J. J.; Dulaiova, H.; Kelly, J. L.; Lucey, P. G.; Lee, E.; Fackrell, J.

2015-12-01

Submarine groundwater discharge (SGD) is a principal conduit for huge volumes of fresh groundwater loss and is a key transport mechanism for nutrient and contaminant pollution to coastal zones worldwide. However, the volumes and spatially and temporally variable nature of SGD is poorly known and requires rapid and high-resolution data acquisition at the scales in which it is commonly observed. Airborne thermal infrared (TIR) remote sensing, using high-altitude manned aircraft and low-altitude remote-controlled unmanned aerial vehicles (UAVs or "Drones") are uniquely qualified for this task, and applicable wherever 0.1°C temperature contrasts exist between discharging and receiving waters. We report on the use of these technologies in combination with in situ radon model studies of SGD volume and nutrient flux from three of the largest Hawaiian Islands. High altitude manned aircraft results produce regional (~300m wide x 100s km coastline) 0.5 to 3.2 m-resolution sea-surface temperature maps accurate to 0.7°C that show point-source and diffuse flow in exquisite detail. Using UAVs offers cost-effective advantages of higher spatial and temporal resolution and instantaneous deployments that can be coordinated simultaneously with any ground-based effort. We demonstrate how TIR-mapped groundwater discharge plume areas may be linearly and highly correlated to in situ groundwater fluxes. We also illustrate how in situ nutrient data may be incorporated into infrared imagery to produce nutrient distribution maps of regional worth. These results illustrate the potential for volumetric quantification and up-scaling of small- to regional-scale SGD. These methodologies provide a tremendous advantage for identifying and differentiating spring-fed, point-sourced, and/or diffuse groundwater discharge into oceans, estuaries, and streams. The integrative techniques are also important precursors for developing best-use and cost-effective strategies for otherwise time-consuming in situ studies, and represent a substantial new asset for land use and coastal zone research and management.

Effects of Surface Finishes and Current Stressing on Interfacial Reaction Characteristics of Sn-3.0Ag-0.5Cu Solder Bumps

NASA Astrophysics Data System (ADS)

Kim, Jae-Myeong; Jeong, Myeong-Hyeok; Yoo, Sehoon; Park, Young-Bae

2012-04-01

The effects of surface finishes on the in situ interfacial reaction characteristics of ball grid array (BGA) Sn-3.0Ag-0.5Cu lead-free solder bumps were investigated under annealing and electromigration (EM) test conditions of 130°C to 175°C with 5.0 × 103 A/cm2. During reflow and annealing, (Cu,Ni)6Sn5 intermetallic compound (IMC) formed at the interface of electroless nickel immersion gold (ENIG) finish. In the case of both immersion Sn and organic solderability preservative (OSP) finishes, Cu6Sn5 and Cu3Sn IMCs formed. Overall, the IMC growth velocity of ENIG was much lower than that of the other finishes. The activation energies of total IMCs were found to be 0.52 eV for ENIG, 0.78 eV for immersion Sn, and 0.72 eV for OSP. The ENIG finish appeared to present an effective diffusion barrier between the Cu substrate and the solder, which leads to better EM reliability in comparison with Cu-based pad systems. The failure mechanisms were explored in detail via in situ EM tests.

On the role of mobile nanoclusters in 2D island nucleation on Si(111)-(7 × 7) surface

NASA Astrophysics Data System (ADS)

Rogilo, D. I.; Fedina, L. I.; Kosolobov, S. S.; Latyshev, A. V.

2018-01-01

Two-dimensional (2D) Si island nucleation has been studied by in situ reflection electron microscopy within a wide temperature range (650-1090 °C ) on large-scale (∼10-100 μm) terraces to exclude the impact of step permeability and adatom sink to steps. The dependence of 2D island concentration N2D on substrate temperature T and Si deposition rate R displays N2D∝Rχexp (E2D/kT) scaling which parameters change from χ≈0.81, E2D≈1.02 eV to χ≈0.5, E2D≈1.8 eV when Si(111) surface converts from (1 × 1) structure to (7 × 7) reconstruction. We propose that this strong E2D rise accompanied by χ reduction is caused by the change of dominating diffusing particles from adatoms to reconstruction induced nanoclusters. Using a rate-equation model developed to account the dynamics of both diffusing species on the Si(111)-(7 × 7) surface, we show that a stable nucleus of a 2D island appears when two mobile nanoclusters merge together while nucleation kinetics is limited by their attachment to island edges.

Modeling diffusion and reaction in soils: 9. The Buckingham-Burdine-Campbell equation for gas diffusivity in undisturbed soil

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

Moldrup, P.; Olesen, T.; Yamaguchi, T.

1999-08-01

Accurate description of gas diffusivity (ratio of gas diffusion coefficients in soil and free air, D{sub s}/D{sub 0}) in undisturbed soils is a prerequisite for predicting in situ transport and fate of volatile organic chemicals and greenhouse gases. Reference point gas diffusivities (R{sub p}) in completely dry soil were estimated for 20 undisturbed soils by assuming a power function relation between gas diffusivity and air-filled porosity ({epsilon}). Among the classical gas diffusivity models, the Buckingham (1904) expression, equal to the soil total porosity squared, best described R{sub p}. Inasmuch, as their previous works implied a soil-type dependency of D{sub s}/D{submore » 0}({epsilon}) in undisturbed soils, the Buckingham R{sub p} expression was inserted in two soil-type-dependent D{sub s}/D{sub 0}({epsilon}) models. One D{sub s}/D{sub 0}({epsilon}) model is a function of pore-size distribution (the Campbell water retention parameter used in a modified Burdine capillary tube model), and the other is a calibrated, empirical function of soil texture (silt + sand fraction). Both the Buckingham-Burdine-Campbell (BBC) and the Buckingham/soil texture-based D{sub s}/D{sub 0}({epsilon}) models described well the observed soil type effects on gas diffusivity and gave improved predictions compared with soil type independent models when tested against an independent data set for six undisturbed surface soils. This study emphasizes that simple but soil-type-dependent power function D{sub s}/D{sub 0}({epsilon}) models can adequately describe and predict gas diffusivity in undisturbed soil. The authors recommend the new BBC model as basis for modeling gas transport and reactions in undisturbed soil systems.« less

Isotopic Exchange in Porous and Dense Magnesium Borohydride.

PubMed

Zavorotynska, Olena; Deledda, Stefano; Li, Guanqiao; Matsuo, Motoaki; Orimo, Shin-ichi; Hauback, Bjørn C

2015-09-01

Magnesium borohydride (Mg(BH4)2) is one of the most promising complex hydrides presently studied for energy-related applications. Many of its properties depend on the stability of the BH4(-) anion. The BH4(-) stability was investigated with respect to H→D exchange. In situ Raman measurements on high-surface-area porous Mg(BH4 )2 in 0.3 MPa D2 have shown that the isotopic exchange at appreciable rates occurs already at 373 K. This is the lowest exchange temperature observed in stable borohydrides. Gas-solid isotopic exchange follows the BH4(-) +D˙ →BH3D(-) +H˙ mechanism at least at the initial reaction steps. Ex situ deuteration of porous Mg(BH4)2 and its dense-phase polymorph indicates that the intrinsic porosity of the hydride is the key behind the high isotopic exchange rates. It implies that the solid-state H(D) diffusion is considerably slower than the gas-solid H→D exchange reaction at the surface and it is a rate-limiting steps for hydrogen desorption and absorption in Mg(BH4)2. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative modeling of an in situ diffusion experiment in granite at the Grimsel Test Site.

PubMed

Soler, Josep M; Landa, Jiri; Havlova, Vaclava; Tachi, Yukio; Ebina, Takanori; Sardini, Paul; Siitari-Kauppi, Marja; Eikenberg, Jost; Martin, Andrew J

2015-08-01

An in situ diffusion experiment was performed at the Grimsel Test Site (Switzerland). Several tracers ((3)H as HTO, (22)Na(+), (134)Cs(+), (131)I(-) with stable I(-) as carrier) were continuously circulated through a packed-off borehole and the decrease in tracer concentrations in the liquid phase was monitored for a period of about 2years. Subsequently, the borehole section was overcored and the tracer profiles in the rock analyzed ((3)H, (22)Na(+), (134)Cs(+)). (3)H and (22)Na(+) showed a similar decrease in activity in the circulation system (slightly larger drop for (3)H). The drop in activity for (134)Cs(+) was much more pronounced. Transport distances in the rock were about 20cm for (3)H, 10cm for (22)Na(+), and 1cm for (134)Cs(+). The dataset (except for (131)I(-) because of complete decay at the end of the experiment) was analyzed with different diffusion-sorption models by different teams (IDAEA-CSIC, UJV-Rez, JAEA) using different codes, with the goal of obtaining effective diffusion coefficients (De) and porosity (ϕ) or rock capacity (α) values. From the activity measurements in the rock, it was observed that it was not possible to recover the full tracer activity in the rock (no activity balance when adding the activities in the rock and in the fluid circulation system). A Borehole Disturbed Zone (BDZ) had to be taken into account to fit the experimental observations. The extension of the BDZ (1-2mm) is about the same magnitude than the mean grain size of the quartz and feldspar grains. IDAEA-CSIC and UJV-Rez tried directly to match the results of the in situ experiment, without forcing any laboratory-based parameter values into the models. JAEA conducted a predictive modeling based on laboratory diffusion data and their scaling to in situ conditions. The results from the different codes have been compared, also with results from small-scale laboratory experiments. Outstanding issues to be resolved are the need for a very large capacity factor in the BDZ for (3)H and the difference between apparent diffusion coefficients (Da) from the in situ experiment and out-leaching laboratory tests. Copyright © 2015 Elsevier B.V. All rights reserved.

Infrared study of CO{sub 2} sorption over 'molecular basket' sorbent consisting of polyethylenimine-modified mesoporous molecular sieve

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

Wang, X.X.; Schwartz, V.; Clark, J.C.

2009-04-15

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75{sup o}C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75{sup o}C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75{sup o}C.« less

In-situ fabrication of diketopyrrolopyrrole-carbazole-based conjugated polymer/TiO2 heterojunction for enhanced visible light photocatalysis

NASA Astrophysics Data System (ADS)

Yang, Long; Yu, Yuyan; Zhang, Jianling; Chen, Fu; Meng, Xiao; Qiu, Yong; Dan, Yi; Jiang, Long

2018-03-01

Aiming at developing highly efficient photocatalysts by broadening the light-harvesting region and suppressing photo-generated electron-hole recombination simultaneously, this work reports rational design and fabrication of donor-acceptor (D-A) conjugated polymer/TiO2 heterojunction catalyst with strong interfacial interactions by a facile in-situ thermal treatment. To expand the light-harvesting window, soluable conjugated copolymers with D-A architecture are prepared by Pd-mediated polycondensation of diketopyrrolopyrrole (DPP) and t-butoxycarbonyl (t-Boc) modified carbazole (Car), and used as visible-light-harvesting antenna to couple with TiO2 nanocrystals. The DPP-Car/TiO2 composites show wide range absorption in 300-1000 nm. To improve the interfacial binding at the interface, a facile in-situ thermal treatment is carried out to cleave the pendant t-Boc groups in carbazole units and liberate the polar amino groups (-NH-) which strongly bind to the surface of TiO2 through dipole-dipole interactions, forming a heterojunction interface. This in-situ thermal treatment changes the surface elemental distribution of TiO2, reinforces the interface bonding at the boundary of conjugated polymers/TiO2 and finally improves the photocatalytic efficiency of DPP-Car/TiO2 under visible-light irradiation. The interface changes are characterized and verified through Fourier-transform infrared spectroscopy (FT-IR), photo images, UV/Vis (solution state and powder diffuse reflection spectroscopy), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), fluorescence, scanning electron microscopy(SEM) and transmission electron microscopy (TEM) techniques. This study provides a new strategy to avoid the low solubility of D-A conjugated polymers and construct highly-efficient conjugated polymer/TiO2 heterojunction by enforcing the interface contact and facilitating charge or energy transfer for the applications in photocatalysis.

Sorption and diffusion of selenium oxyanions in granitic rock

NASA Astrophysics Data System (ADS)

Ikonen, Jussi; Voutilainen, Mikko; Söderlund, Mervi; Jokelainen, Lalli; Siitari-Kauppi, Marja; Martin, Andrew

2016-09-01

The processes controlling diffusion and sorption of radionuclides have been studied extensively in the laboratory, whereas, only a few in-situ experiments have been carried out in order to study in-situ diffusion over the long-term (several years). This is largely due to the fact that in-situ experiments are typically time consuming and cost intensive, and it is commonly accepted that laboratory scale tests are well-established approaches to characterizing the properties of geological media. In order to assess the relevance of laboratory experiments, the Swiss National Cooperative for Disposal of Radioactive Waste (Nagra) have been conducting extensive experiments in the Underground Rock Laboratory (URL) at the Grimsel Test Site (GTS) in order to study radionuclide transport and retention in-situ. One of the elements used in these experiments is non-radioactive selenium, as an analog for the radiotoxic isotope Se-79, which is present in radioactive waste. In this work, two laboratory through-diffusion experiments using selenium as a tracer were carried out in block (decimeter) scale rock specimens to support one of the ongoing radionuclide transport and retention in-situ experiment at the GTS mentioned above. The though-diffusion tests of selenium were performed under atmospheric conditions in both Kuru grey granite (KGG) and Grimsel granodiorite (GG). The decrease of selenium concentration in an inlet hole drilled into each of the rock samples and the breakthrough of selenium into sampling holes drilled around the inlet were analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The effective diffusion (De) and distribution coefficients (Kd) of selenium were then determined from the changes of selenium concentration in the inlet and sampling holes using a Time-Domain Diffusion (TDD) simulations. In addition, Kd of selenium was measured by batch sorption experiments as a function of pH and Se concentration in atmospheric conditions and nitrogen atmosphere. The speciation of selenium was studied by HPLC-ICP-MS in simulated ground waters of each of the rock types. The Kd of selenium was found to be in the range of (6.2-7.0 ± 2.0) × 10- 3 m3/kg in crushed rock whereas the Kd obtained from block scale through diffusion experiment varied between (1.5 ± 0.3) × 10- 3 m3/kg and (1.0 ± 0.6) × 10- 4 m3/kg. The De of selenium was significantly higher for GG; De = (2.5 ± 1.5) × 10- 12 m2/s than for KGG; De = (7 ± 2) × 10- 13 m2/s due to the higher permeability of GG compared with KGG.

Sorption and diffusion of selenium oxyanions in granitic rock.

PubMed

Ikonen, Jussi; Voutilainen, Mikko; Söderlund, Mervi; Jokelainen, Lalli; Siitari-Kauppi, Marja; Martin, Andrew

2016-09-01

The processes controlling diffusion and sorption of radionuclides have been studied extensively in the laboratory, whereas, only a few in-situ experiments have been carried out in order to study in-situ diffusion over the long-term (several years). This is largely due to the fact that in-situ experiments are typically time consuming and cost intensive, and it is commonly accepted that laboratory scale tests are well-established approaches to characterizing the properties of geological media. In order to assess the relevance of laboratory experiments, the Swiss National Cooperative for Disposal of Radioactive Waste (Nagra) have been conducting extensive experiments in the Underground Rock Laboratory (URL) at the Grimsel Test Site (GTS) in order to study radionuclide transport and retention in-situ. One of the elements used in these experiments is non-radioactive selenium, as an analog for the radiotoxic isotope Se-79, which is present in radioactive waste. In this work, two laboratory through-diffusion experiments using selenium as a tracer were carried out in block (decimeter) scale rock specimens to support one of the ongoing radionuclide transport and retention in-situ experiment at the GTS mentioned above. The though-diffusion tests of selenium were performed under atmospheric conditions in both Kuru grey granite (KGG) and Grimsel granodiorite (GG). The decrease of selenium concentration in an inlet hole drilled into each of the rock samples and the breakthrough of selenium into sampling holes drilled around the inlet were analyzed using Inductively Coupled Plasma Mass Spectrometry (ICP-MS). The effective diffusion (De) and distribution coefficients (Kd) of selenium were then determined from the changes of selenium concentration in the inlet and sampling holes using a Time-Domain Diffusion (TDD) simulations. In addition, Kd of selenium was measured by batch sorption experiments as a function of pH and Se concentration in atmospheric conditions and nitrogen atmosphere. The speciation of selenium was studied by HPLC-ICP-MS in simulated ground waters of each of the rock types. The Kd of selenium was found to be in the range of (6.2-7.0±2.0)×10(-3)m(3)/kg in crushed rock whereas the Kd obtained from block scale through diffusion experiment varied between (1.5±0.3)×10(-3)m(3)/kg and (1.0±0.6)×10(-4)m(3)/kg. The De of selenium was significantly higher for GG; De=(2.5±1.5)×10(-12)m(2)/s than for KGG; De=(7±2)×10(-13)m(2)/s due to the higher permeability of GG compared with KGG. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of cement alkalinity, exposure conditions and steel-concrete interface on the time-to-corrosion and chloride threshold for reinforcing steel in concrete

NASA Astrophysics Data System (ADS)

Nam, Jingak

Effects of (1) cement alkalinity (low, normal and high), (2) exposure conditions (RH and temperature), (3) rebar surface condition (as-received versus cleaned) and (4) density and distribution of air voids at the steel-concrete interface on the chloride threshold and time-to-corrosion for reinforcing steel in concrete have been studied. Also, experiments were performed to evaluate effects of RH and temperature on the diffusion of chloride in concrete and develop a method for ex-situ pH measurement of concrete pore water. Once specimens were fabricated and exposed to a corrosive chloride solution, various experimental techniques were employed to determine time-to-corrosion, chloride threshold, diffusion coefficient and void density along the rebar trace as well as pore water pH. Based upon the resultant data, several findings related to the above parameters have been obtained as summarized below. First, time for the corrosion initiation was longest for G109 concrete specimens with high alkalinity cement (HA). Also, chloride threshold increased with increasing time-to-corrosion and cement alkalinity. Consequently, the HA specimens exhibited the highest chloride threshold compared to low and normal alkalinity ones. Second, high temperature and temperature variations reduced time-to-corrosion of reinforcing steel in concrete since chloride diffusion was accelerated at higher temperature and possibly by temperature variations. The lowest chloride threshold values were found for outdoor exposed specimens suggesting that variation of RH or temperature (or both) facilitated rapid chloride diffusion. Third, an elevated time-to-corrosion and chloride threshold values were found for the wire brushed steel specimens compared to as-received ones. The higher ratio of [OH-]/[Fe n+] on the wire brushed steel surface compared to that of as-received case can be the possible cause because the higher ratio of this parameter enables the formation of a more protective passive film on the rebar. Fourth, voids at the steel-concrete interface facilitated passive film breakdown and onset of localized corrosion. This tendency for corrosion initiation increased in proportion to void size irrespective of specimen type. Also, [Cl -]th decreased with increasing void diameter. In addition, new ex-situ leaching method for determining concrete pore water alkalinity was developed.

In situ codoping of a CuO absorber layer with aluminum and titanium: the impact of codoping and interface engineering on the performance of a CuO-based heterojunction solar cell

NASA Astrophysics Data System (ADS)

Masudy-Panah, Saeid; Radhakrishnan, K.; Ru, Tan Hui; Yi, Ren; Wong, Ten It; Dalapati, Goutam Kumar

2016-09-01

Aluminum-doped cupric oxide (CuO:Al) was prepared via an out-diffusion process of Al from an Al-coated substrate into the deposited CuO thin film upon thermal treatment. The effect of the annealing temperature on the structural and optical properties of CuO:Al was investigated in detail. The influence of Al incorporation on the photovoltaic properties was then investigated by preparing a p-CuO:Al/n-Si heterojunction solar cell. A significant improvement in the performance of the solar cell was achieved by controlling the out-diffusion of Al. A novel in situ method to co-dope CuO with Al and titanium (Ti) has been proposed to demonstrate CuO-based solar cells with the front surface field (FSF) design. The FSF design was created by depositing a CuO:Al layer followed by a Ti-doped CuO (CuO:Ti) layer. This is the first successful experimental demonstration of the codoping of a CuO thin film and CuO thin film solar cells with the FSF design. The open circuit voltage (V oc), short circuit current density (J sc) and fill factor (FF) of the fabricated solar cells were significantly higher for the FSF device compared to devices without FSF. The FF of this device improved by 68% through the FSF design and a record efficiency ɳ of 2% was achieved. The improvement of the solar cell properties is mainly attributed to the reduction of surface recombination, which influences the charge carrier collection.

Interfacial Cu + promoted surface reactivity: Carbon monoxide oxidation reaction over polycrystalline copper-titania catalysts

DOE PAGES

Senanayake, S. D.; Pappoe, N. A.; Nguyen-Phan, T. -D.; ...

2016-10-01

We have studied the catalytic carbon monoxide (CO) oxidation (CO+0.5O2 → CO2) reaction using a powder catalyst composed of both copper (5wt% loading) and titania (CuOx-TiO2). Our study was focused on revealing the role of Cu, and the interaction between Cu and TiO2, by systematic comparison between two nanocatalysts, CuOx-TiO2 and pure CuOx. We interrogated these catalysts under in situ conditions using X-ray Diffraction (XRD), X-ray Absorption Fine Structure (XAFS) and Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) to probe the structure and electronic properties of the catalyst at all stages of the reaction and simultaneously probe the surface statesmore » or intermediates of this reaction. With the aid of several ex situ characterization techniques including Transmission Electron Microscopy (TEM), the local catalyst morphology and structure was also studied. Our results show that a CuOx-TiO2 system is more active than bulk CuOx for the CO oxidation reaction due to its lower onset temperature and better stability at higher temperatures. Our results also suggests that a surface Cu+ species observed in the CuOx-TiO2 interface are likely to be a key player in the CO oxidation mechanism, while implicating that the stabilization of this species is probably associated with the oxide-oxide interface. Both in situ DRIFTS and XAFS measurements reveal that there is likely to be a Cu(Ti)-O mixed oxide at this interface. We discuss the nature of this Cu(Ti)-O interface and interpret its role on the CO oxidation reaction.« less

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

Wolfram, Phillip J.; Ringler, Todd D.

Meridional diffusivity is assessed in this paper for a baroclinically unstable jet in a high-latitudeIdealized Circumpolar Current (ICC) using the Model for Prediction Across Scales-Ocean (MPAS-O) and the online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) diagnostic via space-time dispersion of particle clusters over 120 monthly realizations of O(10 6) particles on 11 potential density surfaces. Diffusivity in the jet reaches values of O(6000 m 2 s -1) and is largest near the critical layer supporting mixing suppression and critical layer theory. Values in the vicinity of the shelf break are suppressed to O(100 m 2 s -1) due tomore » the presence of westward slope front currents. Diffusivity attenuates less rapidly with depth in the jet than both eddy velocity and kinetic energy scalings would suggest. Removal of the mean flow via high-pass filtering shifts the nonlinear parameter (ratio of the eddy velocity to eddy phase speed) into the linear wave regime by increasing the eddy phase speed via the depth-mean flow. Low-pass filtering, in contrast, quantifies the effect of mean shear. Diffusivity is decomposed into mean flow shear, linear waves, and the residual nonhomogeneous turbulence components, where turbulence dominates and eddy-produced filamentation strained by background mean shear enhances mixing, accounting for ≥ 80% of the total diffusivity relative to mean shear [O(100 m 2 s -1)], linear waves [O(1000 m 2 s -1)], and undecomposed full diffusivity [O(6000 m 2 s -1)]. Finally, diffusivity parameterizations accounting for both the nonhomogeneous turbulence residual and depth variability are needed.« less

In situ estimation of the effective chemical diffusion coefficient of a rock matrix in a fractured aquifer

USGS Publications Warehouse

Gebrekristos, R.A.; Shapiro, A.M.; Usher, B.H.

2008-01-01

An in situ method of estimating the effective diffusion coefficient for a chemical constituent that diffuses into the primary porosity of a rock is developed by abruptly changing the concentration of the dissolved constituent in a borehole in contact with the rock matrix and monitoring the time-varying concentration. The experiment was conducted in a borehole completed in mudstone on the campus of the University of the Free State in Bloemfontein, South Africa. Numerous tracer tests were conducted at this site, which left a residual concentration of sodium chloride in boreholes that diffused into the rock matrix over a period of years. Fresh water was introduced into a borehole in contact with the mudstone, and the time-varying increase of chloride was observed by monitoring the electrical conductivity (EC) at various depths in the borehole. Estimates of the effective diffusion coefficient were obtained by interpreting measurements of EC over 34 d. The effective diffusion coefficient at a depth of 36 m was approximately 7.8??10-6 m2/d, but was sensitive to the assumed matrix porosity. The formation factor and mass flux for the mudstone were also estimated from the experiment. ?? Springer-Verlag 2007.

Hybrid Nanoscale Architecture of Wound Dressing with Super Hydrophilic, Antimicrobial, and Ultralow Fouling Attributes.

PubMed

Depan, D; Misra, R D K

2015-02-01

Currently available wound dressings to heal thermal and chronic wounds are unable to respond to the challenges of resistance to bacterial infection, protein adsorption, and increased levels of wound exudates. To this end, we have conceived the fabrication of a new and ideal wound dressing with a number of key attributes. They include effective antimicrobial activity in a controlled manner, ultralow fouling property that provides resistance to protein adsorption and bacterial adhesion, maintain a moist but not saturated environment to promote healing, and is non-adherent and effective in the presence of heavy wound exudate. The novel approach to reduce infection and bacterial colonization involves incorporation of a unique silver-clay nanohybrid architecture in zwitterionic polymer, poly(sulfobetaine). The innovative concept of silver-clay hybrid structure enables us to obtain high, sustained, and diffusion-controlled antimicrobial activity of silver eluting polymer. The sustained and diffusion-controlled high antimicrobial efficiency is obtained through a process involving in situ precipitation of silver nanoparticles with large surface area on the surface of clay platelets. Furthermore, the use of recently developed zwitterionic polymer, poly(sulfobetaine) [poly(SB)] for wound dressing, provides antifouling property, which resists protein adsorption.

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

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

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

Inert gas enhanced laser-assisted purification of platinum electron-beam-induced deposits

DOE PAGES

Stanford, Michael G.; Lewis, Brett B.; Noh, Joo Hyon; ...

2015-06-30

Electron-beam-induced deposition patterns, with composition of PtC 5, were purified using a pulsed laser-induced purification reaction to erode the amorphous carbon matrix and form pure platinum deposits. Enhanced mobility of residual H 2O molecules via a localized injection of inert Ar–H 2 (4%) is attributed to be the reactive gas species for purification of the deposits. Surface purification of deposits was realized at laser exposure times as low as 0.1 s. The ex situ purification reaction in the deposit interior was shown to be rate-limited by reactive gas diffusion into the deposit, and deposit contraction associated with the purification processmore » caused some loss of shape retention. To circumvent the intrinsic flaws of the ex situ anneal process, in situ deposition and purification techniques were explored that resemble a direct write atomic layer deposition (ALD) process. First, we explored a laser-assisted electron-beam-induced deposition (LAEBID) process augmented with reactive gas that resulted in a 75% carbon reduction compared to standard EBID. Lastly, a sequential deposition plus purification process was also developed and resulted in deposition of pure platinum deposits with high fidelity and shape retention.« less

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

Moorhouse, Saul J.; Wu, Yue; O’Hare, Dermot, E-mail: dermot.ohare@chem.ox.ac.uk

A newly developed in situ monochromatic high-energy X-ray diffraction setup was used to investigate the synthesis of MOFs using cation-impregnated polymer resin beads as a ion source. The Co–NDC–DMF (NDC=2,6-naphthalenedicarboxylate; DMF=dimethylformamide) system was investigated, a system which is known to produce at least three distinct frameworks. It was found that the resin-assisted synthesis results in the preferential formation of a topology previously impossible to synthesise in bulk, while the comparable nitrate-salt synthesis appeared to form an alternative phases. It was also found that the resin-assisted synthesis is highly diffusion-controlled. - Graphical abstract: In situ monochromatic high-energy X-ray diffraction study ofmore » a MOF synthesis. - Highlights: • Resin-assisted solvothermal MOF synthesis was studied using in situ diffraction. • Full kinetics of reaction can be obtained from in situ data. • Kinetics show that this resin-assisted synthesis is diffusion controlled. • Resin-assisted synthesis enables the production of an alternative bulk phase.« less

Effect drug loading process on dissolution mechanism of encapsulated amoxicillin trihydrate in hydrogel semi-IPN chitosan methyl cellulose with pore forming agent KHCO3 as a floating drug delivery system

NASA Astrophysics Data System (ADS)

Fithawati, Garnis; Budianto, Emil

2018-04-01

Common treatment for Helicobacter pylori by repeated oral consumption of amoxicillin trihydrate is not effective. Amoxicillin trihydrate has a very short residence time in stomach which leads into its ineffectiveness. Residence time of amoxicillin trihydrate can be improved by encapsulating amoxicillin trihydrate into a floating drug delivery system. In this study, amoxicillin trihydrate is encapsulated into hydrogel semi-IPN chitosan methyl cellulose matrix as a floating drug delivery system and then treated with 20% KHCO3 as pore forming agent. Drug loading process used are in-situ loading and post loading. In-situ loading process has higher efficiency percentage and dissolution percentage than post loading process. In-situ loading process resulted 100% efficiency with 92,70% dissolution percentage. Post loading process resulted 98,7% efficiency with 90,42% dissolution percentage. Mechanism of drug dissolution study by kinetics approach showed both in-situ loading process and post loading process are diffusion and degradation process (n=0,4913) and (n=0,4602) respectively. These results are supported by characterization data from optical microscope and scanning electron microscopy (SEM). Data from optical microscope showed both loading process resulted in coarser hydrogel surface. Characterization using SEM showed elongated pores in both loading process after dissolution test.

Mutual influence of molecular diffusion in gas and surface phases

NASA Astrophysics Data System (ADS)

Hori, Takuma; Kamino, Takafumi; Yoshimoto, Yuta; Takagi, Shu; Kinefuchi, Ikuya

2018-01-01

We develop molecular transport simulation methods that simultaneously deal with gas- and surface-phase diffusions to determine the effect of surface diffusion on the overall diffusion coefficients. The phenomenon of surface diffusion is incorporated into the test particle method and the mean square displacement method, which are typically employed only for gas-phase transport. It is found that for a simple cylindrical pore, the diffusion coefficients in the presence of surface diffusion calculated by these two methods show good agreement. We also confirm that both methods reproduce the analytical solution. Then, the diffusion coefficients for ink-bottle-shaped pores are calculated using the developed method. Our results show that surface diffusion assists molecular transport in the gas phase. Moreover, the surface tortuosity factor, which is known to be uniquely determined by physical structure, is influenced by the presence of gas-phase diffusion. This mutual influence of gas-phase diffusion and surface diffusion indicates that their simultaneous calculation is necessary for an accurate evaluation of the diffusion coefficients.

Dynamic observation on the growth behaviors in manganese silicide/silicon nanowire heterostructures.

PubMed

Hsieh, Yu-Hsun; Chiu, Chung-Hua; Huang, Chun-Wei; Chen, Jui-Yuan; Lin, Wan-Jhen; Wu, Wen-Wei

2015-02-07

Metal silicide nanowires (NWs) are very interesting materials with diverse physical properties. Among the silicides, manganese silicide nanostructures have attracted wide attention due to their several potential applications, including in microelectronics, optoelectronics, spintronics and thermoelectric devices. In this work, we exhibited the formation of pure manganese silicide and manganese silicide/silicon nanowire heterostructures through solid state reaction with line contacts between manganese pads and silicon NWs. Dynamical process and phase characterization were investigated by in situ transmission electron microscopy (in situ TEM) and spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), respectively. The growth dynamics of the manganese silicide phase under thermal effects were systematically studied. Additionally, Al2O3, serving as the surface oxide, altered the growth behavior of the MnSi nanowire, enhancing the silicide/Si epitaxial growth and effecting the diffusion process in the silicon nanowire as well. In addition to fundamental science, this significant study has great potential in advancing future processing techniques in nanotechnology and related applications.

Copper silicide/silicon nanowire heterostructures: in situ TEM observation of growth behaviors and electron transport properties.

PubMed

Chiu, Chung-Hua; Huang, Chun-Wei; Chen, Jui-Yuan; Huang, Yu-Ting; Hu, Jung-Chih; Chen, Lien-Tai; Hsin, Cheng-Lun; Wu, Wen-Wei

2013-06-07

Copper silicide has been studied in the applications of electronic devices and catalysts. In this study, Cu3Si/Si nanowire heterostructures were fabricated through solid state reaction in an in situ transmission electron microscope (TEM). The dynamic diffusion of the copper atoms in the growth process and the formation mechanism are characterized. We found that two dimensional stacking faults (SF) may retard the growth of Cu3Si. Due to the evidence of the block of edge-nucleation (heterogeneous) by the surface oxide, center-nucleation (homogeneous) is suggested to dominate the silicidation. Furthermore, the electrical transport properties of various silicon channel length with Cu3Si/Si heterostructure interfaces and metallic Cu3Si NWs have been investigated. The observations not only provided an alternative pathway to explore the formation mechanisms and interface properties of Cu3Si/Si, but also suggested the potential application of Cu3Si at nanoscale for future processing in nanotechnology.

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

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Ultra small angle x-ray scattering in complex mixtures of triacylglycerols

NASA Astrophysics Data System (ADS)

Peyronel, Fernanda; Quinn, Bonnie; Marangoni, Alejandro G.; Pink, David A.

2014-11-01

Ultra-small angle x-ray scattering (USAXS) has been used to elucidate, in situ, the aggregation structure of unsheared model edible oils. Each system comprised one or two solid lipids and a combination of liquid lipids. The 3D nano- to micro-structures of each system were characterized. The length scale investigated, using the Bonse-Hart camera at beamline ID-15D at the Advanced Photon Source, ANL, ranged from 300 Å-10 µm. Using the Unified Fit model, level-1 analysis showed that the scatterers were 2D objects with either a smooth, a rough, or a diffuse surface. These 2D objects had an average radius of gyration Rg1 between 200-1500 Å. Level-2 analysis displayed a slope between -1 and -2. Use of the Guinier-Porod model gave s ≈ 1 thus showing that it was cylinders (TAGwoods) aggregating with fractal dimension 1 ≤ D2 ≤ 2. D2 = 1 is consistent with 1D structures formed from TAGwoods, while D2 = 2 implies that the TAGwoods had formed structures characteristic of diffusion or reaction limited cluster-cluster aggregation (DLCA/RLCA). These aggregates exhibited radii of gyration, Rg2, between 2500 and 6500 Å. Level-3 analyses showed diffuse surfaces, for most of the systems. These interpretations are in accord with theoretical models which studied crystalline nano-platelets (CNPs) coated with nano-scale layers arising from phase separation at the CNP surfaces. These layers could be due to either liquid-liquid phase separation with the CNPs coated, uniformly or non-uniformly, by a diffuse layer of TAGs, or solid-liquid phase separation with the CNPs coated by a rough layer of crystallites. A fundamental understanding of the self-organizing structures arising in these systems helps advance the characterization of fat crystal networks from nanometres to micrometres. This research can be used to design novel fat structures that use healthier fats via nano- and meso-scale structural engineering.

Ex-situ biogas upgrading and enhancement in different reactor systems.

PubMed

Kougias, Panagiotis G; Treu, Laura; Benavente, Daniela Peñailillo; Boe, Kanokwan; Campanaro, Stefano; Angelidaki, Irini

2017-02-01

Biogas upgrading is envisioned as a key process for clean energy production. The current study evaluates the efficiency of different reactor configurations for ex-situ biogas upgrading and enhancement, in which externally provided hydrogen and carbon dioxide were biologically converted to methane by the action of hydrogenotrophic methanogens. The methane content in the output gas of the most efficient configuration was >98%, allowing its exploitation as substitute to natural gas. Additionally, use of digestate from biogas plants as a cost efficient method to provide all the necessary nutrients for microbial growth was successful. High-throughput 16S rRNA sequencing revealed that the microbial community was resided by novel phylotypes belonging to the uncultured order MBA08 and to Bacteroidales. Moreover, only hydrogenotrophic methanogens were identified belonging to Methanothermobacter and Methanoculleus genera. Methanothermobacter thermautotrophicus was the predominant methanogen in the biofilm formed on top of the diffuser surface in the bubble column reactor. Copyright © 2016 Elsevier Ltd. All rights reserved.

Weathering-limited hillslope evolution in carbonate landscapes

NASA Astrophysics Data System (ADS)

Godard, Vincent; Ollivier, Vincent; Bellier, Olivier; Miramont, Cécile; Shabanian, Esmaeil; Fleury, Jules; Benedetti, Lucilla; Guillou, Valéry; Aster Team

2016-07-01

Understanding topographic evolution requires integrating elementary processes acting at the hillslope scale into the long-wavelength framework of landscape dynamics. Recent progress has been made in the quantification of denudation of eroding landscapes and its links with topography. Despite these advances, data is still sparse in carbonate terrain, which covers a significant part of the Earth's surface. In this study, we measured both long-term denudation rates using in situ-produced 36Cl concentrations in bedrock and regolith clasts and surface convexity at 12 sites along ridges of the Luberon carbonate range in Provence, Southeastern France. Starting from ∼30 mm/ka for the lowering of the summit plateau surface, denudation linearly increases with increasing hilltop convexity up to ∼70 mm/ka, as predicted by diffusive mass transport theory. Beyond this point denudation rates appear to be insensitive to the increase in hilltop convexity. We interpret this constant denudation as indicating a transition from a regime where hillslope evolution is primarily controlled by diffusive downslope regolith transport, toward a situation in which denudation is limited by the rate at which physical and chemical weathering processes can produce clasts and lower the hilltop. Such an abrupt transition into a weathering-limited dynamics may prevent hillslope denudation from balancing the rate of base level fall imposed by the river network and could potentially explain the development of high local relief in many Mediterranean carbonate landscapes.

In situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion as potential electrode materials for energy applications

NASA Astrophysics Data System (ADS)

Mombrú, Dominique; Romero, Mariano; Faccio, Ricardo; Castiglioni, Jorge; Mombrú, Alvaro W.

2017-06-01

In situ preparation of polyaniline-ceramic nanocomposites has recently demonstrated that the electrical properties are highly improved with respect to the typical ex situ preparations. In this report, we present for the first time, to the best of our knowledge, the in situ growth of titanium oxide quantum dots in polyaniline host via water vapor flow diffusion as an easily adaptable route to prepare other ceramic-polymer nanocomposites. The main relevance of this method is the possibility to prepare ceramic quantum dots from alkoxide precursors using water vapor flow into any hydrophobic polymer host and to achieve good homogeneity and size-control. In addition, we perform full characterization by means of high-resolution transmission electron microscopy, X-ray powder diffraction, small angle X-ray scattering, thermogravimetric and calorimetric analyses, confocal Raman microscopy and impedance spectroscopy analyses. The presence of the polymer host and interparticle Coulomb repulsive interactions was evaluated as an influence for the formation of 3-8 nm equally-sized quantum dots independently of the concentration. The polyaniline polaron population showed an increase for the quantum dots diluted regime and the suppression at the concentrated regime, ascribed to the formation of chemical bonds at the interface, which was confirmed by theoretical simulations. In agreement with the previous observation, the in situ growth of ceramic quantum dots in polyaniline host via water vapor flow diffusion could be very useful as a novel approach to prepare electrode materials for energy conversion and storage applications.

30 CFR 206.264 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false In-situ and surface gasification and... THE INTERIOR MINERALS REVENUE MANAGEMENT PRODUCT VALUATION Federal Coal § 206.264 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in-situ or...

30 CFR 206.463 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 2 2010-07-01 2010-07-01 false In-situ and surface gasification and... THE INTERIOR MINERALS REVENUE MANAGEMENT PRODUCT VALUATION Indian Coal § 206.463 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in-situ or...

Hydrogen in rocks: an energy source for deep microbial communities

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Dickinson, J. Thomas; Cash, Michele

2002-01-01

To survive in deep subsurface environments, lithotrophic microbial communities require a sustainable energy source such as hydrogen. Though H2 can be produced when water reacts with fresh mineral surfaces and oxidizes ferrous iron, this reaction is unreliable since it depends upon the exposure of fresh rock surfaces via the episodic opening of cracks and fissures. A more reliable and potentially more voluminous H2 source exists in nominally anhydrous minerals of igneous and metamorphic rocks. Our experimental results indicate that H2 molecules can be derived from small amounts of H2O dissolved in minerals in the form of hydroxyl, OH- or O3Si-OH, whenever such minerals crystallized in an H2O-laden environment. Two types of experiments were conducted. Single crystal fracture experiments indicated that hydroxyl pairs undergo an in situ redox conversion to H2 molecules plus peroxy links, O3Si/OO\\SiO3. While the peroxy links become part of the mineral structure, the H2 molecules diffused out of the freshly fractured mineral surfaces. If such a mechanism occurred in natural settings, the entire rock column would become a volume source of H2. Crushing experiments to facilitate the outdiffusion of H2 were conducted with common crustal igneous rocks such as granite, andesite, and labradorite. At least 70 nmol of H2/g diffused out of coarsely crushed andesite, equivalent at standard pressure and temperature to 5,000 cm3 of H2/m3 of rock. In the water-saturated, biologically relevant upper portion of the rock column, the diffusion of H2 out of the minerals will be buffered by H2 saturation of the intergranular water film.

Aqueous sodium borohydride induced thermally stable porous zirconium oxide for quick removal of lead ions

PubMed Central

Nayak, Nadiya B.; Nayak, Bibhuti B.

2016-01-01

Aqueous sodium borohydride (NaBH4) is well known for its reducing property and well-established for the development of metal nanoparticles through reduction method. In contrary, this research paper discloses the importance of aqueous NaBH4 as a precipitating agent towards development of porous zirconium oxide. The boron species present in aqueous NaBH4 play an active role during gelation as well as phase separated out in the form of boron complex during precipitation, which helps to form boron free zirconium hydroxide [Zr(OH)4] in the as-synthesized condition. Evolved in-situ hydrogen (H2) gas-bubbles also play an important role to develop as-synthesized loose zirconium hydroxide and the presence of intra-particle voids in the loose zirconium hydroxide help to develop porous zirconium oxide during calcination process. Without any surface modification, this porous zirconium oxide quickly adsorbs almost hundred percentages of toxic lead ions from water solution within 15 minutes at normal pH condition. Adsorption kinetic models suggest that the adsorption process was surface reaction controlled chemisorption. Quick adsorption was governed by surface diffusion process and the adsorption kinetic was limited by pore diffusion. Five cycles of adsorption-desorption result suggests that the porous zirconium oxide can be reused efficiently for removal of Pb (II) ions from aqueous solution. PMID:26980545

In-situ XRD and EDS method study on the oxidation behaviour of Ni-Cu sulphide ore.

PubMed

Li, Guangshi; Cheng, Hongwei; Xiong, Xiaolu; Lu, Xionggang; Xu, Cong; Lu, Changyuan; Zou, Xingli; Xu, Qian

2017-06-12

The oxidation mechanism of sulfides is the key issue during the sulphide-metallurgy process. In this study, the phase transformation and element migration were clearly demonstrated by in-situ laboratory-based X-ray diffraction (XRD) and energy-dispersive X-ray spectroscopy (EDS), respectively. The reaction sequence and a four-step oxidation mechanism were proposed and identified. The elemental distribution demonstrated that at a low temperature, the Fe atoms diffused outward and the Ni/Cu atoms migrated toward the inner core, whereas the opposite diffusion processes were observed at a higher temperature. Importantly, the unique visual presentation of the oxidation behaviour provided by the combination of in-situ XRD and EDS might be useful for optimising the process parameters to improve the Ni/Cu extraction efficiency during Ni-Cu sulphide metallurgy.

Effects of Coke Deposits on the Catalytic Performance of Large Zeolite H-ZSM-5 Crystals during Alcohol-to-Hydrocarbon Reactions as Investigated by a Combination of Optical Spectroscopy and Microscopy

PubMed Central

Nordvang, Emily C; Borodina, Elena; Ruiz-Martínez, Javier; Fehrmann, Rasmus; Weckhuysen, Bert M

2015-01-01

The catalytic activity of large zeolite H-ZSM-5 crystals in methanol (MTO) and ethanol-to-olefins (ETO) conversions was investigated and, using operando UV/Vis measurements, the catalytic activity and deactivation was correlated with the formation of coke. These findings were related to in situ single crystal UV/Vis and confocal fluorescence micro-spectroscopy, allowing the observation of the spatiotemporal formation of intermediates and coke species during the MTO and ETO conversions. It was observed that rapid deactivation at elevated temperatures was due to the fast formation of aromatics at the periphery of the H-ZSM-5 crystals, which are transformed into more poly-aromatic coke species at the external surface, preventing the diffusion of reactants and products into and out of the H-ZSM-5 crystal. Furthermore, we were able to correlate the operando UV/Vis spectroscopy results observed during catalytic testing with the single crystal in situ results. PMID:26463581

Amazon Deforestation Fires Increase Plant Productivity through Changes in Diffuse Radiation

NASA Astrophysics Data System (ADS)

Rap, A.; Reddington, C.; Spracklen, D. V.; Mercado, L.; Haywood, J. M.; Bonal, D.; Butt, N.; Phillips, O.

2013-12-01

Over the past few decades a large increase in carbon storage has been observed in undisturbed forests across Amazonia. The reason for such a sink is unclear, although many possible mechanisms have been suggested, including changes in temperature, carbon dioxide, precipitation, clouds, and solar radiation. In this work we focus on one such mechanism, namely the increase in plant photosynthesis due to changes in diffuse radiation caused by atmospheric aerosols from large-scale deforestation fires that now occur throughout the Amazon region. We estimate that this mechanism has increased dry season (August-September) net primary productivity (NPP) by up to 30% across wide regions of the Amazon. We conclude that aerosol from deforestation fires may be responsible for a substantial fraction of the Amazon carbon sink that has been observed. Our approach is based on the combined use of three models: (i) the Global Model of Aerosol Processes (GLOMAP), (ii) the Edwards-Slingo radiation model, and (iii) the UK Met Office JULES land-surface scheme, constrained against in-situ aerosol and radiation observation datasets from several Amazonian sites. A 10 year (1999-2008) GLOMAP simulation using GFED3 biomass burning emissions is first evaluated against aerosol observations, indicating that the model is able to capture the Amazon aerosol seasonality, with enhanced concentrations during the dry season driven by biomass burning. The radiation scheme is then shown to be in good agreement with total and diffuse radiation in-situ observations, the model being able to capture the high total and low diffuse radiation flux in the dry season, as well as the low total and high diffuse radiation flux in the wet season. We then use our modelling framework to quantify the contribution of deforestation fires to diffuse/direct radiation fraction and forest productivity. We calculate that deforestation fires increase dry season diffuse radiation by up to 60% or 30 Wm-2. Finally, we use the JULES model to show that this increase in diffuse radiation is responsible for a substantial growth in gross primary productivity (GPP), enhancing Amazon-wide dry-season GPP by 5% with local increases of up to 15%. Most of this GPP response results in an increase in NPP, estimated in the dry season at 10% across the Amazon with local increases as large as 30%. This substantial NPP enhancement spatially matches observed increases in forest biomass storage across the Amazon. We thus suggest that deforestation fires have an important impact on the Amazon carbon budget and attempt to estimate the fraction of the observed forest carbon sink that can be attributed to this mechanism. Change [%] in diffuse radiation due to deforestation

Experimental measurements of the ground cloud effluents and cloud growth for the May 20, 1975, Titan 3C launch at Air Force Eastern Test Range, Florida

NASA Technical Reports Server (NTRS)

Gregory, G. L.; Storey, R. W., Jr.

1977-01-01

The experiment included surface level and airborne in situ cloud measurements of the exhaust effluents from the Titan IIIC solid rocket boosters. Simultaneous visible spectrum photographic pictures of the ground cloud as well as infrared imaging of the cloud were obtained to study the cloud rise, growth, and direction of travel within the earth's surface mixing layer. The NASA multilayer diffusion model predictions of cloud growth, direction of travel, and expected surface level effluent concentrations were made prior to launch and after launch using measured meteorological conditions. Prelaunch predictions were used to position the effluent monitoring instruments, and the postlaunch predictions were compared with the measured data. Measurement results showed that surface level effluent values were low, often below the detection limits of the instrumentation. The maximum surface level hydrogen chloride concentration measured 50 parts per billion at about 8 km from the launch pad. The maximum observed in-cloud (airborne measurement) hydrogen chloride concentration was 7 per million.

43 CFR 3931.60 - Maps of underground and surface mine workings and in situ surface operations.

Code of Federal Regulations, 2014 CFR

2014-10-01

... workings and in situ surface operations. 3931.60 Section 3931.60 Public Lands: Interior Regulations... § 3931.60 Maps of underground and surface mine workings and in situ surface operations. Maps of... in plan views. Maps must be based on accurate surveys and certified by a professional engineer...

43 CFR 3931.60 - Maps of underground and surface mine workings and in situ surface operations.

Code of Federal Regulations, 2012 CFR

2012-10-01

... workings and in situ surface operations. 3931.60 Section 3931.60 Public Lands: Interior Regulations... § 3931.60 Maps of underground and surface mine workings and in situ surface operations. Maps of... in plan views. Maps must be based on accurate surveys and certified by a professional engineer...

43 CFR 3931.60 - Maps of underground and surface mine workings and in situ surface operations.

Code of Federal Regulations, 2013 CFR

2013-10-01

... workings and in situ surface operations. 3931.60 Section 3931.60 Public Lands: Interior Regulations... § 3931.60 Maps of underground and surface mine workings and in situ surface operations. Maps of... in plan views. Maps must be based on accurate surveys and certified by a professional engineer...

43 CFR 3931.60 - Maps of underground and surface mine workings and in situ surface operations.

Code of Federal Regulations, 2011 CFR

2011-10-01

... workings and in situ surface operations. 3931.60 Section 3931.60 Public Lands: Interior Regulations....60 Maps of underground and surface mine workings and in situ surface operations. Maps of underground... reference to sea level. When required by the BLM, include vertical projections and cross sections in plan...

Structure and Dynamics of Confined Alcohol-Water Mixtures.

PubMed

Bampoulis, Pantelis; Witteveen, Jorn P; Kooij, E Stefan; Lohse, Detlef; Poelsema, Bene; Zandvliet, Harold J W

2016-07-26

The effect of confinement between mica and graphene on the structure and dynamics of alcohol-water mixtures has been studied in situ and in real time at the molecular level by atomic force microscopy (AFM) at room temperature. AFM images reveal that the adsorbed molecules are segregated into faceted alcohol-rich islands on top of an ice layer on mica, surrounded by a pre-existing multilayer water-rich film. These faceted islands are in direct contact with the graphene surface, revealing a preferred adsorption site. Moreover, alcohol adsorption at low relative humidity (RH) reveals a strong preference of the alcohol molecules for the ordered ice interface. The growth dynamics of the alcohol islands is governed by supersaturation, temperature, the free energy of attachment of molecules to the island edge and two-dimensional (2D) diffusion. The measured diffusion coefficients display a size dependence on the molecular size of the alcohols, and are about 6 orders of magnitude smaller than the bulk diffusion coefficients, demonstrating the effect of confinement on the behavior of the alcohols. These experimental results provide new insights into the behavior of multicomponent fluids in confined geometries, which is of paramount importance in nanofluidics and biology.

Novel electrospun gas diffusion layers for polymer electrolyte membrane fuel cells: Part I. Fabrication, morphological characterization, and in situ performance

NASA Astrophysics Data System (ADS)

Chevalier, S.; Lavielle, N.; Hatton, B. D.; Bazylak, A.

2017-06-01

In this first of a series of two papers, we report an in-depth analysis of the impact of the gas diffusion layer (GDL) structure on the polymer electrolyte membrane (PEM) fuel cell performance through the use of custom GDLs fabricated in-house. Hydrophobic electrospun nanofibrous gas diffusion layers (eGDLs) are fabricated with controlled fibre diameter and alignment. The eGDLs are rendered hydrophobic through direct surface functionalization, and this molecular grafting is achieved in the absence of structural alteration. The fibre diameter, chemical composition, and electrical conductivity of the eGDL are characterized, and the impact of eGDL structure on fuel cell performance is analysed. We observe that the eGDL facilitates higher fuel cell power densities compared to a commercial GDL (Toray TGP-H-60) at highly humidified operating conditions. The ohmic resistance of the fuel cell is found to significantly increase with increasing inter-fiber distance. It is also observed that the addition of a hydrophobic treatment enhances membrane hydration, and fibres perpendicularly aligned to the channel direction may enhance the contact area between the catalyst layer and the GDL.

Formulation development of physiological environment responsive periodontal drug delivery system for local delviery of metronidazole benzoate.

PubMed

Dabhi, Mahesh R; Sheth, Navin R

2013-03-01

The objective of the present investigation was to develop and evaluate physiological environment responsive periodontal drug delivery system (PERPDDS) for local delivery of metronidazole benzoate. Poly-ϵ-caprolactone an in situ precipitating polymer was used in combination with, carbopol 934P, a pH simulative polymer to develop PERPDDS. The prepared PERPDDS was evaluated for various parameters such as in vitro gelling capacity, viscosity, rheology, compatibility study, and in vitro diffusion study. A 3(2) full factorial design was used to investigate the influence of formulation variables. Drug release data from all formulations were fitted to different kinetic models and the korsemeyer-peppas model was found the best fit model. The value of diffusional exponent (n) was in between 0.3283 and 0.3979 indicating purely fickian diffusion release mechanism. Increasing the concentration of each polymeric component increases viscosity, and time for 50% and 90% drug release was observed and graphically represented by the surface response and contour plots.

Mercury Na exospheric emission related to solar disturbances

NASA Astrophysics Data System (ADS)

Orsini, S.; Mangano, V.; Milillo, A.; Plainaki, C.; Mura, A.; Massetti, S.; Raines, J. M.; De Angelis, E.; Rispoli, R.; Lazzarotto, F.; Aronica, A.

2017-09-01

A first attempt to use Na exospheric emission at Mercury as a proxy of CME transit is presented, in a kind of planetary space weather. The link existing between the dayside exosphere Na pattern at Mercury and the solar wind-magnetosphere-surface interactions is investigated. This goal is pursued by analyzing the Na hourly average distributions, as observed by the ground-based THEMIS solar telescope during 10 selected periods between 2012 and 2013 (seeing <2"), when also data from MESSENGER were available. Very often a two-peak pattern of variable intensity is observed, symmetrically located at high latitudes in both hemispheres. Occasionally, the signal is instead diffused above the sub-solar region. We compare these different Na emission patterns with the time profiles of proton fluxes and magnetic field data, as measured in-situ by MESSENGER. Among these 10 cases, only in one occasion the Na signal is all the time diffused above the subsolar region, and only in this case the MESSENGER data indicate the occurrence of significant solar CME perturbations.

Quantifying residual, eddy, and mean flow effects on mixing in an idealized circumpolar current

DOE PAGES

Wolfram, Phillip J.; Ringler, Todd D.

2017-07-13

Meridional diffusivity is assessed in this paper for a baroclinically unstable jet in a high-latitudeIdealized Circumpolar Current (ICC) using the Model for Prediction Across Scales-Ocean (MPAS-O) and the online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) diagnostic via space-time dispersion of particle clusters over 120 monthly realizations of O(10 6) particles on 11 potential density surfaces. Diffusivity in the jet reaches values of O(6000 m 2 s -1) and is largest near the critical layer supporting mixing suppression and critical layer theory. Values in the vicinity of the shelf break are suppressed to O(100 m 2 s -1) due tomore » the presence of westward slope front currents. Diffusivity attenuates less rapidly with depth in the jet than both eddy velocity and kinetic energy scalings would suggest. Removal of the mean flow via high-pass filtering shifts the nonlinear parameter (ratio of the eddy velocity to eddy phase speed) into the linear wave regime by increasing the eddy phase speed via the depth-mean flow. Low-pass filtering, in contrast, quantifies the effect of mean shear. Diffusivity is decomposed into mean flow shear, linear waves, and the residual nonhomogeneous turbulence components, where turbulence dominates and eddy-produced filamentation strained by background mean shear enhances mixing, accounting for ≥ 80% of the total diffusivity relative to mean shear [O(100 m 2 s -1)], linear waves [O(1000 m 2 s -1)], and undecomposed full diffusivity [O(6000 m 2 s -1)]. Finally, diffusivity parameterizations accounting for both the nonhomogeneous turbulence residual and depth variability are needed.« less

Spatiotemporal interpolation of discharge across a river network by using synthetic SWOT satellite data

NASA Astrophysics Data System (ADS)

Paiva, Rodrigo C. D.; Durand, Michael T.; Hossain, Faisal

2015-01-01

Recent efforts have sought to estimate river discharge and other surface water-related quantities using spaceborne sensors, with better spatial coverage but worse temporal sampling as compared with in situ measurements. The Surface Water and Ocean Topography (SWOT) mission will provide river discharge estimates globally from space. However, questions on how to optimally use the spatially distributed but asynchronous satellite observations to generate continuous fields still exist. This paper presents a statistical model (River Kriging-RK), for estimating discharge time series in a river network in the context of the SWOT mission. RK uses discharge estimates at different locations and times to produce a continuous field using spatiotemporal kriging. A key component of RK is the space-time river discharge covariance, which was derived analytically from the diffusive wave approximation of Saint Venant's equations. The RK covariance also accounts for the loss of correlation at confluences. The model performed well in a case study on Ganges-Brahmaputra-Meghna (GBM) River system in Bangladesh using synthetic SWOT observations. The correlation model reproduced empirically derived values. RK (R2=0.83) outperformed other kriging-based methods (R2=0.80), as well as a simple time series linear interpolation (R2=0.72). RK was used to combine discharge from SWOT and in situ observations, improving estimates when the latter is included (R2=0.91). The proposed statistical concepts may eventually provide a feasible framework to estimate continuous discharge time series across a river network based on SWOT data, other altimetry missions, and/or in situ data.

In situ reworking /gardening/ of the lunar surface - Evidence from the Apollo cores

NASA Technical Reports Server (NTRS)

Morris, R. V.

1978-01-01

The in situ reworking (gardening) of the lunar surface by impacting projectiles creates an in situ reworking zone extending horizontally over the entire regolith surface and extending vertically from the surface to a depth which varies from place-to-place on the moon. On the basis of available evidence, the 'high-maturity' zones observed at the top of the lunar cores have resulted from the in situ reworking of the present-day lunar surface. The temporal variation of the in situ reworking depth was investigated using depths inferred from maturity I sub s/FeO and Al-26 profiles of Apollo cores. The observed temporal variation of the in situ reworking depth in units of centimeters is equal to 2.2 times the time (in units of million years) to the 0.45th power.

Comparison of precursor infiltration into polymer thin films via atomic layer deposition and sequential vapor infiltration using in-situ quartz crystal microgravimetry

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

Padbury, Richard P.; Jur, Jesse S., E-mail: jsjur@ncsu.edu

Previous research exploring inorganic materials nucleation behavior on polymers via atomic layer deposition indicates the formation of hybrid organic–inorganic materials that form within the subsurface of the polymer. This has inspired adaptations to the process, such as sequential vapor infiltration, which enhances the diffusion of organometallic precursors into the subsurface of the polymer to promote the formation of a hybrid organic–inorganic coating. This work highlights the fundamental difference in mass uptake behavior between atomic layer deposition and sequential vapor infiltration using in-situ methods. In particular, in-situ quartz crystal microgravimetry is used to compare the mass uptake behavior of trimethyl aluminummore » in poly(butylene terephthalate) and polyamide-6 polymer thin films. The importance of trimethyl aluminum diffusion into the polymer subsurface and the subsequent chemical reactions with polymer functional groups are discussed.« less

Modeling ground thermal regime of an ancient buried ice body in Beacon Valley, Antarctica using a 1-D heat equation with latent heat effect

NASA Astrophysics Data System (ADS)

Liu, L.; Sletten, R. S.; Hallet, B.; Waddington, E. D.; Wood, S. E.

2013-12-01

An ancient massive ice body buried under several decimeters of debris in Beacon Valley, Antarctica is believed to be over one million years old, making it older than any known glacier or ice cap. It is fundamentally important as a reservoir of water, proxy for climatic information, and an expression of the periglacial landscape. It is also one of Earth's closest analog for widespread, near-surface ice found in Martian soils and ice-cored landforms. We are interested in understanding controls on how long this ice may persist since our physical model of sublimation suggests it should not be stable. In these models, the soil temperatures and the gradient are important because it determines the direction and magnitude of the vapor flux, and thus sublimation rates. To better understand the heat transfer processes and constrain the rates of processes governing ground ice stability, a model of the thermal behavior of the permafrost is applied to Beacon Valley, Antarctica. It calculates soil temperatures based on a 1-D thermal diffusion equation using a fully implicit finite volume method (FVM). This model is constrained by soil physical properties and boundary conditions of in-situ ground surface temperature measurements (with an average of -23.6oC, a maximum of 20.5oC and a minimum of -54.3oC) and ice-core temperature record at ~30 m. Model results are compared to in-situ temperature measurements at depths of 0.10 m, 0.20 m, 0.30 m, and 0.45 m to assess the model's ability to reproduce the temperature profile for given thermal properties of the debris cover and ice. The model's sensitivity to the thermal diffusivity of the permafrost and the overlaying debris is also examined. Furthermore, we incorporate the role of ice condensation/sublimation which is calculated using our vapor diffusion model in the 1-D thermal diffusion model to assess potential latent heat effects that in turn affect ground ice sublimation rates. In general, the model simulates the ground thermal regime well. Detailed temperature comparison suggests that the 1-D thermal diffusion model results closely approximate the measured temperature at all depths with the average square root of the mean squared error (SRMSE) of 0.15oC; a linear correlation between modeled and measured temperatures yields an average R2 value of 0.9997. Prominent seasonal temperature variations diminish with depth, and it equilibrates to mean annual temperature at about 21.5 m depth. The amount of heat generated/consumed by ice condensation/sublimation is insufficient to significantly impact the thermal regime.

Surface-Sensitive and Bulk Studies on the Complexation and Photosensitized Degradation of Catechol by Iron(III) as a Model for Multicomponent Aerosol Systems

NASA Astrophysics Data System (ADS)

Al-abadleh, H. A.; Tofan-Lazar, J.; Situm, A.; Ruffolo, J.; Slikboer, S.

2013-12-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

In Situ Activation of Microcapsules

NASA Technical Reports Server (NTRS)

Morrison, Dennis R. (Inventor); Mosier, Benjamin (Inventor)

2000-01-01

Disclosed are microcapsules comprising a polymer shell enclosing two or more immiscible liquid phases in which a drug, or a prodrug and a drug activator are partitioned into separate phases. or prevented from diffusing out of the microcapsule by a liquid phase in which the drug is poorly soluble. Also disclosed are methods of using the microcapsules for in situ activation of drugs where upon exposure to an appropriate energy source the internal phases mix and the drug is activated in situ.

Mechanistic Study of CO 2 Photoreduction with H 2 O on Cu/TiO 2 Nanocomposites by in Situ X-ray Absorption and Infrared Spectroscopies

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

Liu, Lianjun; Zhao, Cunyu; Miller, Jeffrey T.

2016-12-15

Cu/TiO2 composites are extensively studied for photocatalytic reduction of CO2 with H2O, but the roles of Cu species (Cu2+, Cu+, or Cu0) is not well understood, and the photocatalyst deactivation mechanism is seldom addressed. In this work, we have employed in situ techniques, i.e., X-ray absorption spectroscopy (XAS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), to explore the surface chemistry of Cu/TiO2 composites under CO2 photoreduction environment. We found that the air-calcined Cu/TiO2 (Cu/Ti(air)) surface was dominated by isolated Cu2+ sites, while the one post-treated with H2 at 200 °C (Cu/Ti(H2)) was rich in Cu+ and oxygen vacancy (VO).more » Cu/Ti(H2) showed more than 50% higher activity than Cu/Ti(air) for CO2 photoreduction to CO, mainly resulting from the synergy of Cu+, OH groups, and VO that could scavenge holes to enhance electron transfer, provide CO2 adsorption sites, and facilitate the activation and conversion of the adsorbed CO2 (HCO3– and CO2–). Meanwhile, the consumption of OH groups and Cu+ active sites by holes may result in the deactivation of Cu/Ti(H2). Moreover, in situ XAS results directly demonstrated that (1) the photoinduced oxidation of Cu+ to Cu2+ changed the surrounding environments of Cu by increasing the coordination number; (2) thermal treatment by H2 could not fully recover the OH and Cu+ sites to their original states; and (3) adding hole scavengers (e.g., methanol) maintained or even increased the more active Cu+ species from the photoreduction of Cu2+, thus leading to a higher and more stable CO2 reduction activity. Findings in this work and the application of in situ XAS technique will help develop a more efficient photocatalyst for CO2 photoreduction and advance the understanding of the reaction mechanism and surface chemistry.« less

A Portable Ground-Based Atmospheric Monitoring System (PGAMS) for the Calibration and Validation of Atmospheric Correction Algorithms Applied to Aircraft and Satellite Images

NASA Technical Reports Server (NTRS)

Schiller, Stephen; Luvall, Jeffrey C.; Rickman, Doug L.; Arnold, James E. (Technical Monitor)

2000-01-01

Detecting changes in the Earth's environment using satellite images of ocean and land surfaces must take into account atmospheric effects. As a result, major programs are underway to develop algorithms for image retrieval of atmospheric aerosol properties and atmospheric correction. However, because of the temporal and spatial variability of atmospheric transmittance it is very difficult to model atmospheric effects and implement models in an operational mode. For this reason, simultaneous in situ ground measurements of atmospheric optical properties are vital to the development of accurate atmospheric correction techniques. Presented in this paper is a spectroradiometer system that provides an optimized set of surface measurements for the calibration and validation of atmospheric correction algorithms. The Portable Ground-based Atmospheric Monitoring System (PGAMS) obtains a comprehensive series of in situ irradiance, radiance, and reflectance measurements for the calibration of atmospheric correction algorithms applied to multispectral. and hyperspectral images. The observations include: total downwelling irradiance, diffuse sky irradiance, direct solar irradiance, path radiance in the direction of the north celestial pole, path radiance in the direction of the overflying satellite, almucantar scans of path radiance, full sky radiance maps, and surface reflectance. Each of these parameters are recorded over a wavelength range from 350 to 1050 nm in 512 channels. The system is fast, with the potential to acquire the complete set of observations in only 8 to 10 minutes depending on the selected spatial resolution of the sky path radiance measurements

Determination of oxygen diffusion kinetics during thin film ruthenium oxidation

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

Coloma Ribera, R., E-mail: r.colomaribera@utwente.nl; Kruijs, R. W. E. van de; Yakshin, A. E.

2015-08-07

In situ X-ray reflectivity was used to reveal oxygen diffusion kinetics for thermal oxidation of polycrystalline ruthenium thin films and accurate determination of activation energies for this process. Diffusion rates in nanometer thin RuO{sub 2} films were found to show Arrhenius behaviour. However, a gradual decrease in diffusion rates was observed with oxide growth, with the activation energy increasing from about 2.1 to 2.4 eV. Further exploration of the Arrhenius pre-exponential factor for diffusion process revealed that oxidation of polycrystalline ruthenium joins the class of materials that obey the Meyer-Neldel rule.

Effect of Ionic Strength and Surface Charge Density on the Kinetics of Cellulose Nanocrystal Thin Film Swelling.

PubMed

Reid, Michael S; Kedzior, Stephanie A; Villalobos, Marco; Cranston, Emily D

2017-08-01

This work explores cellulose nanocrystal (CNC) thin films (<50 nm) and particle-particle interactions by investigating film swelling in aqueous solutions with varying ionic strength (1-100 mM). CNC film hydration was monitored in situ via surface plasmon resonance, and the kinetics of liquid uptake were quantified. The contribution of electrostatic double-layer forces to film swelling was elucidated by using CNCs with different surface charges (anionic sulfate half ester groups, high and low surface charge density, and cationic trimethylammonium groups). Total water uptake in the thin films was found to be independent of ionic strength and surface chemistry, suggesting that in the aggregated state van der Waals forces dominate over double-layer forces to hold the films together. However, the rate of swelling varied significantly. The water uptake followed Fickian behavior, and the measured diffusion constants decreased with the ionic strength gradient between the film and the solution. This work highlights that nanoparticle interactions and dispersion are highly dependent on the state of particle aggregation and that the rate of water uptake in aggregates and thin films can be tailored based on surface chemistry and solution ionic strength.

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature.

PubMed

Yang, Yang; Kushima, Akihiro; Han, Weizhong; Xin, Huolin; Li, Ju

2018-04-11

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. Here, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can match the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass-glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.

The hydroxyl species and acid sites on diatomite surface: a combined IR and Raman study

NASA Astrophysics Data System (ADS)

Yuan, P.; Wu, D. Q.; He, H. P.; Lin, Z. Y.

2004-04-01

Diffuse reflectance infrared Fourier transform spectroscopy (DRIFT), Raman spectroscopy of adsorbed pyridine molecules (Py-Raman) and in situ Py-IR have been used to investigate the hydroxyl species and acid sites on diatomite surfaces. The Lewis (L) and Brønsted (B) acid sites, and various hydroxyl species, including isolated hydroxyl groups, H-bonded hydroxyl groups and physically adsorbed water, are identified. The L acid sites in diatomite samples are resulted from the clay impurities, and the B acid sites are resulted from some moderate strength H-bonded hydroxyl groups. At room temperature, both of the isolated and H-bonded silanols associate with the physically adsorbed water by hydrogen bond. After calcination treatment, physically adsorbed water will be desorbed from the silanols, and the silanols will condense with the increase of temperature. Generally, the H-bonded silanols condense more easily than the isolated ones. The properties of surface hydroxyl species of diatomaceous silica are more similar to precipitated silica rather than fumed silica.

Stabilization of Oxidized Copper Nanoclusters in Confined Spaces

DOE PAGES

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang; ...

2018-01-04

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Nondestructive estimation of depth of surface opening cracks in concrete beams

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

Arne, Kevin; In, Chiwon; Kurtis, Kimberly

Concrete is one of the most widely used construction materials and thus assessment of damage in concrete structures is of the utmost importance from both a safety point of view and a financial point of view. Of particular interest are surface opening cracks that extend through the concrete cover, as this can expose the steel reinforcement bars underneath and induce corrosion in them. This corrosion can lead to significant subsequent damage in concrete such as cracking and delamination of the cover concrete as well as rust staining on the surface of concrete. Concrete beams are designed and constructed in suchmore » a way to provide crack depths up to around 13 cm. Two different types of measurements are made in-situ to estimate depths of real surface cracks (as opposed to saw-cut notches) after unloading: one based on the impact-echo method and the other one based on the diffuse ultrasonic method. These measurements are compared to the crack depth visually observed on the sides of the beams. Discussions are given as to the advantages and disadvantages of each method.« less

Mathematical model investigation of long-term transport of ocean-dumped sewage sludge related to remote sensing

NASA Technical Reports Server (NTRS)

Kuo, C. Y.; Modena, T. D.

1979-01-01

An existing, three-dimensional, Eulerian-Lagrangian finite-difference model was modified and used to examine the transport processes of dumped sewage sludge in the New York Bight. Both in situ and laboratory data were utilized in an attempt to approximate model inputs such as mean current speed, horizontal diffusion coefficients, particle size distributions, and specific gravities. The results presented are a quantitative description of the fate of a negatively buoyant sewage sludge plume resulting from continuous and instantaneous barge releases. Concentrations of the sludge near the surface were compared qualitatively with those remotely sensed. Laboratory study was performed to investigate the behavior of sewage sludge dumping in various ambient density conditions.

In-situ observation of impurity diffusion boundary layer in silicon Czochralski growth

NASA Astrophysics Data System (ADS)

Kakimoto, Koichi; Eguchi, Minoru; Watanabe, Hisao; Hibiya, Taketoshi

1990-01-01

In-situ observation of the impurity diffusion boundary layer during single crystal growth of indium-doped silicon was carried out by X-ray radiography. The difference in the transmitted X-ray image compared with molten silicon just beneath the crystal-melt interface was attributed to the concentration of indium impurities having a larger absorption coefficient. The intensity profile of the transmitted X-ray can be reproduced by a transmittance calculation that considers the meniscus shape and impurity distribution. The impurity distribution profile near the crystal-melt interface was estimated using the Burton-Prim-Slichter (BPS) equation. The observed impurity diffusion boundary layer thickness was about 0.5 mm. It was found that the boundary layer thickness was not constant in the radial direction, which cannot be explained by the BPS theory, since it is based on a one-dimensional calculation.

Highly electroconductive mesoporous graphene nanofibers and their capacitance performance at 4 V.

PubMed

Cui, Chaojie; Qian, Weizhong; Yu, Yuntao; Kong, Chuiyan; Yu, Bo; Xiang, Lan; Wei, Fei

2014-02-12

We report the fabrication of one-dimensional highly electroconductive mesoporous graphene nanofibers (GNFs) by a chemical vapor deposition method using MgCO3·3H2O fibers as the template. The growth of such a unique structure underwent the first in situ decomposition of MgCO3·3H2O fibers to porous MgO fibers, followed by the deposition of carbon on the MgO surface, the removal of MgO by acidic washing, and the final self-assembly of wet graphene from single to double layer in drying process. GNFs exhibited good structural stability, high surface area, mesopores in large amount, and electrical conductivity 3 times that of carbon nanotube aggregates. It, used as an electrode in a 4 V supercapacitor, exhibited high energy density in a wide range of high power density and excellent cycling stability. The short diffusion distance for ions of ionic liquids electrolyte to the surface of GNFs yielded high surface utilization efficiency and a capacitance up to 15 μF/cm(2), higher than single-walled carbon nanotubes.

Back-junction back-contact n-type silicon solar cell with diffused boron emitter locally blocked by implanted phosphorus

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

Müller, Ralph, E-mail: ralph.mueller@ise.fraunhofer.de; Schrof, Julian; Reichel, Christian

2014-09-08

The highest energy conversion efficiencies in the field of silicon-based photovoltaics have been achieved with back-junction back-contact (BJBC) silicon solar cells by several companies and research groups. One of the most complex parts of this cell structure is the fabrication of the locally doped p- and n-type regions, both on the back side of the solar cell. In this work, we introduce a process sequence based on a synergistic use of ion implantation and furnace diffusion. This sequence enables the formation of all doped regions for a BJBC silicon solar cell in only three processing steps. We observed that implantedmore » phosphorus can block the diffusion of boron atoms into the silicon substrate by nearly three orders of magnitude. Thus, locally implanted phosphorus can be used as an in-situ mask for a subsequent boron diffusion which simultaneously anneals the implanted phosphorus and forms the boron emitter. BJBC silicon solar cells produced with such an easy-to-fabricate process achieved conversion efficiencies of up to 21.7%. An open-circuit voltage of 674 mV and a fill factor of 80.6% prove that there is no significant recombination at the sharp transition between the highly doped emitter and the highly doped back surface field at the device level.« less

Data-driven fault mechanics: Inferring fault hydro-mechanical properties from in situ observations of injection-induced aseismic slip

NASA Astrophysics Data System (ADS)

Bhattacharya, P.; Viesca, R. C.

2017-12-01

In the absence of in situ field-scale observations of quantities such as fault slip, shear stress and pore pressure, observational constraints on models of fault slip have mostly been limited to laboratory and/or remote observations. Recent controlled fluid-injection experiments on well-instrumented faults fill this gap by simultaneously monitoring fault slip and pore pressure evolution in situ [Gugleilmi et al., 2015]. Such experiments can reveal interesting fault behavior, e.g., Gugleilmi et al. report fluid-activated aseismic slip followed only subsequently by the onset of micro-seismicity. We show that the Gugleilmi et al. dataset can be used to constrain the hydro-mechanical model parameters of a fluid-activated expanding shear rupture within a Bayesian framework. We assume that (1) pore-pressure diffuses radially outward (from the injection well) within a permeable pathway along the fault bounded by a narrow damage zone about the principal slip surface; (2) pore-pressure increase ativates slip on a pre-stressed planar fault due to reduction in frictional strength (expressed as a constant friction coefficient times the effective normal stress). Owing to efficient, parallel, numerical solutions to the axisymmetric fluid-diffusion and crack problems (under the imposed history of injection), we are able to jointly fit the observed history of pore-pressure and slip using an adaptive Monte Carlo technique. Our hydrological model provides an excellent fit to the pore-pressure data without requiring any statistically significant permeability enhancement due to the onset of slip. Further, for realistic elastic properties of the fault, the crack model fits both the onset of slip and its early time evolution reasonably well. However, our model requires unrealistic fault properties to fit the marked acceleration of slip observed later in the experiment (coinciding with the triggering of microseismicity). Therefore, besides producing meaningful and internally consistent bounds on in-situ fault properties like permeability, storage coefficient, resolved stresses, friction and the shear modulus, our results also show that fitting the complete observed time history of slip requires alternative model considerations, such as variations in fault mechanical properties or friction coefficient with slip.

Simultaneous measurement of X-ray specular reflection and off-specular diffuse scattering from liquid surfaces using a two-dimensional pixel array detector: the liquid-interface reflectometer of BL37XU at SPring-8.

PubMed

Yano, Yohko F; Uruga, Tomoya; Tanida, Hajime; Toyokawa, Hidenori; Terada, Yasuko; Yamada, Hironari

2010-07-01

An X-ray reflectometer for simultaneous measurement of specular and off-specular reflection of liquid surfaces is described. The reflectometer, equipped with a two-dimensional single X-ray photon-counting pixel array detector obtained the full range of X-ray specular and off-specular reflections in an extremely short time (1 s). Both the specular and off-specular reflection of water exhibited good agreement with the predicted capillary-wave theory within the appropriate instrumental resolution. The approach is also demonstrated on an aqueous solution of 1-dodecyl-3-methylimidazolium chloride. The monolayer in which the dodecyl chain faces upwards and the Cl(-) anion locates next to the imidazolium ring formed on the water surface was found to be laterally homogeneous. The use of a pixel array detector will be particularly powerful for in situ measurements to investigate both out-of-plane and in-plane structures simultaneously, not only for liquid surfaces but also for other thin films.

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

NASA Astrophysics Data System (ADS)

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

2009-12-01

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

Characterization and In-Situ Monitoring of ZnSe Crystal Growth by Seeded PVT for Microgravity Applications

NASA Technical Reports Server (NTRS)

Feth, Shari T.

2001-01-01

Crystal growth from the vapor phase continues to play a significant role in the production of II-VI semiconductor compounds (ZnO, ZnTe, CdTe, etc.) and SiC. As compared to melt growth methods (where available) the advantages are: (1) lower growth temperature(s); (2) reduction in defect concentration; (3) additional purification; and (4) enhanced crystal perfection. A powerful tool in determining the mechanism of PVT is microgravity. Under normal gravity conditions the transport mechanism is a superposition of diffusive and convective fluxes. Microgravity offers the possibility of studying the transport properties without the influence of convective effects. Research on the crystal growth of ZnSe by PVT (P.I.: Su of NASA/MSFC) will help to clarify the effects of convection on crystal growth. A crystal growth furnace with in-situ and real time optical monitoring capabilities was constructed and used to monitor the vapor composition and growing crystal surface morphology during the PVT growth of ZnSe. Using photoluminescence and SIMS, ex-situ, the incorporation of point defects (Zn vacancy) and impurities was found to be correlated to the gravity vector due to the influence of the convective flow. A summary of the results to date will be presented.

Diffusion and surface alloying of gradient nanostructured metals

PubMed Central

Lu, Ke

2017-01-01

Gradient nanostructures (GNSs) have been optimized in recent years for desired performance. The diffusion behavior in GNS metals is crucial for understanding the diffusion mechanism and relative characteristics of different interfaces that provide fundamental understanding for advancing the traditional surface alloying processes. In this paper, atomic diffusion, reactive diffusion, and surface alloying processes are reviewed for various metals with a preformed GNS surface layer. We emphasize the promoted atomic diffusion and reactive diffusion in the GNS surface layer that are related to a higher interfacial energy state with respect to those in relaxed coarse-grained samples. Accordingly, different surface alloying processes, such as nitriding and chromizing, have been modified significantly, and some diffusion-related properties have been enhanced. Finally, the perspectives on current research in this field are discussed. PMID:28382244

A novel in-situ method for real-time monitoring of gas transport in soil

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Maier, Martin; Schack-Kirchner, Helmer; Lang, Friederike

2017-04-01

Gas exchange between soil and atmosphere is important for the biogeochemistry of soils. Gas transport in soil is commonly assumed to be governed by molecular diffusion and is usually described by the soil gas diffusion coefficient DS characterizing the ability of the soil to "transport passively" gas through the soil. One way to determine DS is sampling soil cores in the field and measuring DS in the lab. Unfortunately this method is destructive and laborious. Moreover, a few previous field studies identified other gas transport processes in soil to significantly enhance the diffusive gas transport. However, until now, no method is available to measure gas transport in situ in the soil. We developed a novel method to monitor gas transport in soil in situ. The method includes a custom made gas sampling device, the continuous injection of an inert tracer gas and inverse gas transport modelling in the soil. The gas sampling device has several sampling depths and can be easily installed into a vertical hole drilled by an auger, which allows for fast installation of the system. Helium (He) as inert tracer gas was injected continuously at the lower end of the device. The resulting steady state distribution of He was used to deduce the depth profile of DS. Gas transport in the soil surrounding the gas-sampling-device/soil system was modeled using the Finite Element Modeling program COMSOL . We tested our new method both in the lab and during two short field studies and compared the results with a reference method using soil cores. DS profiles obtained by our in-situ method were consistent with DS profiles determined based on soil core analyses. During a longer monitoring field campaign, typical soil-moisture effects upon gas diffusivity such as an increase during a drying period or a decrease after rain could be observed consistently. Under windy conditions we additionally measured for the first time the direct enhancement of gas transport in soil due to wind-induced pressure-pumping which could increase the effective DS up to 30% in the topsoil. Our novel monitoring method can be quickly and easily installed and allows for monitoring continuously soil gas transport over a long time. It allows monitoring physical modifications of soil gas diffusivity due to rain events or evaporation but it also allows studying non-diffusive gas transport processes in the soil.

Erosion processes in molassic cliffs: the role of the rock surface temperature and atmospheric conditions

NASA Astrophysics Data System (ADS)

Carrea, Dario; Abellán, Antonio; Guerin, Antoine; Jaboyedoff, Michel; Voumard, Jérémie

2014-05-01

The morphology of the Swiss Plateau is modeled by numerous steep cliffs of Molasse. These cliffs are mainly composed of sub-horizontal alternated layers of sandstone, shale and conglomerates deposed in the Alps foreland basin during the Tertiary period. These Molasse cliffs are affected by erosion processes inducing numerous rockfall events. Thus, it is relevant to understand how different external factors influence Molasse erosion rates. In this study, we focus on analyzing temperature variation during a winter season. As pilot study area we selected a cliff which is formed by a sub-horizontal alternation of outcropping sandstone and shale. The westward facing test site (La Cornalle, Vaud, Switzerland), which is a lateral scarp of a slow moving landslide area, is currently affected by intense erosion. Regarding data acquisition, we monitored both in-situ rock and air temperatures at 15 minutes time-step since October 2013: (1) on the one hand we measured Ground Surface Temperature (GST) at near-surface (0.1 meter depth) using a GST mini-datalogger M-Log5W-Rock model; (2) On the other hand we monitored atmospheric conditions using a weather station (Davis Vantage pro2 plus) collecting numerous parameters (i.e. temperature, irradiation, rain, wind speed, etc.). Furthermore, the area was also seasonally monitored by Ground-Based (GB) LiDAR since 2010 and monthly monitored since September 2013. In order to understand how atmospheric conditions (such as freeze and thaw effect) influence the erosion of the cliff, we modeled the temperature diffusion through the rock mass. To this end, we applied heat diffusion and radiation equation using a 1D temperature profile, obtaining as a result both temperature variations at different depths together with the location of the 0°C isotherm. Our model was calibrated during a given training set using both in-situ rock temperatures and atmospheric conditions. We then carried out a comparison with the rockfall events derived from the 3D GB-LiDAR datasets in order to quantify the erosion rates and to correlate it with atmospheric conditions, aiming to analyze which parameters influence Molasse erosion process.

Ionic liquids behave as dilute electrolyte solutions

PubMed Central

Gebbie, Matthew A.; Valtiner, Markus; Banquy, Xavier; Fox, Eric T.; Henderson, Wesley A.; Israelachvili, Jacob N.

2013-01-01

We combine direct surface force measurements with thermodynamic arguments to demonstrate that pure ionic liquids are expected to behave as dilute weak electrolyte solutions, with typical effective dissociated ion concentrations of less than 0.1% at room temperature. We performed equilibrium force–distance measurements across the common ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]) using a surface forces apparatus with in situ electrochemical control and quantitatively modeled these measurements using the van der Waals and electrostatic double-layer forces of the Derjaguin–Landau–Verwey–Overbeek theory with an additive repulsive steric (entropic) ion–surface binding force. Our results indicate that ionic liquids screen charged surfaces through the formation of both bound (Stern) and diffuse electric double layers, where the diffuse double layer is comprised of effectively dissociated ionic liquid ions. Additionally, we used the energetics of thermally dissociating ions in a dielectric medium to quantitatively predict the equilibrium for the effective dissociation reaction of [C4mim][NTf2] ions, in excellent agreement with the measured Debye length. Our results clearly demonstrate that, outside of the bound double layer, most of the ions in [C4mim][NTf2] are not effectively dissociated and thus do not contribute to electrostatic screening. We also provide a general, molecular-scale framework for designing ionic liquids with significantly increased dissociated charge densities via judiciously balancing ion pair interactions with bulk dielectric properties. Our results clear up several inconsistencies that have hampered scientific progress in this important area and guide the rational design of unique, high–free-ion density ionic liquids and ionic liquid blends. PMID:23716690

Ionospheric Irregularities at Mars Probed by MARSIS Topside Sounding

NASA Astrophysics Data System (ADS)

Harada, Y.; Gurnett, D. A.; Kopf, A. J.; Halekas, J. S.; Ruhunusiri, S.

2018-01-01

The upper ionosphere of Mars contains a variety of perturbations driven by solar wind forcing from above and upward propagating atmospheric waves from below. Here we explore the global distribution and variability of ionospheric irregularities around the exobase at Mars by analyzing topside sounding data from the Mars Advanced Radar for Subsurface and Ionosphere Sounding (MARSIS) instrument on board Mars Express. As irregular structure gives rise to off-vertical echoes with excess propagation time, the diffuseness of ionospheric echo traces can be used as a diagnostic tool for perturbed reflection surfaces. The observed properties of diffuse echoes above unmagnetized regions suggest that ionospheric irregularities with horizontal wavelengths of tens to hundreds of kilometers are particularly enhanced in the winter hemisphere and at high solar zenith angles. Given the known inverse dependence of neutral gravity wave amplitudes on the background atmospheric temperature, the ionospheric irregularities probed by MARSIS are most likely associated with plasma perturbations driven by atmospheric gravity waves. Though extreme events with unusually diffuse echoes are more frequently observed for high solar wind dynamic pressures during some time intervals, the vast majority of the diffuse echo events are unaffected by varying solar wind conditions, implying limited influence of solar wind forcing on the generation of ionospheric irregularities. Combination of remote and in situ measurements of ionospheric irregularities would offer the opportunity for a better understanding of the ionospheric dynamics at Mars.

Silver Nanocube and Nanobar Growth via Anisotropic Monomer Addition and Particle Attachment Processes

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

Xiao, Dongdong; Wu, Zhigang; Song, Miao

Understanding the growth mechanism of noble metal nanocrystals during solution synthesis is of significant importance for shape and property control. However, much remains unknown about the growth pathways of metal nanoparticles due to lack of direct observation. Using an in-situ transmission electron microscopy technique, we directly observed Ag nanocube and nanobar growth in aqueous solution through both classical monomer-by-monomer addition and non-classical particle attachment processes. During the particle attachment process, Ag nanocubes and nanobars formed via both oriented and non-oriented attachment. Our calculations, along with dynamics of the observed attachment, showed that van der Waals force overcame hydrodynamic and frictionmore » forces and drove the particles toward each other. During classical growth, an anisotropic growth was also revealed, and the resulting unsymmetrical shape constituted an intermediate state for Ag nanocube growth. We hypothesized that the temporary symmetry breaking resulted from different growth rates on {001} surfaces due to a local surface concentration variation caused by the imbalance between the consumption of Ag+ near the surface and the diffusion of Ag+ from bulk to surface.« less

Infrared Study of CO2 Sorption over ?Molecular Basket? Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve

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

Overbury, Steven; Wang, Xiaoxing; Clark, Jason

2009-01-01

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75 C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75 C. Comparative IR examination of the CO{sub 2} sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO{sub 2}-amine interaction patterns.« less

Molecular-level spectroscopic investigations of the complexation and photodegradation of catechol to/by iron(III)

NASA Astrophysics Data System (ADS)

Al-Abadleh, Hind; Tofan-Lazar, Julia; Situm, Arthur; Slikboer, Samantha

2014-05-01

Surface water plays a crucial role in facilitating or inhibiting surface reactions in atmospheric aerosols. Little is known about the role of surface water in the complexation of organic molecules to transition metals in multicomponent aerosol systems. We will show results from real time diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) experiments for the in situ complexation of catechol to Fe(III) and its photosensitized degradation under dry and humid conditions. Catechol was chosen as a simple model for humic-like substances (HULIS) in aerosols and aged polyaromatic hydrocarbons (PAH). It has also been detected in secondary organic aerosols (SOA) formed from the reaction of hydroxyl radicals with benzene. Given the importance of the iron content in aerosols and its biogeochemistry, our studies were conducted using FeCl3. For comparison, these surface-sensitive studies were complemented with bulk aqueous ATR-FTIR, UV-vis, and HPLC measurements for structural, quantitative and qualitative information about complexes in the bulk, and potential degradation products. The implications of our studies on understanding interfacial and condensed phase chemistry relevant to multicomponent aerosols, water thin islands on buildings, and ocean surfaces containing transition metals will be discussed.

Thermal annealing dynamics of carbon-coated LiFePO{sub 4} nanoparticles studied by in-situ analysis

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

Krumeich, Frank, E-mail: krumeich@inorg.chem.ethz.ch; Waser, Oliver; Pratsinis, Sotiris E.

The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO{sub 4}-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO{sub 4}-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO{sub 4} starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further tomore » T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO{sub 4} particles (diameter in the range 300–400 nm), in agreement with ex-situ experiments. - Graphical abstract: TEM images of a typical sample area recorded at room temperature and after heating in-situ heating reveal the growth of particles and the formation of empty carbon cages. - Highlights: • LiFePO{sub 4} coated by a carbon shell is produced by flame spray pyrolysis. • The amorphous LiFePO{sub 4} starts to crystallize at 400 °C as revealed by in-situ XRD. • Crystal growth was visualized by TEM heating experiments. • The formation of empty carbon cages starts at 700 °C.« less

Electrochemical formation and characterization of Au nanostructures on a highly ordered pyrolytic graphite surface

NASA Astrophysics Data System (ADS)

Gómez, José J. Arroyo; Zubieta, Carolina; Ferullo, Ricardo M.; García, Silvana G.

2016-02-01

The electrochemical formation of Au nanoparticles on a highly ordered pyrolytic graphite (HOPG) substrate using conventional electrochemical techniques and ex-situ AFM is reported. From the potentiostatic current transients studies, the Au electrodeposition process on HOPG surfaces was described, within the potential range considered, by a model involving instantaneous nucleation and diffusion controlled 3D growth, which was corroborated by the microscopic analysis. Initially, three-dimensional (3D) hemispherical nanoparticles distributed on surface defects (step edges) of the substrate were observed, with increasing particle size at more negative potentials. The double potential pulse technique allowed the formation of rounded deposits at low deposition potentials, which tend to form lines of nuclei aligned in defined directions leading to 3D ordered structures. By choosing suitable nucleation and growth pulses, one-dimensional (1D) deposits were possible, preferentially located on step edges of the HOPG substrate. Quantum-mechanical calculations confirmed the tendency of Au atoms to join selectively on surface defects, such as the HOPG step edges, at the early stages of Au electrodeposition.

Generating a Simulated Fluid Flow Over an Aircraft Surface Using Anisotropic Diffusion

NASA Technical Reports Server (NTRS)

Rodriguez, David L. (Inventor); Sturdza, Peter (Inventor)

2013-01-01

A fluid-flow simulation over a computer-generated aircraft surface is generated using a diffusion technique. The surface is comprised of a surface mesh of polygons. A boundary-layer fluid property is obtained for a subset of the polygons of the surface mesh. A pressure-gradient vector is determined for a selected polygon, the selected polygon belonging to the surface mesh but not one of the subset of polygons. A maximum and minimum diffusion rate is determined along directions determined using a pressure gradient vector corresponding to the selected polygon. A diffusion-path vector is defined between a point in the selected polygon and a neighboring point in a neighboring polygon. An updated fluid property is determined for the selected polygon using a variable diffusion rate, the variable diffusion rate based on the minimum diffusion rate, maximum diffusion rate, and angular difference between the diffusion-path vector and the pressure-gradient vector.

30 CFR 1206.463 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Indian Coal § 1206.463 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

30 CFR 1206.463 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Indian Coal § 1206.463 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

30 CFR 1206.264 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Federal Coal § 1206.264 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

30 CFR 1206.264 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false In-situ and surface gasification and... developed by in-situ or surface gasification or liquefaction technology, the lessee shall propose the value... ENFORCEMENT, DEPARTMENT OF THE INTERIOR Natural Resources Revenue PRODUCT VALUATION Federal Coal § 1206.264 In...

30 CFR 1206.264 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Federal Coal § 1206.264 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

30 CFR 1206.463 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Indian Coal § 1206.463 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

30 CFR 1206.463 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false In-situ and surface gasification and... developed by in-situ or surface gasification or liquefaction technology, the lessee shall propose the value... ENFORCEMENT, DEPARTMENT OF THE INTERIOR Natural Resources Revenue PRODUCT VALUATION Indian Coal § 1206.463 In...

30 CFR 1206.264 - In-situ and surface gasification and liquefaction operations.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false In-situ and surface gasification and..., DEPARTMENT OF THE INTERIOR NATURAL RESOURCES REVENUE PRODUCT VALUATION Federal Coal § 1206.264 In-situ and surface gasification and liquefaction operations. If an ad valorem Federal coal lease is developed by in...

Generating a Simulated Fluid Flow over a Surface Using Anisotropic Diffusion

NASA Technical Reports Server (NTRS)

Rodriguez, David L. (Inventor); Sturdza, Peter (Inventor)

2016-01-01

A fluid-flow simulation over a computer-generated surface is generated using a diffusion technique. The surface is comprised of a surface mesh of polygons. A boundary-layer fluid property is obtained for a subset of the polygons of the surface mesh. A gradient vector is determined for a selected polygon, the selected polygon belonging to the surface mesh but not one of the subset of polygons. A maximum and minimum diffusion rate is determined along directions determined using the gradient vector corresponding to the selected polygon. A diffusion-path vector is defined between a point in the selected polygon and a neighboring point in a neighboring polygon. An updated fluid property is determined for the selected polygon using a variable diffusion rate, the variable diffusion rate based on the minimum diffusion rate, maximum diffusion rate, and the gradient vector.

Stabilized liquid membrane device (SLMD) for the passive, integrative sampling of labile metals in water

USGS Publications Warehouse

Brumbaugh, W.G.; Petty, J.D.; Huckins, J.N.; Manahan, S.E.

2002-01-01

A stabilized liquid membrane device (SLMD) is described for potential use as an in situ, passive, integrative sampler for cadmium (Cd), cobalt (Co), copper (Cu), nickel (Ni), lead (Pb), and zinc (Zn) in natural waters. The SLMD (patent pending) consists of a 2.5-cm-wide by 15-cm-long strip of low-density polyethylene (LDPE) layflat tubing containing 1 mL of an equal mixture (v/v) of oleic acid (cis-9-octadecenoic acid) and EMO-8Q (7-[4-ethyl-1-methyloctyl]-8-quinolinol). The reagent mixture continuously diffuses to the exterior surface of the LDPE membrane, and provides for sequestration of several divalent metals for up to several weeks. Depending on sampler configuration, concentration factors of several thousand can be realized for these metal ions after just a few days. In addition to in situ deployment, the SLMD may be useful for laboratory determination of labile metal species in grab samples. Methods for minimizing the effects of water flow on the sampling rate are currently under investigation.

Silver Film Surface Modification by Ion Bombardment Decreases Surface Plasmon Resonance Absorption.

PubMed

Fryauf, David M; Diaz Leon, Juan J; Phillips, Andrew C; Kobayashi, Nobuhiko P

2017-05-10

Silver thin films covered with dielectric films serving as protective coatings are desired for telescope mirrors, but durable coatings have proved elusive. As part of an effort to develop long-lived protected-silver mirrors, silver thin films were deposited by electron beam evaporation using a physical vapor deposition system at the University of California Observatories Astronomical Coatings Lab. The silver films were later covered with a stack of dielectric films utilizing silicon nitride and titanium dioxide deposited by ion-assisted electron beam evaporation to fabricate protected mirrors. In-situ argon ion bombardment was introduced after silver deposition and prior to the deposition of dielectric films to assess its effects on the performance of the mirrors. We found that ion bombardment of the silver influenced surface morphology and reflectivity, and these effects correlated with time between silver deposition and ion bombardment. The overall reflectivity at wavelengths in the range of 350-800 nm was found to improve due to ion bombardment, which was qualitatively interpreted as a result of decreased surface plasmon resonance coupling. We suggest that the observed decrease in coupling is caused by silver grain boundary pinning due to ion bombardment suppressing silver surface diffusion, forming smoother silver-dielectric interfaces.

Analysis of diffusion in curved surfaces and its application to tubular membranes

PubMed Central

Klaus, Colin James Stockdale; Raghunathan, Krishnan; DiBenedetto, Emmanuele; Kenworthy, Anne K.

2016-01-01

Diffusion of particles in curved surfaces is inherently complex compared with diffusion in a flat membrane, owing to the nonplanarity of the surface. The consequence of such nonplanar geometry on diffusion is poorly understood but is highly relevant in the case of cell membranes, which often adopt complex geometries. To address this question, we developed a new finite element approach to model diffusion on curved membrane surfaces based on solutions to Fick’s law of diffusion and used this to study the effects of geometry on the entry of surface-bound particles into tubules by diffusion. We show that variations in tubule radius and length can distinctly alter diffusion gradients in tubules over biologically relevant timescales. In addition, we show that tubular structures tend to retain concentration gradients for a longer time compared with a comparable flat surface. These findings indicate that sorting of particles along the surfaces of tubules can arise simply as a geometric consequence of the curvature without any specific contribution from the membrane environment. Our studies provide a framework for modeling diffusion in curved surfaces and suggest that biological regulation can emerge purely from membrane geometry. PMID:27733625

Diffusion in biofilms respiring on electrodes

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

Renslow, Ryan S.; Babauta, Jerome T.; Majors, Paul D.

2012-11-15

The goal of this study was to measure spatially and temporally resolved effective diffusion coefficients (De) in biofilms respiring on electrodes. Two model electrochemically active biofilms, Geobacter sulfurreducens PCA and Shewanella oneidensis MR-1, were investigated. A novel nuclear magnetic resonance microimaging perfusion probe capable of simultaneous electrochemical and pulsed-field gradient nuclear magnetic resonance (PFG-NMR) techniques was used. PFG-NMR allowed for noninvasive, nondestructive, high spatial resolution in situ De measurements in living biofilms respiring on electrodes. The electrodes were polarized so that they would act as the sole terminal electron acceptor for microbial metabolism. We present our results as both two-dimensionalmore » De heat maps and surface-averaged relative effective diffusion coefficient (Drs) depth profiles. We found that (1) Drs decreases with depth in G. sulfurreducens biofilms, following a sigmoid shape; (2) Drs at a given location decreases with G. sulfurreducens biofilm age; (3) average De and Drs profiles in G. sulfurreducens biofilms are lower than those in S. oneidensis biofilms—the G. sulfurreducens biofilms studied here were on average 10 times denser than the S. oneidensis biofilms; and (4) halting the respiration of a G. sulfurreducens biofilm decreases the De values. Density, reflected by De, plays a major role in the extracellular electron transfer strategies of electrochemically active biofilms.« less

Finding the best windows: An apparent environmental threshold determines which diffuse flows are dominated by subsurface microbes

NASA Astrophysics Data System (ADS)

Olins, H. C.; Rogers, D.; Scholin, C. A.; Preston, C. J.; Vidoudez, C.; Ussler, W.; Pargett, D.; Jensen, S.; Roman, B.; Birch, J. M.; Girguis, P. R.

2014-12-01

Hydrothermal vents are hotspots of microbial primary productivity often described as "windows into the subsurface biosphere." High temperature vents have received the majority of research attention, but cooler diffuse flows are as, if not more, important a source of heat and chemicals to the overlying ocean. We studied patterns of in situ gene expression and co-registered geochemistry in order to 1) describe the diversity and physiological poise of active microbial communities that span thermal and geochemical gradients from active diffuse flow to background vent field seawater, and 2) determine to what extent seawater or subsurface microbes were active throughout this environment. Analyses of multiple metatranscriptomes from 5 geochemically distinct sites (some from samples preserved in situ) show that proximate diffuse flows showed strikingly different transcription profiles. Specifically, caldera background and some diffuse flows were similar, both dominated by seawater-derived Gammaproteobacteria despite having distinct geochemistries. Intra-field community shows evidence of increased primary productivity throughout the entire vent field and not just at individual diffuse flows. In contrast, a more spatially limited, Epsilonproteobacteria-dominated transcription profile from the most hydrothermally-influenced diffuse flow appeared to be driven by the activity of vent-endemic microbes, likely reflecting subsurface microbial activity. We suggest that the microbial activity within many diffuse flow vents is primarily attributable to seawater derived Gammaproteobacterial sulfur oxidizers, while in certain other flows vent-endemic Epsilonproteobactiera are most active. These data reveal a diversity in microbial activity at diffuse flows that has not previously been recognized, and reshapes our thinking about the relative influence that different microbial communities may have on local processes (such as primary production) and potentially global biogeochemical cycles.

Structural, chemical, and magnetic properties of Fe films grown on InAs(100)

NASA Astrophysics Data System (ADS)

Ruppel, L.; Witte, G.; Wöll, Ch.; Last, T.; Fischer, S. F.; Kunze, U.

2002-12-01

The structure of epitaxial Fe films grown on an InAs(100)-c(8×2)/(4×2) surface has been studied in situ by means of low-energy electron diffraction and x-ray photoelectron spectroscopy, while their magnetic properties were characterized ex situ by superconducting quantum interference device magnetometry at temperatures of 5 300 K. Deposition of iron at room temperature or below leads to the formation of a thin iron arsenide layer that floats on the Fe film upon further deposition. Postdeposition annealing causes no significant improvement of the film structure but activates a further arsenic diffusion through the Fe film. Significant exchange-bias effects were found at low temperatures for insufficiently capped and partially oxidized Fe films, and are attributed to noncollinear spin order at the Ag capping layer/Fe interface. For perfect, nonoxidized Fe films, such a noncollinear spin order at the Fe/InAs interface is excluded as no thermomagnetic irreversibilities were found. This indicates that the spin order at the Fe/InAs interface is suitable for spin injection.

Polymer diffusion in the interphase between surface and solution.

PubMed

Weger, Lukas; Weidmann, Monika; Ali, Wael; Hildebrandt, Marcus; Gutmann, Jochen Stefan; Hoffmann-Jacobsen, Kerstin

2018-05-22

Total internal reflection fluorescence correlation spectroscopy (TIR-FCS) is applied to study the self-diffusion of polyethylene glycol solutions in the presence of weakly attractive interfaces. Glass coverslips modified with aminopropyl- and propyl-terminated silanes are used to study the influence of solid surfaces on polymer diffusion. A model of three phases of polymer diffusion allows to describe the experimental fluorescence autocorrelation functions. Besides the two-dimensional diffusion of adsorbed polymer on the substrate and three-dimensional free diffusion in bulk solution, a third diffusion time scale is observed with intermediate diffusion times. This retarded three-dimensional diffusion in solution is assigned to long range effects of solid surfaces on diffusional dynamics of polymers. The respective diffusion constants show Rouse scaling (D~N -1 ) indicating a screening of hydrodynamic interactions by the presence of the surface. Hence, the presented TIR-FCS method proves to be a valuable tool to investigate the effect of surfaces on polymer diffusion beyond the first adsorbed polymer layer on the 100 nm length scale.

In situ stress relaxation mechanism of a superelastic NiTi shape memory alloy under hydrogen charging

NASA Astrophysics Data System (ADS)

Elkhal Letaief, Wissem; Hassine, Tarek; Gamaoun, Fehmi

2017-02-01

On account of its good biocompatibility, superelastic Ni-Ti arc wire alloys have been successfully used in orthodontic clinics. Nevertheless, delayed fracture in the oral cavity caused by hydrogen diffusion can be observed. The in situ stress relaxation susceptibility of a Ni-Ti shape memory alloy towards hydrogen embrittlement has been examined with respect to the current densities and imposed deformations. Orthodontic wires have been relaxed at different martensite volume fractions using current densities of 5, 10 and 20 A/m2 at 20 °C. The in situ relaxation stress shows that, for an imposed strain at the middle of the austenite-martensite transformation, the specimen fractures at the martensite-austenite reverse transformation. However, for an imposed strain at the beginning of the austenite-martensite plateau, the stress decreases in a similar way to the full austenite structure. Moreover, the stress plateau has been recorded at the reverse transformation for a short period. For the fully martensite structure, embrittlement occurs at a higher stress value. This behaviour is attributed to the interaction between the in situ austenite phase expansion and the diffusion of hydrogen in the different volume fractions of the martensite phase, produced at an imposed strain.

In vitro evaluation of suspoemulsions for in situ-forming polymeric microspheres and controlled release of progesterone.

PubMed

Turino, Ludmila N; Mariano, Rodolfo N; Mengatto, Luciano N; Luna, Julio A

2015-01-01

One possibility to obtain a higher dose of drug in a lower formulation volume can be by using of saturated quantity of drug in one of the phases of an emulsion. These formulations are called suspoemulsions (S/O/W). When a hydrophobic polymer is added to the organic phase of suspoemulsions, these formulations can be used to entrap the drug inside microspheres after in situ precipitation of the polymer-drug-excipients mix. In this work, performance and stability of progesterone suspensions in triacetin as organic phase of suspoemulsions were evaluated. These formulations were compared with O/W emulsions. Mathematical models were used to study in vitro release profiles. The results confirmed that S/O/W systems could be an attractive alternative to O/W formulations for the entrapment of progesterone inside poly(d,l-lactide-co-glycolide) microspheres. Diffusive-based models fit the in vitro release of progesterone from in situ-formed microspheres. For longer release periods, a time-dependent diffusion coefficient was successfully estimated.

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.

In Situ Gold Nanoparticle Gradient Formation in a 3D Meso- and Macroporous Polymer Matrix.

PubMed

Penders, Jelle; Rajasekharan, Anand K; Hulander, Mats; Andersson, Martin

2017-08-01

Herein, the development and characterization of a 3D gradient structure of gold nanoparticles is described. The gradient of gold nanoparticles is made in situ in a macroporous nonionic block copolymer hydrogel matrix, through gold ion diffusion control. The polymer provides a matrix for diffusion of gold ions, acts as a template for controlling nanoparticle growth, and facilitates the in situ reduction of gold ions to gold nanoparticles. A clear gradient in gold nanoparticles is observed across the 3D space of the polymer matrix using scanning electron microscopy, fluorescence microscopy, atomic force microscopy, and thermogravimetric analysis. The particle gradient is further functionalized with both hydrophobic and hydrophilic groups via thiol-gold linkage to demonstrate the ability to form gradients with different chemical functionalities. Using additive manufacturing, the polymer can also be printed as a porous network with possible applications for 3D cell culturing in, e.g., biomaterials research. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Not just fractal surfaces, but surface fractal aggregates: Derivation of the expression for the structure factor and its applications

NASA Astrophysics Data System (ADS)

Besselink, R.; Stawski, T. M.; Van Driessche, A. E. S.; Benning, L. G.

2016-12-01

Densely packed surface fractal aggregates form in systems with high local volume fractions of particles with very short diffusion lengths, which effectively means that particles have little space to move. However, there are no prior mathematical models, which would describe scattering from such surface fractal aggregates and which would allow the subdivision between inter- and intraparticle interferences of such aggregates. Here, we show that by including a form factor function of the primary particles building the aggregate, a finite size of the surface fractal interfacial sub-surfaces can be derived from a structure factor term. This formalism allows us to define both a finite specific surface area for fractal aggregates and the fraction of particle interfacial sub-surfaces at the perimeter of an aggregate. The derived surface fractal model is validated by comparing it with an ab initio approach that involves the generation of a "brick-in-a-wall" von Koch type contour fractals. Moreover, we show that this approach explains observed scattering intensities from in situ experiments that followed gypsum (CaSO4 ṡ 2H2O) precipitation from highly supersaturated solutions. Our model of densely packed "brick-in-a-wall" surface fractal aggregates may well be the key precursor step in the formation of several types of mosaic- and meso-crystals.

Controlled surface diffusion in plasma-enhanced chemical vapor deposition of GaN nanowires.

PubMed

Hou, Wen Chi; Hong, Franklin Chau-Nan

2009-02-04

This study investigates the growth of GaN nanowires by controlling the surface diffusion of Ga species on sapphire in a plasma-enhanced chemical vapor deposition (CVD) system. Under nitrogen-rich growth conditions, Ga has a tendency to adsorb on the substrate surface diffusing to nanowires to contribute to their growth. The significance of surface diffusion on the growth of nanowires is dependent on the environment of the nanowire on the substrate surface as well as the gas phase species and compositions. Under nitrogen-rich growth conditions, the growth rate is strongly dependent on the surface diffusion of gallium, but the addition of 5% hydrogen in nitrogen plasma instantly diminishes the surface diffusion effect. Gallium desorbs easily from the surface by reaction with hydrogen. On the other hand, under gallium-rich growth conditions, nanowire growth is shown to be dominated by the gas phase deposition, with negligible contribution from surface diffusion. This is the first study reporting the inhibition of surface diffusion effects by hydrogen addition, which can be useful in tailoring the growth and characteristics of nanowires. Without any evidence of direct deposition on the nanowire surface, gallium and nitrogen are shown to dissolve into the catalyst for growing the nanowires at 900 degrees C.

In Situ Analyses of Methane Oxidation Associated with the Roots and Rhizomes of a Bur Reed, Sparganium Eurycarpum, in a Maine Wetland

NASA Technical Reports Server (NTRS)

King, Gary M.

1996-01-01

Methane oxidation associated with the belowground tissues of a common aquatic macrophyte, the burweed Sparganium euryearpum, was assayed in situ by a chamber technique with acetylene or methyl fluoride as a methanotrophic inhibitor at a headspace concentration of 3 to 4%. Acetylene and methyl fluoride inhibited both methane oxidation and peat methanogenesis. However, inhibition of methanogenesis resulted in no obvious short-term effect on methane fluxes. Since neither inhibitor adversely affected plant metabolism and both inhibited methanotrophy equally well, acetylene was employed for routine assays because of its low cost and ease of use. Root-associated methanotrophy consumed a variable but significant fraction of the total potential methane flux; values varied between 1 and 58% (mean +/- standard deviation, 27.0% +/- 6.0%), with no consistent temporal or spatial pattern during late summer. The absolute amount of methane oxidized was not correlated with the total potential methane flux; this suggested that parameters other than methane availability (e.g., oxygen availability) controlled the rates of methane oxidation. Estimates of diffusive methane flux and oxidation at the peat surface indicated that methane emission occurred primarily through aboveground plant tissues; the absolute magnitude of methane oxidation was also greater in association with roots than at the peat surface. However, the relative extent of oxidation was greater at the latter locus.

Extracting surface diffusion coefficients from batch adsorption measurement data: application of the classic Langmuir kinetics model.

PubMed

Chu, Khim Hoong

2017-11-09

Surface diffusion coefficients may be estimated by fitting solutions of a diffusion model to batch kinetic data. For non-linear systems, a numerical solution of the diffusion model's governing equations is generally required. We report here the application of the classic Langmuir kinetics model to extract surface diffusion coefficients from batch kinetic data. The use of the Langmuir kinetics model in lieu of the conventional surface diffusion model allows derivation of an analytical expression. The parameter estimation procedure requires determining the Langmuir rate coefficient from which the pertinent surface diffusion coefficient is calculated. Surface diffusion coefficients within the 10 -9 to 10 -6  cm 2 /s range obtained by fitting the Langmuir kinetics model to experimental kinetic data taken from the literature are found to be consistent with the corresponding values obtained from the traditional surface diffusion model. The virtue of this simplified parameter estimation method is that it reduces the computational complexity as the analytical expression involves only an algebraic equation in closed form which is easily evaluated by spreadsheet computation.

In situ visualization of metallurgical reactions in nanoscale Cu/Sn diffusion couples

NASA Astrophysics Data System (ADS)

Yin, Qiyue; Gao, Fan; Gu, Zhiyong; Stach, Eric A.; Zhou, Guangwen

2015-03-01

The Cu-Sn metallurgical soldering reaction in two-segmented Cu-Sn nanowires is studied by in situ transmission electron microscopy. By varying the relative lengths of Cu and Sn segments, we show that the metallurgical reaction results in a Cu-Sn solid solution for small Sn/Cu length ratio while Cu-Sn intermetallic compounds (IMCs) for larger Sn/Cu length ratios. Upon heating the nanowires to ~500 °C, two phase transformation pathways occur, η-Cu6Sn5 --> ε-Cu3Sn --> δ-Cu41Sn11 for nanowires with a long Cu segment and η-Cu6Sn5 --> ε-Cu3Sn --> γ-Cu3Sn with a short Cu segment. The evolution of Kirkendall voids in the nanowires demonstrates that Cu diffuses faster than Sn in IMCs. Void growth results in the nanowire breakage that shuts off the inter-diffusion of Cu and Sn and thus leads to changes in the phase transformation pathway in the IMCs.

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

Zhang, Hailin; Li, Ping; Wang, Zheming

Boehmite (γ-AlOOH) was synthesized to selectively adsorb V(V) from K 2CrO 4-KVO 3-H 2O solutions with highly concentrated Cr(VI) and low concentration V(V). The synthesized γ-AlOOH has a BET surface area of 433.2 m 2/g and an average pore size of 3.5 nm. It possesses a maximum adsorption capacity of V(V) of 1.53 mmol/g from K 2CrO 4-KVO 3-H 2O solutions. The adsorption of V(V) onto γ-AlOOH follows the Langmuir isotherm model and pseudo-second-order kinetics equation by forming innersphere complexes while the Cr(VI) adsorption forms both inner-sphere and outer-sphere chromate complexes depending on solution pH. The γ-AlOOH was further synthesizedmore » in situ by adding HNO 3 into the K 2CrO 4-KAlO 2- KVO 3-H 2O solutions and then used for synchronous adsorption of V(V) and Cr(VI), resulting in increased adsorption capacity of V(V) of 2.88 mmol/g and decreased adsorption capacity of Cr(VI) to 0.073 mmol/g, respectively. In the latter process, adsorption pH values were adjustable, and adsorption reached equilibrium instantaneously, supporting a novel in situ synthesis and adsorption integration strategy with adjustable surface charge of adsorbent and disappearance of diffusion effect.« less

Surface morphology of vacuum-evaporated pentacene film on Si substrate studied by in situ grazing-incidence small-angle X-ray scattering: I. The initial stage of formation of pentacene film

NASA Astrophysics Data System (ADS)

Hirosawa, Ichiro; Watanabe, Takeshi; Koganezawa, Tomoyuki; Kikuchi, Mamoru; Yoshimoto, Noriyuki

2018-03-01

The progress of the surface morphology of a growing sub-monolayered pentacene film on a Si substrate was studied by in situ grazing-incidence small angle X-ray scattering (GISAXS). The observed GISAXS profiles did not show sizes of pentacene islands but mainly protuberances on the boundaries around pentacene film. Scattering of X-ray by residual pits in the pentacene film was also detected in the GISAXS profiles of an almost fully covered film. The average radius of pentacene protuberances increased from 13 to 24 nm as the coverage increased to 0.83 monolayer, and the most frequent radius was almost constant at approximately 9 nm. This result suggests that the population of larger protuberances increase with increasing lengths of boundaries of the pentacene film. It can also be considered that the detected protuberances were crystallites of pentacene, since the average size of protuberances was nearly equal to crystallite sizes of pentacene films. The almost constant characteristic distance of 610 nm and amplitudes of pair correlation functions at low coverages suggest that the growth of pentacene films obeyed the diffusion-limited aggregation (DLA) model, as previously reported. It is also considered that the sites of islands show a triangular distribution for small variations of estimated correlation distances.

Ni-silicide growth kinetics in Si and Si/SiO2 core/shell nanowires.

PubMed

Ogata, K; Sutter, E; Zhu, X; Hofmann, S

2011-09-07

A systematic study of the kinetics of axial Ni silicidation of as-grown and oxidized Si nanowires (SiNWs) with different crystallographic orientations and core diameters ranging from ∼ 10 to 100 nm is presented. For temperatures between 300 and 440 °C the length of the total axial silicide intrusion varies with the square root of time, which provides clear evidence that the rate limiting step is diffusion of Ni through the growing silicide phase(s). A retardation of Ni-silicide formation for oxidized SiNWs is found, indicative of a stress induced lowering of the diffusion coefficients. Extrapolated growth constants indicate that the Ni flux through the silicided NW is dominated by surface diffusion, which is consistent with an inverse square root dependence of the silicide length on the NW diameter as observed for (111) orientated SiNWs. In situ TEM silicidation experiments show that NiSi(2) is the first forming phase for as-grown and oxidized SiNWs. The silicide-SiNW interface is thereby atomically abrupt and typically planar. Ni-rich silicide phases subsequently nucleate close to the Ni reservoir, which for as-grown SiNWs can lead to a complete channel break-off for prolonged silicidation due to significant volume expansion and morphological changes.

Ni-Silicide Growth Kinetics in Si and Si/SiO2 Core/Shell Nanowires

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

Hofmann, S.; Sutter, E.; Ogata, K.

A systematic study of the kinetics of axial Ni silicidation of as-grown and oxidized Si nanowires (SiNWs) with different crystallographic orientations and core diameters ranging from {approx} 10 to 100 nm is presented. For temperatures between 300 and 440 C the length of the total axial silicide intrusion varies with the square root of time, which provides clear evidence that the rate limiting step is diffusion of Ni through the growing silicide phase(s). A retardation of Ni-silicide formation for oxidized SiNWs is found, indicative of a stress induced lowering of the diffusion coefficients. Extrapolated growth constants indicate that the Nimore » flux through the silicided NW is dominated by surface diffusion, which is consistent with an inverse square root dependence of the silicide length on the NW diameter as observed for <111> orientated SiNWs. In situ TEM silicidation experiments show that NiSi{sub 2} is the first forming phase for as-grown and oxidized SiNWs. The silicide-SiNW interface is thereby atomically abrupt and typically planar. Ni-rich silicide phases subsequently nucleate close to the Ni reservoir, which for as-grown SiNWs can lead to a complete channel break-off for prolonged silicidation due to significant volume expansion and morphological changes.« less

Synergistic damage effects of vacuum ultraviolet photons and O2 in SiCOH ultra-low-k dielectric films

NASA Astrophysics Data System (ADS)

Lee, J.; Graves, D. B.

2010-10-01

Damage incurred during plasma processing, leading to increases in dielectric constant k, is a persistent problem with porous ultra-low-k dielectric films, such as SiCOH. Although most of the proposed mechanisms of plasma-induced damage focus on the role of ion bombardment and radical attack, we show that plasma-generated vacuum ultraviolet (VUV) photons can play a role in creating damage leading to increases in the dielectric constant of this material. Using a vacuum beam apparatus with a calibrated VUV lamp, we show that 147 nm VUV photons impacting SiCOH results in post-exposure adsorption and reaction with water vapour from the atmosphere to form silanol bonds, thereby raising the dielectric constant. Furthermore, the level of damage increases synergistically under simultaneous exposure to VUV photons and O2. The vacuum beam photon fluences are representative of typical plasma processes, as measured in a separate plasma tool. Fourier-transform infrared (FTIR) spectroscopy (ex situ) and mass spectrometry (in situ) imply that O2 reacts with methyl radicals formed from scissioned Si-C bonds to create CO2 and H2O, the latter combining with Si dangling bonds to generate more SiOH groups than with photon exposure alone. In addition, sample near-surface diffusivity, manipulated through ion bombardment and sample heating, can be seen to affect this process. These results demonstrate that VUV photo-generated surface reactions can be potent contributors to ultra-low-k dielectric SiCOH film plasma-induced damage, and suggest that they could play analogous roles in other plasma-surface interactions.

High-pressure spectroscopic measurement on diffusion with a diamond-anvil cell

NASA Astrophysics Data System (ADS)

Aoki, K.; Katoh, Eriko; Yamawaki, H.; Fujihisa, H.; Sakashita, M.

2003-04-01

We report a diamond-anvil-cell (DAC) technique developed for spectroscopic measurement on the diffusion process in molecular solids at high pressure. The diffusion processes of atoms, molecules, or their ionic species are investigated for a bilayer specimen by measuring the variation of infrared vibrational spectra with time. The experimental procedures for the protonic and molecular diffusion measurements on ice at 400 K and 10.2 GPa are presented as an example study. The in situ spectroscopic technique with a DAC significantly extends the pressure range accessible for diffusion measurement. The diffusion process at a rate of 10-16-10-14 m2/s can currently be observed at temperatures of 300-600 K and pressures up to several tens of gigaPascals.

Modeling Transport of Cesium in Grimsel Granodiorite With Micrometer Scale Heterogeneities and Dynamic Update of Kd

NASA Astrophysics Data System (ADS)

Voutilainen, Mikko; Kekäläinen, Pekka; Siitari-Kauppi, Marja; Sardini, Paul; Muuri, Eveliina; Timonen, Jussi; Martin, Andrew

2017-11-01

Transport and retardation of cesium in Grimsel granodiorite taking into account heterogeneity of mineral and pore structure was studied using rock samples overcored from an in situ diffusion test at the Grimsel Test Site. The field test was part of the Long-Term Diffusion (LTD) project designed to characterize retardation properties (diffusion and distribution coefficients) under in situ conditions. Results of the LTD experiment for cesium showed that in-diffusion profiles and spatial concentration distributions were strongly influenced by the heterogeneous pore structure and mineral distribution. In order to study the effect of heterogeneity on the in-diffusion profile and spatial concentration distribution, a Time Domain Random Walk (TDRW) method was applied along with a feature for modeling chemical sorption in geological materials. A heterogeneous mineral structure of Grimsel granodiorite was constructed using X-ray microcomputed tomography (X-μCT) and the map was linked to previous results for mineral specific porosities and distribution coefficients (Kd) that were determined using C-14-PMMA autoradiography and batch sorption experiments, respectively. After this the heterogeneous structure contains information on local porosity and Kd in 3-D. It was found that the heterogeneity of the mineral structure on the micrometer scale affects significantly the diffusion and sorption of cesium in Grimsel granodiorite at the centimeter scale. Furthermore, the modeled in-diffusion profiles and spatial concentration distributions show similar shape and pattern to those from the LTD experiment. It was concluded that the use of detailed structure characterization and quantitative data on heterogeneity can significantly improve the interpretation and evaluation of transport experiments.

A novel (ex situ) method to quantify oxygen diffusion coefficient of polymer fuel cells backing and catalyst layers

NASA Astrophysics Data System (ADS)

Baricci, Andrea; Casalegno, Andrea

2016-09-01

Limiting current density of oxygen reduction reaction in polymer electrolyte fuel cells is determined by several mass transport resistances that lower the concentration of oxygen on the catalyst active site. Among them, diffusion across porous media plays a significant role. Despite the extensive experimental activity documented in PEMFC literature, only few efforts have been dedicated to the measurement of the effective transport properties in porous layers. In the present work, a methodology for ex situ measurement of the effective diffusion coefficient and Knudsen radius of porous layers for polymer electrolyte fuel cells (gas diffusion layer, micro porous layer and catalyst layer) is described and applied to high temperature polymer fuel cells State of Art materials. Regression of the measured quantities by means of a quasi 2D physical model is performed to quantify the Knudsen effect, which is reported to account, respectively, for 30% and 50% of the mass transport resistance in micro porous layer and catalyst layer. On the other side, the model reveals that pressure gradient consequent to permeation in porous layers of high temperature polymer fuel cells has a negligible effect on oxygen concentration in relevant operating conditions.

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.

A study of the diffusion dynamics and concentration distribution of gold nanospheres (GNSs) without fluorescent labeling inside live cells using fluorescence single particle spectroscopy.

PubMed

Liu, Fangchao; Dong, Chaoqing; Ren, Jicun

2018-03-15

Colloidal gold nanospheres (GNSs) have become important nanomaterials in biomedical applications due to their special optical properties, good chemical stability, and biocompatibility. However, measuring the diffusion coefficients or concentration distribution of GNSs within live cells accurately without any extra fluorescent labeling in situ has still not been resolved. In this work, a single particle method is developed to study the concentration distribution of folic acid-modified GNSs (FA-GNSs) internalized via folate receptors, and investigates their diffusion dynamics within live cells using single particle fluorescence correlation spectroscopy (FCS). We optimized the experimental conditions and verified the feasibility of 30 nm GNSs without extra fluorescence labeling being used for single particle detection inside live cells. Then, the FCS characterization strategy was used to measure the concentration and diffusion coefficient distributions of GNSs inside live cells and the obtained results were basically in agreement with those obtained by TEM. The results demonstrate that our strategy is characterized as an in situ, nondestructive, rapid and dynamic method for the assay of live cells, and it may be widely used in the further design of GNP-based drug delivery and therapeutics.

High-power lithium ion batteries based on preorganized necklace type Li4Ti5O12/VACNT nano-composites

NASA Astrophysics Data System (ADS)

Pawlitzek, Fabian; Pampel, Jonas; Schmuck, Martin; Althues, Holger; Schumm, Benjamin; Kaskel, Stefan

2016-09-01

Li4Ti5O12 as anode material for high power Li+-ion batteries is very promising due to its unique electronic properties. However, the lack of electronic conductivity as well as the low Li+-ion diffusion coefficient are major drawbacks in achieving high power densities. In this work, therefore, we prepared a nano-composite consisting of vertically aligned carbon nanotube arrays decorated with in-situ grown necklace type Li4Ti5O12 nanoparticles. Owing to this structure the electrodes exhibit outstanding rate performances with specific capacities of 110 mAh g-1 up to 300C and cycling performance with high capacity retention of 97% after 500 cycles at 10C. Thus, the combination of short Li+-ion diffusion distances within Li4Ti5O12 particles, remarkable electronic conductivity by carbon nanotubes directly grown on the current collector as well as a high contact surface area due to an open pore geometry is essential in achieving high power Li4Ti5O12 anodes.

Primary submucosal nodular plasmacytoma of the stomach: a poorly recognized variant of gastric lymphoma.

PubMed

Kanzawa, Maki; Hirai, Chihoko; Morinaga, Yukiko; Kawakami, Fumi; Hara, Shigeo; Matsuoka, Hiroshi; Itoh, Tomoo

2013-02-20

Gastric plasmacytoma (GP) is a rare variant of gastric lymphomas. In the exceptional event that a patient presents with GP, the lesion occupies the mucosal layer in the vast majority of cases. Here we report a case of nodular plasmacytoma confined to the submucosa with no evidence of Helicobacter pylori (Hp) infection. The patient was a 59-year old female presenting with no particular symptoms. The tumor was well-demarcated and consisted of a diffuse monomorphic proliferation of plasma cells with numerous lymphoid follicles scattered throughout the tumor. The mucosal surface was intact and not associated with any tumor nodules. The cells were diffusely positive for CD79a, Bob1, EMA and IgA and consistently negative for CD3, CD19, CD20, PAX5, CD56, IgM and IgG. Additionally, in situ hybridization demonstrated clonality in the form of λ light-chain restriction. This submucosal nodular proliferation pattern of plasmacytoma is poorly recognized and considered to be a novel variant of lymphoma. The virtual slide(s) for this article can be found here: http://www.diagnosticpathology.diagnomx.eu/vs/3489998708673079.

Geostatistical Analysis of Surface Temperature and In-Situ Soil Moisture Using LST Time-Series from Modis

NASA Astrophysics Data System (ADS)

Sohrabinia, M.; Rack, W.; Zawar-Reza, P.

2012-07-01

The objective of this analysis is to provide a quantitative estimate of the fluctuations of land surface temperature (LST) with varying near surface soil moisture (SM) on different land-cover (LC) types. The study area is located in the Canterbury Plains in the South Island of New Zealand. Time series of LST from the MODerate resolution Imaging Spectro-radiometer (MODIS) have been analysed statistically to study the relationship between the surface skin temperature and near-surface SM. In-situ measurements of the skin temperature and surface SM with a quasi-experimental design over multiple LC types are used for validation. Correlations between MODIS LST and in-situ SM, as well as in-situ surface temperature and SM are calculated. The in-situ measurements and MODIS data are collected from various LC types. Pearson's r correlation coefficient and linear regression are used to fit the MODIS LST and surface skin temperature with near-surface SM. There was no significant correlation between time-series of MODIS LST and near-surface SM from the initial analysis, however, careful analysis of the data showed significant correlation between the two parameters. Night-time series of the in-situ surface temperature and SM from a 12 hour period over Irrigated-Crop, Mixed-Grass, Forest, Barren and Open- Grass showed inverse correlations of -0.47, -0.68, -0.74, -0.88 and -0.93, respectively. These results indicated that the relationship between near-surface SM and LST in short-terms (12 to 24 hours) is strong, however, remotely sensed LST with higher temporal resolution is required to establish this relationship in such time-scales. This method can be used to study near-surface SM using more frequent LST observations from a geostationary satellite over the study area.

Microanalytical investigation of degradation issues in Byzantine wall paintings

NASA Astrophysics Data System (ADS)

Sotiropoulou, S.; Daniilia, Sister; Miliani, C.; Rosi, F.; Cartechini, L.; Papanikola-Bakirtzis, D.

2008-07-01

The St. Euthymius wall paintings, in the Cathedral of Thessaloniki, dated 1303 AD., are stylistically attributed to the School of Panselinos, one of the most important painters of Palaeologean Art. An in situ non-invasive study has been carried out as part of a MOLAB project (a mobile laboratory accessible through the Eu-ARTECH project, funded by the EC 6th FP) combining different analytical techniques such as XRF, mid-FTIR and UV-vis diffuse reflectance spectroscopy. It was during this comprehensive in situ study that certain scientific queries were raised about sensitive areas, where indications of the phenomena of decay requested further attention. A subsequent laboratory study of selected cross-sections using microscopic analysis with μFTIR, SEM-EDS and μRaman, further confirmed the identification of only the atypical in situ observations. The comparative interpretation of all respective results on the specific regions of interest permitted the identification of several degradation phenomena which justify certain aesthetic or stylistic incoherences in the representations. Namely, (i) thermal dehydration of the yellow ochre explaining the reddish appearance of the flesh tones and halos as an accidental effect of the fire; (ii) thermal degradation of azurite converted to tenorite explaining the atypical instance of dark lightings on the purple garments; (iii) degradation of red lead employed in the lightings of the red garments; (iv) widespread presence of oxalates in the paint surface.

Constraining processes of landscape change with combined in situ cosmogenic 14C-10Be analysis

NASA Astrophysics Data System (ADS)

Hippe, Kristina

2017-10-01

Reconstructing Quaternary landscape evolution today frequently builds upon cosmogenic-nuclide surface exposure dating. However, the study of complex surface exposure chronologies on the 102-104 years' timescale remains challenging with the commonly used long-lived radionuclides (10Be, 26Al, 36Cl). In glacial settings, key points are the inheritance of nuclides accumulated in a rock surface during a previous exposure episode and (partial) shielding of a rock surface after the main deglaciation event, e.g. during phases of glacier readvance. Combining the short-lived in situ cosmogenic 14C isotope with 10Be dating provides a valuable approach to resolve and quantify complex exposure histories and burial episodes within Lateglacial and Holocene timescales. The first studies applying the in situ14C-10Be pair have demonstrated the great benefit from in situ14C analysis for unravelling complex glacier chronologies in various glacial environments worldwide. Moreover, emerging research on in situ14C in sedimentary systems highlights the capacity of combined in situ14C-10Be analysis to quantify sediment transfer times in fluvial catchments or to constrain changes in surface erosion rates. Nevertheless, further methodological advances are needed to obtain truly routine and widely available in situ14C analysis. Future development in analytical techniques has to focus on improving the analytical reproducibility, reducing the background level and determining more accurate muonic production rates. These improvements should allow extending the field of applications for combined in situ14C-10Be analysis in Earth surface sciences and open up a number of promising applications for dating young sedimentary deposits and the quantification of recent changes in surface erosion dynamics.

Anomalous Surface Diffusion of Protons on Lipid Membranes

PubMed Central

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

2014-01-01

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

Anomalous surface diffusion of protons on lipid membranes.

PubMed

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

2014-07-01

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

Enhanced the performance of graphene oxide/polyimide hybrid membrane for CO2 separation by surface modification of graphene oxide using polyethylene glycol

NASA Astrophysics Data System (ADS)

Wu, Li-guang; Yang, Cai-hong; Wang, Ting; Zhang, Xue-yang

2018-05-01

Polyethylene glycol (PEG) with different molecular weights was first used to modify graphene oxide (GO) samples. Subsequently, polyimide (PI) hybrid membranes containing modified-GO were fabricated via in situ polymerization. The separation performance of these hybrid membranes was evaluated using permeation experiments for CO2 and N2 gases. The morphology characterization showed that PEG with suitable molecular weight could be successfully grafted on the GO surface. PEG modification altered the surface properties of GO and introduced defective structures onto GO surface. This caused strong surface polarity and high free volume of membranes containing PEG-modified GO, thereby improving the separation performance of membranes. The addition of PEG-GO with low molecular weight effectively increased gas diffusion through hybrid membranes. The hybrid membranes containing PEG-GO with large molecular weight had high solubility performance for CO2 gas due to the introduction of numerous polar groups into polymeric membranes. With the loading content of modified GO, the CO2 gas permeability of hybrid membranes initially increased but eventually decreased. The optimal content of modified GO in membranes reached 3.0 wt%. When too much PEG added (exceeding 30 g), some impurities formed on GO surface and some aggregates appeared in the resulting hybrid membrane, which depressed the membrane performance.

Technique for examining biological materials using diffuse reflectance spectroscopy and the kubelka-munk function

DOEpatents

Alfano, Robert R.; Yang, Yuanlong

2003-09-02

Method and apparatus for examining biological materials using diffuse reflectance spectroscopy and the Kubelka-Munk function. In one aspect, the method is used to determine whether a tissue sample is cancerous or not and comprises the steps of (a) measuring the diffuse reflectance from the tissue sample at a first wavelength and at a second wavelength, wherein the first wavelength is a wavelength selected from the group consisting of 255-265 nm and wherein the second wavelength is a wavelength selected from the group consisting of 275-285 nm; (b) using the Kubelka-Munk function to transform the diffuse reflectance measurement obtained at the first and second wavelengths; and (c) comparing a ratio or a difference of the transformed Kubelka-Munk measurements at the first and second wavelengths to appropriate standards determine whether or not the tissue sample is cancerous. One can use the spectral profile of KMF between 250 nm to 300 nm to determine whether or not the tissue sample is cancerous or precancerous. According to the value at the first and second wavelengths determine whether or not the malignant tissue is invasive or mixed invasive and in situ or carcinoma in situ.

Dip-pen nanolithography on (bio)reactive monolayer and block-copolymer platforms: deposition of lines of single macromolecules.

PubMed

Salazar, Ramon B; Shovsky, Alexander; Schönherr, Holger; Vancso, G Julius

2006-11-01

The application of atomic force microscopy (AFM) tip-mediated molecular transfer (dip-pen nanolithography or DPN) to fabricate nanopatterned (bio)reactive platforms based on dendrimers on reactive self-assembled monolayer (SAM) and polymer thin films is discussed. The transfer of high-molar-mass polyamidoamine (PAMAM) dendrimers (generation 5) and the rapid in situ covalent attachment of the deposited adsorbates onto reactive N-hydroxysuccinimide (NHS) terminated SAMs on gold and NHS-activated polystyrene-block-poly(tert-butyl acrylate) (PS(690)-b-PtBA(1210)) block copolymer thin films were investigated as strategies to suppress line broadening by surface diffusion in DPN. By exploiting carefully controlled environmental conditions (such as temperature and relative humidity), scan rates, and in particular the covalent attachment of the dendrimers to the reactive films, the observed line broadening and hence the lateral diffusion of dendrimers was substantially less pronounced compared to that observed with DPN of thiols on gold. By this method, high-definition patterns of dendrimers were conveniently fabricated down to 30-nm length scales. The presence of primary amino groups in the deposited dendrimers ultimately offers the possibility to anchor biochemically relevant molecules, such as proteins and polypeptides, to these nanostructured platforms for a wide range of possible applications in the life sciences and in particular for the investigation of controlled cell-surface interactions.

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature

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

Yang, Yang; Kushima, Akihiro; Han, Weizhong

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. In this letter, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can matchmore » the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass–glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.« less

Liquid-Like, Self-Healing Aluminum Oxide during Deformation at Room Temperature

DOE PAGES

Yang, Yang; Kushima, Akihiro; Han, Weizhong; ...

2018-02-28

Effective protection from environmental degradation relies on the integrity of oxide as diffusion barriers. Ideally, the passivation layer can repair its own breaches quickly under deformation. While studies suggest that the native aluminum oxide may manifest such properties, it has yet to be experimentally proven because direct observations of the air-environmental deformation of aluminum oxide and its initial formation at room temperature are challenging. In this letter, we report in situ experiments to stretch pure aluminum nanotips under O 2 gas environments in a transmission electron microscope (TEM). We discovered that aluminum oxide indeed deforms like liquid and can matchmore » the deformation of Al without any cracks/spallation at moderate strain rate. At higher strain rate, we exposed fresh metal surface, and visualized the self-healing process of aluminum oxide at atomic resolution. Unlike traditional thin-film growth or nanoglass consolidation processes, we observe seamless coalescence of new oxide islands without forming any glass–glass interface or surface grooves, indicating greatly accelerated glass kinetics at the surface compared to the bulk.« less

Desired crystal oriented LiFePO4 nanoplatelets in situ anchored on a graphene cross-linked conductive network for fast lithium storage.

PubMed

Wang, Bo; Liu, Anmin; Abdulla, Wael Al; Wang, Dianlong; Zhao, X S

2015-05-21

Electron transfer and lithium ion diffusion rates are the key factors limiting the lithium ion storage in anisotropic LiFePO4 electrodes. In this work, we employed a facile solvothermal method to synthesize a "platelet-on-sheet" LiFePO4/graphene composite (LFP@GNs), which is LiFePO4 nanoplatelets in situ grown on graphene sheets with highly oriented (010) facets of LiFePO4 crystals. Such a two-phase contact mode with graphene sheets cross-linked to form a three-dimensional porous network is favourable for both fast lithium ion and electron transports. As a result, the designed LFP@GNs displayed a high rate capability (∼56 mA h g(-1) at 60 C) and long life cycling stability (∼87% capacity retention over 1000 cycles at 10 C). For comparison purposes, samples ex situ modified with graphene (LFP/GNs) as well as pure LiFePO4 platelets (LFP) were also prepared and investigated. More importantly, the obtained LFP@GNs can be used as a basic unit for constructing more complex structures to further improve electrochemical performance, such as coating the exposed LFP surface with a thin layer of carbon to build a C@LFP@GN composite to further enhance its cycling stability (∼98% capacity retention over 1000 cycles at 10 C).

Magic angle spinning nuclear magnetic resonance apparatus and process for high-resolution in situ investigations

DOEpatents

Hu, Jian Zhi; Sears, Jr., Jesse A.; Hoyt, David W.; Mehta, Hardeep S.; Peden, Charles H. F.

2015-11-24

A continuous-flow (CF) magic angle sample spinning (CF-MAS) NMR rotor and probe are described for investigating reaction dynamics, stable intermediates/transition states, and mechanisms of catalytic reactions in situ. The rotor includes a sample chamber of a flow-through design with a large sample volume that delivers a flow of reactants through a catalyst bed contained within the sample cell allowing in-situ investigations of reactants and products. Flow through the sample chamber improves diffusion of reactants and products through the catalyst. The large volume of the sample chamber enhances sensitivity permitting in situ .sup.13C CF-MAS studies at natural abundance.

CD20-Positive nodal natural killer/T-cell lymphoma with cutaneous involvement.

PubMed

Tsai, Yi-Chiun; Chen, Chi-Kuan; Wu, Yu-Hung

2015-09-01

CD20-positive natural killer (NK)/T-cell lymphoma is extremely rare. We describe a case of a CD20-positive nodal NK/T-cell lymphoma with cutaneous involvement in a 32-year-old man. The patient presented with fever, night sweats, right inguinal lymphadenopathy and multiple violaceous to erythematous nodules and plaques on the back and bilateral legs. Immunohistochemical analysis showed diffusely and strongly positive staining for CD3, CD3 epsilon, CD43, CD56, TIA-1 and CD20 but negative staining for other B-cell markers, including CD79a and PAX-5 and T-cell markers CD5 and CD7. The tumor cell nuclei were diffusely positive for Epstein-Barr virus-encoded RNA in situ hybridization. A partial clinical response was observed after chemotherapy, indicated by the decreased size of the lymph nodes and skin lesions. It is a diagnostic challenge to deal with lymphoma cells that present with the surface proteins of both T- and B-cells. © 2015 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

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

Zhang, Li; Wu, Zili; Nelson, Nicholas

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Improvement of water management in a vapor feed direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Masdar, M. Shahbudin; Tsujiguchi, Takuya; Nakagawa, Nobuyoshi

Water transport in a vapor feed direct methanol fuel cell was improved by fixing a hydrophobic air filter (HAF) at the cathode. Effects of the HAF properties and the fixed positions, i.e., just on the cathode surface or by providing a certain space from the surface, of the HAF on the water transport as well as the power generation performance were investigated. The water transport was evaluated by measuring the partial pressure of water, PH2O , and methanol, PCH3OH , at the anode gas layer using in situ mass spectrometry with a capillary probe and also the water and methanol fluxes across the electrode structure using a conventional method. The HAF with the highest hydrophobicity and the highest flow resistance had the strongest effect on increasing the water back diffusion from the cathode to the anode through the membrane and increasing the current density. It was noted that the HAF fixation by providing a space from the cathode surface was more effective in increasing JWCO and the current density than that of the direct placement on the cathode surface. There was an optimum distance for the HAF placement depending on the humidity of the outside air.

Effect of confining pressure on diffusion coefficients in clay-rich, low-permeability sedimentary rocks.

PubMed

Xiang, Y; Al, T; Mazurek, M

2016-12-01

The effect of confining pressure (CP) on the diffusion of tritiated-water (HTO) and iodide (I - ) tracers through Ordovician rocks from the Michigan Basin, southwestern Ontario, Canada, and Opalinus Clay from Schlattingen, Switzerland was investigated in laboratory experiments. Four samples representing different formations and lithologies in the Michigan Basin were studied: Queenston Formation shale, Georgian Bay Formation shale, Cobourg Formation limestone and Cobourg Formation argillaceous limestone. Estimated in situ vertical stresses at the depths from which the samples were retrieved range from 12.0 to 17.4MPa (Michigan Basin) and from 21 to 23MPa (Opalinus Clay). Effective diffusion coefficients (D e ) were determined in through-diffusion experiments. With HTO tracer, applying CP resulted in decreases in D e of 12.5% for the Queenston Formation shale (CP max =12MPa), 30% for the Georgian Bay Formation shale (15MPa), 34% for the Cobourg Formation limestone (17.4MPa), 31% for the Cobourg Formation argillaceous limestone (17.4MPa) and 43-46% for the Opalinus Clay (15MPa). Decreases in D e were larger for the I - tracer: 13.8% for the Queenston shale, 42% for the Georgian Bay shale, 50% for the Cobourg Formation limestone, 55% for the Cobourg Formation argillaceous limestone and 63-68% for the Opalinus Clay. The tracer-specific nature of the response is attributed to an increasing influence of anion exclusion as the pore size decreases at higher CP. Results from the shales (including Opalinus Clay) indicate that the pressure effect on D e can be represented by a linear relationship between D e and ln(CP), which provides valuable predictive capability. The nonlinearity results in a relatively small change in D e at high CP, suggesting that it is not necessary to apply the exact in situ pressure conditions in order to obtain a good estimate of the in situ diffusion coefficient. Most importantly, the CP effect on shale is reversible (±12%) suggesting that, for argillaceous rocks, it is possible to obtain D e values that are representative of the in-situ condition by conducting measurements on re-pressurized samples that were obtained with standard drilling practices. This may not be the case for brittle rock samples as the results from limestone suggest that irreversible damage occurred during the pressure cycling. Copyright © 2016 Elsevier B.V. All rights reserved.

Molecular dynamics study of nanodroplet diffusion on smooth solid surfaces

NASA Astrophysics Data System (ADS)

Niu, Zhao-Xia; Huang, Tao; Chen, Yong

2018-10-01

We perform molecular dynamics simulations of Lennard-Jones particles in a canonical ensemble to study the diffusion of nanodroplets on smooth solid surfaces. Using the droplet-surface interaction to realize a hydrophilic or hydrophobic surface and calculating the mean square displacement of the center-of-mass of the nanodroplets, the random motion of nanodroplets could be characterized by shorttime subdiffusion, intermediate-time superdiffusion, and long-time normal diffusion. The short-time subdiffusive exponent increases and almost reaches unity (normal diffusion) with decreasing droplet size or enhancing hydrophobicity. The diffusion coefficient of the droplet on hydrophobic surfaces is larger than that on hydrophilic surfaces.

MO-AB-BRA-02: Modeling Nanoparticle-Eluting Spacer Degradation During Brachytherapy Application with in Situ Dose-Painting

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

Boateng, F; Ngwa, W; Harvard Medical School, Boston, MA

Purpose: Brachytherapy application with in situ dose-painting using gold nanoparticles (GNP) released from GNP-loaded brachytherapy spacers has been proposed as an innovative approach to increase therapeutic efficacy during brachytherapy. This work investigates the dosimetric impact of slow versus burst release of GNP from next generation biodegradable spacers. Methods: Mathematical models were developed based on experimental data to study the release of GNP from a spacer designed with FDA approved poly(lactic-co-glycolic acid) (PLGA) polymer. The diffusion controlled released process and PLGA polymer degradation kinetics was incorporated in the calculations for the first time. An in vivo determined diffusion coefficient was usedmore » for determining the concentration profiles and corresponding dose enhancement based on initial GNP-loading concentrations of 7 mg/g. Results: The results showed that there is significant delay before the concentration profile of GNP diffusion in the tumor is similar to that when burst release is assumed as in previous studies. For example, in the case of burst release after spacer administration, it took up to 25 days for all the GNP to be released from the spacer using diffusion controlled release process only. However, it took up to 45 days when a combined model for both diffusion and polymer degradation processes was used. Based on the tumor concentration profiles, a significant dose enhancement factor (DEF >20%), could be attained at a tumor distances of 5 mm from a spacer loaded with 10 nm GNP sizes. Conclusion: The results highlight the need to take the slow release of GNP from spacers and factors such as biodegradation of polymers into account in research development of GNP-eluting spacers for brachytherapy applications with in-situ dose-painting using gold nanoparticles. The findings suggest that I-125 may be the more appropriate for such applications given the relatively longer half-live compared to other radioisotopes like Pd-103 and Cs-131.« less

Large eddy simulation modeling of particle-laden flows in complex terrain

NASA Astrophysics Data System (ADS)

Salesky, S.; Giometto, M. G.; Chamecki, M.; Lehning, M.; Parlange, M. B.

2017-12-01

The transport, deposition, and erosion of heavy particles over complex terrain in the atmospheric boundary layer is an important process for hydrology, air quality forecasting, biology, and geomorphology. However, in situ observations can be challenging in complex terrain due to spatial heterogeneity. Furthermore, there is a need to develop numerical tools that can accurately represent the physics of these multiphase flows over complex surfaces. We present a new numerical approach to accurately model the transport and deposition of heavy particles in complex terrain using large eddy simulation (LES). Particle transport is represented through solution of the advection-diffusion equation including terms that represent gravitational settling and inertia. The particle conservation equation is discretized in a cut-cell finite volume framework in order to accurately enforce mass conservation. Simulation results will be validated with experimental data, and numerical considerations required to enforce boundary conditions at the surface will be discussed. Applications will be presented in the context of snow deposition and transport, as well as urban dispersion.

In Situ Transmission Electron Microscopy Study of Electron Beam-Induced Transformations in Colloidal Cesium Lead Halide Perovskite Nanocrystals.

PubMed

Dang, Zhiya; Shamsi, Javad; Palazon, Francisco; Imran, Muhammad; Akkerman, Quinten A; Park, Sungwook; Bertoni, Giovanni; Prato, Mirko; Brescia, Rosaria; Manna, Liberato

2017-02-28

An increasing number of studies have recently reported the rapid degradation of hybrid and all-inorganic lead halide perovskite nanocrystals under electron beam irradiation in the transmission electron microscope, with the formation of nanometer size, high contrast particles. The nature of these nanoparticles and the involved transformations in the perovskite nanocrystals are still a matter of debate. Herein, we have studied the effects of high energy (80/200 keV) electron irradiation on colloidal cesium lead bromide (CsPbBr 3 ) nanocrystals with different shapes and sizes, especially 3 nm thick nanosheets, a morphology that facilitated the analysis of the various ongoing processes. Our results show that the CsPbBr 3 nanocrystals undergo a radiolysis process, with electron stimulated desorption of a fraction of bromine atoms and the reduction of a fraction of Pb 2+ ions to Pb 0 . Subsequently Pb 0 atoms diffuse and aggregate, giving rise to the high contrast particles, as previously reported by various groups. The diffusion is facilitated by both high temperature and electron beam irradiation. The early stage Pb nanoparticles are epitaxially bound to the parent CsPbBr 3 lattice, and evolve into nonepitaxially bound Pb crystals upon further irradiation, leading to local amorphization and consequent dismantling of the CsPbBr 3 lattice. The comparison among CsPbBr 3 nanocrystals with various shapes and sizes evidences that the damage is particularly pronounced at the corners and edges of the surface, due to a lower diffusion barrier for Pb 0 on the surface than inside the crystal and the presence of a larger fraction of under-coordinated atoms.

Quantifying the Influence of Near-Surface Water-Energy Budgets on Soil Thermal Properties Using a Network of Coupled Meteorological and Vadose Zone Instrument Arrays in Indiana, USA

NASA Astrophysics Data System (ADS)

Naylor, S.; Gustin, A. R.; Ellett, K. M.

2012-12-01

Weather stations that collect reliable, sustained meteorological data sets are becoming more widely distributed because of advances in both instrumentation and data server technology. However, sites collecting soil moisture and soil temperature data remain sparse with even fewer locations where complete meteorological data are collected in conjunction with soil data. Thanks to the advent of sensors that collect continuous in-situ thermal properties data for soils, we have gone a step further and incorporated thermal properties measurements as part of hydrologic instrument arrays in central and northern Indiana. The coupled approach provides insights into the variability of soil thermal conductivity and diffusivity attributable to geologic and climatological controls for various hydrogeologic settings. These data are collected to facilitate the optimization of ground-source heat pumps (GSHPs) in the glaciated Midwest by establishing publicly available data that can be used to parameterize system design models. A network of six monitoring sites was developed in Indiana. Sensors that determine thermal conductivity and diffusivity using radial differential temperature measurements around a heating wire were installed at 1.2 meters below ground surface— a typical depth for horizontal GSHP systems. Each site also includes standard meteorological sensors for calculating reference evapotranspiration following the methods by the Food and Agriculture Organization (FAO) of the United Nations. Vadose zone instrumentation includes time domain reflectometry soil-moisture and temperature sensors installed at 0.3-meter depth intervals down to a 1.8-meter depth, in addition to matric potential sensors at 0.15, 0.3, 0.6, and 1.2 meters. Cores collected at 0.3-meter intervals were analyzed in a laboratory for grain size distribution, bulk density, thermal conductivity, and thermal diffusivity. Our work includes developing methods for calibrating thermal properties sensors based on known standards and comparing measurements from transient line heat source devices. Transform equations have been developed to correct in-situ measurements of thermal conductivity and comparing these results with soil moisture data indicates that thermal conductivity can increase by as much as 25 percent during wetting front propagation. Thermal dryout curves have also been modeled based on laboratory conductivity data collected from core samples to verify field measurements, and alternatively, temperature profile data are used to calibrate near-surface temperature gradient models. We compare data collected across various spatial scales to assess the potential for upscaling near-surface thermal regimes based on available soils data. A long-term goal of the monitoring effort is to establish continuous data sets that determine the effect of climate variability on soil thermal properties such that expected ranges in thermal conductivity can be used to determine optimal ground-coupling loop lengths for GSHP systems.

Cerium migration during PEM fuel cell assembly and operation

DOE PAGES

Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; ...

2015-09-14

Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane ceriummore » gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.« less

Direct observation of X-ray induced atomic motion using scanning tunneling microscope combined with synchrotron radiation.

PubMed

Saito, Akira; Tanaka, Takehiro; Takagi, Yasumasa; Hosokawa, Hiromasa; Notsu, Hiroshi; Ohzeki, Gozo; Tanaka, Yoshihito; Kohmura, Yoshiki; Akai-Kasaya, Megumi; Ishikawa, Tetsuya; Kuwahara, Yuji; Kikuta, Seishi; Aono, Masakazu

2011-04-01

X-ray induced atomic motion on a Ge(111)-c(2 x 8) clean surface at room temperature was directly observed with atomic resolution using a synchrotron radiation (SR)-based scanning tunneling microscope (STM) system under ultra high vacuum condition. The atomic motion was visualized as a tracking image by developing a method to merge the STM images before and after X-ray irradiation. Using the tracking image, the atomic mobility was found to be strongly affected by defects on the surface, but was not dependent on the incident X-ray energy, although it was clearly dependent on the photon density. The atomic motion can be attributed to surface diffusion, which might not be due to core-excitation accompanied with electronic transition, but a thermal effect by X-ray irradiation. The crystal surface structure was possible to break even at a lower photon density than the conventionally known barrier. These results can alert X-ray studies in the near future about sample damage during measurements, while suggesting the possibility of new applications. Also the obtained results show a new availability of the in-situ SR-STM system.

Optical and electronic properties of sub-surface conducting layers in diamond created by MeV B-implantation at elevated temperatures

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

Willems van Beveren, L. H., E-mail: laurensw@unimelb.edu.au; Bowers, H.; Ganesan, K.

2016-06-14

Boron implantation with in-situ dynamic annealing is used to produce highly conductive sub-surface layers in type IIa (100) diamond plates for the search of a superconducting phase transition. Here, we demonstrate that high-fluence MeV ion-implantation, at elevated temperatures avoids graphitization and can be used to achieve doping densities of 6 at. %. In order to quantify the diamond crystal damage associated with implantation Raman spectroscopy was performed, demonstrating high temperature annealing recovers the lattice. Additionally, low-temperature electronic transport measurements show evidence of charge carrier densities close to the metal-insulator-transition. After electronic characterization, secondary ion mass spectrometry was performed to mapmore » out the ion profile of the implanted plates. The analysis shows close agreement with the simulated ion-profile assuming scaling factors that take into account an average change in diamond density due to device fabrication. Finally, the data show that boron diffusion is negligible during the high temperature annealing process.« less

High-flexibility combinatorial peptide synthesis with laser-based transfer of monomers in solid matrix material.

PubMed

Loeffler, Felix F; Foertsch, Tobias C; Popov, Roman; Mattes, Daniela S; Schlageter, Martin; Sedlmayr, Martyna; Ridder, Barbara; Dang, Florian-Xuan; von Bojničić-Kninski, Clemens; Weber, Laura K; Fischer, Andrea; Greifenstein, Juliane; Bykovskaya, Valentina; Buliev, Ivan; Bischoff, F Ralf; Hahn, Lothar; Meier, Michael A R; Bräse, Stefan; Powell, Annie K; Balaban, Teodor Silviu; Breitling, Frank; Nesterov-Mueller, Alexander

2016-06-14

Laser writing is used to structure surfaces in many different ways in materials and life sciences. However, combinatorial patterning applications are still limited. Here we present a method for cost-efficient combinatorial synthesis of very-high-density peptide arrays with natural and synthetic monomers. A laser automatically transfers nanometre-thin solid material spots from different donor slides to an acceptor. Each donor bears a thin polymer film, embedding one type of monomer. Coupling occurs in a separate heating step, where the matrix becomes viscous and building blocks diffuse and couple to the acceptor surface. Furthermore, we can consecutively deposit two material layers of activation reagents and amino acids. Subsequent heat-induced mixing facilitates an in situ activation and coupling of the monomers. This allows us to incorporate building blocks with click chemistry compatibility or a large variety of commercially available non-activated, for example, posttranslationally modified building blocks into the array's peptides with >17,000 spots per cm(2).

A novel passive water sampler for in situ sampling of antibiotics.

PubMed

Chen, Chang-Er; Zhang, Hao; Jones, Kevin C

2012-05-01

Passive water sampling has several advantages over active methods; it provides time-integrated data, can save on time and cost compared to active methods, and yield high spatial resolution data through co-deployment of simple, cheap units. However, one problem with many sampler designs in current use is that their uptake rates for trace substances of interest are flow-rate dependent, thereby requiring calibration data and other information to enable water concentrations to be derived from the mass per sampler. However, the 'family' of samplers employing the principle of diffusive gradients in thin films (DGT) provides an in situ means of quantitatively measuring labile species in aquatic systems without field calibration. So far, this technique has only been tested and applied in inorganic substances: metals, radionuclides, nutrients, etc. Design and applications of DGT to trace organic contaminants ('o-DGT') would be of widespread interest. This study describes the laboratory testing and performance characteristics of o-DGT, with the antibiotic sulfamethoxazole (SMX) as a model compound and XAD18 as the novel binding agent. o-DGT uptake of SMX increased with time and decreased with diffusion layer thickness, confirming the principle for SMX. XAD18 showed sufficiently high capacity for SMX for routine field applications. o-DGT measurement of SMX was independent of pH (6-9) and ionic strength (0.001-0.1 M) and not affected by flow rate once above static conditions. The diffusion coefficient of SMX in the sampler was measured using an independent diffusion cell and information is presented to allow temperature correction and derivation of aqueous concentrations from deployed samplers. The potential use of o-DGT for in situ measurement of pharmaceutical antibiotics is confirmed by this study and applications are briefly discussed.

Dynamics of Phenanthrenequinone on Carbon Nano-Onion Surfaces Probed by Quasielastic Neutron Scattering

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

Anjos, Daniela M; Mamontov, Eugene; Brown, Gilbert M

We used quasielastic neutron scattering (QENS) to study the dynamics of phenanthrenequinone (PQ) on the surface of onion-like carbon (OLC), or so called carbon onions, as a function of surface coverage and temperature. For both the high- and low-coverage samples, we observed two diffusion processes; a faster process and nearly an order of magnitude slower process. On the high-coverage surface, the slow diffusion process is of long-range translational character, whereas the fast diffusion process is spatially localized on the length scale of ~ 4.7 . On the low-coverage surface, both diffusion processes are spatially localized; on the same length scalemore » of ~ 4.7 for the fast diffusion and a somewhat larger length scale for the slow diffusion. Arrhenius temperature dependence is observed except for the long-range diffusion on the high-coverage surface. We attribute the fast diffusion process to the generic localized in-cage dynamics of PQ molecules, and the slow diffusion process to the long-range translational dynamics of PQ molecules, which, depending on the coverage, may be either spatially restricted, or long-range. On the low-coverage surface, uniform surface coverage is not attained, and the PQ molecules experience the effect of spatial constraints on their long-range translational dynamics. Unexpectedly, the dynamics of PQ molecules on OLC as a function of temperature and surface coverage bears qualitative resemblance to the dynamics of water molecules on oxide surfaces, including practically temperature-independent residence times for the low-coverage surface. The dynamics features that we observed may be universal across different classes of surface adsorbates.« less

Preparation and Thermoelectric Characteristics of ITO/PtRh:PtRh Thin Film Thermocouple

NASA Astrophysics Data System (ADS)

Zhao, Xiaohui; Wang, Hongmin; Zhao, Zixiang; Zhang, Wanli; Jiang, Hongchuan

2017-12-01

Thin film thermocouples (TFTCs) can provide more precise in situ temperature measurement for aerospace propulsion systems without disturbance of gas flow and surface temperature distribution of the hot components. ITO /PtRh:PtRh TFTC with multilayer structure was deposited on alumina ceramic substrate by magnetron sputtering. After annealing, the TFTC was statically calibrated for multiple cycles with temperature up to 1000 °C. The TFTC with excellent stability and repeatability was realized for the negligible variation of EMF in different calibration cycles. It is believed that owing to oxygen diffusion barriers by the oxidation of top PtRh layer and Schottky barriers formed at the grain boundaries of ITO, the variation of the carrier concentration of ITO film is minimized. Meanwhile, the life time of TFTC is more than 30 h in harsh environment. This makes ITO/PtRh:PtRh TFTC a promising candidate for precise surface temperature measurement of hot components of aeroengines.

Preparation and Thermoelectric Characteristics of ITO/PtRh:PtRh Thin Film Thermocouple.

PubMed

Zhao, Xiaohui; Wang, Hongmin; Zhao, Zixiang; Zhang, Wanli; Jiang, Hongchuan

2017-12-15

Thin film thermocouples (TFTCs) can provide more precise in situ temperature measurement for aerospace propulsion systems without disturbance of gas flow and surface temperature distribution of the hot components. ITO/PtRh:PtRh TFTC with multilayer structure was deposited on alumina ceramic substrate by magnetron sputtering. After annealing, the TFTC was statically calibrated for multiple cycles with temperature up to 1000 °C. The TFTC with excellent stability and repeatability was realized for the negligible variation of EMF in different calibration cycles. It is believed that owing to oxygen diffusion barriers by the oxidation of top PtRh layer and Schottky barriers formed at the grain boundaries of ITO, the variation of the carrier concentration of ITO film is minimized. Meanwhile, the life time of TFTC is more than 30 h in harsh environment. This makes ITO/PtRh:PtRh TFTC a promising candidate for precise surface temperature measurement of hot components of aeroengines.

Direct integration of polycrystalline graphene into light emitting diodes by plasma-assisted metal-catalyst-free synthesis.

PubMed

Kim, Yong Seung; Joo, Kisu; Jerng, Sahng-Kyoon; Lee, Jae Hong; Moon, Daeyoung; Kim, Jonghak; Yoon, Euijoon; Chun, Seung-Hyun

2014-03-25

The integration of graphene into devices is a challenging task because the preparation of a graphene-based device usually includes graphene growth on a metal surface at elevated temperatures (∼1000 °C) and a complicated postgrowth transfer process of graphene from the metal catalyst. Here we report a direct integration approach for incorporating polycrystalline graphene into light emitting diodes (LEDs) at low temperature by plasma-assisted metal-catalyst-free synthesis. Thermal degradation of the active layer in LEDs is negligible at our growth temperature, and LEDs could be fabricated without a transfer process. Moreover, in situ ohmic contact formation is observed between DG and p-GaN resulting from carbon diffusion into the p-GaN surface during the growth process. As a result, the contact resistance is reduced and the electrical properties of directly integrated LEDs outperform those of LEDs with transferred graphene electrodes. This relatively simple method of graphene integration will be easily adoptable in the industrialization of graphene-based devices.

Opposing effects of humidity on rhodochrosite surface oxidation.

PubMed

Na, Chongzheng; Tang, Yuanzhi; Wang, Haitao; Martin, Scot T

2015-03-03

Rhodochrosite (MnCO3) is a model mineral representing carbonate aerosol particles containing redox-active elements that can influence particle surface reconstruction in humid air, thereby affecting the heterogeneous transformation of important atmospheric constituents such as nitric oxides, sulfur dioxides, and organic acids. Using in situ atomic force microscopy, we show that the surface reconstruction of rhodochrosite in humid oxygen leads to the formation and growth of oxide nanostructures. The oxidative reconstruction consists of two consecutive processes with distinctive time scales, including a long waiting period corresponding to slow nucleation and a rapid expansion phase corresponding to fast growth. By varying the relative humidity from 55 to 78%, we further show that increasing humidity has opposing effects on the two processes, accelerating nucleation from 2.8(±0.2) × 10(-3) to 3.0(±0.2) × 10(-2) h(-1) but decelerating growth from 7.5(±0.3) × 10(-3) to 3.1(±0.1) × 10(-3) μm(2) h(-1). Through quantitative analysis, we propose that nanostructure nucleation is controlled by rhodochrosite surface dissolution, similar to the dissolution-precipitation mechanism proposed for carbonate mineral surface reconstruction in aqueous solution. To explain nanostructure growth in humid oxygen, a new Cabrera-Mott mechanism involving electron tunneling and solid-state diffusion is proposed.

Analysis of diffusion in curved surfaces and its application to tubular membranes.

PubMed

Klaus, Colin James Stockdale; Raghunathan, Krishnan; DiBenedetto, Emmanuele; Kenworthy, Anne K

2016-12-01

Diffusion of particles in curved surfaces is inherently complex compared with diffusion in a flat membrane, owing to the nonplanarity of the surface. The consequence of such nonplanar geometry on diffusion is poorly understood but is highly relevant in the case of cell membranes, which often adopt complex geometries. To address this question, we developed a new finite element approach to model diffusion on curved membrane surfaces based on solutions to Fick's law of diffusion and used this to study the effects of geometry on the entry of surface-bound particles into tubules by diffusion. We show that variations in tubule radius and length can distinctly alter diffusion gradients in tubules over biologically relevant timescales. In addition, we show that tubular structures tend to retain concentration gradients for a longer time compared with a comparable flat surface. These findings indicate that sorting of particles along the surfaces of tubules can arise simply as a geometric consequence of the curvature without any specific contribution from the membrane environment. Our studies provide a framework for modeling diffusion in curved surfaces and suggest that biological regulation can emerge purely from membrane geometry. © 2016 Klaus, Raghunathan, et al. This article is distributed by The American Society for Cell Biology under license from the author(s). Two months after publication it is available to the public under an Attribution–Noncommercial–Share Alike 3.0 Unported Creative Commons License (http://creativecommons.org/licenses/by-nc-sa/3.0).

In situ visualization of metallurgical reactions in nanoscale Cu/Sn diffusion couples

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

Yin, Qiyue; Stach, Eric A.; Gao, Fan

2015-02-10

The Cu–Sn metallurgical soldering reaction in two-segmented Cu–Sn nanowires is visualized by in-situ transmission electron microscopy. By varying the relative lengths of Cu and Sn segments, we show that the metallurgical reaction starts at ~ 200 ° with the formation of a Cu–Sn solid solution for the Sn/Cu length ratio smaller than 1:5 while the formation of Cu–Sn intermetallic compounds (IMCs) for larger Sn/Cu length ratios. Upon heating the nanowires up to ~ 500 °C, two phase transformation pathways occur, η-Cu₆Sn₅ → ε-Cu₃Sn → δ-Cu₄₁Sn₁₁ for nanowires with a long Cu segment and η-Cu₆Sn₅ → ε-Cu₃Sn → γ-Cu₃Sn with amore » short Cu segment. The dynamic in situ TEM visualization of the evolution of Kirkendall voids demonstrates that Cu diffuses faster both in Sn and IMCs than that of Sn in Cu₃ and IMCs, which is the underlying cause of the dependence of the IMC formation and associated phase evolution on the relative lengths of the Cu and Sn segments.« less

On the resilience of helical magnetic fields to turbulent diffusion and the astrophysical implications

NASA Astrophysics Data System (ADS)

Blackman, Eric G.; Subramanian, Kandaswamy

2013-02-01

The extent to which large-scale magnetic fields are susceptible to turbulent diffusion is important for interpreting the need for in situ large-scale dynamos in astrophysics and for observationally inferring field strengths compared to kinetic energy. By solving coupled evolution equations for magnetic energy and magnetic helicity in a system initialized with isotropic turbulence and an arbitrarily helical large-scale field, we quantify the decay rate of the latter for a bounded or periodic system. The magnetic energy associated with the non-helical large-scale field decays at least as fast as the kinematically estimated turbulent diffusion rate, but the decay rate of the helical part depends on whether the ratio of its magnetic energy to the turbulent kinetic energy exceeds a critical value given by M1, c = (k1/k2)2, where k1 and k2 are the wavenumbers of the large and forcing scales. Turbulently diffusing helical fields to small scales while conserving magnetic helicity requires a rapid increase in total magnetic energy. As such, only when the helical field is subcritical can it so diffuse. When supercritical, it decays slowly, at a rate determined by microphysical dissipation even in the presence of macroscopic turbulence. In effect, turbulent diffusion of such a large-scale helical field produces small-scale helicity whose amplification abates further turbulent diffusion. Two curious implications are that (1) standard arguments supporting the need for in situ large-scale dynamos based on the otherwise rapid turbulent diffusion of large-scale fields require re-thinking since only the large-scale non-helical field is so diffused in a closed system. Boundary terms could however provide potential pathways for rapid change of the large-scale helical field. (2) Since M1, c ≪ 1 for k1 ≪ k2, the presence of long-lived ordered large-scale helical fields as in extragalactic jets do not guarantee that the magnetic field dominates the kinetic energy.

Vanadium As a Potential Membrane Material for Carbon Capture: Effects of Minor Flue Gas Species.

PubMed

Yuan, Mengyao; Liguori, Simona; Lee, Kyoungjin; Van Campen, Douglas G; Toney, Michael F; Wilcox, Jennifer

2017-10-03

Vanadium and its surface oxides were studied as a potential nitrogen-selective membrane material for indirect carbon capture from coal or natural gas power plants. The effects of minor flue gas components (SO 2 , NO, NO 2 , H 2 O, and O 2 ) on vanadium at 500-600 °C were investigated by thermochemical exposure in combination with X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and in situ X-ray diffraction (XRD). The results showed that SO 2 , NO, and NO 2 are unlikely to have adsorbed on the surface vanadium oxides at 600 °C after exposure for up to 10 h, although NO and NO 2 may have exhibited oxidizing effects (e.g., exposure to 250 ppmv NO/N 2 resulted in an 2.4 times increase in surface V 2 O 5 compared to exposure to just N 2 ). We hypothesize that decomposition of surface vanadium oxides and diffusion of surface oxygen into the metal bulk are both important mechanisms affecting the composition and morphology of the vanadium membrane. The results and hypothesis suggest that the carbon capture performance of the vanadium membrane can potentially be strengthened by material and process improvements such as alloying, operating temperature reduction, and flue gas treatment.

The role of CO 2 as a soft oxidant for dehydrogenation of ethylbenzene to styrene over a high-surface-area ceria catalyst

DOE PAGES

Zhang, Li; Wu, Zili; Nelson, Nicholas; ...

2015-09-22

Catalytic performance and the nature of surface adsorbates were investigated for high-surface-area ceria during ethylbenzene oxidative dehydrogenation (ODH) reaction using CO2 as a soft oxidant. A template assisted method was used to synthesize the high-surface-area ceria. The interactions between ethylbenzene, styrene and CO2 on the surface of ceria and the role of CO2 for the ethylbenzene ODH reaction have been investigated in detail by using activity test, in situ Diffuse Reflectance Infrared and Raman spectroscopy. Not only did CO2 as an oxidant favor the higher yield of styrene, but it also inhibited the deposition of coke during the ethylbenzene ODHmore » reaction. Ethylbenzene ODH reaction over ceria followed a two-step pathway: Ethylbenzene is first dehydrogenated to styrene with H2 formed simultaneously, and then CO2 reacts with H2 via the reverse water gas shift. The styrene produced can easily polymerize to form polystyrene, a key intermediate for coke formation. In the absence of CO2, the polystyrene transforms into graphite-like coke at temperatures above 500 °C, which leads to catalyst deactivation. While in the presence of CO2, the coke deposition can be effectively removed via oxidation with CO2.« less

Bioassays with caged hyalella azteca to determine in situ toxicity downstream of two Saskatchewan, Canada, uranium operations.

PubMed

Robertson, Erin L; Liber, Karsten

2007-11-01

The main objectives of this in situ study were to evaluate the usefulness of an in situ bioassay to determine if downstream water bodies at the Key Lake and Rabbit Lake uranium operations (Saskatchewan, Canada) were toxic to Hyalella azteca and, if toxicity was observed, to differentiate between the contribution of surface water and sediment contamination to in situ toxicity. These objectives were achieved by performing 4-d in situ bioassays with laboratory-reared H. azteca confined in specially designed, paired, surface water and sediment exposure chambers. Results from the in situ bioassays revealed significant mortality, relative to the respective reference site, at the exposure sites at both Key Lake (p

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

NASA Astrophysics Data System (ADS)

Marquardt, Katharina; Dohmen, Ralf; Wagner, Johannes

2014-05-01

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

Enhanced diffusion on oscillating surfaces through synchronization

NASA Astrophysics Data System (ADS)

Wang, Jin; Cao, Wei; Ma, Ming; Zheng, Quanshui

2018-02-01

The diffusion of molecules and clusters under nanoscale confinement or absorbed on surfaces is the key controlling factor in dynamical processes such as transport, chemical reaction, or filtration. Enhancing diffusion could benefit these processes by increasing their transport efficiency. Using a nonlinear Langevin equation with an extensive number of simulations, we find a large enhancement in diffusion through surface oscillation. For helium confined in a narrow carbon nanotube, the diffusion enhancement is estimated to be over three orders of magnitude. A synchronization mechanism between the kinetics of the particles and the oscillating surface is revealed. Interestingly, a highly nonlinear negative correlation between diffusion coefficient and temperature is predicted based on this mechanism, and further validated by simulations. Our results provide a general and efficient method for enhancing diffusion, especially at low temperatures.

Decomposition of jellyfish carrion in situ: Short-term impacts on infauna, benthic nutrient fluxes and sediment redox conditions.

PubMed

Chelsky, Ariella; Pitt, Kylie A; Ferguson, Angus J P; Bennett, William W; Teasdale, Peter R; Welsh, David T

2016-10-01

Jellyfish often form blooms that persist for weeks to months before they collapse en masse, resulting in the sudden release of large amounts of organic matter to the environment. This study investigated the biogeochemical and ecological effects of the decomposition of jellyfish in a shallow coastal lagoon in New South Wales, Australia. Catostylus mosaicus carrion was added to the surface of shallow sub-tidal sediments and biogeochemical parameters and macrofaunal abundance immediately below the jellyfish carrion were measured over three days. Sediment plots without jellyfish served as controls. Sediment oxygen demand and carbon and nitrogen efflux increased by up to 60-fold in the jellyfish plots, compared to control plots, and dissolved organic nutrient fluxes were more sustained than in previous studies due to the use of fresh rather than frozen biomass. The decomposing jellyfish progressively altered sediment redox conditions, indicated by an increase in porewater iron (II) and sulfide concentrations measured by high-resolution in situ diffusive samplers. Abundance of some macrofaunal taxa in the jellyfish plots decreased relative to controls, however, the abundance of a carnivorous gastropod, which was presumably feeding on the carrion, increased in the jellyfish plots. While jellyfish carrion may be a food source for some macrofauna, low oxygen conditions coupled with the accumulation of toxic dissolved sulfides in the near-surface sediments may explain the overall change in the macroinfaunal community. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterizing surface temperature and clarity of Kuwait's seawaters using remotely sensed measurements and GIS analyses

NASA Astrophysics Data System (ADS)

Alsahli, Mohammad M. M.

Kuwait sea surface temperature (SST) and water clarity are important water characteristics that influence the entire Kuwait coastal ecosystem. The spatial and temporal distributions of these important water characteristics should be well understood to obtain a better knowledge about this productive coastal environment. The aim of this project was therefore to study the spatial and temporal distributions of: Kuwait SST using Moderate Resolution Imaging Spectroradiometer (MODIS) images collected from January 2003 to July 2007; and Kuwait Secchi Disk Depth (SDD), a water clarity measure, using Sea-viewing Wide Field-of-view Sensor (SeaWiFS) and MODIS data collected from November 1998 to October 2004 and January 2003 to June 2007, respectively. Kuwait SST was modeled based on the linear relationship between level 2 MODIS SST data and in situ SST data. MODIS SST images showed a significant relationship with in situ SST data ( r2= 0.98, n = 118, RMSE = 0.7°C). Kuwait SST images derived from MODIS data exhibited three spatial patterns of Kuwait SST across the year that were mainly attributed to the northwestern counterclockwise water circulation of the Arabian Gulf, and wind direction and intensity. The temporal variation of Kuwait SST was greatly influenced by the seasonal variation of solar intensity and air temperatures. Kuwait SDD was measured through two steps: first, computing the diffuse light attenuation coefficient at 490 nm, Kd(490), and 488 nm, Kd(488), derived from SeaWiFS and MODIS, respectively, using a semi-analytical algorithm; second, establishing two SDD models based on the empirical relationship of Kd(490) and Kd(488) with in situ SDD data. Kd(490) and Kd(488) showed a significant relationship with in situ SDD data ( r2= 0.67 and r2= 0.68, respectively). Kuwait SDD images showed distinct spatial and temporal patterns of Kuwait water clarity that were mainly attributed to three factors: the Shatt Al-Arab discharge, water circulation, and coastal currents. The SeaWiFS and MODIS data compared to in situ measurements provided a comprehensive view of the studied seawater characteristics that improved their overall estimation within Kuwait's waters. Also, the near-real-time availability of SeaWiFS and MODIS data and their highly temporal resolution make them a very advantageous tool for studying coastal environments. Thus, I recommend involving this method in monitoring Kuwait coastal environments.

In Situ Growth of Mesoporous Silica with Drugs on Titanium Surface and Its Biomedical Applications.

PubMed

Wan, Mimi; Zhang, Jin; Wang, Qi; Zhan, Shuyue; Chen, Xudong; Mao, Chun; Liu, Yuhong; Shen, Jian

2017-06-07

Mesoporous silica has been developed for the modification of titanium surfaces that are used as implant materials. Yet, the traditional modification methods failed to effectively construct mesoporous silica on the titanium surface evenly and firmly, in which the interaction between mesoporous silica and titanium was mainly physical. Here, in situ growth of mesoporous silica on a titanium surface was performed using a simple evaporation-induced self-assembly strategy. Meantime, in situ introduction of drugs (heparin and vancomycin) to mesoporous silica was also adopted to improve the drug-loading amount. Both the above-mentioned processes were completed at the same time. Transmission electron microscopy, N 2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, and water contact angle measurements were used to characterize the structure of the mesoporous silica film. Results indicated that the mesoporous silica film that in situ grew on the titanium surface was smooth, thin, transparent, and stable. Cytotoxicity, proliferation performance of osteoblast cells, and in vitro and in vivo studies of the antibacterial activity of the coating were tested. This is the first study to modify the titanium surface by the in situ growth of a mesoporous silica coating with two kinds of drugs. The stability of the mesoporous silica coating can be attributed to the chemical bonding between dopamine and silicon hydroxyl of the mesoporous silica coating, and the smooth surface of mesoporous silica is a result of the method of in situ growth. The large amount of drug-loading also could be ascribed to the in situ introduction of drugs during the synthetic process. The strategy proposed in this work will bring more possibilities for the preparation of advanced functional materials based on the combination of mesoporous structure and metallic materials.

Patterned surfaces in the drying of films composed of water, polymer, and alcohol

NASA Astrophysics Data System (ADS)

Fichot, Julie; Heyd, Rodolphe; Josserand, Christophe; Chourpa, Igor; Gombart, Emilie; Tranchant, Jean-Francois; Saboungi, Marie-Louise

2012-12-01

A study of the complex drying dynamics of polymeric mixtures with optical microscopy and gravimetric measurement is presented. Droplet formation is observed, followed by a collapse that leads to the residual craters in the dried film. The process is followed in situ under well-defined temperature and hygrometric conditions to determine the origin and nature of these droplets and craters. The drying process is usually completed within 1 h. The observations are explained using a simple diffusion model based on experimental results collected from mass and optical measurements as well as Raman confocal microspectrometry. Although the specific polymeric mixtures used here are of interest to the cosmetic industry, the general conclusions reached can apply to other polymeric aqueous solutions with applications to commercial and artistic painting.

H2O in rhyolitic glasses and melts: Measurement, speciation, solubility, and diffusion

NASA Astrophysics Data System (ADS)

Zhang, Youxue

1999-11-01

Dissolved H2O in silicate melts and glasses plays a crucial role in volcanic eruptions on terrestrial planets and affects glass properties and magma evolution. In this paper, major progress on several aspects of the H2O-melt (or glass) system is reviewed, consistency among a variety of data is investigated, discrepancies are evaluated, and confusion is clarified. On the infrared measurement of total H2O and species concentrations, calibration for a variety of glasses has been carried out at room temperature. The measurements for H2O in rhyolitic glasses have undergone the most scrutiny, resulting in the realization that absorptivities for the near-infrared bands depend on total H2O content. Although the variation of the absorptivities does not seem to significantly affect the determination of total H2O, it does affect the determination of molecular H2O and OH species concentrations. Calibration of the infrared technique for H2O in rhyolitic glasses still needs much improvement, especially at high total H2O. Furthermore, it is now almost certain that the molar absorptivities also depend on the measurement temperature in in situ studies. Hence it will be necessary to carry out calibrations in situ at high temperatures. On H2O speciation, results from two experimental approaches, the quench technique and the in situ technique, are very different, leading to controversy in our understanding of true speciation. A solution is presented to reconcile this controversy. It is almost certain that the quench technique does not suffer from a quench problem, but interpretation of in situ results suffered from ignoring the dependence of the molar absorptivities on measurement temperature. Accurate calibration at high temperatures is necessary for the quantitative application of the in situ technique to H2O speciation in silicate melts and glasses. On H2O solubility in silicate melts, recent experimental work has significantly expanded the T-P range of solubility measurements, and recent solubility models fill a gap for predicting solubility for a wide range of melt compositions. I present a solubility model for rhyolitic and quasi-rhyolitic melts over a wide range of T and P (500°-1350°C, 0-8 kbar) by incorporating the role of speciation. The solubility model is able to recover the experimental solubility data and has extrapolative value, although the partial molar volume of H2O derived from the solubility model differs from that derived from density measurements. On H2O diffusion, recent studies on H2O diffusion in a quasi-rhyolitic melt at 800°-1200°C, 0.5-5 kbar, and up to 7% total H2O not only provide important new diffusion data, but are also challenging earlier understanding of H2O diffusion based on data in rhyolitic glasses at 400°-550°C, 1 bar, and 0.2-1.8% total H2O. A comparison between the earlier model and recent data is made. The recent high-temperature diffusivities at total H2O ≤ 2% can be predicted by the earlier model. However, at higher total H2O, the earlier model fails. New work is under way to understand the diffusion mechanisms at high H2O contents.

An in situ method for real-time monitoring of soil gas diffusivity

NASA Astrophysics Data System (ADS)

Laemmel, Thomas; Maier, Martin; Schack-Kirchner, Helmer; Lang, Friederike

2016-04-01

Soil aeration is an important factor for the biogeochemistry of soils. Generally, gas exchange between soil and atmosphere is assumed to be governed by molecular diffusion and by this way fluxes can be calculated using by Fick's Law. The soil gas diffusion coefficient DS represents the proportional factor between the gas flux and the gas concentration gradient in the soil and reflects the ability of the soil to "transport passively" gas through the soil. One common way to determine DS is taking core samples in the field and measuring DS in the lab. Unfortunately this method is destructive and laborious and it can only reflect a small fraction of the whole soil. As a consequence, uncertainty about the resulting effective diffusivity on the profile scale, i.e. the real aeration status remains. We developed a method to measure and monitor DS in situ. The set-up consists of a custom made gas sampling device, the continuous injection of an inert tracer gas and inverse gas transport modelling in the soil. The gas sampling device has seven sampling depths (from 0 to -43 cm of depth) and can be easily installed into vertical holes drilled by an auger, which allows for fast installation of the system. Helium (He) as inert tracer gas was injected continuously at the lower end of the device. The resulting steady state distribution of He was used to deduce the DS depth distribution of the soil. For Finite Element Modeling of the gas-sampling-device/soil system the program COMSOL was used. We tested our new method both in the lab and in a field study and compared the results with a reference lab method using soil cores. DS profiles obtained by our in-situ method were consistent with DS profiles determined based on soil core analyses. Soil gas profiles could be measured with a temporal resolution of 30 minutes. During the field study, there was an important rain event and we could monitor the decrease in soil gas diffusivity in the top soil due to water infiltration. The effect of soil water infiltration deeper into the soil on soil gas diffusivity could be observed during the following hours. Our new DS determination device can be quickly and easily installed and allows for monitoring continuously soil gas transport over a long time. It allows following modifications of soil gas diffusivity due to rain events. In addition it enables the analysis of non-diffusive soil gas transport processes.

In situ imaging of the soldering reactions in nanoscale Cu/Sn/Cu and Sn/Cu/Sn diffusion couples

NASA Astrophysics Data System (ADS)

Yin, Qiyue; Gao, Fan; Gu, Zhiyong; Wang, Jirui; Stach, Eric A.; Zhou, Guangwen

2018-01-01

The soldering reactions of three-segmented Sn/Cu/Sn and Cu/Sn/Cu diffusion couples are monitored by in-situ transmission electron microscopy to reveal the metallurgical reaction mechanism and the associated phase transformation pathway. For Sn/Cu/Sn diffusion couples, there is no ɛ-Cu3Sn formation due to the relatively insufficient Cu as compared to Sn. Kirkendall voids form initially in the Cu segment and then disappear due to the volume expansion associated with the continued intermetallic compound (IMC) formation as the reaction progresses. The incoming Sn atoms react with Cu to form η-Cu6Sn5, and the continuous reaction then transforms the entire nanowire to η-Cu6Sn5 grains with remaining Sn. With continued heating slightly above the melting point of Sn, an Sn-rich liquid phase forms between η-Cu6Sn5 grains. By contrast, the reaction in the Cu/Sn/Cu diffusion couples results in the intermetallic phases of both Cu3Sn and Cu6Sn5 and the development of Cu6Sn5 bulges on Cu3Sn grains. Kirkendall voids form in the two Cu segments, which grow and eventually break the nanowire into multiple segments.

Surface phenomena revealed by in situ imaging: studies from adhesion, wear and cutting

NASA Astrophysics Data System (ADS)

Viswanathan, Koushik; Mahato, Anirban; Yeung, Ho; Chandrasekar, Srinivasan

2017-03-01

Surface deformation and flow phenomena are ubiquitous in mechanical processes. In this work we present an in situ imaging framework for studying a range of surface mechanical phenomena at high spatial resolution and across a range of time scales. The in situ framework is capable of resolving deformation and flow fields quantitatively in terms of surface displacements, velocities, strains and strain rates. Three case studies are presented demonstrating the power of this framework for studying surface deformation. In the first, the origin of stick-slip motion in adhesive polymer interfaces is investigated, revealing a intimate link between stick-slip and surface wave propagation. Second, the role of flow in mediating formation of surface defects and wear particles in metals is analyzed using a prototypical sliding process. It is shown that conventional post-mortem observation and inference can lead to erroneous conclusions with regard to formation of surface cracks and wear particles. The in situ framework is shown to unambiguously capture delamination wear in sliding. Third, material flow and surface deformation in a typical cutting process is analyzed. It is shown that a long-standing problem in the cutting of annealed metals is resolved by the imaging, with other benefits such as estimation of energy dissipation and power from the flow fields. In closure, guidelines are provided for profitably exploiting in situ observations to study large-strain deformation, flow and friction phenomena at surfaces that display a variety of time-scales.

Leapfrog Diffusion Mechanism for One-Dimensional Chains on Missing-Row Reconstructed Surfaces

NASA Astrophysics Data System (ADS)

Montalenti, F.; Ferrando, R.

1999-02-01

We analyze the in-channel diffusion of dimers and longer n-adatom chains on Au and Pt (110) \\(1×2\\) surfaces by molecular dynamics simulations. From our calculations it arises that, on the missing-row reconstructed surface, a novel diffusion process, called leapfrog, dominates over concerted jumps, thus becoming the most frequent diffusion mechanism.

Fluorescence-correlation spectroscopy study of molecular transport within reversed-phase chromatographic particles compared to planar model surfaces.

PubMed

Cooper, Justin; Harris, Joel M

2014-12-02

Reversed-phase liquid chromatography (RPLC) is a widely used technique for molecular separations. Stationary-phase materials for RPLC generally consist of porous silica-gel particles functionalized with n-alkane ligands. Understanding motions of molecules within the interior of these particles is important for developing efficient chromatographic materials and separations. To characterize these dynamics, time-resolved spectroscopic methods (photobleach recovery, fluorescence correlation, single-molecule imaging) have been adapted to measure molecular diffusion rates, typically at n-alkane-modified planar silica surfaces, which serve as models of chromatographic interfaces. A question arising from these studies is how dynamics of molecules on a planar surface relate to motions of molecules within the interior of a porous chromatographic particle. In this paper, imaging-fluorescence-correlation spectroscopy is used to measure diffusion rates of a fluorescent probe molecule 1,1'-dioctadecyl-3,3,3'3'-tetramethylindocarbocyanine perchlorate (DiI) within authentic RPLC porous silica particles and compared with its diffusion at a planar C18-modified surface. The results show that surface diffusion on the planar C18 substrate is much faster than the diffusion rate of the probe molecule through a chromatographic particle. Surface diffusion within porous particles, however, is governed by molecular trajectories along the tortuous contours of the interior surface of the particles. By accounting for the greater surface area that a molecule must explore to diffuse macroscopic distances through the particle, the molecular-scale diffusion rates on the two surfaces can be compared, and they are virtually identical. These results provide support for the relevance of surface-diffusion measurements made on planar model surfaces to the dynamic behavior of molecules on the internal surfaces of porous chromatographic particles.

How a Nanodroplet Diffuses on Smooth Surfaces

NASA Astrophysics Data System (ADS)

Li, Chu; Huang, Jizu; Li, Zhigang

2016-11-01

In this study, we investigate how nanodroplets diffuse on smooth surfaces through molecular dynamics (MD) simulations and theoretical analyses. The simulations results show that the surface diffusion of nanodroplet is different from that of single molecules and solid nanoparticles. The dependence of nanodroplet diffusion coefficient on temperature is surface wettability dependent, which undergoes a transition from linear to nonlinear as the surface wettability is weakened due to the coupling of temperature and surface energy. We also develop a simple relation for the diffusion coefficient by using the contact angle and contact radius of the droplet. It works well for different surface wettabilities and sized nanodroplets, as confirmed by MD simulations. This work was supported by the Research Grants Council of the Hong Kong Special Administrative Region under Grant No. 615312.

Metaproteogenomic Profiling of Microbial Communities Colonizing Actively Venting Hydrothermal Chimneys

PubMed Central

Pjevac, Petra; Meier, Dimitri V.; Markert, Stephanie; Hentschker, Christian; Schweder, Thomas; Becher, Dörte; Gruber-Vodicka, Harald R.; Richter, Michael; Bach, Wolfgang; Amann, Rudolf; Meyerdierks, Anke

2018-01-01

At hydrothermal vent sites, chimneys consisting of sulfides, sulfates, and oxides are formed upon contact of reduced hydrothermal fluids with oxygenated seawater. The walls and surfaces of these chimneys are an important habitat for vent-associated microorganisms. We used community proteogenomics to investigate and compare the composition, metabolic potential and relative in situ protein abundance of microbial communities colonizing two actively venting hydrothermal chimneys from the Manus Basin back-arc spreading center (Papua New Guinea). We identified overlaps in the in situ functional profiles of both chimneys, despite differences in microbial community composition and venting regime. Carbon fixation on both chimneys seems to have been primarily mediated through the reverse tricarboxylic acid cycle and fueled by sulfur-oxidation, while the abundant metabolic potential for hydrogen oxidation and carbon fixation via the Calvin–Benson–Bassham cycle was hardly utilized. Notably, the highly diverse microbial community colonizing the analyzed black smoker chimney had a highly redundant metabolic potential. In contrast, the considerably less diverse community colonizing the diffusely venting chimney displayed a higher metabolic versatility. An increased diversity on the phylogenetic level is thus not directly linked to an increased metabolic diversity in microbial communities that colonize hydrothermal chimneys. PMID:29696004

Significant increase of Curie temperature in nano-scale BaTiO{sub 3}

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

Li, Yueliang; Liao, Zhenyu; Fang, Fang

2014-11-03

The low Curie temperature (T{sub c} = 130 °C) of bulk BaTiO{sub 3} greatly limits its applications. In this work, the phase structures of BaTiO{sub 3} nanoparticles with sizes ranging from 2.5 nm to 10 nm were studied at various temperatures by using aberration-corrected transmission electron microscopy (TEM) equipped with an in-situ heating holder. The results implied that each BaTiO{sub 3} nanoparticle was composed of different phases, and the ferroelectric ones were observed in the shells due to the complicated surface structure. The ferroelectric phases in BaTiO{sub 3} nanoparticles remained at 600 °C, suggesting a significant increase of T{sub c}. Based on the in-situ TEM resultsmore » and the data reported by others, temperature-size phase diagrams for BaTiO{sub 3} particles and ceramics were proposed, showing that the phase transition became diffused and the T{sub c} obviously increased with decreasing size. The present work sheds light on the design and fabrication of advanced devices for high temperature applications.« less

In situ high temperature microwave microscope for nondestructive detection of surface and sub-surface defects.

PubMed

Wang, Peiyu; Li, Zhencheng; Pei, Yongmao

2018-04-16

An in situ high temperature microwave microscope was built for detecting surface and sub-subsurface structures and defects. This system was heated with a self-designed quartz lamp radiation module, which is capable of heating to 800°C. A line scanning of a metal grating showed a super resolution of 0.5 mm (λ/600) at 1 GHz. In situ scanning detections of surface hole defects on an aluminium plate and a glass fiber reinforced plastic (GFRP) plate were conducted at different high temperatures. A post processing algorithm was proposed to remove the background noises induced by high temperatures and the 3.0 mm-spaced hole defects were clearly resolved. Besides, hexagonal honeycomb lattices were in situ detected and clearly resolved under a 1.0 mm-thick face panel at 20°C and 50°C, respectively. The core wall positions and bonding width were accurately detected and evaluated. In summary, this in situ microwave microscope is feasible and effective in sub-surface detection and super resolution imaging at different high temperatures.

Anisotropic diffusion at the field scale in a 4-year multi-tracer diffusion and retention experiment - I: Insights from the experimental data

NASA Astrophysics Data System (ADS)

Gimmi, Thomas; Leupin, Olivier X.; Eikenberg, Jost; Glaus, Martin A.; Van Loon, Luc R.; Waber, H. Niklaus; Wersin, Paul; Wang, Hao A. O.; Grolimund, Daniel; Borca, Camelia N.; Dewonck, Sarah; Wittebroodt, Charles

2014-01-01

Claystones are considered worldwide as barrier materials for nuclear waste repositories. In the Mont Terri underground research laboratory (URL), a nearly 4-year diffusion and retention (DR) experiment has been performed in Opalinus Clay. It aimed at (1) obtaining data at larger space and time scales than in laboratory experiments and (2) under relevant in situ conditions with respect to pore water chemistry and mechanical stress, (3) quantifying the anisotropy of in situ diffusion, and (4) exploring possible effects of a borehole-disturbed zone. The experiment included two tracer injection intervals in a borehole perpendicular to bedding, through which traced artificial pore water (APW) was circulated, and a pressure monitoring interval. The APW was spiked with neutral tracers (HTO, HDO, H2O-18), anions (Br, I, SeO4), and cations (Na-22, Ba-133, Sr-85, Cs-137, Co-60, Eu-152, stable Cs, and stable Eu). Most tracers were added at the beginning, some were added at a later stage. The hydraulic pressure in the injection intervals was adjusted according to the measured value in the pressure monitoring interval to ensure transport by diffusion only. Concentration time-series in the APW within the borehole intervals were obtained, as well as 2D concentration distributions in the rock at the end of the experiment after overcoring and subsampling which resulted in ∼250 samples and ∼1300 analyses. As expected, HTO diffused the furthest into the rock, followed by the anions (Br, I, SeO4) and by the cationic sorbing tracers (Na-22, Ba-133, Cs, Cs-137, Co-60, Eu-152). The diffusion of SeO4 was slower than that of Br or I, approximately proportional to the ratio of their diffusion coefficients in water. Ba-133 diffused only into ∼0.1 m during the ∼4 a. Stable Cs, added at a higher concentration than Cs-137, diffused further into the rock than Cs-137, consistent with a non-linear sorption behavior. The rock properties (e.g., water contents) were rather homogeneous at the centimeter scale, with no evidence of a borehole-disturbed zone. In situ anisotropy ratios for diffusion, derived for the first time directly from field data, are larger for HTO and Na-22 (∼5) than for anions (∼3-4 for Br and I). The lower ionic strength of the pore water at this location (∼0.22 M) as compared to locations of earlier experiments in the Mont Terri URL (∼0.39 M) had no notable effect on the anion accessible pore fraction for Cl, Br, and I: the value of 0.55 is within the range of earlier data. Detailed transport simulations involving different codes will be presented in a companion paper.

Metallic phases of cobalt-based catalysts in ethanol steam reforming: The effect of cerium oxide

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

Lin, Sean S.-Y.; Kim, Do Heui; Ha, Su Y.

2009-02-28

The catalytic activity of cobalt in the production of hydrogen via ethanol steam reforming has been investigated in its relation to the crystalline structure of metallic cobalt. At a reaction temperature of 350 8C, the specific hydrogen production rates show that hexagonal close-packed (hcp) cobalt possesses higher activity than face-centered cubic (fcc) cobalt. However, at typical reaction temperatures (400– 500 8C) for ethanol steam reforming, hcp cobalt is transformed to less active fcc cobalt, as confirmed by in situ X-ray diffractometry (XRD). The addition of CeO2 promoter (10 wt.%) stabilizes the hcp cobalt structure at reforming temperatures up to 600more » 8C. Moreover, during the pre-reduction process, CeO2 promoter prevents sintering during the transformation of Co3O4 to hcp cobalt. Both reforming experiments and in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the surface reactions were modified by CeO2 promoter on 10% Ce–Co (hcp) to give a lower CO selectivity and a higher H2 yield as compared with the unpromoted hcp Co.« less

Facile fabrication of well-defined hydrogel beads with magnetic nanocomposite shells.

PubMed

Liu, Hongxia; Wang, Chaoyang; Gao, Quanxing; Chen, Jianxin; Ren, Biye; Liu, Xinxing; Tong, Zhen

2009-07-06

Well-defined magnetic nanocomposite beads with alginate gel cores and shells of iron oxide (gamma-Fe(2)O(3)) nanoparticles were prepared by self-assembly of colloidal particles at liquid-liquid interfaces and subsequent in situ gelation. Fe(2)O(3) nanoparticles could spontaneously adsorb onto the water droplet surfaces to stabilize water-in-hexane emulsions. Water droplets containing sodium alginate were in situ gelled by calcium cations, which were released from calcium-ethylenediamine tetraacetic acid (Ca-EDTA) chelate by decreasing pH value through slow hydrolysis of d-glucono-delta-lactone (GDL). The resulting hybrid beads with a core-shell structure were easily collected by removing hexane. This facile and high efficient fabrication had a 100% yield and could be carried out at room temperature. Insulin microcrystal was encapsulated into the hybrid beads by dispersing them in the aqueous solution of alginate sodium in the fabrication process. The sustained release could be obtained due to the dual barriers of the hydrogel core and the close-packed inorganic shell. The release curves were nicely fitted by the Weibull equation and the release followed Fickian diffusion. The hybrid beads may find applications as delivery vehicles for biomolecules, drugs, cosmetics, food supplements and living cells.

In situ optical diagnostic for monitoring or control of sodium diffusion in photovoltaics manufacturing

DOEpatents

Li, Jian; Levi, Dean; Contreras, Miguel; Glynn, Stephen

2015-09-15

A method of fabricating a photovoltaic device 100, includes the steps of providing a glass substrate 102, depositing a molybdenum layer 104 on a surface of the glass substrate, directing light through the glass substrate to the near-substrate region of the molybdenum layer 206, detecting an optical property of the near-substrate region of the molybdenum layer after interaction with the incident light 208 and determining a density of the near-substrate region of the molybdenum layer from the detected optical property 210. A molybdenum deposition parameter may be controlled based upon the determined density of the near-substrate region of the molybdenum layer 218. A non-contact method measures a density of the near-substrate region of a molybdenum layer and a deposition chamber 300.

Reactive solid surface morphology variation via ionic diffusion.

PubMed

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih

2012-08-14

In gas-solid reactions, one of the most important factors that determine the overall reaction rate is the solid morphology, which can be characterized by a combination of smooth, convex and concave structures. Generally, the solid surface structure varies in the course of reactions, which is classically noted as being attributed to one or more of the following three mechanisms: mechanical interaction, molar volume change, and sintering. Here we show that if a gas-solid reaction involves the outward ionic diffusion of a solid-phase reactant then this outward ionic diffusion could eventually smooth the surface with an initial concave and/or convex structure. Specifically, the concave surface is filled via a larger outward diffusing surface pointing to the concave valley, whereas the height of the convex surface decreases via a lower outward diffusion flux in the vertical direction. A quantitative 2-D continuum diffusion model is established to analyze these two morphological variation processes, which shows consistent results with the experiments. This surface morphology variation by solid-phase ionic diffusion serves to provide a fourth mechanism that supplements the traditionally acknowledged solid morphology variation or, in general, porosity variation mechanisms in gas-solid reactions.

In Situ SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

PubMed Central

Johnson, Grant E.; Gunaratne, K. Don Dasitha; Laskin, Julia

2014-01-01

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces. PMID:24961913

In Situ SIMS and IR Spectroscopy of Well-Defined Surfaces Prepared by Soft Landing of Mass-Selected Ions

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

Johnson, Grant E.; Gunaratne, Kalupathirannehelage Don D.; Laskin, Julia

2014-06-16

Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy)3]2+, onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivitymore » of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces.« less

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-07-01

Release of trace gases from surface snow on earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analysed by means of X-ray-computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures, surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature-dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. For this, a snow sample with an artificially high amount of ice grains was produced and the grain boundary surface measured using thin sections. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

On the nucleation and initial film growth of rod-like organic molecules

NASA Astrophysics Data System (ADS)

Winkler, Adolf

2016-10-01

In this article, some fundamental topics related to the initial steps of organic film growth are reviewed. General conclusions will be drawn based on experimental results obtained for the film formation of oligophenylene and pentacene molecules on gold and mica substrates. Thin films were prepared via physical vapor deposition under ultrahigh-vacuum conditions and characterized in-situ mainly by thermal desorption spectroscopy, and ex-situ by X-ray diffraction and atomic force microscopy. In this short review article the following topics will be discussed: What are the necessary conditions to form island-like films which are either composed of flat-lying or of standing molecules? Does a wetting layer exist below and in between the islands? What is the reason behind the occasionally observed bimodal island size distribution? Can one describe the nucleation process with the diffusion-limited aggregation model? Do the impinging molecules directly adsorb on the surface or rather via a hot-precursor state? Finally, it will be described how the critical island size can be determined by an independent measurement of the deposition rate dependence of the island density and the capture-zone distribution via a universal relationship.

In situ REM and ex situ SPM studies of silicon (111) surface

NASA Astrophysics Data System (ADS)

Aseev, A. L.; Kosolobov, S. S.; Latyshev, A. V.; Song, Se Ahn; Saranin, A. A.; Zotov, A. V.; Lifshits, V. G.

2005-09-01

Combination of experimental methods, including ultrahigh vacuum in situ reflection electron microscopy, scanning tunnelling microscopy and atomic force microscopy, has been applied for analysis of surface structure and dynamic processes on silicon (111) surfaces during sublimation, rapid temperature cooling, oxygen reactions and metal-silicon surface phase formation. From analysis of triangular negative islands, 0.08 nm in depth, which were forming during quenching, it was deduced the effective activation energy of the island generation is equalled to 0.35 eV and made conclusion that the (1 × 1) (7 × 7) phase transition on Si(111) assumes to be responsible for the negative island nucleation. On the base of the in situ REM study, the dependence of step motion, initiated by surface vacancies generation during oxygen-silicon interaction, on the terrace width was measured. Peculiarities of the initial stages of silicon surface oxidation at low pressures were considered. From precision measurements, the top silicon atom density was determined for the metal-silicon surface phase formed during Na, Ca, Mg and Ag deposition on clean silicon (111) surface.

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.

Validation of Direct Normal Irradiance from Meteosat Second Generation

NASA Astrophysics Data System (ADS)

Meyer, Angela; Stöckli, Reto; Vuilleumier, Laurent; Wilbert, Stefan; Zarzalejo, Luis

2016-04-01

We present a validation study of Direct Normal Irradiance (DNI) derived from MSG/SEVIRI radiance measurements over the site of Plataforma Solar de Almeria (PSA), a solar power plant in Southern Spain. The 1 km x 1 km site of PSA hosts about a dozen pyrheliometers operated by the German Aerospace Centre (DLR) and the Centre for Energy, Environment and Technological Research (CIEMAT). They provide high-quality long-term measurements of surface DNI on a site of the scale of the MSG/SEVIRI pixel resolution. This makes the PSA DNI measurements a dataset particularly well suited for satellite validation purposes. The satellite-based surface DNI was retrieved from MSG/SEVIRI radiances by the HelioMont algorithm (Stöckli 2013) that forms part of the Heliosat algorithm family (e.g. Müller et al., 2004). We have assessed the accuracy of this DNI product for the PSA site by comparing with the in-situ measured DNIs of June 2014 - July 2015. Despite a generally good agreement, the HelioMont DNI exhibits a significant low bias at the PSA site, that is most pronounced during clear-sky periods. We present a bias correction method and discuss (1) the role of circumsolar diffuse radiation and (2) the role of climatological vs. reanalysis-based aerosol optical properties therein. We also characterize and assess the temporal variability of the HelioMont DNI as compared to the in situ measured DNIs, and will discuss and quantify the uncertainties in both DNI datasets.

DGT Passive Sampling for Quantitative in Situ Measurements of Compounds from Household and Personal Care Products in Waters.

PubMed

Chen, Wei; Li, Yanying; Chen, Chang-Er; Sweetman, Andrew J; Zhang, Hao; Jones, Kevin C

2017-11-21

Widespread use of organic chemicals in household and personal care products (HPCPs) and their discharge into aquatic systems means reliable, robust techniques to monitor environmental concentrations are needed. The passive sampling approach of diffusive gradients in thin-films (DGT) is developed here and demonstrated to provide in situ quantitative and time-weighted average (TWA) measurement of these chemicals in waters. The novel technique is developed for HPCPs, including preservatives, antioxidants and disinfectants, by evaluating the performance of different binding agents. Ultrasonic extraction of binding gels in acetonitrile gave good and consistent recoveries for all test chemicals. Uptake by DGT with HLB (hydrophilic-lipophilic-balanced) as the binding agent was relatively independent of pH (3.5-9.5), ionic strength (0.001-0.1 M) and dissolved organic matter (0-20 mg L -1 ), making it suitable for applications across a wide range of environments. Deployment time and diffusion layer thickness dependence experiments confirmed DGT accumulated chemicals masses are consistent with theoretical predictions. The technique was further tested and applied in the influent and effluent of a wastewater treatment plant. Results were compared with conventional grab-sampling and 24-h-composited samples from autosamplers. DGT provided TWA concentrations over up to 18 days deployment, with minimal effects from biofouling or the diffusive boundary layer. The field application demonstrated advantages of the DGT technique: it gives in situ analyte preconcentration in a simple matrix, with more quantitative measurement of the HPCP analytes.

Platinum supported on titanium–ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles

PubMed Central

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-01

We report a unique and highly stable electrocatalyst—platinum (Pt) supported on titanium–ruthenium oxide (TRO)—for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile—namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst—Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm−2 at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm−2 for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern. PMID:24367118

Platinum supported on titanium-ruthenium oxide is a remarkably stable electrocatayst for hydrogen fuel cell vehicles.

PubMed

Parrondo, Javier; Han, Taehee; Niangar, Ellazar; Wang, Chunmei; Dale, Nilesh; Adjemian, Kev; Ramani, Vijay

2014-01-07

We report a unique and highly stable electrocatalyst-platinum (Pt) supported on titanium-ruthenium oxide (TRO)-for hydrogen fuel cell vehicles. The Pt/TRO electrocatalyst was exposed to stringent accelerated test protocols designed to induce degradation and failure mechanisms identical to those seen during extended normal operation of a fuel cell automobile-namely, support corrosion during vehicle startup and shutdown, and platinum dissolution during vehicle acceleration and deceleration. These experiments were performed both ex situ (on supports and catalysts deposited onto a glassy carbon rotating disk electrode) and in situ (in a membrane electrode assembly). The Pt/TRO was compared against a state-of-the-art benchmark catalyst-Pt supported on high surface-area carbon (Pt/HSAC). In ex situ tests, Pt/TRO lost only 18% of its initial oxygen reduction reaction mass activity and 3% of its oxygen reduction reaction-specific activity, whereas the corresponding losses for Pt/HSAC were 52% and 22%. In in situ-accelerated degradation tests performed on membrane electrode assemblies, the loss in cell voltage at 1 A · cm(-2) at 100% RH was a negligible 15 mV for Pt/TRO, whereas the loss was too high to permit operation at 1 A · cm(-2) for Pt/HSAC. We clearly show that electrocatalyst support corrosion induced during fuel cell startup and shutdown is a far more potent failure mode than platinum dissolution during fuel cell operation. Hence, we posit that the need for a highly stable support (such as TRO) is paramount. Finally, we demonstrate that the corrosion of carbon present in the gas diffusion layer of the fuel cell is only of minor concern.

A novel active-passive sampling approach for measuring time-averaged concentrations of pollutants in water.

PubMed

Amato, Elvio D; Covaci, Adrian; Town, Raewyn M; Hereijgers, Jonas; Bellekens, Ben; Giacometti, Valentina; Breugelmans, Tom; Weyn, Maarten; Dardenne, Freddy; Bervoets, Lieven; Blust, Ronny

2018-06-14

Passive sampling with in situ devices offers several advantages over traditional sampling methods (i.e., discrete spot sampling), however, data interpretation from conventional passive samplers is hampered by difficulties in estimating the thickness of the diffusion layer at the sampler/medium interface (δ), often leading to inaccurate determinations of target analyte concentrations. In this study, the performance of a novel device combining active and passive sampling was investigated in the laboratory. The active-passive sampling (APS) device is comprised of a diffusion cell fitted with a pump and a flowmeter. Three receiving phases traditionally used in passive sampling devices (i.e., chelex resin, Oasis HLB, and silicone rubber), were incorporated in the diffusion cell and allowed the simultaneous accumulation of cationic metals, polar, and non-polar organic compounds, respectively. The flow within the diffusion cell was accurately controlled and monitored, and, combined with diffusion coefficients measurements, enabled the average δ to be estimated. Strong agreement between APS and time-averaged total concentrations measured in discrete water samples was found for most of the substances investigated. Accuracies for metals ranged between 87 and 116%, except Cu and Pb (∼50%), whilst accuracies between 64 and 101%, and 92 and 151% were achieved for polar and non-polar organic compounds, respectively. These results indicate that, via a well-defined in situ preconcentration step, the proposed APS approach shows promise for monitoring the concentration of a range of pollutants in water. Copyright © 2018 Elsevier Ltd. All rights reserved.

Strong Surface Diffusion Mediated Glancing-Angle Deposition: Growth, Recrystallization and Reorientation of Tin Nanorods

NASA Astrophysics Data System (ADS)

Wang, Huan-Hua; Shi, Yi-Jian; William, Chu; Yigal, Blum

2008-01-01

Different from usual glancing-angle deposition where low surface diffusion is necessary to form nanorods, strong surface diffusion mediated glancing-angle deposition is exemplified by growing tin nanorod films on both silicon and glass substrates simultaneously via thermal evaporation. During growth, the nanorods were simultaneously baked by the high-temperature evaporator, and therefore re-crystallized into single crystals in consequence of strong surface diffusion. The monocrystalline tin nanorods have a preferred orientation perpendicular to the substrate surface, which is quite different from the usual uniformly oblique nanorods without recrystallization.

Stratified mucin-producing intraepithelial lesion with invasive carcinoma: 12 cases with immunohistochemical and ultrastructural findings.

PubMed

Onishi, Junji; Sato, Yuichiro; Sawaguchi, Akira; Yamashita, Atsushi; Maekawa, Kazunari; Sameshima, Hiroshi; Asada, Yujiro

2016-09-01

Stratified mucin-producing intraepithelial lesion (SMILE) is considered to be a variant of adenocarcinoma in situ (defined as intraepithelial malignant glandular epithelium without invasion) or adenosquamous carcinoma in situ of the uterine cervix. However, recent study suggested that SMILE is more similar to high-grade squamous epithelial lesion by their immunohistochemical findings. An invasive form of SMILE "invasive stratified mucin-producing carcinoma (ISMC)" has been also proposed, but immunohistochemical features are not well documented. Therefore, this study aimed to clarify the immunohistochemical characteristics of SMILE and ISMC. Twelve cases of SMILE were found among 445 patients (2.7%) with high-grade intraepithelial lesions or invasive carcinomas, 3 of whom had solely intraepithelial disease with SMILE component (mean age, 37 years; range, 30-48 years) and 9 with invasive carcinomas (mean age, 47 years; range, 37-66 years; including ISMC). Immunohistochemically, SMILE and ISMC were diffusely positive for p16 and CAM5.2, focally for IMP3, and almost negative or only focally positive for p63. Nuclear signals in SMILE and invasive carcinomas were detected by human papillomavirus (HPV) in situ hybridization; 5 cases showed HPV16 and/or HPV18 polymerase chain reaction products. The ultrastructural study of 1 case showed surface microvilli and small vacuolar structure in SMILE; ISMC had mucous-like vacuoles, many mitochondria and intracytoplasmic lumen but lacked tonofilament. These findings were more similar to adenocarcinoma in situ or adenocarcinoma than squamous intraepithelial lesion or squamous cell carcinoma. We suggest that SMILE is an intraepithelial neoplasm and ISMC is an invasive form of SMILE. Copyright © 2016 Elsevier Inc. All rights reserved.

Real-time observation of Cu2ZnSn(S,Se)4 solar cell absorber layer formation from nanoparticle precursors.

PubMed

Mainz, Roland; Walker, Bryce C; Schmidt, Sebastian S; Zander, Ole; Weber, Alfons; Rodriguez-Alvarez, Humberto; Just, Justus; Klaus, Manuela; Agrawal, Rakesh; Unold, Thomas

2013-11-07

The selenization of Cu-Zn-Sn-S nanocrystals is a promising route for the fabrication of low-cost thin film solar cells. However, the reaction pathway of this process is not completely understood. Here, the evolution of phase formation, grain size, and elemental distributions is investigated during the selenization of Cu-Zn-Sn-S nanoparticle precursor thin films by synchrotron-based in situ energy-dispersive X-ray diffraction and fluorescence analysis as well as by ex situ electron microscopy. The precursor films are heated in a closed volume inside a vacuum chamber in the presence of selenium vapor while diffraction and fluorescence signals are recorded. The presented results reveal that during the selenization the cations diffuse to the surface to form large grains on top of the nanoparticle layer and the selenization of the film takes place through two simultaneous reactions: (1) a direct and fast formation of large grained selenides, starting with copper selenide which is subsequently transformed into Cu2ZnSnSe4; and (2) a slower selenization of the remaining nanoparticles. As a consequence of the initial formation of copper selenides at the surface, the subsequent formation of CZTSe starts under Cu-rich conditions despite an overall Cu-poor composition of the film. The implications of this process path for the film quality are discussed. Additionally, the proposed growth model provides an explanation for the previously observed accumulation of carbon from the nanoparticle precursor beneath the large grained layer.

How Do Organic Vapors Swell Ultrathin Films of Polymer of Intrinsic Microporosity PIM-1?

PubMed

Ogieglo, Wojciech; Rahimi, Khosorov; Rauer, Sebastian Bernhard; Ghanem, Bader; Ma, Xiaohua; Pinnau, Ingo; Wessling, Matthias

2017-07-27

Dynamic sorption of ethanol and toluene vapor into ultrathin supported films of polymer of intrinsic microporosity PIM-1 down to a thickness of 6 nm are studied with a combination of in situ spectroscopic ellipsometry and in situ X-ray reflectivity. Both ethanol and toluene significantly swell the PIM-1 matrix and, at the same time, induce persistent structural relaxations of the frozen-in glassy PIM-1 morphology. For ethanol below 20 nm, three effects were identified. First, the swelling magnitude at high vapor pressures is reduced by about 30% as compared to that of thicker films. Second, at low penetrant activities (below 0.3p/p 0 ), films below 20 nm are able to absorb slightly more penetrant as compared with thicker films despite a similar swelling magnitude. Third, for the ultrathin films, the onset of the dynamic penetrant-induced glass transition P g has been found to shift to higher values, indicating higher resistance to plasticization. All of these effects are consistent with a view where immobilization of the superglassy PIM-1 at the substrate surface leads to an arrested, even more rigid, and plasticization-resistant, yet still very open, microporous structure. PIM-1 in contact with the larger and more condensable toluene shows very complex, heterogeneous swelling dynamics, and two distinct penetrant-induced relaxation phenomena, probably associated with the film outer surface and the bulk, are detected. Following the direction of the penetrant's diffusion, the surface seems to plasticize earlier than the bulk, and the two relaxations remain well separated down to 6 nm film thickness, where they remarkably merge to form just a single relaxation.

Effect of Aging and Surface Interactions on the Diffusion of Endogenous Compounds in Latent Fingerprints Studied by Mass Spectrometry Imaging.

PubMed

O'Neill, Kelly C; Lee, Young Jin

2018-05-01

The ability to determine the age of fingerprints would be immeasurably beneficial in criminal investigations. We explore the possibility of determining the age of fingerprints by analyzing various compounds as they diffuse from the ridges to the valleys of fingerprints using matrix-assisted laser desorption/ionization mass spectrometry imaging. The diffusion of two classes of endogenous fingerprint compounds, fatty acids and triacylglycerols (TGs), was studied in fresh and aged fingerprints on four surfaces. We expected higher molecular weight TGs would diffuse slower than fatty acids and allow us to determine the age of older fingerprints. However, we found interactions between endogenous compounds and the surface have a much stronger impact on diffusion than molecular weight. For example, diffusion of TGs is faster on hydrophilic plain glass or partially hydrophilic stainless steel surfaces, than on a hydrophobic Rain-x treated surface. This result further complicates utilizing a diffusion model to age fingerprints. © 2017 American Academy of Forensic Sciences.

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

Sampling Soil CO2 for Isotopic Flux Partitioning: Non Steady State Effects and Methodological Biases

NASA Astrophysics Data System (ADS)

Snell, H. S. K.; Robinson, D.; Midwood, A. J.

2014-12-01

Measurements of δ13C of soil CO2 are used to partition the surface flux into autotrophic and heterotrophic components. Models predict that the δ13CO2 of the soil efflux is perturbed by non-steady state (NSS) diffusive conditions. These could be large enough to render δ13CO2 unsuitable for accurate flux partitioning. Field studies sometimes find correlations between efflux δ13CO2 and flux or temperature, or that efflux δ13CO2 is not correlated as expected with biological drivers. We tested whether NSS effects in semi-natural soil were comparable with those predicted. We compared chamber designs and their sensitivity to changes in efflux δ13CO2. In a natural soil mesocosm, we controlled temperature to generate NSS conditions of CO2 production. We measured the δ13C of soil CO2 using in situ probes to sample the subsurface, and dynamic and forced-diffusion chambers to sample the surface efflux. Over eight hours we raised soil temperature by 4.5 OC to increase microbial respiration. Subsurface CO2 concentration doubled, surface efflux became 13C-depleted by 1 ‰ and subsurface CO2 became 13C-enriched by around 2 ‰. Opposite changes occurred when temperature was lowered and CO2 production was decreasing. Different chamber designs had inherent biases but all detected similar changes in efflux δ13CO2, which were comparable to those predicted. Measurements using dynamic chambers were more 13C-enriched than expected, probably due to advection of CO2 into the chamber. In the mesocosm soil, δ13CO2 of both efflux and subsurface was determined by physical processes of CO2 production and diffusion. Steady state conditions are unlikely to prevail in the field, so spot measurements of δ13CO2 and assumptions based on the theoretical 4.4 ‰ diffusive fractionation will not be accurate for estimating source δ13CO2. Continuous measurements could be integrated over a period suitable to reduce the influence of transient NSS conditions. It will be difficult to disentangle biologically driven changes in soil δ13CO2 from physical controls, particularly as they occur on similar timescales and are driven by the same environmental variables, such as temperature, moisture and daylight.

Novel biodegradable hydrogel sponge containing curcumin and honey for wound healing.

PubMed

Momin, M; Kurhade, S; Khanekar, P; Mhatre, S

2016-06-01

To develop and evaluate a biodegradable superporous hydrogel based wound healing composite of chitosan and alginate incorporated with curcumin and honey. A 3(2) factorial design was adopted to optimise the honey-curcumin hydrogel composite sponge (CHS). Sodium alginate and chitosan were dissolved in deionised water and 1% aqueous acetic acid solution at room temperature, respectively. Ethanolic solution of curcumin was poured into the chitosan solution followed by an addition of sodium alginate solution. In situ polymerisation was carried out by adding acrylamide base components to the polymeric solution of curcumin. Finally, honey was added with slow stirring and a sponge was cast on a glass surface by solvent evaporation at 45ºC. The produced sponge was assessed for swelling capacity, moisture loss, tensile strength, biocompatibility, bioadhesion, biodegradation, drug diffusion and wound healing properties. The morphology of CHS was studied by scanning electron microscopy (SEM). The optimised CHS demonstrated a high swelling capacity (111.05 ± 05%), tensile strength (4323gm/mm(2)), in vitro drug diffusion (75.03 ± 3.59%/20days), bioadhesion (20 ± 0.2mg force) and ability of water vapour transmission. A rapid induction of tissue granulation and re-epithelialisation was observed. Time to complete healing (94.14 ± 1.04% wound contraction) was 7 ± 2 days. This study has shown that honey-curcumin hydrogel composite sponge can be formulated by a simple mixing and in situ polymerisation method. The hydrogel base provided a dry wound bed due to excellent fluid absorption capacity. Chitosan and honey contributed to effective faster wound healing. We recommend further clinical studies of the soft sponge wound healing composite for diabetic foot or pressure ulcers.

[In situ diffuse reflectance FTIR spectroscopy study of CO adsorption on Ni2P/mesoporous molecule sieve catalysts].

PubMed

Liu, Qian-qian; Ji, Sheng-fu; Wu, Ping-yi; Hu, Lin-hua; Huang, Xiao-fan; Zhu, Ji-qin; Li, Cheng-yue

2009-05-01

Abstract The supported nickel phosphate precursors were prepared by incipient wetness impregnation using nickel nitrate as nickel source, diammonium hydrogen phosphate as phosphorus source, and MCM-41, MCM-48, SBA-15 and SBA-16 as supports, respectively. Then, the supported Ni2 P catalysts were prepared by temperature-programmed reduction in flowing Hz from their nickel phosphate precursors. The in situ diffuse reflectance FTIR spectroscopy (DRIFTS) analysis with the probe molecule CO was carried out to characterize the surface properties. The results indicated that there were significant differences in the spectral features of the samples. The upsilon(CO) absorbances observed for adsorbed CO on mesoporous molecule sieve was attributed to weak physical adsorption. There are four different kinds of upsilon(CO) absorbances observed for adsorbed CO on Ni2 P/MCM-41 catalyst with the following assignments: (1) the formation of Ni(CO)4 at 2055 cm(-1). (2) CO terminally bonded to cus Ni(delta+) (0

Multi-scale monitoring of a marine geologic methane source in the Santa Barbara Channel using imaging spectrometry, ARCTAS-CARB in situ sampling and coastal hourly total hydrocarbon measurements

NASA Astrophysics Data System (ADS)

Bradley, E. S.; Leifer, I.; Roberts, D.; Dennison, P. E.; Margolis, J.; Moritsch, M.; Diskin, G. S.; Sachse, G. W.

2009-12-01

The Coal Oil Point (COP) hydrocarbon seep field off the coast of Santa Barbara, CA is one of the most active and best-studied marine geologic methane sources in the world and contributes to elevated terrestrial methane concentrations downwind. In this study, we investigate the spatiotemporal variability of this local source and the influence of meteorological conditions on transport and concentration. A methane plume emanating from Trilogy Seep was mapped with the Airborne Visible Infrared Imaging Spectrometer at a 7.5 m resolution with a short-wave infrared band ratio technique. This structure agrees with the local wind speed and direction and is orthogonal to the surface currents. ARCTAS-CARB aircraft in situ sampling of lower-troposphere methane is compared to sub-hour total hydrocarbon concentration (THC) measurements from the Santa Barbara Air Pollution Control District (SBAPCD) station located near COP. Hourly SBAPCD THC values from 1980-2008 demonstrate a decrease in seep source strength until the late 1990s, followed by a consistent increase. The occurrence of elevated SBAPCD THC values for onshore wind conditions as well as numerous positive outliers as high as 17 ppm suggests that seep field emissions are both quasi-steady state and transient, direct (bubble) and diffuse (outgassing). As demonstrated for the COP seeps, the combination of imaging spectrometry, aircraft in situ sampling, and ground-based monitoring provides a powerful approach for understanding local methane sources and transport processes.

MSATT Workshop on Innovative Instrumentation for the In Situ Study of Atmosphere-Surface Interactions on Mars

NASA Technical Reports Server (NTRS)

Fegley, Bruce, Jr. (Editor); Waenke, Heinrich (Editor)

1992-01-01

Papers accepted for the Mars Surface and Atmosphere Through Time (MSATT) Workshop on Innovative Instruments for the In Situ Study of Atmosphere-Surface Interaction of Mars, 8-9 Oct. 1992 in Mainz, Germany are included. Topics covered include: a backscatter Moessbauer spectrometer (BaMS) for use on Mars; database of proposed payloads and instruments for SEI missions; determination of martian soil mineralogy and water content using the Thermal Analyzer for Planetary Soils (TAPS); in situ identification of the martian surface material and its interaction with the martian atmosphere using DTA/GC; mass spectrometer-pyrolysis experiment for atmospheric and soil sample analysis on the surface of Mars; and optical luminescence spectroscopy as a probe of the surface mineralogy of Mars.

Investigation of instability of M23C6 particles in F82H steel under electron and ion irradiation conditions

NASA Astrophysics Data System (ADS)

Kano, Sho; Yang, Huilong; Shen, Jingjie; Zhao, Zishou; McGrady, John; Hamaguchi, Dai; Ando, Mamami; Tanigawa, Hiroyasu; Abe, Hiroaki

2018-04-01

In order to clarify the instability of M23C6 in F82H steel under irradiation, both electron irradiation using a high voltage electron microscope (HVEM) and ion irradiation using an ion accelerator were performed. For the electron irradiation, in-situ observation under 2 MV electron irradiation and ex-situ high resolution electron microscopic (HREM) analysis were utilized to evaluate the response of M23C6 against irradiation. The temperature dependence of the irradiation induced instability of the carbide was first confirmed: 293 K < T < 573 K, by observation of lowering in contrast at the periphery of carbides, 698 K < T < 773 K, fragmentation at the interface between carbides and matrix, and at 773 K, formation and coarsening of new particles near the periphery of M23C6. HREM analysis showed the loss of the lattice fringe contrast at the pre-existing M23C6 precipitates at temperatures ranging from 473 to 773 K, indicating severe loss of crystallinity due to dissolution of the constituent atoms though irradiation-enhanced diffusion under the vacancy diffusion by the focused electron beam irradiation. For the ion irradiation, 10.5 MeV-Fe3+ ion was applied to bombard the F82H steel at 673 K to achieve the displacement damage of ≈20 dpa at the depth of 1.0 μm from surface. Cross-section TEM specimens were prepared by a focused ion beam technique. The shrinkage of carbide particles was observed especially near the irradiation surface. Besides, the lattice fringes at the periphery of carbide were observed in the irradiated M23C6 by the HREM analysis, which is different from that observed in the electron irradiation. It was clarified that the instability of M23C6 is dependent on the irradiation conditions, indicating that the flow rate of vacancy type defects might be the key factor to cause the dissolution of constituent atoms of carbide particles into matrix under irradiation.

Ex situ and in situ characterization of patterned photoreactive thin organic surface layers using friction force microscopy

PubMed Central

Shen, Quan; Edler, Matthias; Griesser, Thomas; Knall, Astrid-Caroline; Trimmel, Gregor; Kern, Wolfgang; Teichert, Christian

2014-01-01

Photolithographic methods allow an easy lateral top-down patterning and tuning of surface properties with photoreactive molecules and polymers. Employing friction force microscopy (FFM), we present here different FFM-based methods that enable the characterization of several photoreactive thin organic surface layers. First, three ex situ methods have been evaluated for the identification of irradiated and non-irradiated zones on the same organosilane sample by irradiation through different types of masks. These approaches are further extended to a time dependent ex situ FFM measurement, which allows to study the irradiation time dependent evolution of the resulting friction forces by sequential irradiation through differently sized masks in crossed geometry. Finally, a newly designed in situ FFM measurement, which uses a commercial bar-shaped cantilever itself as a noncontact shadow mask, enables the determination of time dependent effects on the surface modification during the photoreaction. SCANNING 36:590–598, 2014. PMID:25183629

Remarkable biocompatibility enhancement of porous NiTi alloys by a new surface modification approach: in-situ nitriding and in vitro and in vivo evaluation.

PubMed

Li, H; Yuan, B; Gao, Y; Chung, C Y; Zhu, M

2011-12-15

An in-situ nitriding method has been developed to modify the outer surface and the pore walls of both open and closed pores of porous NiTi shape memory alloys (SMAs) as part of their sintering process. XRD and XPS examinations revealed that the modified layer is mainly TiN. The biocompatibility of the in-situ nitrided sample has been characterized by its corrosion resistance, cell adherence, and implant surgery. The in-situ nitrided porous NiTi SMAs exhibit much better corrosion resistance, cell adherence, and bone tissue induced capability than the porous NiTi alloys without surface modification. Furthermore, the released Ni ion content in the blood of rabbit is reduced greatly by the in-situ nitriding. The excellent biocompatibility of in-situ nitrided sample is attributed to the formation of the TiN layer on all the pore walls including both open and closed pores. Copyright © 2011 Wiley Periodicals, Inc.

The role of electrostatic interactions in protease surface diffusion and the consequence for interfacial biocatalysis.

PubMed

Feller, Bob E; Kellis, James T; Cascão-Pereira, Luis G; Robertson, Channing R; Frank, Curtis W

2010-12-21

This study examines the influence of electrostatic interactions on enzyme surface diffusion and the contribution of diffusion to interfacial biocatalysis. Surface diffusion, adsorption, and reaction were investigated on an immobilized bovine serum albumin (BSA) multilayer substrate over a range of solution ionic strength values. Interfacial charge of the enzyme and substrate surface was maintained by performing the measurements at a fixed pH; therefore, electrostatic interactions were manipulated by changing the ionic strength. The interfacial processes were investigated using a combination of techniques: fluorescence recovery after photobleaching, surface plasmon resonance, and surface plasmon fluorescence spectroscopy. We used an enzyme charge ladder with a net charge ranging from -2 to +4 with respect to the parent to systematically probe the contribution of electrostatics in interfacial enzyme biocatalysis on a charged substrate. The correlation between reaction rate and adsorption was determined for each charge variant within the ladder, each of which displayed a maximum rate at an intermediate surface concentration. Both the maximum reaction rate and adsorption value at which this maximum rate occurs increased in magnitude for the more positive variants. In addition, the specific enzyme activity increased as the level of adsorption decreased, and for the lowest adsorption values, the specific enzyme activity was enhanced compared to the trend at higher surface concentrations. At a fixed level of adsorption, the specific enzyme activity increased with positive enzyme charge; however, this effect offers diminishing returns as the enzyme becomes more highly charged. We examined the effect of electrostatic interactions on surface diffusion. As the binding affinity was reduced by increasing the solution ionic strength, thus weakening electrostatic interaction, the rate of surface diffusion increased considerably. The enhancement in specific activity achieved at the lowest adsorption values is explained by the substantial rise in surface diffusion at high ionic strength due to decreased interactions with the surface. Overall, knowledge of the electrostatic interactions can be used to control surface parameters such as surface concentration and surface diffusion, which intimately correlate with surface biocatalysis. We propose that the maximum reaction rate results from a balance between adsorption and surface diffusion. The above finding suggests enzyme engineering and process design strategies for improving interfacial biocatalysis in industrial, pharmaceutical, and food applications.

Investigating the oxidation mechanism of tantalum nanoparticles at high heating rates

NASA Astrophysics Data System (ADS)

DeLisio, Jeffery B.; Wang, Xizheng; Wu, Tao; Egan, Garth C.; Jacob, Rohit J.; Zachariah, Michael R.

2017-12-01

Reduced diffusion length scales and increased specific surface areas of nanosized metal fuels have recently demonstrated increased reaction rates for these systems, increasing their relevance in a wide variety of applications. The most commonly employed metal fuel, aluminum, tends to oxidize rapidly near its melting point (660 °C) in addition to undergoing a phase change of the nascent oxide shell. To further expand on the understanding of nanosized metal fuel oxidation, tantalum nanoparticles were studied due to their high melting point (3017 °C) in comparison to aluminum. Both traditional slow heating rate and in-situ high heating rate techniques were used to probe the oxidation of tantalum nanoparticles in oxygen containing environments in addition to nanothermite mixtures. When oxidized by gas phase oxygen, the oxide shell of the tantalum nanoparticles rapidly crystallized creating cracks that may attribute to enhanced oxygen diffusion into the particle. In the case of tantalum based nanothermites, oxide shell crystallization was shown to induce reactive sintering with the metal oxide resulting in a narrow range of ignition temperatures independent of the metal oxide used. The oxidation mechanism was modeled using the Deal-Grove model to extract rate parameters, and theoretical burn times for tantalum based nanocomposites were calculated.

Estimation of Land Surface Fluxes and Their Uncertainty via Variational Data Assimilation Approach

NASA Astrophysics Data System (ADS)

Abdolghafoorian, A.; Farhadi, L.

2016-12-01

Accurate estimation of land surface heat and moisture fluxes as well as root zone soil moisture is crucial in various hydrological, meteorological, and agricultural applications. "In situ" measurements of these fluxes are costly and cannot be readily scaled to large areas relevant to weather and climate studies. Therefore, there is a need for techniques to make quantitative estimates of heat and moisture fluxes using land surface state variables. In this work, we applied a novel approach based on the variational data assimilation (VDA) methodology to estimate land surface fluxes and soil moisture profile from the land surface states. This study accounts for the strong linkage between terrestrial water and energy cycles by coupling the dual source energy balance equation with the water balance equation through the mass flux of evapotranspiration (ET). Heat diffusion and moisture diffusion into the column of soil are adjoined to the cost function as constraints. This coupling results in more accurate prediction of land surface heat and moisture fluxes and consequently soil moisture at multiple depths with high temporal frequency as required in many hydrological, environmental and agricultural applications. One of the key limitations of VDA technique is its tendency to be ill-posed, meaning that a continuum of possibilities exists for different parameters that produce essentially identical measurement-model misfit errors. On the other hand, the value of heat and moisture flux estimation to decision-making processes is limited if reasonable estimates of the corresponding uncertainty are not provided. In order to address these issues, in this research uncertainty analysis will be performed to estimate the uncertainty of retrieved fluxes and root zone soil moisture. The assimilation algorithm is tested with a series of experiments using a synthetic data set generated by the simultaneous heat and water (SHAW) model. We demonstrate the VDA performance by comparing the (synthetic) true measurements (including profile of soil moisture and temperature, land surface water and heat fluxes, and root water uptake) with VDA estimates. In addition, the feasibility of extending the proposed approach to use remote sensing observations is tested by limiting the number of LST observations and soil moisture observations.

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.

Temperature-dependent structure and phase variation of nickel silicide nanowire arrays prepared by in situ silicidation

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

Liu, Hailong; She, Guangwei, E-mail: shegw@mail.ipc.ac.cn; Mu, Lixuan

Graphical abstract: Display Omitted Highlight: ► Nickel silicides nanowire arrays prepared by a simple in situ silicidation method. ► Phases of nickel silicides could be varied by tuning the reaction temperature. ► A growth model was proposed for the nickel silicides nanowires. ► Diffusion rates of Ni and Si play a critical role for the phase variation. -- Abstract: In this paper, we report an in situ silicidizing method to prepare nickel silicide nanowire arrays with varied structures and phases. The in situ reaction (silicidation) between Si and NiCl{sub 2} led to conversion of Si nanowires to nickel silicide nanowires.more » Structures and phases of the obtained nickel silicides could be varied by changing the reaction temperature. At a relatively lower temperature of 700 °C, the products are Si/NiSi core/shell nanowires or NiSi nanowires, depending on the concentration of NiCl{sub 2} solution. At a higher temperature (800 °C and 900 °C), other phases of the nickel silicides, including Ni{sub 2}Si, Ni{sub 31}Si{sub 12}, and NiSi{sub 2}, were obtained. It is proposed that the different diffusion rates of Ni and Si atoms at different temperatures played a critical role in the formation of nickel silicide nanowires with different phases.« less

Role of large-scale slip in mode II fracture of bimaterial interface produced by diffusion bonding

NASA Astrophysics Data System (ADS)

Fox, M. R.; Ghosh, A. K.

2001-08-01

Bimaterial interfaces present in diffusion-bonded (and in-situ) composites are often not flat interfaces. The unevenness of the interface can result not only from interface reaction products but also from long-range waviness associated with the surfaces of the component phases bonded together. Experimental studies aimed at determining interface mechanical properties generally ignore the departure in the local stress due to waviness and assume a theoretically flat interface. Furthermore, the commonly used testing methods involving superimposed tension often renders the interface so extremely brittle that if microplastic effects were present it becomes impossible to perceive them. This article examines the role of waviness of the interface and microplastic effects on crack initiation. To do this, a test was selected that provides significant stability against crack growth by superimposing compressive stresses. Mode II interface fracture was studied for NiAl/Mo model laminates using a recently developed asymmetrically loaded shear (ALS) interface shear test. The ALS test may be viewed as opposite of the laminate bend test. In the bend test, shear at the interface is created via tension on one surface of the bend, while in the ALS test, shear is created by compression on one side of the interface relative to the other. Normal to the interface, near the crack tip, an initially compressive state is replaced by slight tension due to Poisson’s expansion of the unbonded part of the compressed beam.

Crystal surface integrity and diffusion measurements on Earth and planetary materials

NASA Astrophysics Data System (ADS)

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

2016-09-01

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

A kinetic model for stress generation in thin films grown from energetic vapor fluxes

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

Chason, E.; Karlson, M.; Colin, J. J.

We have developed a kinetic model for residual stress generation in thin films grown from energetic vapor fluxes, encountered, e.g., during sputter deposition. The new analytical model considers sub-surface point defects created by atomic peening, along with processes treated in already existing stress models for non-energetic deposition, i.e., thermally activated diffusion processes at the surface and the grain boundary. According to the new model, ballistically induced sub-surface defects can get incorporated as excess atoms at the grain boundary, remain trapped in the bulk, or annihilate at the free surface, resulting in a complex dependence of the steady-state stress on themore » grain size, the growth rate, as well as the energetics of the incoming particle flux. We compare calculations from the model with in situ stress measurements performed on a series of Mo films sputter-deposited at different conditions and having different grain sizes. The model is able to reproduce the observed increase of compressive stress with increasing growth rate, behavior that is the opposite of what is typically seen under non-energetic growth conditions. On a grander scale, this study is a step towards obtaining a comprehensive understanding of stress generation and evolution in vapor deposited polycrystalline thin films.« less

In situ detection of porosity initiation during aluminum thin film anodizing

NASA Astrophysics Data System (ADS)

Van Overmeere, Quentin; Nysten, Bernard; Proost, Joris

2009-02-01

High-resolution curvature measurements have been performed in situ during aluminum thin film anodizing in sulfuric acid. A well-defined transition in the rate of internal stress-induced curvature change is shown to allow for the accurate, real-time detection of porosity initiation. The validity of this in situ diagnostic tool was confirmed by a quantitative analysis of the spectral density distributions of the anodized surfaces. These were obtained by analyzing ex situ atomic force microscopy images of surfaces anodized for different times, and allowed to correlate the in situ detected transition in the rate of curvature change with the appearance of porosity.

Influence of surface oxides on hydrogen-sensitive Pd:GaN Schottky diodes

NASA Astrophysics Data System (ADS)

Weidemann, O.; Hermann, M.; Steinhoff, G.; Wingbrant, H.; Lloyd Spetz, A.; Stutzmann, M.; Eickhoff, M.

2003-07-01

The hydrogen response of Pd:GaN Schottky diodes, prepared by in situ and ex situ deposition of catalytic Pd Schottky contacts on Si-doped GaN layers is compared. Ex situ fabricated devices show a sensitivity towards molecular hydrogen, which is about 50 times higher than for in situ deposited diodes. From the analysis of these results, we conclude that adsorption sites for atomic hydrogen in Pd:GaN sensors are provided by an oxidic intermediate layer. In addition, in situ deposited Pd Schottky contacts reveal lower barrier heights and drastically higher reverse currents. We suggest that the passivation of the GaN surface before ex situ deposition of Pd also results in quenching of leakage paths caused by structural defects.

In situ and ex situ spectroscopic monitoring of biochar's surface functional groups

USDA-ARS?s Scientific Manuscript database

A number of studies described the higher heating temperature (HHT) as the primary pyrolysis parameter dictating the biochar property: surface functional group and fixed carbon contents, O/C, H/C ratios, and Brunauer-Emmett-Teller (BET) surface area. In order to produce desirable biochar properties ...

Grain boundary diffusion behaviors in hot-deformed Nd2Fe14B magnets by PrNd-Cu low eutectic alloys

NASA Astrophysics Data System (ADS)

Tang, Xu; Chen, Renjie; Li, Ming; Jin, Chaoxiang; Yin, Wenzong; Lee, Don; Yan, Aru

2018-01-01

High coercivity of hot-deformed Nd2Fe14B magnets was obtained by grain boundary diffusion. Comparable squareness and similar magnetic properties for samples diffusing from side and pole surfaces show little discrepancies if quantities of the infiltrated PrNd-Cu low eutectic alloys is enough to obtain sufficient diffusion. However, the microstructures and higher characteristic peak ratios show preferable orientation of grains near surfaces of the sample diffused from side surfaces than that from pole surfaces. Amorphous Nd-rich phases and crystal Fe-rich phases were both observed in the diffused magnets. The enhancement of coercivity is considered to be resulted from grain boundary optimization and magnetic isolation which is caused by the thickened nonmagnetic intergranular phases.

In situ studies of surface of NiFe 2O 4 catalyst during complete oxidation of methane

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

Zhang, Shiran; Shan, Junjun; Nie, Longhui

2015-12-21

Here, NiFe 2O 4 with an inverse spinel structure exhibits high activity for a complete oxidation of methane at 400 °C–425 °C and a higher temperature. The surface of the catalyst and its adsorbates were well characterized with ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and in situ infrared spectroscopy (IR). In situ studies of the surface of NiFe 2O 4 using AP-XPS suggest the formation of methoxy-like and formate-like intermediates at a temperature lower than 200 °C, supported by the observed vibrational signatures in in situ IR studies. Evolutions of C1s photoemission features and the nominal atomic ratios of C/(Nimore » + Fe) of the catalyst surface suggest that the formate-like intermediate is transformed to product molecules CO 2 and H 2O in the temperature range of 250–300 °C. In situ studies suggest the formation of a spectator, – O lattice – CH 2 – O lattice –. It strongly bonds to surface through C–O bonds and cannot be activated even at 400 °C.« less

Surface conservation laws at microscopically diffuse interfaces.

PubMed

Chu, Kevin T; Bazant, Martin Z

2007-11-01

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

High Temperature Oxidation of Nickel-based Cermet Coatings Composed of Al2O3 and TiO2 Nanosized Particles

NASA Astrophysics Data System (ADS)

Farrokhzad, M. A.; Khan, T. I.

2014-09-01

New technological challenges in oil production require materials that can resist high temperature oxidation. In-Situ Combustion (ISC) oil production technique is a new method that uses injection of air and ignition techniques to reduce the viscosity of bitumen in a reservoir and as a result crude bitumen can be produced and extracted from the reservoir. During the in-situ combustion process, production pipes and other mechanical components can be exposed to air-like gaseous environments at extreme temperatures as high as 700 °C. To protect or reduce the surface degradation of pipes and mechanical components used in in-situ combustion, the use of nickel-based ceramic-metallic (cermet) coating produced by co-electrodeposition of nanosized Al2O3 and TiO2 have been suggested and earlier research on these coatings have shown promising oxidation resistance against atmospheric oxygen and combustion gases at elevated temperatures. Co-electrodeposition of nickel-based cermet coatings is a low-cost method that has the benefit of allowing both internal and external surfaces of pipes and components to be coated during a single electroplating process. Research has shown that the volume fraction of dispersed nanosized Al2O3 and TiO2 particles in the nickel matrix which affects the oxidation resistance of the coating can be controlled by the concentration of these particles in the electrolyte solution, as well as the applied current density during electrodeposition. This paper investigates the high temperature oxidation behaviour of novel nanostructured cermet coatings composed of two types of dispersed nanosized ceramic particles (Al2O3 and TiO2) in a nickel matrix and produced by coelectrodeposition technique as a function of the concentration of these particles in the electrolyte solution and applied current density. For this purpose, high temperature oxidation tests were conducted in dry air for 96 hours at 700 °C to obtain mass changes (per unit of area) at specific time intervals. Statistical techniques as described in ASTM G16 were used to formulate the oxidation mass change as a function of time. The cross-section and surface of the oxidized coatings were examined for both visual and chemical analyses using wavelength dispersive x-ray spectroscopy (WDS) element mapping, X-ray Diffraction (XRD) and Energy-dispersive X-ray spectroscopy (EDS). The results showed that the volume fraction for each type of particle in the nickel matrix corresponded to its partial molar concentration in the electrolyte solutions. Increase in volume fraction of particles in the nickel matrix was correlated to lower oxidation rates. It was concluded that formation of Ni3TiO5 and NiTiO3 compounds can reduce the oxidation rate of cermet coatings by capturing some inward diffusing oxygen ions resulting in a lower number of nickel cations diffusing upward into the oxide layer.

Reversible on-surface wiring of resistive circuits.

PubMed

Inkpen, Michael S; Leroux, Yann R; Hapiot, Philippe; Campos, Luis M; Venkataraman, Latha

2017-06-01

Whilst most studies in single-molecule electronics involve components first synthesized ex situ , there is also great potential in exploiting chemical transformations to prepare devices in situ . Here, as a first step towards this goal, we conduct reversible reactions on monolayers to make and break covalent bonds between alkanes of different lengths, then measure the conductance of these molecules connected between electrodes using the scanning tunneling microscopy-based break junction (STM-BJ) method. In doing so, we develop the critical methodology required for assembling and disassembling surface-bound single-molecule circuits. We identify effective reaction conditions for surface-bound reagents, and importantly demonstrate that the electronic characteristics of wires created in situ agree with those created ex situ . Finally, we show that the STM-BJ technique is unique in its ability to definitively probe surface reaction yields both on a local (∼50 nm 2 ) and pseudo-global (≥10 mm 2 ) level. This investigation thus highlights a route to the construction and integration of more complex, and ultimately functional, surface-based single-molecule circuitry, as well as advancing a methodology that facilitates studies beyond the reach of traditional ex situ synthetic approaches.

Diffusion of volatile organics through porous snow: impact of surface adsorption and grain boundaries

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Wren, S. N.; Schreiber, S.; Riche, F.; Schneebeli, M.; Ammann, M.

2013-03-01

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the polar regions. The gas-phase diffusion of methanol and of acetone through the interstitial air of snow was investigated in a well-controlled laboratory study in the temperature range of 223 to 263 K. The aim of this study was to evaluate how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion on timescales up to 1 h. The diffusive loss of these two volatile organics into packed snow samples was measured using a chemical ionization mass spectrometer. The structure of the snow was analyzed by means of X-ray computed micro-tomography. The observed diffusion profiles could be well described based on gas-phase diffusion and the known structure of the snow sample at temperatures ≥ 253 K. At colder temperatures surface interactions start to dominate the diffusive transport. Parameterizing these interactions in terms of adsorption to the solid ice surface, i.e. using temperature dependent air-ice partitioning coefficients, better described the observed diffusion profiles than the use of air-liquid partitioning coefficients. No changes in the diffusive fluxes were observed by increasing the number of grain boundaries in the snow sample by a factor of 7, indicating that for these volatile organic trace gases, uptake into grain boundaries does not play a role on the timescale of diffusion through porous surface snow. In conclusion, we have shown that the diffusivity can be predicted when the structure of the snowpack and the partitioning of the trace gas to solid ice is known.

Imaging fluorescence-correlation spectroscopy for measuring fast surface diffusion at liquid/solid interfaces.

PubMed

Cooper, Justin T; Harris, Joel M

2014-08-05

The development of techniques to probe interfacial molecular transport is important for understanding and optimizing surface-based analytical methods including surface-enhanced spectroscopies, biological assays, and chemical separations. Single-molecule-fluorescence imaging and tracking has been used to measure lateral diffusion rates of fluorescent molecules at surfaces, but the technique is limited to the study of slower diffusion, where molecules must remain relatively stationary during acquisition of an image in order to build up sufficient intensity in a spot to detect and localize the molecule. Although faster time resolution can be achieved by fluorescence-correlation spectroscopy (FCS), where intensity fluctuations in a small spot are related to the motions of molecules on the surface, long-lived adsorption events arising from surface inhomogeneity can overwhelm the correlation measurement and mask the surface diffusion of the moving population. Here, we exploit a combination of these two techniques, imaging-FCS, for measurement of fast interfacial transport at a model chromatographic surface. This is accomplished by rapid imaging of the surface using an electron-multiplied-charged-coupled-device (CCD) camera, while limiting the acquisition to a small area on the camera to allow fast framing rates. The total intensity from the sampled region is autocorrelated to determine surface diffusion rates of molecules with millisecond time resolution. The technique allows electronic control over the acquisition region, which can be used to avoid strong adsorption sites and thus minimize their contribution to the measured autocorrelation decay and to vary the acquisition area to resolve surface diffusion from adsorption and desorption kinetics. As proof of concept, imaging-FCS was used to measure surface diffusion rates, interfacial populations, and adsorption-desorption rates of 1,1'-dioctadecyl-3,3,3'3'-tetramethylindocarbocyanine (DiI) on planar C18- and C1-modified surfaces.

Diffusion accessibility as a method for visualizing macromolecular surface geometry.

PubMed

Tsai, Yingssu; Holton, Thomas; Yeates, Todd O

2015-10-01

Important three-dimensional spatial features such as depth and surface concavity can be difficult to convey clearly in the context of two-dimensional images. In the area of macromolecular visualization, the computer graphics technique of ray-tracing can be helpful, but further techniques for emphasizing surface concavity can give clearer perceptions of depth. The notion of diffusion accessibility is well-suited for emphasizing such features of macromolecular surfaces, but a method for calculating diffusion accessibility has not been made widely available. Here we make available a web-based platform that performs the necessary calculation by solving the Laplace equation for steady state diffusion, and produces scripts for visualization that emphasize surface depth by coloring according to diffusion accessibility. The URL is http://services.mbi.ucla.edu/DiffAcc/. © 2015 The Protein Society.

Effect of Ti Substrate Ion Implantation on the Physical Properties of Anodic TiO2 Nanotubes

NASA Astrophysics Data System (ADS)

Jedi-Soltanabadi, Zahra; Ghoranneviss, Mahmood; Ghorannevis, Zohreh; Akbari, Hossein

2018-03-01

The influence of nitrogen-ion implantation on the titanium (Ti) surface is studied. The nontreated Ti and the Ti treated with ion implantation were anodized in an ethylene-glycol-based electrolyte solution containing 0.3 wt% ammonium fluoride (NH4F) and 3 vol% deionized (DI) water at a potential of 60 V for 1 h at room temperature. The current density during the growth of the TiO2 nanotubes was monitored in-situ. The surface roughnesses of the Ti substrates before and after the ion implantation were investigated with atomic force microscopy (AFM). The surface roughness was lower for the treated Ti substrate. The morphology of the anodic TiO2 nanotubes was studied by using field-emission scanning electron microscopy (FESEM). Clearly, the titanium nanotubes grown on the treated substrate were longer. In addition, some ribs were observed on their walls. The optical band gap of the anodic TiO2 nanotubes was characterized by using a diffuse reflection spectral (DRS) analysis. The anodic TiO2 nanotubes grown on the treated Ti substrate revealed a band gap energy of approximately 3.02 eV.

Surface transport mechanisms in molecular glasses probed by the exposure of nano-particles

NASA Astrophysics Data System (ADS)

Ruan, Shigang; Musumeci, Daniele; Zhang, Wei; Gujral, Ankit; Ediger, M. D.; Yu, Lian

2017-05-01

For a glass-forming liquid, the mechanism by which its surface contour evolves can change from bulk viscous flow at high temperatures to surface diffusion at low temperatures. We show that this mechanistic change can be conveniently detected by the exposure of nano-particles native in the material. Despite its high chemical purity, the often-studied molecular glass indomethacin contains low-concentration particles approximately 100 nm in size and 0.3% in volume fraction. Similar particles are present in polystyrene, another often-used model. In the surface-diffusion regime, particles are gradually exposed in regions vacated by host molecules, for example, the peak of a surface grating and the depletion zone near a surface crystal. In the viscous-flow regime, particle exposure is not observed. The surface contour around an exposed particle widens over time in a self-similar manner as 3 (Bt)1/4, where B is a surface mobility constant and the same constant obtained by surface grating decay. This work suggests that in a binary system composed of slow- and fast-diffusing molecules, slow-diffusing molecules can be stranded in surface regions vacated by fast-diffusing molecules, effectively leading to phase separation.

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.

Creating and optimizing interfaces for electric-field and photon-induced charge transfer.

PubMed

Park, Byoungnam; Whitham, Kevin; Cho, Jiung; Reichmanis, Elsa

2012-11-27

We create and optimize a structurally well-defined electron donor-acceptor planar heterojunction interface in which electric-field and/or photon-induced charge transfer occurs. Electric-field-induced charge transfer in the dark and exciton dissociation at a pentacene/PCBM interface were probed by in situ thickness-dependent threshold voltage shift measurements in field-effect transistor devices during the formation of the interface. Electric-field-induced charge transfer at the interface in the dark is correlated with development of the pentacene accumulation layer close to PCBM, that is, including interface area, and dielectric relaxation time in PCBM. Further, we demonstrate an in situ test structure that allows probing of both exciton diffusion length and charge transport properties, crucial for optimizing optoelectronic devices. Competition between the optical absorption length and the exciton diffusion length in pentacene governs exciton dissociation at the interface. Charge transfer mechanisms in the dark and under illumination are detailed.

Direct observation of spherulitic growth stages of CaCO 3 in a poly(acrylic acid)-chitosan system: In situ SPM study

NASA Astrophysics Data System (ADS)

Ulčinas, A.; Butler, M. F.; Heppenstall-Butler, M.; Singleton, S.; Miles, M. J.

2007-09-01

Crystallization of a CaCO 3 thin film from supersaturated solution on chitosan in the presence of poly-acrylic acid was investigated by in situ AFM and SNOM. It was directly observed that crystallization proceeds through characteristic stages consistent with the theory of spherulitic growth: development of individual branches, build-up of larger scale "lobe" features, followed by overgrowth and ripening. We propose that crystallization of CaCO 3 on chitosan in the presence of poly(acrylic acid) (PAA) proceeds in a gelatinous matrix formed by PAA stabilized amorphous CaCO 3; the spherulitic character of crystallization is initiated by the high viscosity of gel and presence of PAA impurities. Characteristic sizes of spherulite features deviate significantly from the prediction based on diffusivity of PAA in water due to low diffusivity of PAA in gel.

Terminalia chebula mediated green and rapid synthesis of gold nanoparticles

NASA Astrophysics Data System (ADS)

Mohan Kumar, Kesarla; Mandal, Badal Kumar; Sinha, Madhulika; Krishnakumar, Varadhan

2012-02-01

Biologically inspired experimental process in synthesising nanoparticles is of great interest in present scenario. Biosynthesis of nanoparticles is considered to be one of the best green techniques in synthesising metal nanoparticles. Here, an in situ green biogenic synthesis of gold nanoparticles using aqueous extracts of Terminalia chebula as reducing and stabilizing agent is reported. Gold nanoparticles were confirmed by surface plasmon resonance in the range of 535 nm using UV-visible spectrometry. TEM analysis revealed that the morphology of the particles thus formed contains anisotropic gold nanoparticles with size ranging from 6 to 60 nm. Hydrolysable tannins present in the extract of T. chebula are responsible for reductions and stabilization of gold nanoparticles. Antimicrobial activity of gold nanoparticles showed better activity towards gram positive S. aureus compared to gram negative E. coli using standard well diffusion method.

Microstructure evolution, thermal stability and fractal behavior of water vapor flow assisted in situ growth poly(vinylcarbazole)-titania quantum dots nanocomposites

NASA Astrophysics Data System (ADS)

Mombrú, Dominique; Romero, Mariano; Faccio, Ricardo; Mombrú, Alvaro W.

2017-12-01

Here, we report a novel strategy for the preparation of TiO2 quantum dots fillers prepared from alkoxide precursor via in situ water vapor flow diffusion into poly(N-vinylcarbazole) host. A detailed characterization by means of infrared and Raman spectroscopy, X-ray powder diffraction, small angle X-ray scattering and differential scanning calorimetry is reported. The growth mechanism of both crystallites and particles was mostly governed by the classical coarsening reaction limited growth and the polymer host showed no detectable chemical modifications at the interface or active participation in the growing process. The main relevance of our strategy respect to the typical sol-gel growth in solution is the possibility of the interruption of the reaction by simple stopping the water vapor flow diffusion into the polymer host thus achieving good control in the nanoparticles size. The thermal stability and fractal behavior of our nanocomposites were also studied by differential scanning calorimetry and in situ small angle X-ray scattering versus temperature. Strong correlations between modifications in the fractal behavior and glass transition or fusion processes were observed for these nanocomposites.

Investigation on H-containing shallow trap of hydrogenated TiO2 with in situ Fourier transform infrared diffuse reflection spectroscopy.

PubMed

Han, Bing; Hang Hu, Yun

2017-07-28

A novel technique, high temperature high pressure in situ Fourier transform infrared diffuse reflection spectroscopy, was successfully used to investigate the formation and stability of shallow trap states in P25 TiO 2 nanoparticles. Two types of shallow traps (with and without H atoms) were identified. The H-containing shallow trap can be easily generated by heating in H 2 atmosphere. However, the trap is unstable in vacuum at 600 °C. In contrast, the H-free shallow trap, which can be formed by heating in vacuum, is stable even at 600 °C. The energy gaps between shallow trap states and the conduction band are 0.09 eV for H-containing shallow trap and 0.13 eV for H-free shallow trap, indicating that the H-containing shallow trap state is closer to the conduction band than that without H.

Investigations of the kinetics of surfactant-assisted growth of cobalt/copper multilayers

NASA Astrophysics Data System (ADS)

Peterson, Brennan Lovelace

Surfactants---a term given to a broad family of surface additives used in thin film growth---provide a potentially useful tool for the deposition engineer. A long history of work on the field has produced a sometimes conflicting view of what surfactants do, and while their efficacy in improving magnetic films is well established, the attendant structural changes remain unclear. Early work on surfactant-assisted growth was generally confined to deposition at near equilibrium conditions: high temperature and very slow deposition rates on very smooth (single crystal) substrates. In the case of low temperature sputter deposition, the kinetic phenomena differ greatly from the near-equilibrium case: high rate, more interlayer diffusive pathways, high grain boundary density, and few well defined atomic steps. There are two major ideas which underlie and explain the use of surfactants. First, they are used to alter growth kinetics of a single material by changing the diffusion barriers on the growing surface. Second, surfactants alter the initial nucleation parameters in heteroepitaxial growth, which is often explained with reference to changes in the surface energy, gamma. Changes to these parameters result, in turn, to variations of the roughness and conformality of thin films grown with the assistance of surfactants. Finally, the roughness and conformality are critical for determining the performance of modern thin film magnetic sensors. As surfactants offer a way to alter the nucleation and growth kinetics, they offer tremendous potential benefits. However, before surfactants are trustworthy deposition tool, a better understanding of their structural effects and underlying surface energy and kinetic changes is necessary. In order to investigate these phenomena, DC magnetron sputtered [Co/Cu] multilayers were deposited on Si/SiO2 substrates using O2 , Ag, Pb, and In as surfactants. Oxygen was introduced during growth at partial pressures ranging from 10-9 to 10-6 Torr, as well as "puffed" onto interfaces. The metallic surfactants (Pb, In, Ag) were deposited at various points in the multilayer---on top of the Co, on top of the Cu, or at the base---in order to determine the most effective position. In order to determine the role surface energy plays in determining surfactant assisted growth, in-situ stress measurements were taken. Surface energy effects are clearly seen in In and Pb deposition, while minimal changes are seen for O2 and Ag. To quantify the microstructural changes, low angle specular and diffuse scatter measurements were made. Specular scatter is sensitive to the film roughness, while diffuse scatter is particularly sensitive to changes to the layer-to-layer roughness correlations. The addition of a constant background of O2 during growth had the largest effect on the conformality and smoothness of the multilayers. Of the metallic surfactants, using Ag led to the greatest improvement in smoothness and correlation. With these results in hand, we posit a few basic models of surfactant activity in the various material systems.

Surface diffusion of a carbon-adatom on Au(110) surfaces

NASA Astrophysics Data System (ADS)

Kim, E.; Safavi-Naini, A.; Hite, D. A.; McKay, K. S.; Pappas, D. P.; Weck, P. F.; Sadeghpour, H. R.

We have investigated the surface diffusion of carbon-adatom on gold surfaces using density functional theory and detailed scanning probe microscopy. The decoherence of trapped-ion quantum gates due to heating of their motional modes is a fundamental science and engineering problem. In an effort to understand heating at the trap-electrode surfaces, we investigate the possible source of noise by focusing on the diffusion of carbon-containing adsorbates onto the Au(110) surface. In this study, we show how the diffusive motion of carbon adatom on gold surface significantly affects the energy landscape and adatom dipole moment variation. A simple model for the diffusion noise, which varies quadratically with the variation of the dipole moment, qualitatively reproduces the measured noise spectrum, and the estimate of the noise spectral density is in accord with measured values. Sandia National Laboratories is a multiprogram laboratory operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Company, for the United States Department of Energy's NNSA under Contract DE-AC04-94AL85000.

Influence of Hydrogen Bonding on the Surface Diffusion of Molecular Glasses: Comparison of Three Triazines

DOE PAGES

Chen, Yinshan; Zhu, Men; Laventure, Audrey; ...

2017-06-26

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

Validation of pore network simulations of ex-situ water distributions in a gas diffusion layer of proton exchange membrane fuel cells with X-ray tomographic images

NASA Astrophysics Data System (ADS)

Agaesse, Tristan; Lamibrac, Adrien; Büchi, Felix N.; Pauchet, Joel; Prat, Marc

2016-11-01

Understanding and modeling two-phase flows in the gas diffusion layer (GDL) of proton exchange membrane fuel cells are important in order to improve fuel cells performance. They are scientifically challenging because of the peculiarities of GDLs microstructures. In the present work, simulations on a pore network model are compared to X-ray tomographic images of water distributions during an ex-situ water invasion experiment. A method based on watershed segmentation was developed to extract a pore network from the 3D segmented image of the dry GDL. Pore network modeling and a full morphology model were then used to perform two-phase simulations and compared to the experimental data. The results show good agreement between experimental and simulated microscopic water distributions. Pore network extraction parameters were also benchmarked using the experimental data and results from full morphology simulations.

Fast diffusion of silver in TiO2 nanotube arrays

PubMed Central

Zhang, Wanggang; Liu, Yiming; Zhou, Diaoyu; Wang, Hui

2016-01-01

Summary Using magnetron sputtering and heat treatment, Ag@TiO2 nanotubes are prepared. The effects of heat-treatment temperature and heating time on the evolution of Ag nanofilms on the surface of TiO2 nanotubes and microstructure of Ag nanofilms are investigated by X-ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. Ag atoms migrate mainly on the outmost surface of the TiO2 nanotubes, and fast diffusion of Ag atoms is observed. The diffusivity for the diffusion of Ag atoms on the outmost surface of the TiO2 nanotubes at 400 °C is 6.87 × 10−18 m2/s, which is three orders of magnitude larger than the diffusivities for the diffusion of Ag through amorphous TiO2 films. The activation energy for the diffusion of Ag atoms on the outmost surface of the TiO2 nanotubes in the temperature range of 300 to 500 °C is 157 kJ/mol, which is less than that for the lattice diffusion of Ag and larger than that for the grain boundary diffusion. The diffusion of Ag atoms leads to the formation of Ag nanocrystals on the outmost surface of TiO2 nanotubes. Probably there are hardly any Ag nanocrystals formed inside the TiO2 nanotubes through the migration of Ag. PMID:27547630

Extended hierarchical solvent perturbations from curved surfaces of mesoporous silica particles in a deep eutectic solvent.

PubMed

Hammons, Joshua A; Zhang, Fan; Ilavsky, Jan

2018-06-15

Many applications of deep eutectic solvents (DES) rely on exploitation of their unique yet complex liquid structures. Due to the ionic nature of the DES components, their diffuse structures are perturbed in the presence of a charged surface. We hypothesize that it is possible to perturb the bulk DES structure far (>100 nm) from a curved, charged surface with mesoscopic dimensions. We performed in situ, synchrotron-based ultra-small angle X-ray scattering (USAXS) experiments to study the solvent distribution near the surface of charged mesoporous silica particles (MPS) (≈0.5 µm in diameter) suspended in both water and a common type of DES (1:2 choline Cl-:ethylene glycol). A careful USAXS analysis reveals that the perturbation of electron density distribution within the DES extends ≈1 μm beyond the particle surface, and that this perturbation can be manipulated by the addition of salt ions (AgCl). The concentration of the pore-filling fluid is greatly reduced in the DES. Notably, we extracted the real-space structures of these fluctuations from the USAXS data using a simulated annealing approach that does not require a priori knowledge about the scattering form factor, and can be generalized to a wide range of complex small-angle scattering problems. Copyright © 2018 Elsevier Inc. All rights reserved.

Surface hydration amplifies single-well protein atom diffusion propagating into the macromolecular core

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

Hong, Liang; Cheng, Xiaolin; Glass, Dennis C.

2012-06-05

The effect of surface hydration water on internal protein motion is of fundamental interest in molecular biophysics. Here, by decomposing the picosecond to nanosecond atomic motion in molecular dynamics simulations of lysozyme at different hydration levels into three components localized single-well diffusion, methyl group rotation, and nonmethyl jumps we show that the effect of surface hydration is mainly to increase the volume of the localized single-well diffusion. As a result, these diffusive motions are coupled in such a way that the hydration effect propagates from the protein surface into the dry core.

Effective diffusion coefficient including the Marangoni effect

NASA Astrophysics Data System (ADS)

Kitahata, Hiroyuki; Yoshinaga, Natsuhiko

2018-04-01

Surface-active molecules supplied from a particle fixed at the water surface create a spatial gradient of the molecule concentration, resulting in Marangoni convection. Convective flow transports the molecules far from the particle, enhancing diffusion. We analytically derive the effective diffusion coefficient associated with the Marangoni convection rolls. The resulting estimated effective diffusion coefficient is consistent with our numerical results and the apparent diffusion coefficient measured in experiments.

Speciation and Bioavailability Measurements of Environmental Plutonium Using Diffusion in Thin Films.

PubMed

Cusnir, Ruslan; Steinmann, Philipp; Christl, Marcus; Bochud, François; Froidevaux, Pascal

2015-11-09

The biological uptake of plutonium (Pu) in aquatic ecosystems is of particular concern since it is an alpha-particle emitter with long half-life which can potentially contribute to the exposure of biota and humans. The diffusive gradients in thin films technique is introduced here for in-situ measurements of Pu bioavailability and speciation. A diffusion cell constructed for laboratory experiments with Pu and the newly developed protocol make it possible to simulate the environmental behavior of Pu in model solutions of various chemical compositions. Adjustment of the oxidation states to Pu(IV) and Pu(V) described in this protocol is essential in order to investigate the complex redox chemistry of plutonium in the environment. The calibration of this technique and the results obtained in the laboratory experiments enable to develop a specific DGT device for in-situ Pu measurements in freshwaters. Accelerator-based mass-spectrometry measurements of Pu accumulated by DGTs in a karst spring allowed determining the bioavailability of Pu in a mineral freshwater environment. Application of this protocol for Pu measurements using DGT devices has a large potential to improve our understanding of the speciation and the biological transfer of Pu in aquatic ecosystems.

High-Performance Quantum Dot Thin-Film Transistors with Environmentally Benign Surface Functionalization and Robust Defect Passivation.

PubMed

Jung, Su Min; Kang, Han Lim; Won, Jong Kook; Kim, JaeHyun; Hwang, ChaHwan; Ahn, KyungHan; Chung, In; Ju, Byeong-Kwon; Kim, Myung-Gil; Park, Sung Kyu

2018-01-31

The recent development of high-performance colloidal quantum dot (QD) thin-film transistors (TFTs) has been achieved with removal of surface ligand, defect passivation, and facile electronic doping. Here, we report on high-performance solution-processed CdSe QD-TFTs with an optimized surface functionalization and robust defect passivation via hydrazine-free metal chalcogenide (MCC) ligands. The underlying mechanism of the ligand effects on CdSe QDs has been studied with hydrazine-free ex situ reaction derived MCC ligands, such as Sn 2 S 6 4- , Sn 2 Se 6 4- , and In 2 Se 4 2- , to allow benign solution-process available. Furthermore, the defect passivation and remote n-type doping effects have been investigated by incorporating indium nanoparticles over the QD layer. Strong electronic coupling and solid defect passivation of QDs could be achieved by introducing electronically active MCC capping and thermal diffusion of the indium nanoparticles, respectively. It is also noteworthy that the diffused indium nanoparticles facilitate charge injection not only inter-QDs but also between source/drain electrodes and the QD semiconductors, significantly reducing contact resistance. With benign organic solvents, the Sn 2 S 6 4- , Sn 2 Se 6 4- , and In 2 Se 4 2- ligand based QD-TFTs exhibited field-effect mobilities exceeding 4.8, 12.0, and 44.2 cm 2 /(V s), respectively. The results reported here imply that the incorporation of MCC ligands and appropriate dopants provide a general route to high-performance, extremely stable solution-processed QD-based electronic devices with marginal toxicity, offering compatibility with standard complementary metal oxide semiconductor processing and large-scale on-chip device applications.

Effects of microwave electric fields on the translational diffusion of dipolar molecules in surface potential: A simulation study

NASA Astrophysics Data System (ADS)

Kapranov, Sergey V.; Kouzaev, Guennadi A.

2018-01-01

Variations of effective diffusion coefficient of polar molecules exposed to microwave electric fields in a surface potential are studied by solving coupled stochastic differential equations of motion with a deterministic component of the surface force. Being an essential tool for the simulation interpretation, a theoretical approach to effective diffusion in surface potential is first developed. The effective diffusion coefficient is represented as the product of the normal diffusion coefficient and potential-dependent correction function, whose temperature dependence is close to the Arrhenius form. The analytically found zero-diffusion condition defines the state of thermal equilibrium at the surface. The diffusion of a water-like dipole molecule in the potential of graphite surface is simulated in the field-free conditions and in the presence of the alternating electric fields of various magnitude intensities and frequencies. Temperature dependence of the correction function exhibits field-induced variations of the effective Lennard-Jones energy parameter. It demonstrates maximum departure from the zero-field value at certain frequencies and intensities, which is associated with variations in the rotational dynamics. A concept of the amplitude-frequency resonance put forward to interpret the simulation results is explained using a heuristic reasoning and is corroborated by semi-quantitative considerations in terms of the Dissado-Hill cluster theory of dielectric relaxation.

High quality HfO{sub 2}/p-GaSb(001) metal-oxide-semiconductor capacitors with 0.8 nm equivalent oxide thickness

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

Barth, Michael; Datta, Suman, E-mail: sdatta@engr.psu.edu; Bruce Rayner, G.

2014-12-01

We investigate in-situ cleaning of GaSb surfaces and its effect on the electrical performance of p-type GaSb metal-oxide-semiconductor capacitor (MOSCAP) using a remote hydrogen plasma. Ultrathin HfO{sub 2} films grown by atomic layer deposition were used as a high permittivity gate dielectric. Compared to conventional ex-situ chemical cleaning methods, the in-situ GaSb surface treatment resulted in a drastic improvement in the impedance characteristics of the MOSCAPs, directly evidencing a much lower interface trap density and enhanced Fermi level movement efficiency. We demonstrate that by using a combination of ex-situ and in-situ surface cleaning steps, aggressively scaled HfO{sub 2}/p-GaSb MOSCAP structuresmore » with a low equivalent oxide thickness of 0.8 nm and efficient gate modulation of the surface potential are achieved, allowing to push the Fermi level far away from the valence band edge high up into the band gap of GaSb.« less

Time-resolved mapping of water diffusion coefficients in a working soft actuator device.

PubMed

Naji, Leila; Chudek, John A; Baker, Richard T

2008-08-14

Diffusion-weighted imaging was employed to spatially map the distribution of the diffusion coefficient of water, D, in bare, water-soaked, Li(+)-exchanged, cast Nafion and in an ionic polymer-metal composite (IPMC) soft actuator element, prepared from this bare Nafion by impregnation with Pt electrodes. D was evaluated in two orthogonal directions: along one of the long dimensions of the sample (Dx) and through its thickness (Dz). D-maps of the IPMC element were obtained both in the absence of an applied potential and in situ during the application of a 3 V dc potential across the thickness of the sample. In the bare Nafion, D-maps showed uniform values of both Dx and Dz of about 6 x 10 (-10) m(2) s(-1). In the IPMC two effects were observed: (i) D at the electroded surfaces of the IPMC was higher than at the center of the sample; (ii) this difference was much greater in Dz than in Dx . Both effects were explained by the influence of the impregnated Pt electrodes on polymer structure. The D-maps in the electrochemical measurements showed high values of D (up to 8 x 10(-10) m(2) s(-1)) at the cathode and low values (from 1 x 10(-10) m(2) s(-1)) at the anode. This was explained in terms of the effect on the Nafion nanostructure of the forced electro-migration of Li(H2O)x(+) species toward the cathode.

Biofilm Shows Spatially Stratified Metabolic Responses to Contaminant Exposure

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

Cao, Bin; Majors, Paul D.; Ahmed, B.

2012-11-01

The objective of this study was to elucidate the spatiotemporal responses of live S. oneidensis MR-1 biofilms to U(VI) (uranyl, UO22+) and Cr(VI) (chromate, CrO42-), important environmental contaminants at DOE contaminated sites. Toward this goal, we applied noninvasive nuclear magnetic resonance (NMR) imaging, diffusion, relaxation and spectroscopy techniques to monitor in situ spatiotemporal responses of S. oneidensis biofilms to U(VI) and Cr(VI) exposure in terms of changes in biofilm structures, diffusion properties, and cellular metabolism. Exposure to U(VI) or Cr(VI) did not appear to change the overall biomass distribution but caused changes in the physicochemical microenvironments inside the biofilm asmore » indicated by diffusion measurements. Changes in the diffusion properties of the biofilms in response to U(VI) and Cr(VI) exposure imply a novel function of the extracellular polymeric substances (EPS) affecting the biotransformation and transport of contaminants in the environment. In the presence of U(VI) or Cr(VI), the anaerobic metabolism of lactate was inhibited significantly, although the biofilms were still capable of reducing U(VI) and Cr(VI). Local concentrations of Cr(III)aq in the biofilm suggested relatively high Cr(VI) reduction activities at the top of the biofilm, near the medium-biofilm interface. The depth-resolved metabolic activities of the biofilm suggested higher diversion effects of gluconeogenesis and C1 metabolism pathways at the bottom of the biofilm and in the presence of U(VI). This study provides a noninvasive means to investigate spatiotemporal responses of biofilms, including surface-associated microbial communities in engineering, natural and medical settings, to various environmental perturbations including exposure to environmental contaminants and antimicrobials.« less

In-column bonded phase polymerization for improved packing uniformity

PubMed Central

Huckabee, Alexis G.; Yerneni, Charu; Jacobson, Rachel E.; Alzate, Edwin J.; Chen, Tse-Hong; Wirth, Mary J.

2017-01-01

It is difficult to pack chromatographic particles having polymeric-bonded phases because solvents used for making a stable slurry cause the polymer layer to swell. Growth of the polymer inside the column (in situ) after packing was investigated and compared with conventional, ex situ polymer growth. The method of activators generated by electron transfer, along with atom-transfer radical polymerization, enabled polymerization under ambient conditions. Nonporous, 0.62 µm silica particles with silane initiators were used. Polyacrylamide films with a hydrated thickness of 23 nm in 75:25 water/isopropanol grew in 55 min for both in situ and ex situ preparations, and the same carbon coverage was observed. Higher chromatographic resolution and better column-to-column reproducibility were observed for in situ polymer growth, as evaluated by hydrophilic interaction liquid chromatography for the model glycoprotein, ribonuclease B. In situ polymer growth was also found to give lower eddy diffusion, as shown by a narrower peak width for injected acetonitrile in 50:50 acetonitrile/water. When columns were packed more loosely, bed collapse occurred quickly for ex situ, but not for in situ, polymer growth. The higher resolution and stability for in situ polymer growth is explained by packing with hard, rather than soft, contacts between particles. PMID:28387037

Fiber-based modulated optical reflectance configuration allowing for offset pump and probe beams

NASA Astrophysics Data System (ADS)

Fleming, A.; Folsom, C.; Jensen, C.; Ban, H.

2016-12-01

A new fiber-based modulated optical reflectance configuration is developed in this work. The technique maintains the fiber-based heating laser (pump) and detection laser (probe) in close proximity at a fixed separation distance in a ceramic ferrule. The pump beam periodically heats the sample inducing thermal waves into the sample. The probe beam measures the temperature response at a known distance from the pump beam over a range of heating modulation frequencies. The thermal diffusivity of the sample may be calculated from the phase response between the input heat flux and the temperature response of a sample having a reflective surface. The unique measurement configuration is ideal for in situ measurements and has many advantages for laboratory-based systems. The design and development of the system are reported along with theoretical justification for the experimental design. The thermal diffusivities of Ge and SiC are measured and found to be within 10% of reported literature values. The diffusivity for SiO2 is measured with a relative difference of approximately 100% from the literature value when the ferrule is in contact with the sample. An additional measurement was made on the SiO2 sample with the ferrule not in contact resulting in a difference of less than 2% from the literature value. The difference in the SiO2 measurement when the ferrule is in contact with the sample is likely due to a parallel heat transfer path through the dual-fiber ferrule assembly.

Fiber-based modulated optical reflectance configuration allowing for offset pump and probe beams.

PubMed

Fleming, A; Folsom, C; Jensen, C; Ban, H

2016-12-01

A new fiber-based modulated optical reflectance configuration is developed in this work. The technique maintains the fiber-based heating laser (pump) and detection laser (probe) in close proximity at a fixed separation distance in a ceramic ferrule. The pump beam periodically heats the sample inducing thermal waves into the sample. The probe beam measures the temperature response at a known distance from the pump beam over a range of heating modulation frequencies. The thermal diffusivity of the sample may be calculated from the phase response between the input heat flux and the temperature response of a sample having a reflective surface. The unique measurement configuration is ideal for in situ measurements and has many advantages for laboratory-based systems. The design and development of the system are reported along with theoretical justification for the experimental design. The thermal diffusivities of Ge and SiC are measured and found to be within 10% of reported literature values. The diffusivity for SiO 2 is measured with a relative difference of approximately 100% from the literature value when the ferrule is in contact with the sample. An additional measurement was made on the SiO 2 sample with the ferrule not in contact resulting in a difference of less than 2% from the literature value. The difference in the SiO 2 measurement when the ferrule is in contact with the sample is likely due to a parallel heat transfer path through the dual-fiber ferrule assembly.

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.

Fibrinogen adsorption onto 316L stainless steel under polarized conditions.

PubMed

Gettens, Robert T T; Gilbert, Jeremy L

2008-04-01

Adsorption of the plasma protein fibrinogen onto electrically polarized 316L stainless steel was observed and quantified using both in situ and ex situ atomic force microscopy (AFM) techniques. Significant differences in fibrinogen adsorption were observed across voltages. Ex situ studies showed significantly lower area coverage (theta) and height of adsorbed Fb on cathodically polarized surfaces when compared to anodically polarized surfaces. Conformational differences in the protein may explain the distinctions in Fb surface area coverage (theta) and height between the anodic and cathodic cases. In situ studies showed significantly slower kinetics of Fb adsorption onto surfaces below -100 mV (vs. Ag/AgCl) compared to surfaces polarized above -100 mV. Electrochemical current density data showed large charge transfer processes (approximately 1 x 10(-5) to 1 x 10(-4) A/cm(2)) taking place on the 316L SS surfaces at voltages below -100 mV (vs. Ag/AgCl). These relatively large current densities point to flux of ionic species away from the surface as a major source of the reduction in adsorption kinetics rather than just hydrophilic or electrostatic effects. Copyright 2007 Wiley Periodicals, Inc.

Modelling Growth and Form of the Scleractinian Coral Pocillopora verrucosa and the Influence of Hydrodynamics

PubMed Central

Chindapol, Nol; Kaandorp, Jaap A.; Cronemberger, Carolina; Mass, Tali; Genin, Amatzia

2013-01-01

The growth of scleractinian corals is strongly influenced by the effect of water motion. Corals are known to have a high level of phenotypic variation and exhibit a diverse range of growth forms, which often contain a high level of geometric complexity. Due to their complex shape, simulation models represent an important option to complement experimental studies of growth and flow. In this work, we analyzed the impact of flow on coral's morphology by an accretive growth model coupled with advection-diffusion equations. We performed simulations under no-flow and uni-directional flow setup with the Reynolds number constant. The relevant importance of diffusion to advection was investigated by varying the diffusion coefficient, rather than the flow speed in Péclet number. The flow and transport equations were coupled and solved using COMSOL Multiphysics. We then compared the simulated morphologies with a series of Computed Tomography (CT) scans of scleractinian corals Pocillopora verrucosa exposed to various flow conditions in the in situ controlled flume setup. As a result, we found a similar trend associated with the increasing Péclet for both simulated forms and in situ corals; that is uni-directional current tends to facilitate asymmetrical growth response resulting in colonies with branches predominantly developed in the upstream direction. A closer look at the morphological traits yielded an interesting property about colony symmetry and plasticity induced by uni-directional flow. Both simulated and in situ corals exhibit a tendency where the degree of symmetry decreases and compactification increases in conjunction with the augmented Péclet thus indicates the significant importance of hydrodynamics. PMID:23326222

Correlation between Photoluminescence and Carrier Transport and a Simple In Situ Passivation Method for High-Bandgap Hybrid Perovskites

DOE PAGES

Stoddard, Ryan J.; Eickemeyer, Felix T.; Katahara, John K.; ...

2017-06-21

High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA 0.83Cs 0.17Pb(I 0.66Br 0.34)more » 3, resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 μm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.« less

Correlation between Photoluminescence and Carrier Transport and a Simple In Situ Passivation Method for High-Bandgap Hybrid Perovskites.

PubMed

Stoddard, Ryan J; Eickemeyer, Felix T; Katahara, John K; Hillhouse, Hugh W

2017-07-20

High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA 0.83 Cs 0.17 Pb(I 0.66 Br 0.34 ) 3 , resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 μm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.

Streaming potential method for characterizing interaction of electrical double layers between rice roots and Fe/Al oxide-coated quartz in situ.

PubMed

Liu, Zhao-Dong; Wang, Hai-Cui; Li, Jiu-Yu; Xu, Ren-Kou

2017-10-01

The interaction between rice roots and Fe/Al oxide-coated quartz was investigated through zeta potential measurements and column leaching experiments in present study. The zeta potentials of rice roots, Fe/Al oxide-coated quartz, and the binary systems containing rice roots and Fe/Al oxide-coated quartz were measured by a specially constructed streaming potential apparatus. The interactions between rice roots and Fe/Al oxide-coated quartz particles were evaluated/deduced based on the differences of zeta potentials between the binary systems and the single system of rice roots. The zeta potentials of the binary systems moved in positive directions compared with that of rice roots, suggesting that there were overlapping of diffuse layers of electric double layers on positively charged Fe/Al oxide-coated quartz and negatively charged rice roots and neutralization of positive charge on Fe/Al oxide-coated quartz with negative charge on rice roots. The greater amount of positive charges on Al oxide led to the stronger interaction of Al oxide-coated quartz with rice roots and the more shift of zeta potential compared with Fe oxide. The overlapping of diffuse layers on Fe/Al oxide-coated quartz and rice roots was confirmed by column leaching experiments. The greater overlapping of diffuse layers on Al oxide and rice roots led to more simultaneous adsorptions of K + and NO 3 - and greater reduction in leachate electric conductivity when the column containing Al oxide-coated quartz and rice roots was leached with KNO 3 solution, compared with the columns containing rice roots and Fe oxide-coated quartz or quartz. When the KNO 3 solution was replaced with deionized water to flush the columns, more K + and NO 3 - were desorbed from the binary system containing Al oxide-coated quartz and rice roots than from other two binary systems, suggesting that the stronger electrostatic interaction between Al oxide and rice roots promoted the desorption of K + and NO 3 - from the binary system and enhanced overlapping of diffuse layers on these oppositely charged surfaces compared with other two binary systems. In conclusion, the overlapping of diffuse layers occurred between positively charged Fe/Al oxides and rice roots, which led to neutralization of opposite charge and affected adsorption and desorption of ions onto and from the charged surfaces of Fe/Al oxides and rice roots.

An in situ vapour phase hydrothermal surface doping approach for fabrication of high performance Co3O4 electrocatalysts with an exceptionally high S-doped active surface.

PubMed

Tan, Zhijin; Liu, Porun; Zhang, Haimin; Wang, Yun; Al-Mamun, Mohammad; Yang, Hua Gui; Wang, Dan; Tang, Zhiyong; Zhao, Huijun

2015-04-04

A facile in situ vapour phase hydrothermal (VPH) surface doping approach has been developed for fabrication of high performance S-doped Co3O4 electrocatalysts with an unprecedentedly high surface S content (>47%). The demonstrated VPH doping approach could be useful for enrichment of surface active sites for other metal oxide electrocatalysts.

Analytical Solution for Transport with Bimolecular Reactions in Fracture-Matrix Systems with Application to In-Situ Chemical Oxidation

NASA Astrophysics Data System (ADS)

Rajaram, H.; Arshadi, M.

2016-12-01

In-situ chemical oxidation (ISCO) is an effective strategy for remediation of DNAPL contamination in fractured rock. During ISCO, an oxidant (e.g. permanganate) is typically injected through fractures and is consumed by bimolecular reactions with DNAPLs such as TCE and natural organic matter in the fracture and the adjacent rock matrix. Under these conditions, moving reaction fronts form and propagate along the fracture and into the rock matrix. The propagation of these reaction fronts is strongly influenced by the heterogeneity/discontinuity across the fracture-matrix interface (advective transport dominates in the fractures, while diffusive transport dominates in the rock matrix). We present analytical solutions for the concentrations of the oxidant, TCE and natural organic matter; and the propagation of the reaction fronts in a fracture-matrix system. Our approximate analytical solutions assume advection and reaction dominate over diffusion/dispersion in the fracture and neglect the latter. Diffusion and reaction with both TCE and immobile natural organic matter in the rock matrix are considered. The behavior of the reaction-diffusion equations in the rock matrix is posed as a Stefan problem where the diffusing oxidant reacts with both diffusing (TCE) and immobile (natural organic matter) reductants. Our analytical solutions establish that the reaction fronts propagate diffusively (i.e. as the square root of time) in both the matrix and the fracture. Our analytical solutions agree very well with numerical simulations for the case of uniform advection in the fracture. We also present extensions of our analytical solutions to non-uniform flows in the fracture by invoking a travel-time transformation. The non-uniform flow solutions are relevant to field applications of ISCO. The approximate analytical solutions are relevant to a broad class of reactive transport problems in fracture-matrix systems where moving reaction fronts occur.

A novel in situ permeation system and its utility in cancer tissue ablation

PubMed Central

WATANABE, MASAMI

2015-01-01

Focal ablation therapy is an emerging treatment modality for localized cancer lesions. It is an attractive strategy for inhibiting tumor progression and preventing morbidity associated with open surgery. As for intratissue drug delivery systems for use in local therapy, the convection-enhanced delivery (CED) of liquid drugs has been utilized, particularly for the treatment of malignant brain tumors. Although the conventional CED system is useful for providing drug/vehicle-based local therapy, there are several reported disadvantages in terms of the ability to control the extent of drug diffusion. We herein developed and validated a novel in situ permeation (ISP)-MW-1 system for achieving intratissue drug diffusion. The ISP system includes a perfusion catheter connected to an injector and aspirator, which enables intratissue perfusion of the solute diluted in the vehicle in the tip-inserted cavity. We subsequently evaluated the utility of the ISP-MW-1 system for in situ permeation in a subcutaneous tumor model in hamsters. Dehydrated ethanol, saline and 50% acetic acid were evaluated as the vehicle, and methylene blue was used as a dissolved substance for evaluating the diffusion of the agent. As a result, almost all of the tumor tissue within the capsule (tumor size: ~3 cm) was permeated with the dehydrated ethanol and 50% acetic acid and partially with the saline. We further demonstrated that ISP treatment with 50% acetic acid completely ablated the subcutaneous tumors in all of the treated hamsters (n=3). Therefore, the ISP-MW-1 system is a promising approach for controlling the intratissue diffusion of therapeutic agents and for providing local ablation therapy for cancer lesions. We believe that this system may be applicable to a broad range of medicinal and industrial fields, such as regenerative medicine, drug delivery systems, biochemistry and material technologies as well as cancer therapy. PMID:26134633

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates

NASA Astrophysics Data System (ADS)

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-01

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

Large-scale uniform bilayer graphene prepared by vacuum graphitization of 6H-SiC(0001) substrates.

PubMed

Wang, Qingyan; Zhang, Wenhao; Wang, Lili; He, Ke; Ma, Xucun; Xue, Qikun

2013-03-06

We report on the preparation of large-scale uniform bilayer graphenes on nominally flat Si-polar 6H-SiC(0001) substrates by flash annealing in ultrahigh vacuum. The resulting graphenes have a single thickness of one bilayer and consist of regular terraces separated by the triple SiC bilayer steps on the 6H-SiC(0001) substrates. In situ scanning tunneling microscopy reveals that suppression of pit formation on terraces and uniformity of SiC decomposition at step edges are the key factors to the uniform thickness. By studying the surface morphologies prepared under different annealing rates, it is found that the annealing rate is directly related to SiC decomposition, diffusion of the released Si/C atoms and strain relaxation, which together determine the final step structure and density of defects.

Prognostic impact of MYC protein expression in central nervous system diffuse large B-cell lymphoma: comparison with MYC rearrangement and MYC mRNA expression.

PubMed

Son, Seung-Myoung; Ha, Sang-Yun; Yoo, Hae-Yong; Oh, Dongryul; Kim, Seok-Jin; Kim, Won-Seog; Ko, Young-Hyeh

2017-01-01

The prognostic role of MYC has been well documented in non-central nervous system diffuse large B-cell lymphoma; however, it remains controversial in central nervous system diffuse large B-cell lymphoma. To investigate the prognostic value of MYC, we analyzed the MYC protein expression by immunohistochemistry, mRNA expression by RNA in situ hybridization, and gene status by fluorescence in situ hybridization in 74 cases of central nervous system diffuse large B-cell lymphoma. Moreover, we examined the correlation between MYC translocation, mRNA expression, and protein expression. The mean percentage of MYC immunopositive cells was 49%. Using a 44% cutoff value, 49 (66%) cases showed MYC protein overexpression. The result of mRNA in situ hybridization using the RNA scope technology was obtained using the H-scoring system; the median value was 34.2. Using the cutoff value of 63.5, 16 (22%) cases showed MYC mRNA overexpression. MYC gene rearrangement was detected in five out of 68 (7%) cases. MYC translocation showed no statistically significant correlation with mRNA expression; however, all MYC translocation-positive cases showed MYC protein overexpression, with a higher mean percentage of MYC protein expression than that of translocation-negative cases (78 vs 48%, P=0.001). The level of MYC mRNA expression was moderately correlated with the level of MYC protein expression (P<0.001). The mean percentage of MYC protein expression in the high MYC mRNA group was higher than that in the low MYC mRNA group (70 vs 47%, P<0.001). A univariate analysis showed that age over 60 years, Eastern Cooperative Oncology Group (ECOG) performance status ≥2 and MYC protein overexpression were significantly associated with an increased risk of death. MYC translocation and MYC mRNA expression had no prognostic significance. On multivariate analysis, MYC protein overexpression and ECOG score retained prognostic significance.

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

NASA Astrophysics Data System (ADS)

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

2004-05-01

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

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

NASA Astrophysics Data System (ADS)

M. C. Sagis, Leonard

2001-03-01

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

Slowdown of surface diffusion during early stages of bacterial colonization

NASA Astrophysics Data System (ADS)

Vourc'h, T.; Peerhossaini, H.; Léopoldès, J.; Méjean, A.; Chauvat, F.; Cassier-Chauvat, C.

2018-03-01

We study the surface diffusion of the model cyanobacterium Synechocystis sp. PCC6803 during the incipient stages of cell contact with a glass surface in the dilute regime. We observe a twitching motility with alternating immobile tumble and mobile run periods, resulting in a normal diffusion described by a continuous-time random walk with a coefficient of diffusion D . Surprisingly, D is found to decrease with time down to a plateau. This is observed only when the cyanobacterial cells are able to produce released extracellular polysaccharides, as shown by a comparative study between the wild-type strain and various polysaccharides-depleted mutants. The analysis of the trajectories taken by the bacterial cells shows that the temporal characteristics of their intermittent motion depend on the instantaneous fraction of visited sites during diffusion. This describes quantitatively the time dependence of D , related to the progressive surface coverage by the polysaccharides. The observed slowdown of the surface diffusion may constitute a basic precursor mechanism for microcolony formation and provides clues for controlling biofilm formation.

Estimation of the radial diffusion coefficient using REE-associated ground Pc 5 pulsations

NASA Astrophysics Data System (ADS)

Fujimoto, A.; Yumoto, K.

2010-12-01

Pc 5 pulsations with frequencies between 1.67 and 6.67 mHz are believed to contribute to the REE in the outer radiation belt during magnetic storms, by means of the observations [Baker et al., 1998; Rostoker et al., 1998; Mathie and Mann, 2000; O'Brien et al., 2001, 2003] and several theoretical studies. The latter studies are roughly categorized into two themes: in-situ acceleration at L lower than 6.6 by wave-particle interactions [Liu et al., 199 9; Summers et al., 1999; Summers and Ma, 2000] and acceleration by radial diffusion from the outer to the inner magnetosphere [Elkington et al., 1999, 2003; Hudson et al., 2000; Kim et al., 2001]. One possible acceleration mechanism is the resonant interaction with Pc 5 toroidal and poloidal pulsations, referred as the radial diffusion mechanism. One of unsolved problems is where and which Pc 5 pulsation mode (toroidal and/or poloidal) play effective role in the radial diffusion process. In order to verify Pc 5 pulsation as the major roles for REEs, we have to examine the time variation of electron phase space density (cf. Green et al., 2004). Electron phase space density is not directly measured, but we can estimate radial diffusion coefficients which determine the electron transportation efficiency, using ground-based magnetic field data. We estimated the radial diffusion coefficient of ground Pc 5 pulsations associated with the Relativistic Electron Enhancement (REE) in the geosynchronous orbit. In order to estimate the radial diffusion coefficient D_LL, we need the value of in-situ Pc 5 electric field power spectral density. In this paper, however, we estimated the equatorial electric field mapped from Pc 5 pulsations power spectral density on the ground. Reciprocal of radial diffusion coefficient describes the timescale T_LL for an electron to diffuse 1 Re. Applying a superposed epoch analysis about timescales T_LL of the radial diffusion for 12 REE events in 2008, we found that when the relativistic electron enhancements occur, T_LL at higher latitude (L larger than 5) is predominantly diffusional, whereas T_LL at lower latitude (L less than 4) is mainly convectional. We concluded that higher-latitude Pc 5 pulsations play more effective roles than lower latitude Pc 5 pulsations in the radial diffusion process.

In situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates for superior Li-ion battery cathodes.

PubMed

Ma, Zhipeng; Fan, Yuqian; Shao, Guangjie; Wang, Guiling; Song, Jianjun; Liu, Tingting

2015-02-04

The low electronic conductivity and one-dimensional diffusion channel along the b axis for Li ions are two major obstacles to achieving high power density of LiFePO4 material. Coating carbon with excellent conductivity on the tailored LiFePO4 nanoparticles therefore plays an important role for efficient charge and mass transport within this material. We report here the in situ catalytic synthesis of high-graphitized carbon-coated LiFePO4 nanoplates with highly oriented (010) facets by introducing ferrocene as a catalyst during thermal treatment. The as-obtained material exhibits superior performances for Li-ion batteries at high rate (100 C) and low temperature (-20 °C), mainly because of fast electron transport through the graphitic carbon layer and efficient Li(+)-ion diffusion through the thin nanoplates.

Implementation of a diffusion convection surface evolution model in WallDYN

NASA Astrophysics Data System (ADS)

Schmid, K.

2013-07-01

In thermonuclear fusion experiments with multiple plasma facing materials the formation of mixed materials is inevitable. The formation of these mixed material layers is a dynamic process driven the tight interaction between transport in the plasma scrape off layer and erosion/(re-) deposition at the surface. To track this global material erosion/deposition balance and the resulting formation of mixed material layers the WallDYN code has been developed which couples surface processes and plasma transport. The current surface model in WallDYN cannot fully handle the growth of layers nor does it include diffusion. However at elevated temperatures diffusion is a key process in the formation of mixed materials. To remedy this shortcoming a new surface model has been developed which, for the first time, describes both layer growth/recession and diffusion in a single continuous diffusion/convection equation. The paper will detail the derivation of the new surface model and compare it to TRIDYN calculations.

True temperature measurement on metallic surfaces using a two-color pyroreflectometer method.

PubMed

Hernandez, D; Netchaieff, A; Stein, A

2009-09-01

In the most common case of optical pyrometry, the major obstacle in determining the true temperature is the knowledge of the thermo-optical properties for in situ conditions. We present experimental results obtained with a method able to determine the true temperature of metallic surfaces above 500 degrees C when there is not parasitic effect by surrounding radiation. The method is called bicolor pyroreflectometry and it is based on Planck's law, Kirchhoff's law, and the assumption of identical reflectivity indicatrixes for the target surface at two different close wavelengths (here, 1.3 and 1.55 microm). The diffusion factor eta(d), the key parameter of the method, is introduced to determine the convergence temperature T(*), which is expected to be equal to the true temperature T. Our goal is to asses this method for different metallic surfaces. The validation of this method is made by comparison with thermocouples. Measurements were made for tungsten, copper, and aluminum samples of different roughnesses, determined by a rugosimeter. After introducing a theoretical model for two-color pyroreflectometry, we give a description of the experimental setup and present experimental applications of the subject method. The quality of the results demonstrates the usefulness of two-color pyroreflectometry to determine the temperatures of hot metals when the emissivity is not known and for the commercially important case of specular surfaces.

30 CFR 870.5 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... situ coal mining means activities conducted on the surface or underground in connection with in-place... not limited to, in situ gasification, in situ leaching, slurry mining, solution mining, bore hole mining, and fluid recovery mining. At this time, part 870 considers only in situ gasification. Inherent...

30 CFR 870.5 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... situ coal mining means activities conducted on the surface or underground in connection with in-place... not limited to, in situ gasification, in situ leaching, slurry mining, solution mining, bore hole mining, and fluid recovery mining. At this time, part 870 considers only in situ gasification. Inherent...

30 CFR 870.5 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... situ coal mining means activities conducted on the surface or underground in connection with in-place... not limited to, in situ gasification, in situ leaching, slurry mining, solution mining, bore hole mining, and fluid recovery mining. At this time, part 870 considers only in situ gasification. Inherent...

30 CFR 870.5 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... situ coal mining means activities conducted on the surface or underground in connection with in-place... not limited to, in situ gasification, in situ leaching, slurry mining, solution mining, bore hole mining, and fluid recovery mining. At this time, part 870 considers only in situ gasification. Inherent...

30 CFR 870.5 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... situ coal mining means activities conducted on the surface or underground in connection with in-place... not limited to, in situ gasification, in situ leaching, slurry mining, solution mining, bore hole mining, and fluid recovery mining. At this time, part 870 considers only in situ gasification. Inherent...

In situ field measurement of leaf water potential using thermocouple psychrometers.

PubMed

Savage, M J; Wiebe, H H; Cass, A

1983-11-01

Thermocouple psychrometers are the only instruments which can measure the in situ water potential of intact leaves, and which can possibly be used to monitor leaf water potential. Unfortunately, their usefulness is limited by a number of difficulties, among them fluctuating temperatures and temperature gradients within the psychrometer, sealing of the psychrometer chamber to the leaf, shading of the leaf by the psychrometer, and resistance to water vapor diffusion by the cuticle when the stomates are closed. Using Citrus jambhiri, we have tested several psychrometer design and operational modifications and showed that in situ psychrometric measurements compared favorably with simultaneous Scholander pressure chamber measurements on neighboring leaves when the latter were corrected for the osmotic potential.

Synthesis of lithium nitride for neutron production target of BNCT by in situ lithium deposition and ion implantation

NASA Astrophysics Data System (ADS)

Ishiyama, S.; Baba, Y.; Fujii, R.; Nakamura, M.; Imahori, Y.

2012-12-01

To achieve high performance of BNCT (Boron Neutron Capture Therapy) device, Li3N/Li/Pd/Cu four layered Li target was designed and the structures of the synthesized four layered target were characterized by X-ray photoelectron spectroscopy. For the purpose of avoiding the radiation blistering and lithium evaporation, in situ vacuum deposition and nitridation techniques were established for in situ production and repairing maintenance of the lithium target. Following conclusions were derived: Uniform lithium layer of a few hundreds nanometer was formed on Pd/Cu multilayer surface by in situ vacuum deposition technique using metallic lithium as a source material. Lithium nitrides were formed by in situ nitridation reaction by the implantation of low-energy nitrogen ions on the deposited lithium layer surface. The chemical states of the nitridated zone were close to the stoichiometric lithium nitride, Li3N. This nitridated zone formed on surface of four layered lithium target is stable for a long time in air condition. The in situ nitridation is effective to protect lithium target from degradation by unfavorable reactions.

Carbon-containing compounds on fusion-related surfaces: Thermal and ion-induced formation and erosion

NASA Astrophysics Data System (ADS)

Linsmeier, Christian

2004-12-01

The deposition of carbon on metals is the unavoidable consequence of the application of different wall materials in present and future fusion experiments like ITER. Presently used and prospected materials besides carbon (CFC materials in high heat load areas) are tungsten and beryllium. The simultaneous application of different materials leads to the formation of surface compounds due to the erosion, transport and re-deposition of material during plasma operations. The formation and erosion processes are governed by widely varying surface temperatures and kinetic energies as well as the spectrum of impinging particles from the plasma. The knowledge of the dependence on these parameters is crucial for the understanding and prediction of the compound formation on wall materials. The formation of surface layers is of great importance, since they not only determine erosion rates, but also influence the ability of the first wall for hydrogen isotope inventory accumulation and release. Surface compound formation, diffusion and erosion phenomena are studied under well-controlled ultra-high vacuum conditions using in-situ X-ray photoelectron spectroscopy (XPS) and ion beam analysis techniques available at a 3 MV tandem accelerator. XPS provides chemical information and allows distinguishing elemental and carbidic phases with high surface sensitivity. Accelerator-based spectroscopies provide quantitative compositional analysis and sensitivity for deuterium in the surface layers. Using these techniques, the formation of carbidic layers on metals is studied from room temperature up to 1700 K. The formation of an interfacial carbide of several monolayers thickness is not only observed for metals with exothermic carbide formation enthalpies, but also in the cases of Ni and Fe which form endothermic carbides. Additional carbon deposited at 300 K remains elemental. Depending on the substrate, carbon diffusion into the bulk starts at elevated temperatures together with additional carbide formation. Depending on the bond nature in the carbide (metallic in the transition metal carbides, ionic e.g. in Be2C), the surface carbide layer is dissolved upon further increased temperatures or remains stable. Carbide formation can also be initiated by ion bombardment, both of chemically inert noble gas ions or C+ or CO+ ions. In the latter case, a deposition-erosion equilibrium develops which leads to a ternary surface layer of constant thickness. A chemical erosion channel is also discussed for the enhanced erosion of thin carbon films on metals by deuterium ions.

Laser-induced desorption determinations of surface diffusion on Rh(111)

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

Seebauer, E.G.; Schmidt, L.D.

Surface diffusion of hydrogen, deuterium and CO on Rh(111) has been investigated by laser-induced thermal desorption (LITD) and compared with previous results for these species on Pt(111) and on other metals. For deuterium in the coverage range 0.02 < theta < 0.33, the pre-exponential factor D/sub 0/ - 8 x 10/sup -2/ cm/sup 2//s, with a diffusion activation energy 3.7 < E/sub diff/ < 4.3 kcal/mol. For CO, E/sub diff/ = 7 kcal/mol, but D/sub 0/ rises from 10/sup -3/ to 10/sup -2/ cm/sup 2//s between theta = 0.01 and 0.40. Values of E/sub diff/ on different surfaces appear tomore » correlate with differences in heats of adsorption in different binding states which form saddle point configurations in surface diffusion. In addition, oxidation reactions on Rh and on several other transition metal surfaces may be limited to CO or H surface diffusion. 30 refs., 3 figs., 1 tab.« less

Surface mass diffusion over an extended temperature range on Pt(111)

NASA Astrophysics Data System (ADS)

Rajappan, M.; Swiech, W.; Ondrejcek, M.; Flynn, C. P.

2007-06-01

Surface mass diffusion is investigated on Pt(111) at temperatures in the range 710-1220 K. This greatly extends the range over which diffusion is known from step fluctuation spectroscopy (SFS). In the present research, a beam of Pt- self-ions is employed to create a suitable structure on step edges. The surface mass diffusion coefficients then follow from the decay of Fourier components observed by low-energy electron microscopy (LEEM) at selected annealing temperatures. The results agree with SFS values where they overlap, and continue smoothly to low temperature. This makes it unlikely that diffusion along step edges plays a major role in step edge relaxation through the temperature range studied. The surface mass diffusion coefficient for the range 710-1520 K deduced from the present work, together with previous SFS data, is Ds = 4 × 10-3 exp(-1.47 eV/kBT) cm2 s-1.

Convection-Diffusion Layer in an "Open Space" for Local Surface Treatment and Microfabrication using a Four-Aperture Microchemical Pen.

PubMed

Mao, Sifeng; Zhang, Yong; Zhang, Weifei; Zeng, Hulie; Nakajima, Hizuru; Lin, Jin-Ming; Uchiyama, Katsumi

2017-09-06

A four-aperture microchemical pen was used to produce a stable convection-diffusion layer in an "open space" for microreactions and microfabrication. The process represents a new method for microreactions and microfabrication in a convection-diffusion layer. To prove the concept of a convection-diffusion layer in an "open space", bovine serum albumin was labeled with 4-fluoro-7-nitro-2,1,3-benzoxadiazole to confirm that the small convection-diffusion layer was effective for local surface treatment. To demonstrate the potential for microfabrication, silver patterns were fabricated on a glass surface with a convection-diffusion layer by using the silver-mirror reaction. The widths of each silver pattern could be easily controlled from 10 to 60 μm. Patterned silver lines with uniform widths or gradient widths were prepared. This is the first proof of concept study of a convection-diffusion layer in an "open space" used in local surface treatment and microfabrication on a surface. The microchemical pen represents a potential method for the region-selective microtreatment of tissues, cells, and other biological interfaces. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Presence of Nitrate-Accumulating Sulfur Bacteria and Their Influence on Nitrogen Cycling in a Shallow Coastal Marine Sediment

PubMed Central

Sayama, Mikio

2001-01-01

Nitrate flux between sediment and water, nitrate concentration profile at the sediment-water interface, and in situ sediment denitrification activity were measured seasonally at the innermost part of Tokyo Bay, Japan. For the determination of sediment nitrate concentration, undisturbed sediment cores were sectioned into 5-mm depth intervals and each segment was stored frozen at −30°C. The nitrate concentration was determined for the supernatants after centrifuging the frozen and thawed sediments. Nitrate in the uppermost sediment showed a remarkable seasonal change, and its seasonal maximum of up to 400 μM was found in October. The directions of the diffusive nitrate fluxes predicted from the interfacial concentration gradients were out of the sediment throughout the year. In contrast, the directions of the total nitrate fluxes measured by the whole-core incubation were into the sediment at all seasons. This contradiction between directions indicates that a large part of the nitrate pool extracted from the frozen surface sediments is not a pore water constituent, and preliminary examinations demonstrated that the nitrate was contained in the intracellular vacuoles of filamentous sulfur bacteria dwelling on or in the surface sediment. Based on the comparison between in situ sediment denitrification activity and total nitrate flux, it is suggested that intracellular nitrate cannot be directly utilized by sediment denitrification, and the probable fate of the intracellular nitrate is hypothesized to be dissimilatory reduction to ammonium. The presence of nitrate-accumulating sulfur bacteria therefore may lower nature's self-purification capacity (denitrification) and exacerbate eutrophication in shallow coastal marine environments. PMID:11472923

Molecular recognition in gas sensing: Results from acoustic wave and in-situ FTIR measurements

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

Hierlemann, A.; Ricco, A.J.; Bodenhoefer, K.

Surface acoustic wave (SAW) measurements were combined with direct, in-situ molecular spectroscopy to understand the interactions of surface-confined sensing films with gas-phase analytes. This was accomplished by collecting Fourier-transform infrared external-reflectance spectra (FTIR-ERS) on operating SAW devices during dosing of their specifically coated surfaces with key analytes.

In situ Raman study on single- and double-walled carbon nanotubes as a function of lithium insertion.

PubMed

Kim, Yoong Ahm; Kojima, Masahito; Muramatsu, Hiroyuki; Umemoto, Souichiro; Watanabe, Takaaki; Yoshida, Kazuto; Sato, Keigo; Ikeda, Takuya; Hayashi, Takuya; Endo, Morinobu; Terrones, Mauricio; Dresselhaus, Mildred S

2006-05-01

We investigated the electrochemical lithium ion (Li(+)) insertion/desertion behavior on highly pure and bundled single- and double-walled carbon nanotubes (SWNTs and DWNTs) using an in situ Raman technique. In general, two storage sites could host Li(+) in SWNT and DWNT bundles when varying an external potential: a) the outer surface sites, and b) the interstitial spaces within the bundles. The most sensitive changes in the tangential mode (TM) of the Raman spectra upon doping with Li(+) can be divided into two regions. The first region was found from 2.8 to 1.0 V (the coverage of Li(+) on the outer surface of a bundled nanotube) and was characterized by the loss of resonant conditions via partial charge transfer, where the G(+) line of the SWNT and the TM of the outer tube of DWNTs experienced a highly depressed intensity, but remained almost constant in frequency. The appearance of a Breit-Wigner-Fano (BWF) profile provided strong evidence of metallic inner tubes within DWNTs. The second region was observed when the applied potentials ranged from 0.9 to 0 V and was characterized by Li(+) diffusion into the interstitial sites of the bundled nanotube material. This phenomenon invoked a large downshift of the G(-) band in SWNTs, and a small downshift of the TM of the inner tube of DWNTs caused by expansion of the C--C bonds due to the charge transferred to the nanotubes, and the disappearance of the BWF profile through the screening effect of the interstitial Li(+) layers.

Standing and sitting adlayers in atomic layer deposition of ZnO

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

Gao, Zhengning; Banerjee, Parag, E-mail: parag.banerjee@wustl.edu; Wu, Fei

The extent of reactivity of diethyl zinc (DEZ) with a hydroxylated surface during atomic layer deposition (ALD) of ZnO using DEZ and water is measured. Two adlayer configurations of DEZ are possible. The “standing” adlayer releases one ethyl group from DEZ. The “sitting” adlayer releases both ethyl groups, thus forming a Zn bridge between two O anions. Density functional theory calculations suggest the sitting configuration is more stable than the standing configuration by 790 meV. In situ quadrupole mass spectroscopy of by-product ethane generated in ALD half cycles indicate that ∼1.56 OH sites react with a DEZ molecule resulting in 71.6%more » of sitting sites. A simple simulation of a “ball-and-stick” DEZ molecule randomly collapsing on a neighboring site remarkably captures this adlayer behavior. It is concluded that DEZ fraction sitting is a competitive process of a standing DEZ molecule collapsing onto an available neighboring hydroxyl site, as sites vie for occupancy via adsorption and surface diffusion.« less

Recent development of a jet-diffuser ejector

NASA Technical Reports Server (NTRS)

Alperin, M.; Wu, J. J.

1980-01-01

The paper considers thrust augmenting ejectors in which the processes of mixing and diffusion are partly carried out downstream of the ejector solid surfaces. A jet sheet surrounding the periphery of a widely diverging diffuser prevents separation and forms a gaseous, curved surface to provide effective diffuser ratio and additional length for mixing of primary and induced flows. Three-dimensional potential flow methods achieved a large reduction in the length of the associated solid surface; primary nozzle design further reduced the volume required by the jet-diffuser ejectors, resulting in thrust augmentation in excess of two, and an overall length of about 2 1/2 times the throat width.

Diffusive Milli-Gels (DMG) for in situ assessment of metal bioavailability: A comparison with labile metal measurement using Chelex columns and acute toxicity to Ceriodaphnia dubia for copper in freshwaters.

PubMed

Perez, Magali; Simpson, Stuart L; Lespes, Gaëtane; King, Josh J; Adams, Merrin S; Jarolimek, Chad V; Grassl, Bruno; Schaumlöffel, Dirk

2016-12-01

Fluctuations in concentrations of bioavailable metals occur in most natural waters. In situ measurements are desirable to predict risks of adverse effects to aquatic organisms. We evaluated Diffusive Milli-Gels (DMG), a new in situ passive sampler, for assessing the bioavailability and toxicity of copper in waters exhibiting a wide range of characteristics. The performance was compared to an established Chelex-column method that measures labile copper concentrations by discrete sampling, and the ability to predict acute toxicity to the cladoceran, Ceriodaphnia dubia. The labile copper concentrations measured by the DMG and Chelex-column methods decreased with increasing dissolved organic carbon (DOC) (1.9-15 mg L -1 ) and hardness (21-270 mg CaCO 3  L -1 hardness), with 20-70% of total dissolved copper being present as labile copper. Toxicity decreased with increasing DOC and hardness. Strong linear relationships existed between the EC50 for C. dubia and DOC, and when the EC50 was related to either the labile copper concentrations measured by DMG (r 2  = 0.874) or the Chelex column (0.956) methods. The study demonstrates that the DMG passive sampler is a relevant tool for the in situ assessment of environmental risks posed by metals whose toxicity is strongly influenced by speciation. Copyright © 2016 Elsevier Ltd. All rights reserved.

Pore-scale lattice Boltzmann simulation of micro-gaseous flow considering surface diffusion effect

DOE PAGES

Wang, Junjian; Kang, Qinjun; Chen, Li; ...

2016-11-21

Some recent studies have shown that adsorbed gas and its surface diffusion have profound influence on micro-gaseous flow through organic pores in shale gas reservoirs. Here, a multiple-relaxation-time (MRT) LB model is adopted to estimate the apparent permeability of organic shale and a new boundary condition, which combines Langmuir adsorption theory with Maxwellian diffusive reflection boundary condition, is proposed to capture gas slip and surface diffusion of adsorbed gas. The simulation results match well with previous studies carried out using Molecular Dynamics (MD) and show that Maxwell slip boundary condition fails to characterize gas transport in the near wall regionmore » under the influence of the adsorbed gas. The total molar flux can be either enhanced or reduced depending on variations in adsorbed gas coverage and surface diffusion velocity. The effects of pore width, pressure as well as Langmuir properties on apparent permeability of methane transport in organic pores are further studied. It is found that the surface transport plays a significant role in determining the apparent permeability, and the variation of apparent permeability with pore size and pressure is affected by the adsorption and surface diffusion.« less

Fabrication of mullite-bonded porous SiC ceramics from multilayer-coated SiC particles through sol-gel and in-situ polymerization techniques

NASA Astrophysics Data System (ADS)

Ebrahimpour, Omid

In this work, mullite-bonded porous silicon carbide (SiC) ceramics were prepared via a reaction bonding technique with the assistance of a sol-gel technique or in-situ polymerization as well as a combination of these techniques. In a typical procedure, SiC particles were first coated by alumina using calcined powder and alumina sol via a sol-gel technique followed by drying and passing through a screen. Subsequently, they were coated with the desired amount of polyethylene via an in-situ polymerization technique in a slurry phase reactor using a Ziegler-Natta catalyst. Afterward, the coated powders were dried again and passed through a screen before being pressed into a rectangular mold to make a green body. During the heating process, the polyethylene was burnt out to form pores at a temperature of about 500°C. Increasing the temperature above 800°C led to the partial oxidation of SiC particles to silica. At higher temperatures (above 1400°C) derived silica reacted with alumina to form mullite, which bonds SiC particles together. The porous SiC specimens were characterized with various techniques. The first part of the project was devoted to investigating the oxidation of SiC particles using a Thermogravimetric analysis (TGA) apparatus. The effects of particle size (micro and nano) and oxidation temperature (910°C--1010°C) as well as the initial mass of SiC particles in TGA on the oxidation behaviour of SiC powders were evaluated. To illustrate the oxidation rate of SiC in the packed bed state, a new kinetic model, which takes into account all of the diffusion steps (bulk, inter and intra particle diffusion) and surface oxidation rate, was proposed. Furthermore, the oxidation of SiC particles was analyzed by the X-ray Diffraction (XRD) technique. The effect of different alumina sources (calcined Al2O 3, alumina sol or a combination of the two) on the mechanical, physical, and crystalline structure of mullite-bonded porous SiC ceramics was studied in the second part of the project. Alumina sol was synthesized by the hydrolysis of Aluminum isopropoxide using the Yoldas method. Alumina sol was homogenous and had a needle-like shape with a thickness of 2--3 nm. Crystalline changes during the heating process of alumina sol were studied using XRD. In addition, Fourier transform infrared (FTIR) spectroscopy was performed to identify the functional groups on the alumina sol surface as a function of temperature. In the third part of the project, the feasibility of the in-situ polymerization technique was investigated to fabricate porous SiC ceramics. In this part, the mixture of SiC and calcined alumina powders were coated by polyethylene via in-situ polymerizing referred to as the polymerization compounding process in a slurry phase. The polymerization was conducted under very moderate operational conditions using the Ziegler-Natta catalyst system. Differential scanning calorimetry (DSC) and TGA analysis and morphological studies (SEM and TEM) revealed the presence of a high density of polyethylene on the surface of SiC and alumina powders. The amount of polymer was controlled by the polymerization reaction time. Most parts of particles were coated by a thin layer of polyethylene and polymer. The porous SiC ceramics, which were fabricated by these treated particles showed higher mechanical and physical properties compared to the samples made without any treatment. The relative intensity of mullite was higher compared to the samples prepared by the traditional process. The effects of the sintering temperature, forming pressure and polymer content were also studied on the physical and mechanical properties of the final product. In the last phase of this research work, the focus of the investigation was to take advantage of both the sol-gel processing and in-situ polymerization method to develop a new process to manufacture mullite-bonded porous SiC ceramic with enhanced mechanical and physical properties. Therefore, first the SiC particles and alumina nano powders were mixed in alumina sol to adjust the alumina weight to 35 wt%. Then, the desired amount of catalyst, which depends on the total surface area of the particles, was grafted onto the surface of the powders under an inert atmosphere. Consequently, the polymerization started from the surface of the substrate. The treated powders were characterized by SEM, XPS and TGA. In addition, the amount of pore-former was determined by TGA analysis. Porous SiC ceramics, which were fabricated by the novel process, consist of mullite, SiC, cristobalite and a small amount of alumina and TiO 2 as a result of reaction of TiCl4 with air. Furthermore, the effect of the sintering temperatures (1500°C, 1550°C and 1600°C) on the crystalline structure of the porous samples was investigated. Furthermore, it was proposed that converting TiCl4 to TiO2 acted as the sintering additive to form mullite at a lower sintering temperature. (Abstract shortened by UMI.).

Electrochemical fabrication of nanoporous copper films in choline chloride-urea deep eutectic solvent.

PubMed

Zhang, Q B; Abbott, Andrew P; Yang, C

2015-06-14

Nanoporous copper films were fabricated by a facile electrochemical alloying/dealloying process without the need of a template. A deep eutectic solvent made from choline chloride (ChCl) and urea was used with zinc oxide as the metal salt. Cyclic voltammetry was used to characterise the electrochemical reduction of zinc and follow Cu-Zn alloy formation on the copper substrate at elevated temperatures from 353 to 393 K. The alloy formation was confirmed by X-ray diffraction spectra. 3D, open and bicontinuous nanoporous copper films were obtained by in situ electrochemically etching (dealloying) of the zinc component in the Cu-Zn surface alloys at an appropriate potential (-0.4 V vs. Ag). This dealloying process was found to be highly temperature dependent and surface diffusion controlled, which involved the self-assembly of copper atoms at the alloy/electrolyte interface. Additionally, the effects of the deposition parameters, including deposition temperature, current density as well as total charge density on resulting the microstructure were investigated by scanning electron microscopy, and atomic force microscope.

SURFACE APPLICATION SYSTEM FOR IN SITU GROUND-WATER BIOREMEDIATION: SITE CHARACTERIZATION AND MODELING

EPA Science Inventory

Surface application offers an inexpensive, noninvasive alternative to injection wells and infiltration galleries for in situ ground-water bioreniediation applications. The technology employs artificial recharge to create favorable hydraulic conditions for mixing and vertical tran...

Reaction Gradients Viewed Inside Single Photoactive Particles

NASA Astrophysics Data System (ADS)

Alpert, P.; Corral Arroyo, P.; Dou, J.; Kreiger, U.; Luo, B.; Peter, T.; Ammann, M.

2017-12-01

In terms of chemical selectivity and spatial resolution, a technique known as scanning transmission X-ray microscopy coupled to near-edge X-ray absorption fine structure spectroscopy (STXM/NEXAFS) is unmatched and will remain so for years into the future. We present a recent development coupling STXM/NEXAFS to a custom-built photochemical environmental reactor in which aerosol particles reside allowing for in situ chemical imaging. A laboratory investigation of metal-organic complex photochemistry was conducted. Transition metals are of great importance to atmospheric chemistry and aerosol photochemical aging due to their ability to catalyze oxidation reactions. Aerosol particles composed of mixtures of citric acid and iron citrate were probed for their organic carbon composition and iron oxidation state under atmospherically relevant conditions. At 40% relative humidity, oxygen diffusion and reaction was severely limited. Fe was reoxidized in the first 200 nm of the particle surface leaving reduced iron in the core. Similar gradients were observed at 60% RH, however waiting approximately 2 hours in the dark resulted in a recovery of the initial Fe(III) concentration. We draw two main conclusions from our findings. Frist, the oxidation gradients must have been the result of anoxic conditions at the interior of aerosol particles. This was predicted using a newly developed model for molecular diffusion through multiple layers with a reaction framework describing the photochemical processing of the metal organic matrix. Second, the lifetime of organic radicals in an anoxic diffusion limited organic matrix must be considerably long ( hours) to completely reoxidize iron as they wait for molecular oxygen. Long radical lifetimes in viscous organic aerosol in turn, could create high radical concentrations or favor radical-radical reactions in particles typically not considered when oxygen is plentiful. Our results impact predictions of aerosol physiochemical properties, e.g. aerosol toxicity, hygroscopicity, lifetime and light scattering properties over time which may be limited and evolve at different rates at the surface or core of particles.

Novel surface diffusion characteristics for a robust pentacene derivative on Au(1 1 1) surfaces

NASA Astrophysics Data System (ADS)

Miller, Ryan A.; Larson, Amanda; Pohl, Karsten

2017-06-01

Molecular dynamics simulations have been performed in both the ab initio and classical mechanics frameworks of 5,6,7-trithiapentacene-13-one (TTPO) molecules on flat Au(1 1 1) surfaces. Results show new surface diffusion characteristics including a strong preference for the molecule to align its long axis parallel to the sixfold Au(1 1 1) symmetry directions and subsequently diffuse along these close-packed directions, and a calculated activation energy for diffusion of 0.142 eV, about four times larger than that for pure pentacene on Au. The temperature-dependent diffusion coefficients were calculated to help quantify the molecular mobility during the experimentally observed process of forming self-assembled monolayers on gold electrodes.

Spacecraft Observations of Oblique Electron Beams Breaking the Frozen-In Law During Asymmetric Reconnection

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

Egedal, J.; Le, Ari; Daughton, William

Fully kinetic simulations of asymmetric magnetic reconnection reveal the presence of magnetic-field-aligned beams of electrons flowing toward the topological magnetic x line. Within the ~ 6d e electron-diffusion region, the beams become oblique to the local magnetic field, providing a unique signature of the electron-diffusion region where the electron frozen-in law is broken. These numerical predictions are confirmed by in situ Magnetospheric Multiscale spacecraft observations during asymmetric reconnection at Earth’s dayside magnetopause.

Spacecraft Observations of Oblique Electron Beams Breaking the Frozen-In Law During Asymmetric Reconnection

DOE PAGES

Egedal, J.; Le, Ari; Daughton, William; ...

2018-01-29

Fully kinetic simulations of asymmetric magnetic reconnection reveal the presence of magnetic-field-aligned beams of electrons flowing toward the topological magnetic x line. Within the ~ 6d e electron-diffusion region, the beams become oblique to the local magnetic field, providing a unique signature of the electron-diffusion region where the electron frozen-in law is broken. These numerical predictions are confirmed by in situ Magnetospheric Multiscale spacecraft observations during asymmetric reconnection at Earth’s dayside magnetopause.

Ion Layer Separation and Equilibrium Zonal Winds in Midlatitude Sporadic E

NASA Technical Reports Server (NTRS)

Earle, G. D.; Kane, T. J.; Pfaff, R. F.; Bounds, S. R.

2000-01-01

In-situ observations of a moderately strong mid-latitude sporadic-E layer show a separation in altitude between distinct sublayers composed of Fe(+), Mg(+), and NO(+). From these observations it is possible to estimate the zonal wind field consistent with diffusive equilibrium near the altitude of the layer. The amplitude of the zonal wind necessary to sustain the layer against diffusive effects is less than 10 meters per second, and the vertical wavelength is less than 10 km.

Effects of Potassium loading and thermal aging on K/Pt/Al2O3 high-temperature lean NOx trap catalysts

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

Luo, Jinyong; Gao, Feng; Kim, Do Heui

2014-03-31

The effects of K loading and thermal aging on the structural properties and high temperature performance of Pt/K/Al2O3 lean NOx trap (LNT) catalysts were investigated using in situ X-ray diffraction (XRD), temperature-programmed decomposition/desorption of NOx (NOx-TPD), transmission electron microscopy (TEM), NO oxidation and NOx storage tests. In situ XRD results demonstrate that KNO3 becomes extremely mobile on the Al2O3 surface, and experiences complex transformations between orthorhombic and rhombohedral structures, accompanied by sintering, melting and thermal decomposition upon heating. NOx storage results show an optimum K loading around 10% for the best performance at high temperatures. At lower K loadings wheremore » the majority of KNO3 stays as a surface layer, the strong interaction between KNO3 and Al2O3 promotes KNO3 decomposition and deteriorates high-temperature performance. At K loadings higher than 10%, the performance drop is not caused by NOx diffusion limitations as for the case of barium-based LNTs, but rather from the blocking of Pt sites by K species, which adversely affects NO oxidation. Thermal aging at 800 ºC severely deactivates the Pt/K/Al2O3 catalysts due to Pt sintering. However, in the presence of potassium, some Pt remains in a dispersed and oxidized form. These Pt species interact strongly with K and, therefore, do not sinter. After a reduction treatment, these Pt species remain finely dispersed, contributing to a partial recovery of NOx storage performance.« less

Computing eddy-driven effective diffusivity using Lagrangian particles

DOE PAGES

Wolfram, Phillip J.; Ringler, Todd D.

2017-08-14

A novel method to derive effective diffusivity from Lagrangian particle trajectory data sets is developed and then analyzed relative to particle-derived meridional diffusivity for eddy-driven mixing in an idealized circumpolar current. Quantitative standard dispersion- and transport-based mixing diagnostics are defined, compared and contrasted to motivate the computation and use of effective diffusivity derived from Lagrangian particles. We compute the effective diffusivity by first performing scalar transport on Lagrangian control areas using stored trajectories computed from online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) using the Model for Prediction Across Scales Ocean (MPAS-O). Furthermore, the Lagrangian scalar transport scheme is comparedmore » against an Eulerian scalar transport scheme. Spatially-variable effective diffusivities are computed from resulting time-varying cumulative concentrations that vary as a function of cumulative area. The transport-based Eulerian and Lagrangian effective diffusivity diagnostics are found to be qualitatively consistent with the dispersion-based diffusivity. All diffusivity estimates show a region of increased subsurface diffusivity within the core of an idealized circumpolar current and results are within a factor of two of each other. The Eulerian and Lagrangian effective diffusivities are most similar; smaller and more spatially diffused values are obtained with the dispersion-based diffusivity computed with particle clusters.« less

Computing eddy-driven effective diffusivity using Lagrangian particles

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

Wolfram, Phillip J.; Ringler, Todd D.

A novel method to derive effective diffusivity from Lagrangian particle trajectory data sets is developed and then analyzed relative to particle-derived meridional diffusivity for eddy-driven mixing in an idealized circumpolar current. Quantitative standard dispersion- and transport-based mixing diagnostics are defined, compared and contrasted to motivate the computation and use of effective diffusivity derived from Lagrangian particles. We compute the effective diffusivity by first performing scalar transport on Lagrangian control areas using stored trajectories computed from online Lagrangian In-situ Global High-performance particle Tracking (LIGHT) using the Model for Prediction Across Scales Ocean (MPAS-O). Furthermore, the Lagrangian scalar transport scheme is comparedmore » against an Eulerian scalar transport scheme. Spatially-variable effective diffusivities are computed from resulting time-varying cumulative concentrations that vary as a function of cumulative area. The transport-based Eulerian and Lagrangian effective diffusivity diagnostics are found to be qualitatively consistent with the dispersion-based diffusivity. All diffusivity estimates show a region of increased subsurface diffusivity within the core of an idealized circumpolar current and results are within a factor of two of each other. The Eulerian and Lagrangian effective diffusivities are most similar; smaller and more spatially diffused values are obtained with the dispersion-based diffusivity computed with particle clusters.« less

Experimental and theoretical studies of the effect of temperature on supercritical CO2 adsorption on illite

NASA Astrophysics Data System (ADS)

Joewondo, N.; Zhang, Y.; Prasad, M.

2016-12-01

Sequestration of carbon dioxide in shale has been a subject of interest as the result of the technological advancement in gas shale production. The process involves injection of CO2 to enhance methane recovery and storing CO2 in depleted shale reservoir at elevated pressures. To better understand both shale production and carbon storage one must study the physical phenomena acting at different scales that control the in situ fluid flow. Shale rocks are complex systems with heterogeneous structures and compositions. Pore structures of these systems are in nanometer scales and have significant gas storage capacity and surface area. Adsorption is prominent in nanometer sized pores due to the high attraction between gas molecules and the surface of the pores. Recent studies attempt to find correlation between storage capacity and the rock composition, particularly the clay content. This study, however, focuses on the study of supercritical adsorption of CO2 on pure clay sample. We have built an in-house manometric experimental setup that can be used to study both the equilibrium and kinetics of adsorption. The experiment is conducted at isothermal condition. The study of equilibrium of adsorption gives insight on the storage capacity of these systems, and the study of the kinetics of adsorption is essential in understanding the resistance to fluid transport. The diffusion coefficient, which can be estimated from the dynamic experimental results, is a parameter which quantify diffusion mobility, and is affected by many factors including pressure and temperature. The first part of this paper briefly discusses the study of both equilibrium and kinetics of the CO2 adsorption on illite. Both static and dynamic measurements on the system are compared to theoretical models available in the literature to estimate the storage capacity and the diffusion time constants. The main part of the paper discusses the effect of varying temperature on the static and dynamic experimental results.

Impact of point-source pollution on phosphorus and nitrogen cycling in stream-bed sediments.

PubMed

Palmer-Felgate, Elizabeth J; Mortimer, Robert J G; Krom, Michael D; Jarvie, Helen P

2010-02-01

Diffusive equilibration in thin films was used to study the cycling of phosphorus and nitrogen at the sediment-water interface in situ and with minimal disturbance to redox conditions. Soluble reactive phosphate (SRP), nitrate, nitrite, ammonium, sulfate, iron, and manganese profiles were measured in a rural stream, 12 m upstream, adjacent to, and 8 m downstream of a septic tank discharge. Sewage fungus adjacent to the discharge resulted in anoxic conditions directly above the sediment. SRP and ammonium increased with depth through the fungus layer to environmentally significant concentrations (440 and 1800 microM, respectively) due to release at the sediment surface. This compared to only 0.8 microM of SRP and 2.0 microM of ammonium in the water column upstream of the discharge. Concomitant removal of ammonium, nitrite and nitrate within 0.5 cm below the fungus-water interface provided evidence for anaerobic ammonium oxidation (anammox). "Hotspots" of porewater SRP (up to 350 microM) at the downstream site demonstrated potential in-stream storage of the elevated P concentrations from the effluent. These results provide direct in situ evidence of phosphorus and nitrogen release from river-bed sediments under anoxic conditions created by sewage-fungus, and highlight the wider importance of redox conditions and rural point sources on in-stream nutrient cycling.

Surface diffusivity measurements on 8mol.% yttrium oxide-zirconia bicrystals via grain boundary grooving experiments

NASA Astrophysics Data System (ADS)

Nassirou, Maissarath

Thermal grooving at grain boundaries (GBs) is a capillary-driven evolution of surface topography in the region where the grain boundary emerges at a free surface. The study of these topographic changes can provide insight into surface energetics, and in our particular case, the measurement of surface diffusivity. We have measured the surface diffusion coefficient of 8mol% Y 2O3-ZrO2 by studying the formation of thermal grooves. We studied a total of five bicrystals, with well defined orientation relationships; random [110] -60°, random [001] -30°, Sigma13 [001]/{510}, Sigma13 [001]/{320}, Sigma5 [001]/{210}. Our calculations employed the Herring relation (1951), in which the variation in the chemical potential is related to changes in topography. The samples were annealed at 1300°C and 1400°C for various period of time. Atomic Force Microscopy was used to determine the exact geometry of the thermal grooves. A first approach consisted of estimating the diffusion coefficient by using Mullins' equation. yx=0= dsDs1/ 4gb2g s12G 5/4( WkTgs) 1/4t 1/4 Where y(x =0) is the groove depth at the GB triple junction, O is the atomic volume, gs is the surface tension, gb is the grain boundary surface energy, ds is the thickness of the diffusion layer, t is the annealing time, and Ds is the surface diffusion coefficient. In Mullins' derivation, the atomic structure of the surface was ignored and it was assumed that the surface energy is independent of crystallographic orientation. In the case of zirconia, the surface energy is anisotropic. We will describe in this work a new approach to measuring surface diffusivity which accounts for the surface energy anisotropy. The study of these bicrystals will emphasize the effect of grain boundary structure on the surface diffusion coefficient, and it is for that purpose that we selected bicrystals with different tilt axes and angles. The results obtained using the equation set we have developed will be compared to those obtained by Mullins, and we show that the anisotropic groove evolution, even when perfectly symmetrical, is much slower than the corresponding isotropic case.

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

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

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

In situ investigation on ultrafast oxygen evolution reactions of water splitting in proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Kang, Zhenye; Yang, Gaoqiang; ...

2017-08-25

We present that the oxygen evolution reaction (OER) is a half reaction in electrochemical devices, including low-temperature water electrolysis, which is considered as one of the most promising methods to generate hydrogen/oxygen for the storage of energy. It is affected by many factors, and its mechanism is still not completely understood. A proton exchange membrane electrolyzer cell (PEMEC) with optical access to the surface of anode catalyst layer (CL) coupled with a distinguished high-speed and micro-scale visualization system (HMVS) was developed to in situ investigate OERs. It was revealed in real time that OERs only occur on the anode CLmore » adjacent to liquid/gas diffusion layer (LGDL). The CL electrical conductivity plays a crucial role in OERs on CLs. The large in-plane electrical resistance of CLs becomes a threshold of OERs over the entire CL, and causes a lot of catalyst waste in the middle of LGDL pores. Moreover, the oxygen bubble nucleation, growth, and detachment and the effect of current density on those processes were also characterized. Here, this study proposes a new approach for better understanding the mechanisms of OERs and optimizing the design and fabrication of membrane electrode assemblies.« less

Regulation of Methane Oxidation in a Freshwater Wetland by Water Table Changes and Anoxia

NASA Technical Reports Server (NTRS)

Roslev, Peter; King, Gary M.

1996-01-01

The effects of water table fluctuations and anoxia on methane emission and methane oxidation were studied in a freshwater marsh. Seasonal aerobic methane oxidation rates varied between 15% and 76% of the potential diffusive methane flux (diffusive flux in the absence of aerobic oxidation). On an annual basis, approximately 43% of the methane diffusing into the oxic zone was oxidized before reaching the atmosphere. The highest methane oxidation was observed when the water table was below the peat surface. This was confirmed in laboratory experiments where short-term decreases in water table levels increased methane oxidation but also net methane emission. Although methane emission was generally not observed during the winter, stems of soft rush (Juncus effusus) emitted methane when the marsh was ice covered. Indigenous methanotrophic bacteria from the wetiand studied were relatively anoxia tolerant. Surface peat incubated under anoxic conditions maintained 30% of the initial methane oxidation capacity after 32 days of anoxia. Methanotrophs from anoxic peat initiated aerobic methane oxidation relatively quickly after oxygen addition (1-7 hours). These results were supported by culture experiments with the methanotroph Methylosinus trichosporium OB3b. This organism maintained a greater capacity for aerobic methane oxidation when starved under anoxic compared to oxic conditions. Anoxic incubation of M. trichosporium OB3b in the presence of sulfide (2 mM) and a low redox potential (-110 mV) did not decrease the capacity for methane oxidation relative to anoxic cultures incubated without sulfide. The results suggest that aerobic methane oxidation was a major regulator of seasonal methane emission front the investigated wetland. The observed water table fluctuations affected net methane oxidation presumably due to associated changes in oxygen gradients. However, changes from oxic to anoxic conditions in situ had relatively little effect on survival of the methanotrophic bacteria and thus on methane oxidation potential per se.

Apparent Activation Energies Associated with Protein Dynamics on Hydrophobic and Hydrophilic Surfaces

PubMed Central

Langdon, Blake B.; Kastantin, Mark; Schwartz, Daniel K.

2012-01-01

With the use of single-molecule total internal reflection fluorescence microscopy (TIRFM), the dynamics of bovine serum albumin (BSA) and human fibrinogen (Fg) at low concentrations were observed at the solid-aqueous interface as a function of temperature on hydrophobic trimethylsilane (TMS) and hydrophilic fused silica (FS) surfaces. Multiple dynamic modes and populations were observed and characterized by their surface residence times and squared-displacement distributions (surface diffusion). Characteristic desorption and diffusion rates for each population/mode were generally found to increase with temperature, and apparent activation energies were determined from Arrhenius analyses. The apparent activation energies of desorption and diffusion were typically higher on FS than on TMS surfaces, suggesting that protein desorption and mobility were hindered on hydrophilic surfaces due to favorable protein-surface and solvent-surface interactions. The diffusion of BSA on TMS appeared to be activationless for several populations, whereas diffusion on FS always exhibited an apparent activation energy. All activation energies were small in absolute terms (generally only a few kBT), suggesting that most adsorbed protein molecules are weakly bound and move and desorb readily under ambient conditions. PMID:22713578

Development of Additive Construction Technologies for Application to Development of Lunar/Martian Surface Structures Using In-Situ Materials

NASA Technical Reports Server (NTRS)

Werkheiser, Niki J.; Fiske, Michael R.; Edmunson, Jennifer E.; Khoshnevis, Berokh

2015-01-01

For long-duration missions on other planetary bodies, the use of in situ materials will become increasingly critical. As human presence on these bodies expands, so must the breadth of the structures required to accommodate them including habitats, laboratories, berms, radiation shielding for natural radiation and surface reactors, garages, solar storm shelters, greenhouses, etc. Planetary surface structure manufacturing and assembly technologies that incorporate in situ resources provide options for autonomous, affordable, pre-positioned environments with radiation shielding features and protection from micrometeorites, exhaust plume debris, and other hazards. The ability to use in-situ materials to construct these structures will provide a benefit in the reduction of up-mass that would otherwise make long-term Moon or Mars structures cost prohibitive. The ability to fabricate structures in situ brings with it the ability to repair these structures, which allows for the self-sufficiency and sustainability necessary for long-duration habitation. Previously, under the auspices of the MSFC In-Situ Fabrication and Repair (ISFR) project and more recently, under the jointly-managed MSFC/KSC Additive Construction with Mobile Emplacement (ACME) project, the MSFC Surface Structures Group has been developing materials and construction technologies to support future planetary habitats with in-situ resources. One such additive construction technology is known as Contour Crafting. This paper presents the results to date of these efforts, including development of novel nozzle concepts for advanced layer deposition using this process. Conceived initially for rapid development of cementitious structures on Earth, it also lends itself exceptionally well to the automated fabrication of planetary surface structures using minimally processed regolith as aggregate, and binders developed from in situ materials as well. This process has been used successfully in the fabrication of construction elements using lunar regolith simulant and Mars regolith simulant, both with various binder materials. Future planned activities will be discussed as well.

Diffusion on Cu surfaces

NASA Technical Reports Server (NTRS)

Karimi, Majid

1993-01-01

Understanding surface diffusion is essential in understanding surface phenomena, such as crystal growth, thin film growth, corrosion, physisorption, and chemisorption. Because of its importance, various experimental and theoretical efforts have been directed to understand this phenomena. The Field Ion Microscope (FIM) has been the major experimental tool for studying surface diffusion. FIM have been employed by various research groups to study surface diffusion of adatoms. Because of limitations of the FIM, such studies are only limited to a few surfaces: nickel, platinum, aluminum, iridium, tungsten, and rhodium. From the theoretical standpoint, various atomistic simulations are performed to study surface diffusion. In most of these calculations the Embedded Atom Method (EAM) along with the molecular static (MS) simulation are utilized. The EAM is a semi-empirical approach for modeling the interatomic interactions. The MS simulation is a technique for minimizing the total energy of a system of particles with respect to the positions of its particles. One of the objectives of this work is to develop the EAM functions for Cu and use them in conjunction with the molecular static (MS) simulation to study diffusion of a Cu atom on a perfect as well as stepped Cu(100) surfaces. This will provide a test of the validity of the EAM functions on Cu(100) surface and near the stepped environments. In particular, we construct a terrace-ledge-kink (TLK) model and calculate the migration energies of an atom on a terrace, near a ledge site, near a kink site, and going over a descending step. We have also calculated formation energies of an atom on the bare surface, a vacancy in the surface, a stepped surface, and a stepped-kink surface. Our results are compared with the available experimental and theoretical results.

Core-shell fuel cell electrodes

DOEpatents

Adzic, Radoslav; Bliznakov, Stoyan; Vukmirovic, Miomir

2017-07-25

Embodiments of the disclosure relate to electrocatalysts. The electrocatalyst may include at least one gas-diffusion layer having a first side and a second side, and particle cores adhered to at least one of the first and second sides of the at least one gas-diffusion layer. The particle cores includes surfaces adhered to the at least one of the first and second sides of the at least one gas-diffusion layer and surfaces not in contact with the at least one gas-diffusion layer. Furthermore, a thin layer of catalytically atoms may be adhered to the surfaces of the particle cores not in contact with the at least one gas-diffusion layer.

Estimation of Chinese surface NO2 concentrations combining satellite data and Land Use Regression

NASA Astrophysics Data System (ADS)

Anand, J.; Monks, P.

2016-12-01

Monitoring surface-level air quality is often limited by in-situ instrument placement and issues arising from harmonisation over long timescales. Satellite instruments can offer a synoptic view of regional pollution sources, but in many cases only a total or tropospheric column can be measured. In this work a new technique of estimating surface NO2 combining both satellite and in-situ data is presented, in which a Land Use Regression (LUR) model is used to create high resolution pollution maps based on known predictor variables such as population density, road networks, and land cover. By employing a mixed effects approach, it is possible to take advantage of the spatiotemporal variability in the satellite-derived column densities to account for daily and regional variations in surface NO2 caused by factors such as temperature, elevation, and wind advection. In this work, surface NO2 maps are modelled over the North China Plain and Pearl River Delta during high-pollution episodes by combining in-situ measurements and tropospheric columns from the Ozone Monitoring Instrument (OMI). The modelled concentrations show good agreement with in-situ data and surface NO2 concentrations derived from the MACC-II global reanalysis.

DIRECT IMAGE PROCESSING OF CORRODING SURFACES APPLIED TO FRICTION STIR WELDING.

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

ISAACS,H.S.ET AL.

An in situ process for visually locating corrosion is presented. The process visually displays image differences obtained by subtracting one digitized image from another. The difference image shows only where changes have taken place during period between the recording of the two images. Changes are due to both corrosion attack of the surface and concentration changes of dissolved corrosion products in solution. Indicators added to the solution assist by decorating sites of corrosion as diffusion and convection of the dissolved products increase the size of the affected region. A study of the initial stages of corrosion of a friction stirmore » welded Al alloy 7075 has been performed using this imaging technique. Pitting potential measurements suggest that there was an initial increased sensitivity to corrosion. The difference image technique demonstrated that it was due to a reformation of the passive film that occurs with Zn containing Al alloys which occurs preferentially along flow protected regions. The most susceptible region of the weld was found to be where both limited deformation and thermal transients are produced during welding.« less

Porous WO3/graphene/polyester textile electrode materials with enhanced electrochemical performance for flexible solid-state supercapacitors.

PubMed

Jin, Li-Na; Liu, Ping; Jin, Chun; Zhang, Jia-Nan; Bian, Shao-Wei

2018-01-15

In this work, a flexible and porous WO 3 /grapheme/polyester (WO 3 /G/PT) textile electrode was successfully prepared by in situ growing WO 3 on the fiber surface inside G/PT composite fabrics. The unique electrode structure facilitates to enhance the energy storage performance because the 3D conductive network constructed by the G/PT increase the electron transportation rate, nanotructured WO 3 exposed enhanced electrochemically active surface area and the hierarchically porous structure improved the electrolyte ion diffusion rate. The optimized WO 3 /G/PT textile electrode exhibited good electrochemical performance with a high areal capacitance of 308.2mFcm -2 at a scan rate of 2mVs -1 and excellent cycling stability. A flexible asymmetric supercapacitor (ASC) device was further fabricated by using the WO 3 /G/PT electrode and G/PT electrode, which exhibited a good specific capacitance of 167.6mFcm -3 and high energy density of 60μWhcm -3 at the power density of 2320 μWcm -3 . Copyright © 2017 Elsevier Inc. All rights reserved.

Nitration of benzo[a]pyrene adsorbed on coal fly ash particles by nitrogen dioxide: role of thermal activation.

PubMed

Kristovich, Robert L; Dutta, Prabir K

2005-09-15

Nitration of benzo[a]pyrene (BaP) by nitrogen dioxide (NO2) adsorbed on the surface of thermally activated coal fly ash and model aluminosilicate particles led to the formation of nitrobenzo[a]pyrenes as verified by extraction and gas chromatography/mass spectrometry (GC/MS). In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) was utilized to follow the nitration reaction on the surface of zeolite Y. Nitrobenzo[a]pyrene formation was observed along with the formation of nitrous acid and nitrate species. The formation of the BaP radical cation was also observed on thermally activated aluminosilicate particles by electron spin resonance (ESR) spectroscopy. On the basis of GC/MS, DRIFTS, and ESR spectroscopy results, a mechanism of nitration involving intermediate BaP radical cations generated on thermally activated aluminosilicate particles is proposed. These observations have led to the hypothesis that nitration of adsorbed polyaromatic hydrocarbons on coal fly ash by reaction with nitrogen oxides can occur in the smokestack, but with the aging of the fly ash particles, the extent of the nitration reaction will be diminished.

An Analysis of Diffuse Light Attenuation in the Northern Gulf of Mexico Hypoxic Zone Using the SeaWiFS Satellite Data Record

DTIC Science & Technology

2011-01-01

ELEMENT NUMBER 0601153N 6. AUTHOR(S) B . Schaeffer, G. Sinclair, J. Lehrter, M. Murrell, J. Kurtz, Richard Gould, D. Yates, G. Smith 5d. PROJECT...continental shelf, hypoxia 16. SECURITY CLASSIFICATION OF: a. REPORT Unclassified b . ABSTRACT Unclassified c. THIS PAGE Unclassified 17. LIMITATION OF...diffuse light at- tenuation were evaluated with a Model II geometric mean linear re- gression (Laws & Archie , 1981) using only in situ data

Doxycycline hyclate-loaded bleached shellac in situ forming microparticle for intraperiodontal pocket local delivery.

PubMed

Phaechamud, Thawatchai; Chanyaboonsub, Nuttapong; Setthajindalert, Orn

2016-10-10

Bleached shellac (BS) is a water-insoluble polyester resin made up of sesquiterpenoid acids esterified with hydroxy aliphatic acids. In this study, BS dissolved in N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and 2-pyrrolidone was used as the internal phase of oil in oil emulsion using olive oil emulsified with glyceryl monostearate (GMS) as the external phase of in situ forming microparticles (ISM). Doxycycline hyclate (DH)-loaded BS ISMs were tested for emulsion stability, viscosity, rheology, transformation into microparticles, syringeability, drug release, surface topography, in vitro degradation and antimicrobial activities against Staphylococcus aureus, Streptococcus mutans and Porphyromonas gingivalis. All emulsions exhibited pseudoplastic flow and notably low syringeability force. Slower transformation from emulsion into microparticles of ISM prepared with 2-pyrrolidone was owing to slower solvent exchange of this solvent which promoted less porous structure of obtained BS matrix microparticles. The system containing 2-pyrrolidone exhibited a higher degradability than that prepared with DMSO. Developed DH-loaded BS ISMs exhibited a sustainable drug release for 47days with Fickian diffusion and effectively inhibited P. gingivalis, S. mutans and S. aureus. Therefore a DH-loaded BS ISM using olive oil containing GMS as the external phase and 2-pyrrolidone as a solvent was a suitable formulation for periodontitis treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

Electric-field noise from carbon-adatom diffusion on a Au(110) surface: First-principles calculations and experiments

NASA Astrophysics Data System (ADS)

Kim, E.; Safavi-Naini, A.; Hite, D. A.; McKay, K. S.; Pappas, D. P.; Weck, P. F.; Sadeghpour, H. R.

2017-03-01

The decoherence of trapped-ion quantum gates due to heating of their motional modes is a fundamental science and engineering problem. This heating is attributed to electric-field noise arising from the trap-electrode surfaces. In this work, we investigate the source of this noise by focusing on the diffusion of carbon-containing adsorbates on the surface of Au(110). We show by density functional theory, based on detailed scanning probe microscopy, how the carbon adatom diffusion on the gold surface changes the energy landscape and how the adatom dipole moment varies with the diffusive motion. A simple model for the diffusion noise, which varies quadratically with the variation of the dipole moment, predicts a noise spectrum, in accordance with the measured values.

In situ spectroscopy of ligand exchange reactions at the surface of colloidal gold and silver nanoparticles

NASA Astrophysics Data System (ADS)

Dinkel, Rebecca; Peukert, Wolfgang; Braunschweig, Björn

2017-04-01

Gold and silver nanoparticles with their tunable optical and electronic properties are of great interest for a wide range of applications. Often the ligands at the surface of the nanoparticles have to be exchanged in a second step after particle formation in order to obtain a desired surface functionalization. For many techniques, this process is not accessible in situ. In this review, we present second-harmonic scattering (SHS) as an inherently surface sensitive and label-free optical technique to probe the ligand exchange at the surface of colloidal gold and silver nanoparticles in situ and in real time. First, a brief introduction to SHS and basic features of the SHS of nanoparticles are given. After that, we demonstrate how the SHS intensity decrease can be correlated to the thiol coverage which allows for the determination of the Gibbs free energy of adsorption and the surface coverage.

MuSET, A High Precision Logging Sensor For Downhole Spontaneous Electrical Potential.

NASA Astrophysics Data System (ADS)

Pezard, P. A.; Gautier, S.; Le Borgne, T.; Deltombe, J.

2008-12-01

MuSET has been designed by ALT and CNRS in the context of the EC ALIANCE research project. It is based on an existing multi-parameter borehole fluid sensor (p, T, Cw, pH, Eh) built by ALT. The new downhole geophysical tool aims to measure subsurface spontaneous electrical potentials (SP) in situ with great precision (< µV). For this, the device includes an unpolazirable Pb/PbCl2 electrode referred to a similar one at surface. Initial field testing in Montpellier (Languedoc, France), Ploemeur (Brittany, France) and Campos (Mallorca, Spain) took advantage of the set of field sites developed as part of ALIANCE then as part of the environmental research observatory (ORE) network for hydrogeology "H+". While Cretaceous marly limestone at Lavalette (Montpellier) proved to be almost exclusively the source of membrane potential, the clay-starved Miocene reefal carbonates of Campos generate a signal dominated by electrokinetic potential. This signal is generated due to nearby agricultural pumping, and associated strong horizontal flow. At the top of the salt to fresh water transtion, a discrepancy between the SP signal and the absence of vertical flow measured with a heat-pulse flowmeter hints at a capacity to detect the "fluid-junction", diffusion potential. At Ploemeur, the altered granite found in the vicinity of faults and fractures is also the source of a SP signal, mostly surface related while most fractures appear to be closed. In all, the MuSET demonstrates a capacity to identify several subsurface sources of natural electrical potential such as diffusion ones (membrane potential in the presence of clays, fickean processes due to pore fluid salinity gradients), or else the electrokinetic potential with pore fluid pressure gradients. While spontaneous electrical currents often loop out of the borehole, MuSET might be used as a radial electrical flowmeter once the diffusion components taken into account.

30 CFR 905.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false Special performance standards-In situ... § 905.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 942.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Special performance standards-In situ... § 942.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 903.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false Special performance standards-In situ... § 903.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, applies to any person who conducts surface coal mining...

30 CFR 942.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false Special performance standards-In situ... § 942.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 942.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false Special performance standards-In situ... § 942.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 942.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 30 Mineral Resources 3 2014-07-01 2014-07-01 false Special performance standards-In situ... § 942.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 905.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false Special performance standards-In situ... § 905.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 905.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Special performance standards-In situ... § 905.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 903.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Special performance standards-In situ... § 903.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, applies to any person who conducts surface coal mining...

30 CFR 942.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Special performance standards-In situ... § 942.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 905.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 30 Mineral Resources 3 2011-07-01 2011-07-01 false Special performance standards-In situ... § 905.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 903.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 30 Mineral Resources 3 2010-07-01 2010-07-01 false Special performance standards-In situ... § 903.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, applies to any person who conducts surface coal mining...

30 CFR 905.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false Special performance standards-In situ... § 905.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, shall apply to any person who conducts surface coal...

30 CFR 903.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 30 Mineral Resources 3 2013-07-01 2013-07-01 false Special performance standards-In situ... § 903.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, applies to any person who conducts surface coal mining...

30 CFR 903.828 - Special performance standards-In situ processing.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 30 Mineral Resources 3 2012-07-01 2012-07-01 false Special performance standards-In situ... § 903.828 Special performance standards—In situ processing. Part 828 of this chapter, Special Permanent Program Performance Standards—In Situ Processing, applies to any person who conducts surface coal mining...

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

Temperature-induced structural evolution of Sm nanoparticles on Al2O3 thin film: An in-situ investigation using SRPES, XPS and STM

NASA Astrophysics Data System (ADS)

Xu, Qian; Hu, Shanwei; Wang, Weijia; Wang, Yan; Ju, Huanxin; Zhu, Junfa

2018-02-01

The structural evolution of Sm nanoclusters on ultrathin film of Al2O3 epitaxially grown on Ni3Al(111) substrate at elevated temperatures was investigated in-situ using synchrotron radiation photoemission spectroscopy (SRPES), X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM). The vapor-deposited metallic Sm onto the Al2O3 thin film at 300 K is partially oxidized, leading to the appearance of both Sm2+ and Sm3+ states at low coverages, due to the charge transfer from Sm to oxide film. The complete oxidation of the Sm, i.e., all Sm2+ converted to Sm3+, occurs when the sample is annealed to 500 K. Further annealing results in the diffusion of Sm into the Al2O3 lattice. At ∼900 K, the formation of a SmAlO3 complex is observed. However, this complex starts to decompose and desorb from the surface at temperature higher than 1200 K. Interestingly, it is found that Sm can promote the oxidation of Ni3Al substrate and thicken the alumina film when Sm is deposited at room temperature onto the Al2O3/Ni3Al(111) substrate followed by annealing in oxygen environment at ∼800 K.

Dynamic interactions between a membrane binding protein and lipids induce fluctuating diffusivity

PubMed Central

Yamamoto, Eiji; Akimoto, Takuma; Kalli, Antreas C.; Yasuoka, Kenji; Sansom, Mark S. P.

2017-01-01

Pleckstrin homology (PH) domains are membrane-binding lipid recognition proteins that interact with phosphatidylinositol phosphate (PIP) molecules in eukaryotic cell membranes. Diffusion of PH domains plays a critical role in biological reactions on membrane surfaces. Although diffusivity can be estimated by long-time measurements, it lacks information on the short-time diffusive nature. We reveal two diffusive properties of a PH domain bound to the surface of a PIP-containing membrane using molecular dynamics simulations. One is fractional Brownian motion, attributed to the motion of the lipids with which the PH domain interacts. The other is temporally fluctuating diffusivity; that is, the short-time diffusivity of the bound protein changes substantially with time. Moreover, the diffusivity for short-time measurements is intrinsically different from that for long-time measurements. This fluctuating diffusivity results from dynamic changes in interactions between the PH domain and PIP molecules. Our results provide evidence that the complexity of protein-lipid interactions plays a crucial role in the diffusion of proteins on biological membrane surfaces. Changes in the diffusivity of PH domains and related membrane-bound proteins may in turn contribute to the formation/dissolution of protein complexes in membranes. PMID:28116358

Characterization of Iridium Coated Rhenium Used in High-Temperature, Radiation-Cooled Rocket Thrusters

NASA Technical Reports Server (NTRS)

Stulen, R. H.; Boehme, D. R.; Clift, W. M.; McCarty, K. F.

1990-01-01

Materials used for radiation-cooled rocket thrusters must be capable of surviving under extreme conditions of high-temperatures and oxidizing environments. While combustion efficiency is optimized at high temperatures, many refractory metals are unsuitable for thruster applications due to rapid material loss from the formation of volatile oxides. This process occurs during thruster operation by reaction of the combustion products with the material surface. Aerojet Technical Systems has developed a thruster cone chamber constructed of Re coated with Ir on the inside surface where exposure to the rocket exhaust occurs. Re maintains its structural integrity at high temperature and the Ir coating is applied as an oxidation barrier. Ir also forms volatile oxide species (IrO2 and IrO3) but at a considerably slower rate than Re. In order to understand the performance limits of Ir-coated Re thrusters, we are investigating the interdiffusion and oxidation kinetics of Ir/Re. The formation of iridium and rhenium oxides has been monitored in situ by Raman spectroscopy during high temperature exposure to oxygen. For pure Ir, the growth of oxide films as thin as approximately 200 A could be easily detected and the formation of IrO2 was observed at temperatures as low as 600 C. Ir/Re diffusion test specimens were prepared by magnetron sputtering of Ir on Re substrates. Concentration profiles were determined by sputter Auger depth profiles of the heat treated specimens. Significant interdiffusion was observed at temperatures as low as 1000 C. Measurements of the activation energy suggest that below 1350 C, the dominant diffusion path is along defects, most likely grain boundaries, rather than bulk diffusion through the grains. The phases that form during interdiffusion have been examined by x ray diffraction. Analysis of heated test specimens indicates that the Ir-Re reaction produces a solid solution phase of Ir dissolved in the HCP structure of Re.

Diffusion of nitrogen oxides and oxygenated volatile organic compounds through snow

NASA Astrophysics Data System (ADS)

Bartels-Rausch, T.; Ammann, M.; Schneebeli, M.; Riche, F.; Wren, S. N.

2013-12-01

Release of trace gases from surface snow on Earth drives atmospheric chemistry, especially in the Polar Regions. The exchange of atmospheric trace gases between snow or firn and atmosphere can also determine how these species are incorporated into glacial ice, which serves as archive. At low wind conditions, such fluxes between the porous surface snow and the overlaying atmosphere are driven by diffusion through the interstitial air. Here we present results from two laboratory studies where we looked at how the structure of the snowpack, the interaction of the trace gases with the snow surface, and the grain boundaries influence the diffusion of NO, NO2, HONO, methanol, and acetone on time scales up to 1 h. The diffusion through a snow sample was the direct observable of the experiments. Results for different snow types are presented, the structures of which were analysed by means of X-ray computed micro-tomography. Grain boundary content was quantified in one sample using a stereological method. The observed diffusion profiles were very well reproduced in simulations based on gas-phase diffusion and the known structure of the snow sample at temperatures above 253 K. At colder temperatures surface interactions start to dominate the diffusion. Parameterizing these in terms of adsorption to the solid ice surface gave much better agreement to the observations than the use of air - liquid partitioning coefficients. This is a central result as field and modelling studies have indicated that the partitioning to liquid water might describe the diffusion through snow much better even at cold temperatures. This will be discussed using our recent results from surface sensitive spectroscopy experiments. No changes in the diffusion was observed by increasing the number of grain boundaries in the snow sample by a factor of 7.

[Application of BaSO4 diffuser plate in 250-400 nm spectral radiance calibration].

PubMed

Jia, Hui; Li, Fu-tian

2004-01-01

Sprayed BaSO4 diffuser plate is the most Lambertian surface actually used in spectral radiance calibration known by now. Its hemispheric reflectance and Bi-directional Reflectance Distribution Functions (BRDF) were measured in the experiment. Its diffuse characteristics were compared with Lambertian surface. In order to calibrate spectral radiance more accurately, the small variation of diffuser's BRDF with scattered angles and the nonuniformity of spectral irradiance on diffuser surface illuminated by the standard lamp should be considered. By integrating the radiation flux reflected by the element area and that entering the entrance slit within the viewing area of spectrometer, the measured spectral radiance can be calculated. Furthermore, the spectral radiance of Lambertian surface whose BRDF was derived from hemispheric reflectance was compared with that from the average of the measured BRDF.

In-situ generation of chlorine dioxide for surface decontamination of produce

USDA-ARS?s Scientific Manuscript database

Fruits and vegetables, particularly fresh-cut products, are frequently contaminated with bacterial pathogens and implicated in foodborne illnesses. The objective of this study was to develop a unique in-situ sequential surface decontamination method for produce using sodium chlorite and acid. The ...

Overall adsorption rate of metronidazole, dimetridazole and diatrizoate on activated carbons prepared from coffee residues and almond shells.

PubMed

Flores-Cano, J V; Sánchez-Polo, M; Messoud, J; Velo-Gala, I; Ocampo-Pérez, R; Rivera-Utrilla, J

2016-03-15

This study analyzed the overall adsorption rate of metronidazole, dimetridazole, and diatrizoate on activated carbons prepared from coffee residues and almond shells. It was also elucidated whether the overall adsorption rate was controlled by reaction on the adsorbent surface or by intraparticle diffusion. Experimental data of the pollutant concentration decay curves as a function of contact time were interpreted by kinetics (first- and second-order) and diffusion models, considering external mass transfer, surface and/or pore volume diffusion, and adsorption on an active site. The experimental data were better interpreted by a first-order than second-order kinetic model, and the first-order adsorption rate constant varied linearly with respect to the surface area and total pore volume of the adsorbents. According to the diffusion model, the overall adsorption rate is governed by intraparticle diffusion, and surface diffusion is the main mechanism controlling the intraparticle diffusion, representing >90% of total intraparticle diffusion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Peripheral Ulcerative Keratitis following Laser in situ Keratomileusis

PubMed Central

Burkholder, Bryn M.; Kuo, Irene C.

2016-01-01

Purpose We report a case of a patient with a history of glomerulonephropathy, not disclosed prior to laser in situ keratomileusis (LASIK), who developed severe postoperative peripheral ulcerative keratitis (PUK) soon after surgery. Method Case report. Results Within a week of surgery, the patient, who had no blepharitis or ocular surface disease, also developed diffuse lamellar keratitis (DLK) that was not contiguous with the PUK. Microbiologic evaluation of the flap interface disclosed no organisms, and no epithelial ingrowth was found. Both PUK and DLK resolved with topical and oral steroid therapy, and the patient's induced refractive error improved over the 12 months following LASIK. Conclusions Necrotizing keratitis has been described after LASIK surgery in patients with or without autoimmune disease. However, to our knowledge, there has been no case of PUK following LASIK. As shown by our patient's clinical course and the typical association of PUK with systemic conditions, patients with a history of atypical postinfectious sequelae may require additional preoperative counseling, vigilant postoperative monitoring, and possibly additional intervention. Because patients do not always divulge medical details, especially if an extraocular site was involved or illness occurred many years prior, this case demonstrates the importance of performing a diligent history that excludes autoimmune disorders or atypical postinfectious sequelae prior to proceeding with keratorefractive intervention. PMID:26889153

Peripheral Ulcerative Keratitis following Laser in situ Keratomileusis.

PubMed

Burkholder, Bryn M; Kuo, Irene C

2016-01-01

We report a case of a patient with a history of glomerulonephropathy, not disclosed prior to laser in situ keratomileusis (LASIK), who developed severe postoperative peripheral ulcerative keratitis (PUK) soon after surgery. Case report. Within a week of surgery, the patient, who had no blepharitis or ocular surface disease, also developed diffuse lamellar keratitis (DLK) that was not contiguous with the PUK. Microbiologic evaluation of the flap interface disclosed no organisms, and no epithelial ingrowth was found. Both PUK and DLK resolved with topical and oral steroid therapy, and the patient's induced refractive error improved over the 12 months following LASIK. Necrotizing keratitis has been described after LASIK surgery in patients with or without autoimmune disease. However, to our knowledge, there has been no case of PUK following LASIK. As shown by our patient's clinical course and the typical association of PUK with systemic conditions, patients with a history of atypical postinfectious sequelae may require additional preoperative counseling, vigilant postoperative monitoring, and possibly additional intervention. Because patients do not always divulge medical details, especially if an extraocular site was involved or illness occurred many years prior, this case demonstrates the importance of performing a diligent history that excludes autoimmune disorders or atypical postinfectious sequelae prior to proceeding with keratorefractive intervention.

Diffusion of GPI-anchored proteins is influenced by the activity of dynamic cortical actin

PubMed Central

Saha, Suvrajit; Lee, Il-Hyung; Polley, Anirban; Groves, Jay T.; Rao, Madan; Mayor, Satyajit

2015-01-01

Molecular diffusion at the surface of living cells is believed to be predominantly driven by thermal kicks. However, there is growing evidence that certain cell surface molecules are driven by the fluctuating dynamics of cortical cytoskeleton. Using fluorescence correlation spectroscopy, we measure the diffusion coefficient of a variety of cell surface molecules over a temperature range of 24–37°C. Exogenously incorporated fluorescent lipids with short acyl chains exhibit the expected increase of diffusion coefficient over this temperature range. In contrast, we find that GPI-anchored proteins exhibit temperature-independent diffusion over this range and revert to temperature-dependent diffusion on cell membrane blebs, in cells depleted of cholesterol, and upon acute perturbation of actin dynamics and myosin activity. A model transmembrane protein with a cytosolic actin-binding domain also exhibits the temperature-independent behavior, directly implicating the role of cortical actin. We show that diffusion of GPI-anchored proteins also becomes temperature dependent when the filamentous dynamic actin nucleator formin is inhibited. However, changes in cortical actin mesh size or perturbation of branched actin nucleator Arp2/3 do not affect this behavior. Thus cell surface diffusion of GPI-anchored proteins and transmembrane proteins that associate with actin is driven by active fluctuations of dynamic cortical actin filaments in addition to thermal fluctuations, consistent with expectations from an “active actin-membrane composite” cell surface. PMID:26378258

3D-CFD analysis of diffusion and emission of VOCs in a FLEC cavity.

PubMed

Zhu, Q; Kato, S; Murakami, S; Ito, K

2007-06-01

This study is performed as a part of research that examines the emission and diffusion characteristics of volatile organic compounds (VOCs) from indoor building materials. In this paper, the flow field and the emission field of VOCs from the surface of building materials in a Field and Laboratory Emission Cell (FLEC) cavity are examined by 3D Computational Fluid Dynamics (CFD) analysis. The flow field within the FLEC cavity is laminar. With a total flow of 250 ml/min, the air velocity near the test material surface ranges from 0.1 to 4.5 cm/s. Three types of emission from building materials are studied here: (i) emission phenomena controlled by internal diffusion, (ii) emission phenomena controlled by external diffusion, and (iii) emission phenomena controlled by mixed diffusion (internal + external diffusion). In the case of internal diffusion material, with respect to the concentration distribution in the cavity, the local VOC emission rate becomes uniform and the FLEC works well. However, in the case of evaporation type (external diffusion) material, or mixed type materials (internal + external diffusion) when the resistance to transporting VOCs in the material is small, the FLEC is not suitable for emission testing because of the thin FLEC cavity. In this case, the mean emission rate is restricted to a small value, since the VOC concentration in the cavity rises to the same value as the surface concentration through molecular diffusion within the thin cavity, and the concentration gradient normal to the surface becomes small. The diffusion field and emission rate depend on the cavity concentration and on the Loading Factor. That is, when the testing material surface in the cavity is partially sealed to decrease the Loading Factor, the emission rate become higher with the decrease in the exposed area of the testing material. The flow field and diffusion field within the FLEC cavity are investigated by CFD method. After presenting a summary of the velocity distributed over the surface of test material and the emission properties of different type materials in FLEC, the paper pointed out that there is a bias in the airflow inside the FLEC cavity but do not influence the result of test emission rate, and the FLEC method is unsuitable for evaporation type materials in which the mass transfer of the surface controls the emission rate.

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

Chen, Yinshan; Zhu, Men; Laventure, Audrey

Surface grating decay measurements have been performed on three closely related molecular glasses to study the effect of intermolecular hydrogen bonds on surface diffusion. The three molecules are derivatives of bis(3,5-dimethyl-phenylamino)-1,3,5-triazine and differ only in the functional group R at the 2-position, with R being C 2H 5, OCH 3, and NHCH 3, and referred to as “Et”, “OMe”, and “NHMe”, respectively. Of the three molecules, NHMe forms more extensive intermolecular hydrogen bonds than Et and OMe and was found to have slower surface diffusion. For Et and OMe, surface diffusion is so fast that it replaces viscous flow asmore » the mechanism of surface grating decay as temperature is lowered. In contrast, no such transition was observed for NHMe under the same conditions, indicating significantly slower surface diffusion. This result is consistent with the previous finding that extensive intermolecular hydrogen bonds slow down surface diffusion in molecular glasses and is attributed to the persistence of hydrogen bonds even in the surface environment. Here, this result is also consistent with the lower stability of the vapor-deposited glass of NHMe relative to those of Et and OMe and supports the view that surface mobility controls the stability of vapor-deposited glasses.« less

Role of solvent in metal-on-metal surface diffusion: A case for rational solvent selection for materials synthesis

NASA Astrophysics Data System (ADS)

Imandi, Venkataramana; Jagannath, Mantha Sai Pavan; Chatterjee, Abhijit

2018-09-01

The effect of solvent on diffusion at metal surfaces is poorly understood despite its importance to morphological evolution during materials processing, corrosion and catalysis. In this article, we probe the metal-solvent interfacial structure, effective nature of interactions and dynamics when a solvent is in contact with a metal using a novel accelerated molecular dynamics simulation technique called temperature programmed molecular dynamics (TPMD). TPMD simulations reveal that surface diffusion of metal-on-metal can be made to vary over orders-of-magnitude by tuning the metal-solvent interaction. Ultimately, the solvent can have an indirect effect on diffusion. As the solvent tugs at the metal surface the separation between the adsorbed metal atom (adatom) and the surface layer can be modulated via metal-solvent interactions. The resulting adatom-surface separation can cause stronger/weaker binding of the adatom to the metal surface, which in turn results in the observed slower/enhanced diffusion in the presence of solvent. We believe this effect is ubiquitous in pure metal and metal alloys and in principle one could rationally select solvent to control the material structural evolution. Implications on materials synthesis are discussed in the context of formation of nanoporous materials.

ZVI (Fe0) desalination: catalytic partial desalination of saline aquifers

NASA Astrophysics Data System (ADS)

Antia, David D. J.

2018-05-01

Globally, salinization affects between 100 and 1000 billion m3 a-1 of irrigation water. The discovery that zero valent iron (ZVI, Fe0) could be used to desalinate water (using intra-particle catalysis in a diffusion environment) raises the possibility that large-scale in situ desalination of aquifers could be undertaken to support agriculture. ZVI desalination removes NaCl by an adsorption-desorption process in a multi-stage cross-coupled catalytic process. This study considers the potential application of two ZVI desalination catalyst types for in situ aquifer desalination. The feasibility of using ZVI catalysts when placed in situ within an aquifer to produce 100 m3 d-1 of partially desalinated water from a saline aquifer is considered.

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

PubMed Central

Zhang, Hua; Wang, Chen; Sun, Han-Lei; Fu, Gang; Chen, Shu; Zhang, Yue-Jiao; Chen, Bing-Hui; Anema, Jason R.; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun

2017-01-01

Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis. PMID:28537269

Dynamics of two-dimensional monolayer water confined in hydrophobic and charged environments.

PubMed

Kumar, Pradeep; Han, Sungho

2012-09-21

We perform molecular dynamics simulations to study the effect of charged surfaces on the intermediate and long time dynamics of water in nanoconfinements. Here, we use the transferable interaction potential with five points (TIP5P) model of a water molecule confined in both hydrophobic and charged surfaces. For a single molecular layer of water between the surfaces, we find that the temperature dependence of the lateral diffusion constant of water up to very high temperatures remains Arrhenius with a high activation energy. In case of charged surfaces, however, the dynamics of water in the intermediate time regime is drastically modified presumably due to the transient coupling of dipoles of water molecules with electric field fluctuations induced by charges on the confining surfaces. Specifically, the lateral mean square displacements display a distinct super-diffusive behavior at intermediate time scale, defined as the time scale between ballistic and diffusive regimes. This change in the intermediate time-scale dynamics in the charged confinement leads to the enhancement of long-time dynamics as reflected in increasing diffusion constant. We introduce a simple model for a possible explanation of the super-diffusive behavior and find it to be in good agreement with our simulation results. Furthermore, we find that confinement and the surface polarity enhance the low frequency vibration in confinement compared to bulk water. By introducing a new effective length scale of coupling between translational and orientational motions, we find that the length scale increases with the increasing strength of the surface polarity. Further, we calculate the correlation between the diffusion constant and the excess entropy and find a disordering effect of polar surfaces on the structure of water. Finally, we find that the empirical relation between the diffusion constant and the excess entropy holds for a monolayer of water in nanoconfinement.